Assessment Attività e Unità di Ricerca 1998-2
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Assessment Attività e Unità di Ricerca 1998-2
Consorzio Interuniversitario Nazionale "La Chimica per l’Ambiente" http://www.unive.it/inca Assessment Attività e Unità di Ricerca 1998-2002 Settembre 2003 2 Indice Unità di ricerca del Consorzio Alessandria Aquila 1 Aquila 2 Bari 1 Bari 2 Bologna 1 Bologna 2 Bologna 3 Bologna 4 Bologna 5 Bologna 6 Bologna 8 Bologna 9 Cagliari 1 Cagliari 2 Cagliari 3 Camerino Caserta Catania 2 Catania 3 Catania 4 Catania 5 Catania 6 Catania 7 Cosenza Ferrara 1 Firenze Genova 1 Genova 2 Genova 3 Lecce Messina 1 Messina 2 Messina 3 Milano 2 Milano 4 Milano 5 Milano Politecnico Napoli 2 Napoli 3 Napoli 4 Napoli 5 Napoli 7 Napoli 8 Napoli 9 Palermo 1 Palermo 2 Palermo 3 Palermo 4 Parma 1 Parma 2 Pavia 1 Pavia 2 Perugia Roma 1 Roma 2 Roma 3 Zerbinati Cerichelli Mazzeo Aresta Curci Marchetti Trifirò Morselli Roda Girotti Trombini Rosini Chiavari Cao Lallai Polcaro Ballini Di Blasio Condorelli Montaudo Arena Librando Crisafulli Corsaro Drioli Maldotti Scozzafava Canepa Del Borghi Mariani Vasapollo Micali Galvagno De Robertis Raganini Galli Rossi Citterio Piccolo Barone Previtera Palumbo Paolillo Iesce Santacesaria Schiavello Rizzuti La Mantia Gianguzza Pochini – Ungaro Sartori Albini Pesavento Savelli Beccari Laganà Petronio p. 4 14 24 29 47 59 77 93 108 123 137 151 161 173 185 196 202 212 223 233 243 255 273 283 293 305 317 322 330 344 351 361 374 383 390 405 414 421 437 448 459 469 478 487 497 500 524 537 553 564 581 593 600 621 634 644 655 3 Roma 4 Sassari 2 Siena Torino 1 Torino 2 Torino 3 Trieste 1 Trieste 2 Trieste 3 Urbino Venezia 1 Venezia 4 Venezia 6 Venezia 7 Verona Viterbo Bianco Gladiali Tiezzi Coluccia Mentasti Pelizzetti Graziani Valentin Reisenhofer Mangani Tundo Botteghi Baldi Marziano Cecchi Giovannozzi 664 671 690 706 732 738 757 766 773 781 798 807 817 825 836 846 Laboratori INCA Marghera Cagliari Catania 859 873 878 Report from the Managing Committee of INCA 902 4 ALESSANDRIA Name of the Research Unit UNIPMN Unità Operativa di Alessandria (Alessandria Operating Unit) Research Leader Prof. Orfeo Zerbinati Contact Person University: Università del Piemonte Orientale “A. Avogadro” (University of Eastern Piedmont “A. Avogadro”) Faculty: Scienze Matematiche, Fisiche e Naturali (Chimica) (Mathematic, Physical and Natural Sciences - Chemistry) Name: Orfeo Zerbinati Mailing Address: Spalto Marengo, 33/35, I-15100 Alessandria Phone : +39 131 287432 Fax : +39 131 287416 E-mail : [email protected] Department: DiSTA - Scienze e Tecnologie Avanzate (DiSTA - Sciences and Advanced Technologies) Thematic area A) Tecnologie di depurazione (membrane, sonochimica, fotocatalisi, elettrochimica e altre). B) Tecnologie innovative di monitoraggio Introduction and Context The Eastern Piedmont University was formally established in 1998. All of its academic staff came from other universities, mainly from those of Turin and of Genoa. Some local situations, of particular relevance for the environment, orient toward this topic the activities of the researchers. Introduction to the Self-evaluation Report The Operating Unit of Alessandria rose in 1998, as soon as our University adhered to INCA. For this reason, data prior to 1998 cannot be indicated, except for publications, that can also demonstrate the continuity of the present activity with respect to the past one. The research and teaching activities of the components of this Unit are mainly focused on environmental topics, both for basic and applied aspects. The main research themes will be described, with respect to the results achieved and future perspectives. The University, the Faculty and the Department The University of Eastern Piedmont has started its courses in 1987, as a part of the activities of the well established University of Turin, with the aim of facilitating the fruition of its teaching and research offer also for those areas of Piedmont situated farther. In 1998 these new activities became officially independent after the institution of a new University. The teaching activities are structured in 10 faculties : Literature and Philosophy, Medicine and Surgery, Social Sciences, Law, Pharmacy, Economy and Mathemathical, Physical and Natural Sciences (MFN Sciences), with approximately 350 units in the academic staff and 5,000 students. The faculties are distributed into three cities, Alessandria, Novara and Vercelli and the MFN Science Faculty has been situated in the city of Alessandria, together with Social Sciences and Law. For its dimensions, the University of Eastern Piedmont can be classified as a small university, but it is relevant for the Piedmont, since before 1998 it was the only, among the biggest Italian Regions, with a single University. The MFN Science Faculty is sub-divided into courses of Biology, Chemistry, Computer Science, Environmental Sciences, Material Sciences, Mathematics and Physics. The young people studying Chemistry are about 100, with an 5 academic staff composed by 19 professors and ricercatori. The largest part of the members of the Science Faculty adhere to the Departments of Science and Advanced Technologies (63) or to the one of Computer Science (14). The Unit The components of the Unit are operating in the fields of Environmental and Analytical Chemistry since 20 years. It is composed by 1 full professor, 3 associated professors and 1 researcher (beginning from October, 2000). The teaching activity concerns general and applied Analytical Chemistry courses, Environmental Chemistry, Physical Chemistry , Chemometrics and Electroanalytical Chemistry. Each academic staff member keeps from 3 to 4 courses per year. At present, 6 PhD students support the research activities of staff members and approximately 10 students are preparing their doctoral thesis. Programme Description and Evaluation 1 Title Transport, Reactivity and Transformation of Organic Compounds in the Environment. 2 Research Leader Prof. Orfeo Zerbinati 2a Sub-programme titles and sub-programme leaders 1. Metodi e strategie per l’analisi e il controllo di acque superficiali e acque potabili- Fiume Scrivia (Methods and Strategies for the Analysis and Control of Surface and Drinkable Waters - Scrivia River) MC Gennaro, E. Marengo, V. Gianotti, S. Angioi 2. Messa a punto di metodi analitici, trattamento statistico dei dati e validazione dei metodi e dei risultati analitici mediante intercalibrazione (Optimisation of Analytical Methods, Statistical Data Analysis, Analytical Results and Methods Validation by means of Intercalibration) MC Gennaro, E. Marengo, V. Gianotti 3. Progetto Aree Depresse Porto Marghera (Depressed Zones Project Porto Marghera) M.C. Gennaro 4. Sisifo (sub-Project : Electrochemical Soil Remediation) O. Zerbinati 3 Composition of the scientific research staff of the unit per 1 January 2002 Names and Titles Year of Rank Birth Maria Carla Gennaro Mauro Causà 1940 1955 Emilio Marengo 1959 Orfeo Zerbinati 1955 Valentina Gianotti Silvia Angioi 1972 1975 Elisa Robotti 1976 Full Professor Associate Professor Associate Professor Associate Professor Ricercatore PhD-student 2000/2001) PhD-student Research Input in fte in 2001 0.4 0.4 after 1993 ; sub-programmes 1,2,3,4 after 1993 ; sub-programme 4 0.4 after 1993 ; sub-programmes 1,2,4 0.5 after 1993 ; sub-programme 4 0.4 0.4 after 1993 ; sub-programme 1,2,4 after 1993 ; sub-programme 1 0.4 after 1993 ; sub-programme 4 Remarks 6 Samuele Meinero 1974 (2001/2002) PhD-student (2002/2003) Total research input 1.0 after 1993 ; sub-programme 4 4.0 Comments No data are available for years before 1998, since the Eastern Piedmont University has formally established in this year. 4 Input of Academic Staff in fte Category Full Professors Associated Professors Ricercatori Post-docs PhD-students Borsisti Total 1997 -------- 1998 0.5 1.5 1999 2000 2001 Total 0.5 1,5 0.7 0.7 1.0 1.7 1.4 1.0 5.1 0.7 1.0 3 1.0 1.0 + 0.7 - 1.0 -1.0 -0.6 Comments Data for 1997 are not reported since the Operating Unit has been constituted one year later. Negative numbers mean that the category decreased by one unit ; e.g. in the year 2000 one bursary became one ricercatore. The growth trend of the Operating Unit, as well as that of the University is evident, particularly as a consequence of the interest demonstrated by Local Administrations toward University and environmental themes. 5 Funding 5.1 Personnel (in fte) Source 1997 1998 University -3.8 CNR -European Union -Other Sponsors -Total -3.8 5.2 Materials and Equipment (in Million Lire) Source University - MURST CNR EU Other Sponsors Total 5.3 1997 1999 2000 -0.3 2001 0.7 Total 4.2 1.0 1.0 -0.3 -0.6 1.0 1.7 1.7 5.9 1998 30 10 1999 30 10 2000 50 2001 55+40 Total 205 20 15 55 31 71 85 135 95 +180 370 406 631 Comments: After an initial period, during which funding was substantially sufficient for supporting the continuation of basic activities of the O.U., a progressive increment of funding occurred in the years 2000 and 2001 and is continuing in 2002. This fact is mainly due to contracts established with local Administrations, that find in the University scientific expertises useful for structuring their policies, mainly in the environmental field. Major sponsors and the character of the liaison 7 Provincia di Alessandria. ATF (Ambiente, Territorio e Formazione) projects. ARPA Alessandria. Contract for the characterisation of a contaminated site. Commissario Straordinario ACNA. Contract for experimenting new technologies for the remediation of contaminated soils. Project “Aree Depresse Porto Marghera”. Città di Chieri (Torino). Contract “Distribuzione spazio temporale di inquinanti atmosferici da traffico autoveicolare” University 6. Progress Report 6.1 Mission Statement The character of the research areas of the Unit are both fundamental and applied, since they cover either fields regarding chemical transformation of pollutants in the environment and the study of non-polluting substitutes of chemicals or processes dangerous for the environment, or the study and characterization of cases of environmental relevance. An important additional field of activity consists with the optimisation and validation of new analytical techniques, useful for supporting the research activities previously mentioned. 1.3The Research Programme The research group, whose components have been active for several years in the fields of environmental and analytical chemistry and in the field of computational chemistry applied to the solution of environmental problems, is presently involved in the following areas of research: • Fate of chemicals in the environment. The abiotic transformation of organic chemicals both in atmospheric, aqueous and soil environments are investigated. With respect to atmospheric environment, fundamental aspects of chlorofluorocarbons (CFC) chemistry are investigated, with the aim of elucidating the chemical characters that affect their stability in the stratosphere. Further, the chemical transformations of volatile hydrocarbons (VOC) deriving from vehicles emission, which lead to the formation of toxic gaseous pollutants in the troposphere, are investigated by measuring their spatial and temporal distribution over large areas and long period of time, in order to elaborate predictive statistical models of urban atmospheric pollution. Aqueous and soil environments are studied with particular reference to specific phenomena regarding transport and fate of highly hydrophilic substances (such as polar aromatic sulfonates, halogenated phenols and anilines) deriving from industrial production of chemicals. • Pollution prevention. New substitutes of CFC are investigated by means of computational techniques, in order of proposing environmentally safer substitutes. With respect to urban pollution, the statistical models of transport and temporal evolution should enable Local Authorities in elaborating strategies for preventing accumulation of atmospheric pollutants. • Environmental remediation. New techniques for the removal of organic pollutants from soil and ground waters are studied, with particular attention to specific cases of contaminated industrial sites. • Advanced analytical techniques. Characterization of situations of environmental relevance requires reliable analytical data. In the case of tropospheric pollutants, new techniques for passive sampling of gaseous species are elaborated and validated, by means of laboratory and field tests. New chromatographic techniques are also developed for separating complex mixtures of polar and ionic organic substances, at microgram and even nanogram per litre levels, in the presence of interfering substances. Extraction steps from soil and water are developed and validated. Advanced statistical techniques are used either for chromatographic and extraction methods development and validation. 1.4Position in Networks Regional co-operation Amministrazione Provinciale di Alessandria Regional Agency for Environmental Protection (ARPA), Department of Alessandria Ausimont S.p.A., Spinetta Marengo (Alessandria) Città di Chieri (Torino) Università di Torino Politecnico di Torino National co-operation (including INCA) University of Urbino 8 INCA Università di Parma International co-operation University of Bradford (U.K.) University of Ljubliana Vrije Universiteit Amsterdam 6.4 Societal Relevance and Impact Among the topics covered by the Research Unit, the most relevant for the society are: Validation of analytical techniques, which are relevant for Regional control agencies, with particular regard to atmospheric and soil pollution control. Monitoring of atmospheric pollutants over urban and suburban areas, whose results are of interest for Local Administrations. Study for safe CFC substitutes, that are particularly relevant for a firms dealing with production and use of these substances. 6.5 Further Indications of Quality and Reputation Prof. MC Gennaro is President of the Analytical Chemistry Division of the Italian Chemical Society. 6.6 Key Publications New Strategies for the Determination of Phenylurea Pesticides by Gas Chromatography with Hot Splitless Inlet System, J. Chromatogr. A, 910 (2001) 79-86 M.C. Gennaro, E. Marengo, V. Gianotti, V. Maurino Optimization of the Separation of mono and di Chloroanilines in Ion Interaction High Performance Chromatography, J. Chromatogr.A 863 (1999) 1-11 E.Marengo, M.C.Gennaro, V.Gianotti, E.Prenesti Simultaneous Determination of Acidic and Basic-Neutral Pesticides in Water at ppt Concentration Level by Ioninteraction Micro-HPLC/MS, Environ. Sci. & Technol 33, 3905-3910 (1999) A.Cappiello, G.Famiglini, F.Mangani, S.Angelino, M.C.Gennaro, Ab Initio Periodic Hartree-Fock Calculations for Interpretation of the Scanning Tunnelling Microscope (STM) Images of Graphite, Lee KH, Causà M, Park SS, J. of Phys. Chem. B, 102, 6020-6024, 1998 Ciclodextrin-Assisted Capillary Electrophoretic Separation of 1,1’-bi-2-Naphthol Atropisomers, O. Zerbinati, F. Trotta, Electrophoresis, 22 (2001) 3578-3852 7. Scientific Output 7.1 Publication Policy The publication policy of the components of this Unit is mainly directed to international journals with the largest impact factors and the widest distribution within the subjects of interest. The number of master’s thesis dissertations remained approximately constant in the last 4 years, but should decline in the future, due to the change in the structure of the courses, which recently started in Italy. There is a relatively widespread spectrum of impact factors and ranking in the journal articles published by the components of the O. U. Of course, there is not always the possibility of having articles published on top journals, but the scientific value of the research developed by O.U. members is demonstrated by several articles published on journals ranking in the top 25%. The overall number of publication is variable, according to the results obtained and the availability of efficient structures, that lacked until 2002. The topics of most of the articles lie within those of the O.U’s mission . 7.2 Numerical data Category PhD-Dissertations 1997 1998 1 1999 2000 1 2001 Total 1 9 Scientific Publications 11 6 15 4 6 42 Professional Publications Master’s Theses 3 5 8 6 6 28 8 Self-evaluation The O.U.’s components are mainly specialized in the fields of analytical chemistry (chemical analysis and chemometrics) and theoretical chemistry, thus they can take advantage from discussing problems from different points of view. The instrumentation necessary to conduct high-level research activity in nowadays present (HPLC-MS, two GC-MS, ICP-MS, 400 MHz NMR, FTIR, Raman spetrometres, Capillary Electrophoresis, Ion Chromatograph, several HPLC systems with DAD, fluorescence and variable wavelength UV-Vis detectors, in addition to basic laboratory equipment) together with efficient laboratory infra-structures. The number of Ph.D. students and bursaries is still quite limited, compared to the staff. The effort for procuring the resources, necessary to encompass this problem, is going to give its results, thanks mainly to the good co-operation with Local Authorities. Appendix I Scientific Output I-1 Overview of Dissertations and Master's Thesis (1997-2001) I.1.1 Dissertations Year 1998 Name PhD-student Stefania Angelino 2000 Valentina Gianotti I.1.2 Master's Thesis Year Year 1997 Name Master’s student Title of the Dissertation Supervisor Name Master’s student Title of the Dissertation Ivana Diana Ricerca di solfonati aromatici in acque naturali (Search for aromatic sulphonates in natural waters) Fabio Alberi Determinazione cromatografica di assorbenti UV in vernici trasparenti per carrozzeria (Determination of UV absorbers in transparent coatings for automotive bodies) Simona Cammarota Separazione di solfonati aromatici mediante HPLC/MS (HPLC-MS separation of aromatic sulphonates) Stefania Ravinale Messa a punto di metodi per la ricerca di inquinanti atmosferici con tecniche di campionamento passivo (Optimization of methods for searching atmospheric pollutants by means of passive sampling techniques) 1997 1997 1998 Title of the Dissertation Development of new methods and their validation. Optimisation by chemometrical methods Supervisor MC Gennaro Sviluppo, ottimizzazione e validazione di metodi cromatografici per l’analisi di campioni ambientali (Development, optimization and validation of chromatographic methods for the analysis of environmental samples) MC Gennaro Supervisor O. Zerbinati MC Gennaro O. Zerbinati O. Zerbinati 10 1998 Daniele Valmorbida 1998 Loretta Badan 1998 Myriam Arca 1999 Melissa Abbà 1999 Enrico Gallese 1999 Alessia Indaco I-2 Metodiche analitiche per la determinazione di microinquinanti organici nel particolato atmosferico (Analytical methods for the determination of organic micropollutants in atmospheric particulated matter) Ottimizzazione di tecniche per l’analisi di fitofarmaci in matrici alimentari (Optimization of techniques for the analysis of phytopharmaceutical products in food products) Studio GC e chemiometrico di reazioni di trasformazione termica di pesticidi fenilureici (GC and chemometric study of the reactions of thermally induced transformation of phenylurea pesticides) Controllo statistico di processo in un’industria vinicola (Statystical control of the process in a wine industry) Analisi multivariata dei componenti dell’aroma in vini moscato per il controllo di qualità (Multivariate analysis of aroma components for the qualità control of muscat wines) Ottimizzazione della tecnica di estrazione di solfonati aromatici polari da campioni di suolo (Optimization of an extraction technique of polar aromatic sulphonates from soil) V. Maurino O. Zerbinati MC Gennaro E. Marengo O. Zerbinati Overview of Scientific Publications (1997-2001) per year 1997 1. An electrochemical process for the degradation of sulfonate- and phenol- derivatives in industrial effluents, M.C. Gennaro, R. Aigotti, O. Zerbinati, S. Pittavino, J. Environ. Sci. Health, A32(3), 735-748 (1997). Thematic area : A 2. Hallucinogenic species in Amanita muscaria. Determination of muscimol and ibotenic acid by ion-interaction HPLC, M.C.Gennaro, D.Giacosa, E.Gioannini, S.Angelino, J. Liq. Chromatogr. & Rel.Technol. 20, 413-424 (1997) .Thematic area : B 3. Heavy metal speciation in anaerobic municipal sludges. Comparison between single and sequential extraction, A.Vanni, M.C.Gennaro, A.Cignetti, B.M.Petronio, G.Petruzzelli, A.Liberatori J.Environm. Sci.Health A32, 14671489 (1997). Thematic area : B 4. Identification and determination of red dyes in confectionery and determination by ion-interaction HPLC, M.C.Gennaro, E.Gioannini, S.Angelino, R.Aigotti, D.Giacosa, J.Chromatogr., 767, 87 (1997). Thematic area : 5. An ion-interaction RP-HPLC method for the determination of the eleven EPA priority pollutant phenols, S.Angelino, M.C.Gennaro, Anal.Chim.Acta, 346, 61-71 (1997). Thematic area : A 6. Resolution optimization in ion-interaction RP-HPLC, M.C.Gennaro, R.Aigotti, S.Angelino Anal.Letters, 30, 2271-2279 (1997). Thematic area : B 7. Determination of fluoxetine and norfluoxetine in human plasma by ion interaction RP-HPLC, M.C.Gennaro, C.Abrigo, U.Albert, F.Bogetto, G.Maina, P.Prolo, L.Ravizza, J.Liq. Chromatogr. & Rel.Technol., 20, 3017-3028 (1997) . Thematic area : B 8. Separation and determination of inorganic anions by reversed-phase high-performance liquid chromatography, M.C.Gennaro, S.Angelino, J.Chromatogr. A, 789, 181-194 (1997) . Thematic area : B 9. Residual effect of application of sewage sludge on heavy metal sorption by soil, G.Petruzzelli, B.M.Petronio, M.C.Gennaro, A.Vanni, A.Liberatori, M.Barbafieri, B.Pezzarossa Ann.Chim. (Rome), 87, 733 (1997) . Thematic area : B 10. Simple and inexpensive analog to digital converter for the PCs parallel port, O. Zerbinati, J. Chem. Educ., 1997, 74 (10), 1241-1242 . Thematic area : 11. Fate of aromatic sulfonates in the environment, O. Zerbinati, M. Vincenti, S. Pittavino, M.C. Gennaro, Chemosphere 35 (10), 1997, 2295-2305 . Thematic area : A 1998 1. E.Marengo, M.C.Gennaro, S.Angelino “ Neural network and experimental design to investigate the effect of five factors in ion-interaction high-performance liquid chromatography” J.Chromatogr. A, 799, 47-55 (1998) . Thematic area : B 11 2. S.Angelino, A.F.Fell, M.C.Gennaro “Development of system suitability tests for ion-interaction reagent chromatography of colorants on reversed-phase packing materials.” J.Chromatogr. A, 797, 65-74 (1998) . Thematic area : B 3. New derivatives of cyclodextrins as chiral selectors for the capillary electrophoretic separation of dichlorprop enantiomers, O. Zerbinati, F. Trotta, C. Giovannoli, C. Baggiani, G. Giraudi, A. Vanni, J. Chromatogr. A, 810, 193200 (1998) . Thematic area : B 4. Neural network and experimental design to investigate the effect of five factors in ion-interaction highperformance liquid chromatography, E.Marengo, M.C.Gennaro, S.Angelino, J.Chromatogr. A, 799, 47-55 (1998) . Thematic area : B 5. Development of system suitability tests for ion-interaction reagent chromatography of colorants on reversedphase packing materials, S.Angelino, A.F.Fell, M.C.Gennaro, J.Chromatogr. A, 797, 65-74 (1998) . Thematic area : B 6. Intercalibration of chromatographic methods in multiresidue pesticide determination, M.C.Gennaro, S.Angelino, V.Maurino, R.Aigotti, A.Liberatori, J.Liq.Chromatogr. & Rel.Technol. 22, 721-734 (1999) . Thematic area : B 1999 1. E.Marengo, M.C.Gennaro, V.Gianotti, E.Prenesti "Optimization of the Separation of mono and di chloroanilines in ion interaction high performance chromatography", J.Chromatogr.A, 863, 1-11 (1999) . Thematic area : B 2. S.Angelino, A.BiancoPrevot, M.C.Gennaro, E.Pramauro, “Ion-interaction high-performance liquid chromatography and micellar electrokinetic capillary chromatography: two complementary techniques for the separation and aromatic sulfonated compounds.” J.Chromatogr. A, 845, 257-271 (1999) . Thematic area : B 3. M.C.Gennaro, S.Angelino, V.Maurino, R.Aigotti, A.Liberatori, “Intercalibration of chromatographic methods in multiresidue pesticide determination.” J.Liq.Chromatogr. & Rel.Technol. 22, 721-734 (1999) . Thematic area : B 4. A.Cappiello, G.Famiglini, F.Mangani, S.Angelino, M.C.Gennaro, "Simultaneous determination of acidic and basic-neutral pesticides in water at ppt concentration level by ion-interaction micro-HPLC/MS " Environ. Sci. & Technol 33, 3905-3910 (1999) . Thematic area : B 5. M.C.Gennaro, S.Angelino, V.Gianotti “Suitability of different C18 silica-based stationary phases for the trasferability of an Ion-Interaction HPLC Method.” Analusis, 27, 742-748 (1999) . Thematic area : B 6. M.C.Gennaro, V.Gianotti, F.Alberi, S.Angelino, M.Scagliotti, “Chromatographic determination of UV absorbers in car paints.” J.Liq.Chromatogr. & Rel.Technolog, 33,2689-2700 (1999) . Thematic area : B 7. E.Marengo, R.Aigotti, V.Maurino, S.Angelino, C.Baiocchi, M.C.Gennaro, “Pattern recognition and classification of Nebbiolo wine as a function of the fungicide treatment of the grape.” Anal.Letters 32, 1653-1673 (1999) . Thematic area : B 8. Trace Aromatic Sulphonates Determination in Natural Water Samples. O. Zerbinati, I. Diana, C. Baiocchi, Int. J. Environ. Anal. Chem., 741, 43-54 (1999) . Thematic area : B 9. Ion-interaction high-performance liquid chromatography and micellar electrokinetic capillary chromatography: two complementary techniques for the separation and aromatic sulfonated compounds, S.Angelino, A.BiancoPrevot, M.C.Gennaro, E.Pramauro, J.Chromatogr. A, 845 , 257-271 (1999) . Thematic area : B 10. M.C.Gennaro, S.Angelino , Chemometric applications in seawater analysis. Marine Chemistry, an Environmental Analytical Chemistry Approach, Water Science and Technology Library, Kluver Academic Publ., (1999) . Thematic area : B 11. Pattern recognition and classification of Nebbiolo wine as a function of the fungicide treatment of the grape, E.Marengo, R.Aigotti, V.Maurino, S.Angelino, C.Baiocchi, M.C.Gennaro, Anal.Letters 32, 1653-1673 (1999) . Thematic area : B 12. Chromatographic determination of UV absorbers in car paints, M.C.Gennaro, V.Gianotti, F.Alberi, S.Angelino, M.Scagliotti, J.Liq.Chromatogr. & Rel.Technol., 2689-2700 (1999) . Thematic area : B 13. Simultaneous determination of acidic and basic-neutral pesticides in water at ppt concentration level by ioninteraction micro-HPLC/MS, A.Cappiello, G.Famiglini, F.Mangani, S.Angelino, M.C. Gennaro, Environ. Sci. & Technol, 33 , 3905-3910 (1999) . Thematic area : B 14. Suitability of different C18 silica-based stationary phases for the trasferability of an Ion-Interaction HPLC Method, M.C.Gennaro, S.Angelino, V.Gianotti, Analusis, (1999) . Thematic area : B 15. Optimization of the Separation of mono and di- chloroanilines in ion interaction HPLC E.Marengo, M.C.Gennaro, V.Gianotti, E.Prenesti, J Chromatogr.A, (1999) . Thematic area : B 2000 1. E.Marengo, M.C.Gennaro, V.Gianotti “ Chemometrically assisted simultaneous separation of 21 aromatic sulfonates in ion-interaction RP-HPLC” Chem. Intell. Lab. System 53, 57-67 (2000) . Thematic area : B 12 2. M.C.Gennaro, E.Marengo, V.Gianotti “Ion-Interaction RP-HPLC Separation of inorganic anions on porous graphitised carbon stationary phase. Comparison with ODS stationary phase.” J.Liq.Chromatogr. & Rel. Technol. 23, 2599-2615 (2000) . Thematic area : B 3. Determination of lithium in wines by ion-chromatography. O. Zerbinati, F. Balduzzi, V. Dell’Oro, J. Chromatogr. A, 881, 645-650 (2000) . Thematic area : B 4. Optimization of the cyclodextrin-assisted capillary electrophoresis separation of enantiomers of phenoxyacid herbicides. O. Zerbinati, F. Trotta, C. Giovannoli, J. Chromatogr. A, 875, 423-430 (2000) . Thematic area : B 2001 1. M.C.Gennaro, C.Abrigo, R.Calvino “Ion interaction reagent reversed-phase high-performance liquid chromatographic determination of anti-tubercolosis drugs and metabolites in biological fluids.” J. Chromatogr. B, 754, 477-486 (2001) . Thematic area : B 2. E.Marengo, M.C.Gennaro, V.Gianotti, S.Angelino “ A test of Robustness Study in IIR-RP-HPLC Separation of Nine Priority Pollutant Phenols.” J. Liq.Chromatogr. & Rel. Technol. 24, 341-353 (2001) . Thematic area : B 3. M.C.Gennaro, E.Marengo, V.Gianotti, V.Maurino “New Strategies for the determination of phenylurea pesticides by gas chromatography with hot splitless inlet system.” J.Chromatogr.A , 910, 79-86 (2001) . Thematic area : B 4. E.Marengo, M.C.Gennaro, V.Gianotti “A Simplex optimised chromatographic separation of cosmesis preservatives. Determination in commercial products.” J.Chromatogr. Sci, 32, 1-6 (2001) . Thematic area : 5. Electrochemical or UV-Photochemical Oxidation of Industrial Wastes Containing Polar Aromatic Sulphonates, O. Zerbinati, S. Pittavino, ESPR - Environ. Sci. Pollut. Res., DOI: http://dx.doi.org/10.1065/espr2001.12.104.6 . Thematic area : A 6. Ciclodextrin-assisted capillary electrophoretic separation of 1,1’-bi-2-naphthol atropisomers, O. Zerbinati, F. Trotta, Electrophoresis, 22 (2001) 3578-3852 . Thematic area : B I-3 Overview of Professional Publications (1997 - 2001) per year 2000 S.Angelino, M.C.Gennaro, in “Handbook of Food Analysis”, Food Science and Technology Series, Nollet Editor, Chapter 21, “HPLC analysis of Organic Bases”, 881-938 (2000) G.Saini, C.Baiocchi, M.C.Gennaro, “Contributo alla conoscenza dell’inquinamento lagunare”, La Ricerca Scientifica per Venezia: il progetto sistema lagunare Veneziano, vol.II, tomo I, 349-370, Edizioni Istituto Veneto di Scienze, Lettere e Arte (2000), Venezia M.C.Gennaro, S.Angelino, in Chemical Processes in Marine Environments, Springer-Verlag Berlin Heidelberg editor, Chapter 22 “Chemometric applications in seawater analysis.” pp.404-424 (2000) 2001 M.C. Gennaro, V. Gianotti, S. Angioi "L'analisi multivariata nell'ottimizzazione dei metodi e nel trattamento dei dati" in “La Cromatografia Ionica nell’analisi alimentare” a cura di Silvano Cavalli e Corrado Sarzanini Ed. Nuova Poligrafica Milanese, Milano (2001) I-4 Other Scientific Output Reports have been written as final outputs of contracts from local authorities or industries. These are available only under permission of the sponsors. Journal Portfolio Analysis Name of the Unit: Research Director: Years included Name of Journal Anal.Chim.Acta Anal.Letters Ann.Chim. (Rome) Analusis UNIPMN Orfeo Zerbinati 1997-2001 Number of Journal Impact Field(s) Articles Factor 1 2.073 Chemistry, Analytical 3 1.130 Chemistry, Analytical 1 0.394 Chemistry, Analytical 2 0.502 Chemistry, Analytical Ranking 13/68 35/66 60/68 53/68 13 Chem. Intell. Lab. System 1 1.412 Automation Systems & Control 28/65 Chemistry, Analytical 30/68 Computer Science, 13/72 Artificial Intelligence Chemosphere Electrophoresis 1 1 1.181 4.282 ESPR – Environ. Sci. Pollut. Res Environ. Sci. & Technol Int. J. Environ. Anal. Chem 1 2 1 0.833 2.707 0.797 J. Environ. Sci. Health J. Liq. Chromatogr. & Rel.Technol J.ChromatogrA J.ChromatogrB J. Chem. Educ. 2 8 14 1 1 J.Chromatogr. Sci 1 Water Science and Technology Library 1 0.376 0.762 2.79 1.91 0.596 0.987 Instruments & 5/48 Instrumentation Environmental Sciences 43/129 Biochemical Research 2/43 Methods Chemistry, Analytical Environmental Sciences Environmental Sciences Chemistry, Analytical 2/68 62/129 2/126 46/68 Environmental Sciences Environmental Sciences Chemistry, Analytical Chemistry, Analytical Chemistry, Analytical Chemistry, Multidisciplinary Chemistry, Analytical 64/129 107/129 48/68 6/68 18/68 70/118 41/68 Comments: The average pro-capita number of published articles per year (1.05 if all of the 2002 composition of the O.U. is considered, 1.68 if only staff members present in 1998 are considered) seems to be adequate, especially if the situation of our newly constituted structure is examined in all its aspects. 18/42, that is 44%, of the articles appeared on journals ranking in the top 25%, thus demonstrating that the policy of the O.U. is privileging the quality, rather than the quantity, of its scientific production. 14 AQUILA AQUILA 1 Name of the Research Unit (AQUILA 1) Research Leader (Prof. Giorgio Cerichelli) University: (L’AQUILA) Contact Person Please specify: Name Prof. Giorgio Cerichelli Mailing Address Dipartimento di Chimica, Ingegneria Chimica e Materiali Phone 0039862433784 Fax 0039862433753 Department: (Dipartimento di Chimica, Ingegneria Chimica e Materiali Mobile 339 3671300 Department of Chemistry, Chemical Engineering and E-mail:[email protected] Materials) Thematic area Faculty: (Scienze MM.FF.NN. Natural Sciences) Please indicate to which thematic area of INCA the unit belong (in priority order): Sintesi ecosostenibili (solventi, fotochimica, catalisi, riciclo e altre). Catalisi eterogenea per le sintesi ecosostenibili e la decontaminazione ambientale. Introduction and Context Introduction to the Self-evaluation Report This self-evaluation report is the second one produced by the research unit CERICHELLI - l'Aquila. Our University is a small one and the dimension of the research unit is small. A strong limitation is that only very recently in l'Aquila started a first level degree in Chemistry, and a Ph.D. course in Chemistry; so for many years we suffered this luck of students. Now things are changing, but due to the very recent changes affecting Italian University system (an abnormous increment in first level degree courses, each one of them request an ad hoc first level chemistry course) our teaching duties have increased without a corresponding increase in teachers. We are trying to face this emergency. My personal opinion is that in the absence of a real evaluation system of University professors we are suffering from a too strong influence of people that are doing little or nothing at all. Even in a Science Faculty it is very hard to convince people that a professor in the University has to carry out research (real, results published in good level Journals) and not only teach few lessons. In other Faculties the situation is even worse. Resources (funds, positions) are attributed on an average basis that reflects only the existing situation and do not take into consideration the future. I hope that in the future something will change otherwise it will be very difficult, almost impossible to maintain what I think is a good level of scientific production, especially referred to funding. The University, the Faculty and the Department The University of L’Aquila is the scientific aggregation center in Abruzzo. Students are not only from Abruzzo but also largely from neighboring regions. The international laboratory of “Gran Sasso” is deeply involved with the natural science faculty, department of physics. There are many international joint research projects; among the others very important in the environmental field is the co-operation with the National Center for Atmospheric Research, University of Colorado at Boulder. The faculties of the University of L’Aquila are the following: Natural Sciences, Engineering, Medical School, Economic Sciences, Scienze Umane and Scienze della Formazione. The numbers of students are about 15,000 and faculties members are about 350; the students at the Natural Sciences faculty are about 2,500 and the faculties members are 88. Figures are a little bit larger than that of 1998 due to a general increase in students enrolment, and to the birth in l'Aquila of the first level degree in Chemistry. This new laurea degree has heavily increased our teaching duties. 15 The Unit The main change with respect to 1998 is the promotion of a ricercatore to Associate Professor. Our unit is an organic chemistry unit working inside the “Dip. di Chimica, Ingegneria Chimica e Materiali” with teaching load for the degree (master) of Chemistry, Environmental Sciences ,Biotechnology and Biological Sciences. The organizational structure consists of: 1 Full professor, 2 Associate professor 1 Ricercatore (Assistant professor) and 2 Ph.D. student. Teaching load is: Organic Chemistry - Environmental Sciences; Organic Chemistry - Biotechnology Organic Chemistry - Biological Sciences; Bioorganic Chemistry - Environmental Sciences; Atmospheric Chemistry - Environmental Sciences; Chemistry for the conservation and restoration of the cultural heritage - Environmental Sciences; Laboratory experimental Chemistry - Biological Sciences. Spectrometric Identification of Organic Compounds – Chemistry Medicinal Chemistry. – Chemistry Organo-Metallic Chemistry - Chemistry Programme Description and Evaluation 1 Title GREEN CHEMISTRY. New synthetic techniques developed to minimize environmental impact of organic synthesis. 2 Research Leader: Giorgio Cerichelli 2a Sub-programme titles and sub-programme leaders: 1 Clean Solvents in Organic Synthesis (Giorgio Cerichelli) 2 Domino reactions (Antonio Arcadi) 3 Composition of the scientific research staff of the unit per 1 January 2002 Names and Titles Year of Rank Birth Giorgio Cerichelli Antonio Arcadi 1946 1954 Fabio Marinelli 1956 Nicoletta Spreti Sabrina Di Giuseppe Loredana D’Anteo Total research input 1961 1974 1973 Full professor Associate professor Associate professor Ricercatore Ph.D.-student Ph.D.-student Research Input in fte in 2001 0.5 0.5 Since 1995 2a 2b 0.5 Since 20012b 0.8 1.0 1.0 4.9 2a 2b 2a Remarks Comments The beginning of the courses of environmental sciences ( since 1993) and the bachelors in biotechnology (since 1996), material sciences (since 1996) and chemistry (1998) determined an increase of the number of courses. In 1997 started a Ph.D. programme, title: CHIMICA per L'AMBIENTE (Chemistry for the Environment) 4 Input of Academic Staff in fte Category 1997 1998 1999 2000 2001 Total 16 Full Professors Associated Professors Ricercatori Post-docs Ph.D.-students Borsisti Total 0.5 .5 1.6 .5 .5 1.6 .5 .5 1.6 .5 .5 1.6 .5 .5 1.6 2.5 2.5 8.0 1 1 1 1 2 6 3 3 3 3 4 16 Comments In the course of 2001 a ricercatore (FM) get promoted to associate professor. We did not modify the above table. His teaching duties are changing. 5 Funding 5.1 Personnel (in fte) Source University CNR European Union Other Sponsors Total 5.2 1997 1998 1999 1 2000 2001 Total 1 1 1 2 Materials and Equipment (in Million Lire) Source University - MURST CNR EU Other Sponsors Total 1997 20 40 1998 90 40 1999 90 40 2000 10 40 2001 10 30 Total 220 180 60 130 130 50 40 410 5.3 Comments: Our group is suffering from the general decrease in research funding in Italy. At the present time the management of CNR is still that one put in charge from the past government, as a consequence government has largely decreased CNR funding. Money coming via MURST has always been very low. We are also suffering from a very "peculiar" local policy for funding. In the current year and in the 3 future ones things will improve due to funds obtained via Ministero Affari Esteri (110000 euros) and PON (co-ordination of a 2.300.000 euros project). * On the figures * On the funding policy 6. Progress Report 6.1 Progress analysis Starting 1998 students had begun to get their degree in Environmental Sciences discussing, within our group, theses in the field of “Green Chemistry”. With respect to 1998 we have increased the research in the field of GREEN CHEMISTRY working mainly into 2 directions: the elimination or reduction of the use of organic solvents in Organic synthesis 1) using surfactants aggregates in water; 2) by using the Domino approach. We increased collaboration within INCA units (Maldotti, chlorinated compounds degradation). We are largely increasing (involving others INCA units) our research activity in the field of protection of cultural goods; it has been funded by MIUR a 3 years (2.3 million euros) research project. 6.2 Position within INCA This research unit within INCA has developed an almost unique experience in the use of surfactants in organic synthesis and in the recovery and degradation of pollutants. Solvents are also reduced by the Domino technique. The 17 use of surfactants supported enzymes in water is another approach the elimination/reduction of the use of organic solvents. 6.3 Key Publications 6.3a - Pietro di Profio, Raimondo Germani, Gianfranco Savelli, Giorgio Cerichelli, Marco Chiarini, Giovanna Mancini, Clifford A. Bunton, and Nicholas D. Gillit. "Effects of Headgroup Strucuture on the Incorporation of Anions into Sulfobetaine Micelles. Kinetics and Physical Evidence." Langmuir 14 (1998) 2662-2669. - B. De Santis, A. L. Iamiceli, R. Marini Bettolo, L. M. Migneco, R. Scarpelli, G. Cerichelli, G. Fabrizi, D. Lamba, “On the Diastereoselectivity of the Aqueous-Acid-Catalized Intramolecular Aldol Condensation of 3Oxocyclohexaneacetaldehydes.” Helv. Chim. Acta 1998; 81, 2375-2387. - Borocci, S., Mancini, G., Cerichelli, G., Luchetti, L., "Conformational Behavior of Aqueous Micelles of Sodium NDodecanoyl-L-prolinate" Langmuir; 1999; 15, 2627-2630; - Cerichelli, G., Luchetti, L., Mancini, G., Savelli, G., "Cyclizations of 2-(-ω-Bromoalkyloxy)phenoxide Ions in Dicationic Surfactants" Langmuir; 1999; 15, 2631-2634. - A. Maldotti, L. Andreotti, A. Molinari, G. Varani, G. Cerichelli, M. Chiarini “Photocatalytic properties of iron porphyrins revisited in aqueous micellar environment: oxygenation of alkenes and reductive degradation of carbon tetrachloride” Green Chem., (2001), 1 42-46. 6.3b - Synthesis of Functionalised Quinolines through Tandem Addition/Annulation Reactions of -(2-Aminophenyl)- ynones. A. Arcadi, F. Marinelli, E.Rossi, Tetrahedron, 1999, 55, 13233-13250. - Palladium-Catalyzed Arylation of α-Methylene-γ−Butyrolactone:3-Benzylfuran-2(5H)-ones vs. (Z)-Benzylidene-γButyrolactones and their Reduction to 3-Benzyl-γ-Butyrolactones A. Arcadi, M. Chiarini, F. Marinelli, Z. Berente, L. Kollàr, Organic letters, 2000, 2, 69-72. - Sequential Alkylation/Transition Metal Catalysed Annulation Reactions of 1,3-Dicarbonyl Compounds with Propargyl Bromide. A. Arcadi, G. Cerichelli, M.Chiarini, S. Di Giuseppe, F. Marinelli, Tetrahedron Lett. 2000, 41, 9195-9198. - Palladium- Catalysed Functionalisation at 4- and 6-Position of the 7-Azaindole System. M. Allegretti, A. Arcadi, F. Marinelli, L. Nicolini, Synlett, 2001, 609-613. - Conversion of Homochiral Amines and α-Aminoesters to Their Chiral 1,2,3,5-Substituted Pyrrole Derivatives via Gold-Catalysed Amination/Annulation Reactions of 2-Propynyl-1,3-dicarbonyls. A. Arcadi, S. Di Giuseppe, F. Marinelli, E. Rossi, Tetrahedron Asymmetry 2001, 12, 2715-2720. 7. Scientific Output 7.1 Publication Policy 7.2 Numerical data Category Ph.D.-Dissertations 1997 1998 1999 2000 2001 1 Total 1 Scientific Publications 9 8 12 13 13 55 3 2 5 10 Professional Publications Master’s Theses 8 Self-evaluation with respect to the previous assessment procedure a person FM get promoted from assistant professor position to associate. In year 2001 started the first year course of the first level degree in chemistry, following the new university organization. Our teaching duties are consequently increasing. We are teaching courses in the following first and second level degrees: 1) Chemistry; 2) Environmental Sciences; 3) Biological Sciences; 4) Biotechnology; 5) Material Sciences. We increased the number of thesis with a stronger environmental motivation. In l’Aquila in January 2002 we 18 had the first student that get an environmental Chemistry Ph.D. working on Green Chemistry. At the present time 9 students are involved in our environmental Chemistry Ph.D. programme (not all of them in our group – prof. Giorgio Cerichelli is the coordinator of the Ph.D. school). Thanks to increase in funding we implemented our equipment, increasing the performances of a spectrophotometer and we buy a new CG-MS system. Professor Cerichelli has been nominated coordinator in charge of an Italia-Argentina cooperation programme on Green Chemistry, research & teaching. Funding on this project will be available 2002 – 2003. Professor Cerichelli is the scientific coordinator of a research project on the safeguard of Cultural Heritage (PON), starting at the end of 2002, funded by 2.3 million euros. The papers that we published are more related to Green Chemistry and we are pushing our efforts mainly in two directions: a) aqueous surfactants solutions as an environmental friendly reaction medium for organic synthesis, both conventional and enzymes assisted; b) Domino reactions as a way to reduce solvents and energy consumption increasing atom efficiency. We think that it is important that even in the future we will devote a part of our activity to Chemistry of Cultural Heritage, because in this way we can also support basic research, that otherwise will not be funded by the present Government. Appendix I Scientific Output I-1 Overview of Dissertations and Master's Thesis (1997-2001) I.1.1 Dissertations Year 2001 Name Ph.D.-student Title of the Dissertation Supervisor Simona Cerritelli New synthetic pathways with low environmental impact Giorgio Cerichelli I.1.2 Master's Thesis Year Name Master’s student Title of the Dissertation Supervisor 1999 Sabrina Di Giuseppe Reazioni Domino come Strumenti di Green Chemistry (Domino Reactions as Tools of “Green Chemistry”) Antonio Arcadi 1999 Andrea Berardinelli Synthesis of Furopyridines as Precursors of HIV-1 on Nucleoside Reverse Transcriptase Inhibitors Antonio Arcadi 1999 Irma Paris Environmental Monitoring Strategies as an Aid in Aquifer Protection Antonio Arcadi 2000 Mauro Panzanaro Synthesis of Butenolides and γ-Butirolactones Antonio Arcadi 2000 Emanuela Paris Study on the chemical degradation of non-ionic surfactants industrially used: their toxicity and of their degradation products. Giorgio Cerichelli 2001 Mirella Nardecchia An Efficient Synthesis of 2,4-Substituted-[1,8]naphtyridines from 3-(2-Amino-5methyl-pyridin-3-yl)-aryl Propinones. Fabio Marinelli 2001 Enrica Bernardini New surfactants for the cleaning of stone art goods Giorgio Cerichelli 2001 Marina Capone A new synthetic approach to the preparation of surfactants of potential biological interest Giorgio Cerichelli 2001 Maria Teresa Di Stefano Reactivity modifications due to micellar surface doping Giorgio Cerichelli 2001 Monica Gili Model reactions as a tool to investigate micellar surfaces Giorgio Cerichelli I-2 Overview of Scientific Publications (1997-2001) per year 1997 - Giorgio Cerichelli, Luciana Luchetti and Giovanna Mancini, “Conformational behavior of aqueous micelles of sodium N-dodecanoyl-N-methylglicinate”, Langmuir, 13 4767—4769, (1997). - Enrico Ballico, Giorgio Cerichelli, Simona Fossa, Barbara Floris, Federico Giordano, “Metallation of Alkynes. Part 8. Substituent Effects in the Acethoxymercuriation of Diarylethynes”, Main Group Metal Chemistry, 20, 301-312 (1997). Paolo De Maria, Antonella Fontana and Giorgio Cerichelli,”Keto-Enol Interconversion of 2-Phenylacetylthiophene”, J. Chem. Soc., Perkin Trans.2, 2329-2334 (1997). 19 - Giorgio Cerichelli and Giovanna Mancini, “NMR Techniques applied to Micellar Systems”, Curr. Opin. Coll. Interface Sci., 2, 641-648 (1997). - Base or Copper promoted Annulation Reactions of Errore. L'origine riferimento non è stata trovata.Aminohydrazones. A. Arcadi, O.A. Attanasi, L. De Crescentini, E. Rossi, Tetrahedron Lett. 1997, 38, 2329-2332. - Sequential Addition/Elimination/Annulation Reactions of 4-Pentynones with Benzylamine and ammonia. A. Arcadi, E. Rossi, Synlett 1997, 667-668. - Regio and Stereoselective Synthesis of (E)-4-arylidene/alkenylidene-3-tosyloxazolidin-2-ones through Palladiumcatalyzed Reactions of Aryl Iodides/Vinyl Triflates with propargyl Tosylcarbamates. A. Arcadi, Synlett 1997, 941-944. - Synthesis of 1,2,3,5-Substituted Pyrroles through Palladium-Catalyzed Reaction of Ethyl 2-Acetyl-4-Petynoate Tosylhydrazone with Aryl Iodides. A. Arcadi, R. Anacardio, G. D’Anniballe, M. Gentile, Synlett 1997, 1315-1317. - 2-Subtituted-5-acetyl-4-hydroxythiazoles. A. Arcadi, O.A. Attanasi, L. De Crescentini, B. Guidi, E. Rossi, S. Santeusanio, Gazz. Chim. Italiana 1997, 127,609612. 1998 - Pietro di Profio, Raimondo Germani, Gianfranco Savelli, Giorgio Cerichelli, Marco Chiarini, Giovanna Mancini, Clifford A. Bunton, and Nicholas D. Gillit. "Effects of Headgroup Strucuture on the Incorporation of Anions into Sulfobetaine Micelles. Kinetics and Physical Evidence." Langmuir 14 (1998) 2662-2669. - E. Fantauzzi, S. Baccella, A. Lepidi, F. Vegliò, M. Chiarini, G. Cerichelli, L. Toro, “Development of a chemical and biological treatment of alkaline industrial waste waters: a preliminary study” Fresenius Envir. Bull. 7 (1998) 934-950 - B. De Santis, A. L. Iamiceli, R. Marini Bettolo, L. M. Migneco, R. Scarpelli, G. Cerichelli, G. Fabrizi, D. Lamba, “On the Diastereoselectivity of the Aqueous-Acid-Catalized Intramolecular Aldol Condensation of 3Oxocyclohexaneacetaldehydes.” Helv. Chim. Acta 1998; 81, 2375-2387. - Ethyl N-(o-Ehynyl) malonoanilide as a Useful Building Block for the Preparation of 3,4-Disubstituted-2(1H)quinolones, 3,4-Disubstituted- and 2,3,4-Trisubstituted-quinolines. A. Arcadi, S. Cacchi, G. Fabrizi, F. Manna, P. Pace, Synlett 1998, 446-448. - Synthesis of functionalised Furans and Pyrroles through Annulation Reactions of 4-Pentynones. A. Arcadi, E. Rossi, Tetrahedron 1998, 15253-15273 L. Brinchi, R. Germani, G. Savelli, N. Spreti, R. Ruzziconi and C.A. Bunton. “Effects of association colloids on elimination from 1,2-dihalo-1,2-diphenylethanes. The role of surfactant structure”. Langmuir, 14, 2656-2661 (1998) L.Brinchi, P.Di Profio, R. Germani, G. Savelli, N. Spreti and C.A. Bunton. “The effects of micellar head group structure on the spontaneous hydrolysis of methyl naphtalene-2-sulphonate. The role of perchlorate ion”. J. Chem. Soc. Perkin Trans. 2, 361-364 (1998). G. Marcozzi, C. Di Domenico, N. Spreti. “Effects of surfactants on the stabilization of the bovine lactoperoxidase activity”. Biotechnology Progress, 14, 653-656 (1998). 1999 - Borocci, S., Mancini, G., Cerichelli, G., Luchetti, L., "Conformational Behavior of Aqueous Micelles of Sodium NDodecanoyl-L-prolinate" Langmuir; 1999; 15, 2627-2630; - Cerichelli, G., Luchetti, L., Mancini, G., Savelli, G., "Cyclizations of 2-(-ω-Bromoalkyloxy)phenoxide Ions in Dicationic Surfactants" Langmuir; 1999; 15, 2631-2634. 20 .- Pyrido[3,4-c]Thiazoles through Combined Palladium-Catalysed Coupling of 2-Substituted-5-Acetyl-4thiazolyltriflates with Alkynes/Annulation Reactions. A. Arcadi, O.A. Attanasi, B. Guidi, E. Rossi, S. Santeusanio, Chemistry Letters 1999, 59-60. - Synthesis and in Vitro and in Vivo Evalaution of 2-(6’-Methoxy-3’,4’-Dihydroxy)-4H-Benzoxazin-4-one as a New Potent Substrate Inhibitor of Human Leukocyte Elastase.A. Arcadi, C. Asti, L. Brandolini, G. Caselli, F. Marinelli, V. Ruggieri, Biorganic & Med. Chem. Lett. 1999, 9, 1291-1294. - Palladium-Catalysed Cyclocarbonylation of o-Ethynylphenols and Vinyl Trfiflates to Form 3-Alkylidene-2coumaranones. A. Arcadi, S.Cacchi, G.Fabrizi, L.Moro, Eur.J.Org.Chem., 1999, 1137-1141. - A New Approach to 2,3-Disubstituted-Benzo[b]furans from o-Alkynylphenols Iodocyclisation/Palladium-Catalysed Reactions. A. Arcadi, S. Cacchi, G. Fabrizi, F. Marinelli, L. Moro, Synlett, 1999, 1432-1435. via 5-endo-dig - Synthesis of Functionalised Quinolines through Tandem Addition/Annulation Reactions of (2-Aminophenyl)- ynones. A. Arcadi, F. Marinelli, E.Rossi, Tetrahedron, 1999, 55, 13233-13250. - 2-Substituted-5-acetyl-4-Thiazolyltriflates as Useful Building Blocks for the Preparation of Functionalised Thiazoles. A. Arcadi, O.A. Attanasi, B. Guidi, E. Rossi, S. Santeusanio, Eur.J.Org.Chem., 1999, 3117-3126. - Palladium-Catalysed Hydrovinylation of Vinyl Triflates with Alkynes. An Approach to the Synthesis of 3-Vinyl-5Hfuran-2-ones. A. Arcadi, S. Cacchi, G. Fabrizi, F. Marinelli, P. Pace, Eur.J.Org.Chem. 1999, 3305-3313. N. Spreti, F. Alfani, M. Cantarella, F. D’Amico, R. Germani, G. Savelli. Chymotrypsin superactivity in aqueous solutions of cationic surfactants”. J. Molec. Catalysis B: Enzymatic, 6, 99-110 (1999). F. De Angelis, R. Nicoletti, N. Spreti and F. Verì. “A new in-vitro model of lignin biosynthesis”. Angew. Chem. Int. Ed., 38, 1283-1285 (1999) . Alfani, M. Cantarella, D. Cifoni, N. Spreti, R. Germani and G. Savelli. “Stabilization of acid phosphatase in DDDACl/n-butyl acetate reverse micelles”. Bioprocess Engineering, 21, 13-19 (1999). 2000 - Baccella S., Cerichelli G., Chiarini M., Ercole C., Fantauzzi E., Lepidi A., Toro L., Vegliò F., “Biological treatment of alkaline industrial waste waters” Proc. Biochem., 2000; 35, 595-602. - Cerichelli G., Mancini G. “Role of Counterions in the Solubilization of Benzene by Cetyltrimethylammonium Aggregates. A Multinuclear NMR Investigation” Langmuir, 16, 182-187, 2000. - Cerichelli G., C. La Mesa, L. Luchetti, G. Mancini. (2000). Role of Counterions in the Catalytic Activity and Phase Equilibria of Phosphonium Salts in Water. Langmuir. vol. 16, pp. 166-171, 2000. - A. Arcadi, G. Cerichelli, M. Chiarini, S. Di Giuseppe, F. Marinelli; “Sequential alkylation/transitino metal catalysed annulation reaction of 1,3-dicarbonyl compounds with propargyl bromide” Tetraedron Lett. (2000), 41, 9195-8 - GNO Collaboration: M. Altmann, M. Balata, P. Belli, E. Bellotti, R. Bernabei, E. Burkert, C. Cattadori, G. Cerichelli, M. Chiarini, M. Cribier, S. d’Angelo, G. Del Re, K.H. Ebert, F.v. Feilitzsch, N. Ferrari, W. Hampel, J. Handt, E. Henrich, G. Heusser, J. Kiko, T. Kirsten, T. Lachenmaier, J. Lanfranchi, M. Laubenstein, D. Motta, W. Rau, H. Richter, S. Wanninger,M. Wojcik, L. Zanotti “GNO solar neutrino observations: results for GNO I” Physics Letters B (2000) 490, 16–26 - Palladium-Catalyzed Arylation of α-Methylene-γ−Butyrolactone:3-Benzylfuran-2(5H)-ones vs. (Z)-Benzylidene-γButyrolactones and their Reduction to 3-Benzyl-γ-Butyrolactones. A. Arcadi, M. Chiarini, F. Marinelli, Z. Berente, L. Kollàr, Organic letters, 2000, 2, 69-72. 21 - The Palladium-Catalysed Reaction of o-alkynyltrifluoroacetanilides with Alkyl halides. An Entry into 2-Substituted 3alkylindoles. A.Arcadi, S. Cacchi, G. Fabrizi, F. Marinelli, Synlett 2000, 393-395. - Synthesis of 2-Acyl- and 2-Ethoxycarbonyl-3-alkylindoles from o-alkynyltrifluoroacetanilides. A. Arcadi, S. Cacchi, G. Fabrizi, F. Marinelli, Synlett 2000, 647-650. - 1,2-Diaza-1,3-butadienes as Powerful Tools in the Synthesis of New 1,6-Dithia-4,9-diazaspiro[4,4]non-2-enes and 1Oxa-6-thia-4,9-diazaspiro[4,4]non-7-enes. A. Arcadi, O.A. Attanasi, B. Guidi, E. Rossi, S. Santeusanio, Synlett 2000, 1464-1467. - The Palladium-Catalyzed Hydroarylation and Hydrovinylation of 3-(o-Acetoxyphenyl)Benzoyloxyphenyl)propynols. A Route to 4-Aryl- and 4-Vinyl-2,2-dimethyl-3-chromenes. A. Arcadi, S. Cacchi, G. Fabrizi, F. Marinelli, P. Pace, Eur. J. Org. Chem. 2000, 4099-4118. and 3-(o- G. Savelli, N. Spreti, P. Di Profio. “Enzyme activity and stability control by amphiphilic self organizing systems in aqueous solutions”. Current Opinion in Colloid & Interface Science, 5, 111-117 (2000). F. Alfani, M. Cantarella, N. Spreti, R. Germani and G. Savelli. “Errore. L'origine riferimento non è stata trovata.-Chymotrypsin superactivity in cetyltrialkylammonium bromide rich media”. Appl. Biochem. Biotech., 88, 1-15 (2000). L. Brinchi, P. Di Profio, R. Germani, G. Savelli, N. Spreti and C.A. Bunton. “The Hammett equation and micellar effects upon SN2 reactions of methyl benzenesulfonates. The role of micellar polarity”. Eur. J. Org. Chem., 23, 38493854 (2000). 2001 - A. Maldotti, L. Andreotti, A. Molinari, G. Varani, G. Cerichelli, M. Chiarini “Photocatalytic properties of iron porphyrins revisited in aqueous micellar environment: oxygenation of alkenes and reductive degradation of carbon tetrachloride” Green Chem., (2001), 1 42-46. - Giorgio Cerichelli “ Water and Soap as a Synthetic Tool “ in GREEN CHEMISTRY SERIES - Collection of Lectures of the Summer Schools on Green Chemistry - Venice 1999, 2000, 2001. Editor: P. Tundo - ISBN 88 88214 00 3- 105111 (2001). - Synthesis of Functionalised Pyrazolones and Imidazolines/Imidazoles through Divergent Annulation Reactions. G. Abbiati, A. Arcadi, O. A. Attanasi, L. De Crescentini, E. Rossi, Tetrahedron 2001, 57, 2031-2038. - Palladium- Catalysed Functionalisation at 4- and 6-Position of the 7-Azaindole System. M. Allegretti, A. Arcadi, F. Marinelli, L. Nicolini, Synlett, 2001, 609-613. - Concise Synthesis of Fused Polycyclic Quinolines. E. Rossi, G. Abbiati, A. Arcadi, F. Marinelli, Tetrahedron Lett., 2001, 42, 3705-3708. - The Palladium-Catalysed Vinylic Subtitution of Aryl/Vinyl Iodides and Triflates with α-Methylene-γ-butyrolactones. An Application to the Synthesis of 3-Allkyl-γButyrolactones through Combined Palladium-Catalysed Coupling/Hydrogenation Reactions. A. Arcadi, M. Chiarini, F. Marinelli, Z. Berente, L. Kollàr, Eur. J. Org. Chem. 2001, 3165-3173. - Gold-Catalysed Sequential Amination/Annulation Reactions of 2-Propynyl-1,3-dicarbonyl Compounds. A. Arcadi, S. Di Giuseppe, F. Marinelli, E. Rossi, Adv. Synth. Catal. 2001, 343, 443-446. - Preparation of 2,5-Disubstituted Oxazoles from N-Propargylamides. A. Arcadi, S. Cacchi, L. Cascia, G. Fabrizi, F. Marinelli, Organic Letters 2001, 3, 2501-2504. - Indole[1,2-c]quinazolines by Palladium-Catalysed Cyclization of Bis(o-trifluoracetamidophenyl) acetylene with aryl and Vinyl Halides or Triflates. Arcadi, S. Cacchi, A. Cassetta, G. Fabrizi, L.M. Parisi, Synlett 2001, 1605-1608. 22 - Conversion of Homochiral Amines and α-Aminoesters to Their Chiral 1,2,3,5-Substituted Pyrrole Derivatives via Gold-Catalysed Amination/Annulation Reactions of 2-Propynyl-1,3-dicarbonyls. A. Arcadi, S. Di Giuseppe, F. Marinelli, E. Rossi, Tetrahedron Asymmetry 2001, 12, 2715-2720. N. Spreti, S. Reale, G. Amicosante, P.Di Profio, R. Germani and G. Savelli. “Infleunce of sulfobetaines on the stability of the Citrobacter diversus ULA-27 lactamase”. Biotechnology Progress, 17, 1008-1013 (2001). N. Spreti, P. Di Profio, L. Brinchi, L. Marte, S. Bufali and G. Savelli. “Activation of -chymotrypsin by cationic additives”. Eur. J. Biochem., 268, 6491-6497 (2001). I-3 Overview of Professional Publications (1997 - 2001) per year Appendix 2 Ranking Scientific Journals Years included: 1997-2001 Name of Journal Number Articles Langmuir 7 of Journal Factor 3.045 J Chem Soc Perk 2 T2 Tetrahedron lett. 3 2.558 Green Chemistry 1 2.111 Helv Cim Acta 1 2.209 Phys Lett B 1 0.849 Main Group 1 Metal Chemistry 0.628 Process Biochem 1 0.744 Environ 1 0.277 Fresn Bull Synlett 1.770 10 2.763 Tetrahedron 3 2.356 Organic Letters 2 3.367 TerahedronAsymmetry Eur J Org Chem 1 2.245 7 2.150 Biorg Med Chem 1 Lett Biotechnology 2 Progress 1.927 1.897 Impact Field Chemistry, Physical Organic Chemistry Organic Chemistry Chemistry, Multidisciplinary Chemistry, Multidisciplinary Physic, Multidisciplinary Chemistry Chemistry, Inorganic & nuclear Biochemistry & Molecular Biology Environmental Sciences Organic Chemistry Organic Chemistry Organic Chemistry Organic Chemistry Organic Chemistry Organic Chemistry Biotechnology &Applied Microbiology Ranking 13/91 21/48 11/48 19/118 18/118 15/48 28/38 245/310 110/127 9/48 13/48 6/48 8/48 15/48 16/48 35/133 23 J. Molec. 1 Catalysis B: Enzymatic Angew. Chem. Int. 1 Ed. Bioprocess 1 Engineering 1.488 Chemistry, Physical 44/91 8.547 5/118 Current Opinion 2 in Colloid & Interface Science Appl. Biochem. 1 Biotech. 2.500 Chemistry, Multidisciplinary Biotechnology &Applied Microbiology Chemistry, Physical 0.673 0.843 88/133 19/91 Biotechnology 75/133 &Applied Microbiology Eur. J. Biochem. 1 2.852 Biochemistry & 99/308 Molecular Biology Chemistry 1 1.633 Chemistry 27/118 Letters Multidisciplinary It is worth note that of the published papers reported in this table 56% have a ranking equal or better than 23%; 35% are in the ranking range 26 - 48% and only 9% of the publications have a ranking ranging between 56% and 87% 24 AQUILA 2 Name of the Research Unit (In Italian and English) AQUILA 2 Analisi Chimica Ambientale Environmental Chemical Analysis University: (In Italian and English) Università dell’Aquila University of L’Aquila Faculty: (In Italian and English) Research Leader (The name of the person in charge of the research programme of the unit) Prof. Pietro Mazzeo Contact Person (The name and address of the person who will act as liaison between the unit and the INCA-Secretariat) Please specify: Name Prof. Pietro Mazzeo Mailing Address Dipartimento di Chimica- Via Vetoio67010-Coppito (L’Aquila) Phone 0862-433759 Fax 0862-433753 E-mail [email protected] Scienze MM. FF. NN. Natural Sciences Department: (In Italian and English) Dipartimento di Chimica, Ingegneria Chimica e Materiali Department of Chemistry, Chemical Engineering and Materials Thematic area Please indicate to which thematic area of INCA the unit belong (in priority order): • Tecnologie innovative di monitoraggio • Chimica degli ecosistemi (chimica del suolo, delle acque e dell’aria; impatto dei prodotti di sintesi sull’ambiente). Introduction and Context The Unit No significant change has taken place. Programme Description and Evaluation 1 Title Determination of toxic residuals in the environment and in foods. 1.Research Leader Prof. Pietro Mazzeo 2a Sub-programme titles and sub-programme leaders (For Units with sub-programmes. If the programme contains separate units or sub-programmes, please explain the organisational structure of the unit) 25 3 Composition of the scientific research staff of the unit per 1 January 2002 Names and Titles Year of Rank Birth Prof. Pietro Mazzeo Dr. Irma Paris Dr. Fabrizio Ruggieri Total research input 1935 1975 1975 Full professor PhD-student PhD-student Research Input in fte in 2001 0.5 1.0 1.0 2.7 Remarks Since 1984 Since 2000 Since 2001 Comments It is very probable in the following 5 years the attainment of a job of researcher as substitution of the previous researcher (G. Carlucci), actually associated professor near an other University. 4 Input of Academic Staff in fte Category Full Professors Associated Professors Ricercatori Post-docs PhD-students Borsisti Total 1997 0.5 1998 .5 1999 .5 2000 .5 2001 .5 Total 2.5 0.8 0.8 0.8 0.8 0.6 3.8 1.0 1.0 1.4 1.0 4.4 2.3 2.3 2.7 2.1 10.7 1.3 Comments The our research group from 2001 is lacking in a researcher (G. Carlucci), actually associated professor near an other University. 5 Funding 5.1 Personnel (in fte) Source University CNR European Union Other Sponsors Total 5.2 * 1998 1999 2000 1.0 2001 0.5 1.0 0.5 2000 2001 Total 1.5 Materials and Equipment (in Million Lire) Source University - MURST CNR EU Other Sponsors Total 5.3 1997 1997 1998 144 144 1999 10 Total 144 10 10 154 Comments: On the figures • On the funding policy The actual perspectives for future fundings from the University and MURST are very poor. This situation will influence very negatively the future activity of our research group. 26 6. Progress Report 6.1 Progress analysis The main objective of our research group is aimed at providing very reliable analytical methods for the determination of toxic residuals in the environment and in foods. The more important result obtained since the 1998 has been the transfer to the new research sector of the previous competences achieved in the fied of the chemical pharmaceutical analysis. 6.2 Position within INCA The position of our research group within INCA is necessarily and strictly connected to the possibility of future fundings. 1.3Key Publications 1) G. Carlucci- Analysis of fluoroquinolones in biological fluids by HPLC- J. Chromatogr. A, 812, 343-367 (1998) 2) G. Carlucci, P. Mazzeo, S. Guadagni, G. Palumbo- Mitomycin C in biological fluids: comparison of disk and cartridge solid-phase extraction and quantitation by HPLC in human plasma and ultrafiltrate- Chromatographia, 50, 561-564 (1999) 3) G. Carlucci, G. Palumbo, P. Mazzeo, M.G. Quaglia- Simultaneous determination of losartan and hydrochlorothiazide in tablets by high-performance liquid chromatography- J. Pharm. Biomed. Anal., 23, 185-189 (2000) 4) G. Carlucci, V. Di Carlo, P. Mazzeo- Simultaneous determination of valsartan and hydrochlorothiazide in tablets by high-performance liquid chromatography- Anal. Lett., 33, 2491-2500 (2000) 5) G. Carlucci, P. Mazzeo, S. Del Governatore, G. Di Giacomo, G. Del Re- Liquid chromatographic method for the analysis of tocopherols in malt sprouts with supercritical fluid extraction- J. Chromatogr. A, 935, 87-91 (2001) 7. Scientific Output 7.1 Publication Policy Our publications in the considered period are still primarily in the field of the pharmaceutical analytical chemistry and on scientific journals with satisfactory ranking and impact factor. The results of the studies in the field of the environmental analytical chemistry are object of some publications in press. 7.2 Numerical data Category PhD-Dissertations 1997 1998 1999 2000 1 2001 Total 1 Scientific Publications 1 1 3 2 1 8 1 2 Professional Publications Master’s Theses 8 1 Self-evaluation The scientific activity of our research group, by taking into consideration the extreme restriction of the number of components and, since 1999, of fundings, is, all things considered, enough satisfactory. Our weakest point is the very limited scientific production in the field of the environmental analytical chemistry, which actually is the sector towards whom are concentrated our efforts. Appendix I Scientific Output I-1 Overview of Dissertations and Master's Thesis (1997-2001) 27 I.1.1 Dissertations Year Name PhD-student 2000 Valeria Di Carlo I.1.2 Master's Thesis Year Name Master’s student Title of the Dissertation 1999 Mauro Malatesta 2001 Fabrizio Ruggieri I-2 Title of the Dissertation Oxygen and pH microelctrodes realization for applications in the environmental analytical chemistry field Validation of a chromatographic method for the simultaneous determination of two active ingredients in antihypertensive drugs Stratigraphic and geochemical study of clastic sediments of the Grotte di Stiffe karst system Supervisor Prof. Pietro Mazzo Supervisor Dr. Giuseppe Carlucci Prof. Pietro Mazzeo Overview of Scientific Publications (1997-2001) per year 1997 1) G. Carlucci, P. Mazzeo- Finasteride in biological fluids: extraction and separation by a graphitized carbon black cartridge and quantification by high-performance liquid chromatography- J. Chromatogr. B, 693, 245-248 (1997) 1998 1) G. Carlucci- Analysis of fluoroquinolones in biological fluids by HPLC- J. Chromatogr. A, 812, 343-367 (1998) 1999 1) G. Carlucci, P. Mazzeo, S. Guadagni, G. Palumbo- Mitomycin C in biological fluids: comparison of disk and cartridge solid-phase extraction and quantitation by HPLC in human plasma and ultrafiltrate- Chromatographia, 50, 561-564 (1999) 2) F. Amicarelli, A. Gasbarri, L. Masciocco, A. Pompili, C. Pacitti, G. Carlucci, G. Palumbo, M. Miranda- The effect of instriatal injection of liposome-entrapped tyrosinase on the dopamine levels in the rat brain- Cellular and Molecular Biology, 45, 1093-1097 (1999) 3) D. Compagnone, V. Di Carlo, L. Bruno, P. Albertano, G. Palleschi- Development of oxygen microsensors for monitoring cyanobacterial photosynthesis in Roman hypogea- Anal. Lett., 32, 213-222 (1999) * 2000 1) G. Carlucci, G. Palumbo, P. Mazzeo, M.G. Quaglia- Simultaneous determination of losartan and hydrochlorothiazide in tablets by high-performance liquid chromatography- J. Pharm. Biomed. Anal., 23, 185-189 (2000) 2) G. Carlucci, V. Di Carlo, P. Mazzeo- Simultaneous determination of valsartan and hydrochlorothiazide in tablets by high-performance liquid chromatography- Anal. Lett., 33, 2491-2500 (2000) 2001 1) G. Carlucci, P. Mazzeo, S. Del Governatore, G. Di Giacomo, G. Del Re- Liquid chromatographic method for the analysis of tocopherols in malt sprouts with supercritical fluid extraction- J. Chromatogr. A, 935, 87-91 (2001) * I-3 Overview of Professional Publications (1997 - 2001) per year I-4 Other Scientific Output 28 Appendix 2 Ranking Scientific Journals Appendix 3 Journal Portfolio Analysis Name of the Unit: Research Director: Years included Name of Journal AQUILA 2...................... Prof. Pietro Mazzeo....................... 1997-2001 J. Chromatogr. A Number Articles 2 J. Chromatogr. B J. Pharm. Biomed. Anal. Chromatographia Anal. Lett. Cell. Mol. Biol. 1 1 1 2 1 of Journal Factor 2.551 1.802 1.013 1.619 0.968 0.97 Impact Field(s) Ranking Chemistry, Analytical 10/65 Chemistry, Analytical Chemistry, Analytical Chemistry, Analytical Chemistry, Analytical 20/65 41/65 22/65 42/65 29 BARI BARI 1 Name of the Research Unit (In Italian and English) Unita’ “Utilizzazione CO2” Unit “CO2 Utilisation” University: (In Italian and English) Universià degli Studi di Bari University of Bari Faculty: (In Italian and English) Facoltà di Scienze Faculty of Sciences Department: (In Italian and English) Dipartimento di Chimica e Centro di Ricerche METEA Department of Chemistry and METEA Research Centre Research Leader (The name of the person in charge of the research programme of the unit) Prof. Michele Aresta Contact Person (The name and address of the person who will act as liaison between the unit and the INCA-Secretariat) Please specify: Name Dr. Angela Dibenedetto Mailing Address Dipartimento di Chimica Università degli Studi di Bari Campus Universitario 70126 Bari Phone +39 080 544 2084 Fax +39 080 544 2083 E-mail [email protected] Thematic area Please indicate to which thematic area of INCA the unit belong (in priority order): 1.Sintesi ecosostenibili (solventi, fotochimica, catalisi, riciclo e altre). 2.Tecnologie biologiche enzimatiche e biomimetiche per le sintesi ecosostenibili e la decontaminazione ambientale. 3.Catalisi eterogenea ecosostenibili e la ambientale. per le sintesi decontaminazione 4.Tecnologie di depurazione (membrane, sonochimica, fotocatalisi, elettrochimica ed altre). The University, the Faculty and the Department The University of Bari is the fifth largest in Italy, with 75000 students, 11 Faculties and 1200 teaching staff. The Faculty of Natural Sciences gathers 8 degrees (Chemistry, Biology, Natural Sciences, Mathematics, Physics, Informatics, Geology, Environmental Sciences) and ca. 8000 students. The Chemistry Department, to which the teaching staff of the Unit belongs, gathers over 60 Professors and Researchers, and 20 PhD students. The University of Bari also operates in Taranto with five Faculties (Economics, Legislation, Literature, Medicine, Natural Sciences) and Prof. Aresta is Pro-Rector for the Taranto seat. In the past, Prof. Aresta has served as Director of the Institute of Inorganic Chemistry and of the Department of Chemistry, and as Dean of the Faculty of Environmental Sciences. He also was Co-ordinator of the Committee for the organisation of Departments and Interdepartmental Centres. He was Member of the Administration Council and Delegate of the Rector for International Programmes. He is now serving as Pro-Rector for the Taranto seat and Director of the Interdepartmental Research Centre on “Environmental Methodologies and Technologies, METEA”, that gathers 25 Professors from different disciplinary areas (Chemistry, Biology, Ecology, Economics, Geology, Legislation, Mathematics). Such Centre is leading several EU, National and Regional Programmes, and bilateral Conventions supported by the Ministry of Foreign Affairs (Russia, Kazakhstan, Brazil) with a budget of over 600 kEuros per year. The Unit 30 The composition of the Unit is categorised below. Prof. Michele Aresta, Prof. Eugenio Quaranta, Prof. Immacolata Tommasi, Dr. Angela Dibenedetto, Junior Researcher Full Associate Associate Professor Professor Professor Within the Department of Chemistry, the Unit has a close co-operation with the Group of Prof. P. Giannoccaro and M. Gargano, who participate in the National Research Project leaded by Prof. M. Aresta on "Strategies for innovative synthetic methodologies". Each Professor has a teaching duty of at least 120 h/y, while Dr. Dibenedetto teaches Laboratory courses for 90 h/y. Courses are tought within different disciplinary areas: Biology, Biotechnnology, Chemistry, Environmental Sciences. In addition to courses for freshmen, specilaistic coures are delivered as: Advanced Inorganic Chemistry, Biotechnology for Fine Chemistry, Envorinmental Biotechnologies, Recovery and Recycling of Materials, Chemical Treatment of Waste, Physical Methods in Inorganic Chemistry, Special Techniques in Inorganic Chemistry. Each Member of the Unit is leader of a Research Theme and of the relevant Project(s), the Co-ordination is duty of Prof. M. Aresta, who also leads a specific Research Theme. Funds are assigned and used per Project. Two PhD Students belong to the Unit, and each year 6 to 8 undergraduate students work at their Thesis Project within the Unit. Students from EU Universities, Russia,Brazil, Poland also join the Unit for short term formation (3 to 6 months) within EU Programmes (Socrates, Leonardo, BRITE, etc) or for long term formation within PhD programmes co-funded by the University and the Ministry.At the moment, two French students (3 m, Socrates Programme) and two Russian students (1 y, bilateral Convention funded by the Ministry) work at the Laboratory, The Unit is also engaged in High Formation Programmes funded by the University and local Authorities, mainly in the area of Environmental Methodologies and Technologies. A Master in this disciplinary area is also leaded by the Unit. The Unit closely co-operates with Institutes of the National Research Council, namely ICOMC and the "Thalassographic Institute", on themes relevant to clean synthetic methodologies,water and sediment depollution, and chemical utilization of algae. Prof. M. Aresta is Director of the latter Institute. Programme Description and Evaluation 1 Title The main research activity is carried out in the area: “The chemistry of complex molecular systems: control of the selectivity and conversion.” 2 Research Leader Prof. Michele Aresta 2a Sub-programme titles and sub-programme leaders New synthetic strategies for the synthesis of complex molecular compounds, Prof. M. Aresta Biotechnologies for Fine Chemistry, Prof. I. Tommasi (EU Project and INCA Project) Synthesis of new homogeneous catalysts, Prof. E. Quaranta (INCA Project) Energy from marine biomass, Dr. A. Dibenedetto (CNR Project) Synthesis of organic carbonates, Prof. M. Aresta (linear), Dr. A. Dibenedetto (cyclic) (MIUR Porject and EU BRITE Project) Soil Remediation, Prof. M. Aresta (INCA Project and PON Project) 3 Composition of the scientific research staff of the unit per 1 January 2002 Names and Titles Year of Rank Birth Prof. M. Aresta Prof. E. Quaranta Prof. I. Tommasi Dr. A. Dibenedetto Total research input 1940 1957 1963 1968 Co-ordinator Project leader Project leader Project leader Research Input in fte in 2001 0.5 0.5 0.5 0.7 2.4 Remarks New synthetic strategies New Catalysts Biotechnology Renewable energy, After 1993 31 No major changes are expected in the very near future. In five years, it is expected that a Full Professor and an Associate Professor join the Group. 4 Input of Academic Staff in fte Category Full Professors Associate Professors Researchers Post-docs PhD-students Contracts Total • • • Funding 5.1 Personnel (in fte) Source University CNR European Union Other Sponsors Total 1 1 2.7 2.7 1999 0.5 0.5 0.7 1 2000 0.5 0.5 1.4 2 1 2.7 5.4 2001 0.5 1 0.7 2 2 5* 11.2 Total 2.5 3 4.2 5 5 5* 24.7 1997 1998 1999 2000 2001 2 Total 2 1 1 1 1 1 6 9 3 6 11 1999 75 10 50 25 160 2000 85 44 50 26 205 2001 85 Total 380 74 240 329 1023 Materials and Equipment (in Million Lire) Source University - MURST CNR EU Other Sponsors Total 5.3 1998 0.5 0.5 0.7 This personnel is under contract within INCA projects. Their contracts will expire October 2002. Post Docs are charged to Projects funded by the Ministry or EU. Other Junior Scientists are contracted on Projects with local Authorities (see below). 5 5.2 1997 0.5 0.5 0.7 1997 60 10 40 25 135 1998 75 10 50 25 160 50 228 363 Comments: 1.On the figures Figures include only funding of projects relevant to the Research discussed in this presentation. As said before, the Unit is involved in other activities which are not relevant to Innovative Syntheses. The Table also includes funding received by INCA for two Projects within the L 488 “Piano INCA”, Cluster Ambiente Terrestre in 2001. 2.On the funding policy The University funding includes funds received from the Ministry and the University of Bari. The former through a research Programme called “Programma di Interesse Nazionale”, the latter through the direct funding of Research Programmes by the University. The local Regional authorities have also funded a Project of the value of 2 MEuros. Such funding was for an activity that is not relevant to the Research discussed here. In fact, it was intended for planning the Regional network for the control of the atmosphere. Also the Unit was Contractor with EU for a BRITE Project of the value of 1 MEuros. Also this Project was outside the research reported here. Such Projects are multidisciplinary Projects managed by METEA. 6. Progress Report 6.1 Mission Statement 32 The Unit is involved since long time in the development of innovative syntheses that respond to the principles of ecoefficiency, through waste reduction at source, energy minimization, atom efficiency, carbon recycling. Such activity has been performed through national and international programmes. The Unit develops such Programme through the preparation of new catalysts, their use in innovative syntheses, avoiding the use of toxic chemicals, with minimization of the amount of organic solvents by solvent shift, and the use of biocatalysts. One of the key issues in the research Programme is the capture and reuse of carbon dioxide as a source of carbon for chemicals. The utilization of carbon dioxide in synthetic chemistry has been for years the main subject of the research of this Unit. Confined at the very beginning to the role of “curiosity”, this approach has recently been considered at the EU level as a strategy for adding value to recovered carbon dioxide, that may make economically viable the capture of CO2 from flue gases and its disposal in natural sinks. The work made during the last years by this Unit has been fully recognized at the international level and appreciated. Prof. M. Aresta has been invited to be Co-Chairman of the Symposium on Carbon Dioxide Utilization yearly organized since 1998 by the Fuel Division of the American Chemical Society. He is also Member of the Scientific Committee of the International Conference on “Greenhouse Gases Technologies, GHGT” managed by IEA-Paris, and Permanent Secretary of the International Conference on “Utilization of Carbon Dioxide”. The approach to problem solving of the Unit results to be an integration of chemical and biochemical strategies. The Unit has recently developed two new biotechnological syntheses carried out by supported enzymes: the synthesis of 4OH-benzoic acid and a trans-methylation reaction, that represent quite unique data in the literature. This research has been funded by the Italian Ministry of the University, Italian Industries, the University of Bari and the EU, through targeted Projects. During the last two years, the Unit also had a key role in INCA Projects as Co-ordinator of a Project on “Soil Remediation”, and partner in two more Projects “Treatment of Industrial water” and “Green chemistry”, within the Piano INCA, L488. Besides this activity, that represents its main area of interest, the Unit has also completed a number of Projects much more oriented to solving practical problems of relevance for local Authorities (Region, Province). Such Projects, that represent an important financial source for the Unit, nevertheless do not represent an important source of scientific publications, mainly because the results are property of local Authorities and are not within the scope of the International Chemical literature. However, such Projects represent important means for the formation of young PostGraduates or Post-Docs and getting them close to solving practical problems. More than fifteen JS were formed in two years in areas like: atmosphere monitoring, use of fixed and mobile control devices, modelling pollutant dispersion, planning a Regional control centre, etc. Another important part of the Research Programme of the Unit are the Environmental Technologies applied either to soil depollution or to water treatment. These research themes have been developed within the INCA programmes funded by the Ministry, L488. However, the research interests of this Unit are spread over different disciplinary areas (Chemistry, Biotechnology, Environmental Sciences) with a different degree of application, from basic research to applied research. 6.2 The Research Programme Research outputs of the Unit will be presented per sector of activity. 1. New synthetic strategies for the synthesis of complex molecular compounds. This activity, funded by the Ministry of the University (MIUR) and the University of Bari (UoB), is devoted to the development of new synthetic strategies that produce chemicals of industrial interest (carbonates, carbamates, isocyanates, carboxylates) by routes alternative to the existing ones. Key issue in this research is the implementation of the principles of: 3.atom economy, 4.waste reduction at source 5.use of non toxic species 6.solvent shift 7.direct syntheses with energy-consumption reduction 8.recycling of carbon. Interesting results were obtained in all areas by using carbon dioxide as source of carbon for the direct carboxylation of organic compounds as amines, alcohol, olefins. Part of this research was carried out in cooperation with Industries and ENIChem owns a patent on the use of organic carbonates for the synthesis of carbamates of toluendiamine (TDA) and methylenedianiline (MDA) that are used for the synthesis of TDI and MDI, starting products for the synthesis of polymers. (Eq. 1a-b) 33 CH3 CH3 CH3 NH2 N=C=O NHC(O)OPh/Me ∆ NH2 1a N=C=O NHC(O)OPh/Me TDA TDI H2N CH2 Me/Ph(O)CHN NH2 CH2 NHC(O)OPh/Me ∆ MDA O=C=N 1b CH2 N=C=O MDI Quite interesting results were also obtained in the application of the oxidative carboxylation of olefins, that allows to convert in one pot an olefin into the relevant carbonate by reaction with dioxygen and carbon dioxide. (Eq. 2) + 1/2 O2 + CO2 cat O C O O This methodology prevents the use of phosgene and has a great potential, supposed that more active catalysts are discovered that may better address the selectivity and yield issues. Of particular interest are the results obtained with the synthesis of optically active carbonates, by carboxylation of optically active epoxides. (Eq. 3) R R O + CO2 cat O C 3 O O In this reaction an ee very close to 100% has been obtained. New catalysts are now under study that may drive reaction 2 to afford optically active carbonates. These topics are specific contributions of the Unit to the scientific community. The carboxylation of alcohol is also a topic of great interest that keeps very busy the Unit. We have discovered new catalysts able to drive the reaction depicted in Eq. 4 that is still under study in order to address both thermodynamic and kinetic issues. O CO 2 + 2 ROH RO OR + H 2O 4 The carboxylation of phenol to afford at room temperature, with 100% selectivity, 4-OH-benzoic acid (Eq. 5) has been achieved by using, for the first time, a supported carboxylation enzyme extracted from anaerobic bacteria. 34 OH OH OH Enzyme P 2O 5 NaOH 5 CO2 COOH Similarly, a supported demethylation enzyme was used for driving at room temperature a transmethylation reaction, a brandly new process, not yet described in the literature. (Eq. 6) OCH3 OH R Enzyme CH3 O + R 6 + OH Cobalamin Supercritical carbon dioxide has been used as solvent and reagent for the synthesis of cyclic carbonates (Eq. 7), a reaction driven by ad hoc designed catalysts formed by metal complexes bearing perfluorurated ligands. O cat O + SC-CO2 O C O 7 O O + In ionic liquids a new very selective (99%) dimerization of methylacrylate has been achieved to afford C-6 units useful for the synthesis of polymers. New functionalized amines have been discovered for the capture of carbon dioxide from gas mixtures, a practice useful for CO2 recovery from flue gases. Besides these synthetic results, new catalysts have been prepared and used, among which we want to emphasise the so called “mixed anhydrides”, biomimetic systems ale to drive carboxylation reactions under very mild conditions. Their general structure is given in Eq. 8 and compared with analogues active in Nature. O - O P O O C X - O Y O P O O C OR Enzyme carboxyphosphate Also, a very interesting activity of carbon dioxide as catalysts has been discovered and described for the carboxylation of amines. All processed are assessed by Life Cycle Assessment with respect to existing ones. 2. Energy from marine biomass This topic is the core of two Projects, funded by the EU and CNR, aimed at assessing the potential of utilisation of marine macro-algae as source of chemicals and energetic products in particular. The extraction of target compounds is made by using Supercritical carbon dioxide or organic solvents or by thermal processes. An assessment of the process, for evaluating the energetic and economic convenience, is carried out at the same time. 3. Soil remediation This topic is also matter of study within the INCA Programme. The conversion of PCBs in soil by direct reductive dehalogenation has been carried out by applying mechanochemical processes. The process is clean and direct. (Eq. 9) C12HxCly + MH 0<x<8 and 2<y<10 C12H10 + MCl 9 35 MH= hydride donor compound (NaH, NaBH4, LiAlH4) In addition to PCBs, other halogenated compounds can be degraded to afford the relevant hydrocarbons. The methodology is safe and does not produce toxic derivatives. Such approach is compared with the thermal desorption of PCBs and their catalytic hydrogenation by using new heterogeneous catalysts. Also, bacteria have been isolated from polluted sediments that may convert halogenated compounds and are now under study. 4. Treatment of industrial water A continuous process for the treatment of green-water (olive-mill water) has been developed within an INCA Programme. This process combines aerobic and anaerobic water treatment. The correct evaluation of the water inlet rate into the reactors has made possible a direct abatement of pollutants (ammonia, phenols, nitrates) in olive-mill water, without any previous dilution, saving, thus, a large amount of fresh water usually added to green-water. Also, the metabolic pathway of a number of reference polyphenols has been followed and the mechanism defined. 5. Future perspectives. The utilization of carbon dioxide will be the core topic of our research for next five years, with the intention of discovering new mild conditions for its utilisation. Besides carboxylation processes, new applications will be sought, also in the area of production of energy-rich compounds. Such approach will be based on the use of biosystems as catalysts or on the use of biomimetic systems. The use of biotechnology for the production of fine chemicals will be another area of application. Shifting from organic solvents to supercritical CO2 or to ionic liquids will be evaluated for their environmental convenience and better performances with respect to existing systems. Also, the use of SC-CO2 as solvent and reagent will be evaluated with much attention. This Programme will be enforced also with the acquisition of new competence within the Unit or by new co-operative actions with national and international Groups. 6.3 Position in Networks As specified above, the co-ordinator of this Unit is at the same time Director of the METEA Research Centre at the University and Director of the CNR Thalassographic Institute in Taranto. This makes available to the Unit many contacts and co-operative activities. In general, Chemistry themes are co-ordinated directly by the Unit, multidisciplinary programmes are co-ordinated by METEA, applied research to water environments is co-ordinated by the Thalassographic Institute. This makes available a network of competence that is very useful for running complex projects. • Intra-university co-operation Due to the variety of activities in which the Unit is involved as co-ordinator or partner, co-operative programmes with several Departments and Centres are active. Mostly, the multidisciplinary research is controlled through METEA, to which the Unit beleongs. The Departments of Computer Science, Geology, Biochemistry, Economics and Legislation, and Physics are major contacts for the Unit. • Regional co-operation The Unit has close relationship with the University of Lecce and the Thalassografic Institute in Taranto. It gives scientific support to the Province of Taranto and the Apulia Region for solving problems dealing with atmosphere, water bodies (internal and external water), soil. The Unit is involved in three POR, or Regional Projects with EU cofunding. • National co-operation (including INCA) The Unit is co-ordinator of the national Project on Complex Systems, that gathers six Universities. Also a CNR Project gathers two Universities and a CNR Institute. Within INCA, the Unit is co-ordinator of a National Project on Soil Remediation and partner in two other Projects, Water Treatment and Green Chemistry. In this way the Unit closely cooperates with Research Groups of over ten Italian Universities, within five Projects. The members of the Unit belong to INCA, and for academic issues to two other Inter-university Consortia, one of which has a special mission within the Environmental Sciences curricula. • International co-operation The Unit co-operates with Institutions of all EU Countries and, through special programmes or bilateral conventions, with Switzerland, Poland, Slovakia, Russia, Kazakhstan, Brazil, Japan. The Unit is running two Socrates, two Leonardo, one BRITE, one COST Project and has two Bilateral Conventions funded by the Ministry of Foreign Affairs. Some of these Projects are high formation programmes. In 2002 the Unit has promoted and organised the First ItalianBrazil Meeting of Inorganic Chemistry, co-funded by CNR and CNPQ, that will take place in Ouro Preto, Brazil. 36 All co-operations are important for the Unit, as they contribute to the growth of the staff and to their international reputation. Within INCA the Unit made a great integration effort during last two years, contributing the expertise and formation experience. The integration of activities was a mutual benefit, and more intense exchanges will be possible in the future if the Unit will have a role within research Projects funded directly by INCA and if an INCA Laboratory will be open in Bari at the METEA Centre. This might promote a better integration into INCA. Apart from the three Projects in which is involved, the Unit took part in several activities organised by INCA, like the school for teachers in Foligno, the Meeting with Russian Chemists within the INTAS Programme, the Meeting in Tunis, etc. Dr. Dibenedetto is co-operating with the INCA President for editing of a Book on Green Chemistry. 6.4 Societal Relevance and Impact The various aspects of the research activity of the Unit are themes that deserve great attention by the international scientific society. For some of them the Unit is a reference point at the International level. For the Carbon Dioxide Utilisation issue, the Unit has a world reputation, as demonstrated by the position of Prof. Aresta and his co-workers within the scientific community, and organisations. The role of co-ordinator that the Unit plays in many programmes, projects and/or circumstances demonstrates the consideration that the Unit has within the scientific community and the University. At the University level, the Unit plays key roles in the Administration and scientific organisation, at the national level is co-ordinator of several Projects, at the EU level plays important roles for the management and evaluation of projects, at the international level there is a recognition of the competence and expertise by outstanding scientists (see for example the recent Review published by Chemical Review with more than 30 Scientists on Carbon Management) and Scientific Societies (Chairmanship of ACS Symposia). The number of invited papers for special issues of International Journals dedicated to outstanding Scientists (5 in the last two years), the invited lectures at each major Symposium or Conference on Carbon Dioxide, the invitation as Visiting Professor within Europe, the number of invited Reviews (four in the last two years), the number of oral presentations at major International Conferences (7 at ACS 2001, 6 at ACS 2002) clearly indicate the International role of the Unit. The number of contracts with several organisations show the acceptance of the scientific competence of the Unit. The role played as consultant of public administrations confirms the reliability and visibility of the Unit. The presence of the Unit in both formation and research international consortia demonstrates the qualification of the Unit in both fields. The management capability is demonstrated by the prominent position occupied at the home University and by the role played by the Unit in the management of International Projects that have gathered up to 35 Institutions. The role of evaluator for EU Projects indicates the confidence of the scientific and public societies. 6.5 Further Indications of Quality and Reputation Prof. Aresta has received the Award of the Italian Chemical Society for his work on Carbon Dioxide Utilisation. Dr. Dibenedetto has received the EU Prize for “An Intelligent Use of Carbon Dioxide Utilisation” granted by the EU and three EU Industries. Contributions by Aresta and Dibenedetto have been selected for three consecutive years as “best ten” within ACS Division Symposia. What reported in previous paragraphs about the role of the Unit and its co-ordinator clarifies the reputation of the Unit at the International level. Recently, Prof. Aresta and Dr. Dibenedetto have been designated as representative of Italy within the International Committee for the evaluation of the emission factors of greenhouse gases of IPCC. 7. Scientific Output 7.1 Publication Policy The results of the research are published at different levels. - Dissertations for Graduates and PhDs, that are made available to the public within the Laboratory and the Department - Technical Reports that are property of the Authorities that grant the project. These can be read by a selected public - Abstracts of Communications at National and International Conferences, - Books with extended abstracts of papers presented at International Conferences and Symposia, - Papers in International Journals, critical Reviews in International Journals, - Books. - The Unit also owns Patents in co-operation with the Ministry, the National Research Council, Industries. Depending on the involvement of the Unit in different kind of projects, there may be a different relative weight of Reports and Scientific publications. As a matter of fact, the work done for the Apulia Region produced a Report of 2000 pages that required the work of ten JS, but no scientific publications. Similarly, a Report for the EU of 600 pages did not produce any scientific publication yet. In the latter case a book is under preparation that will published by Kluwer in 2002. Also, Prof. M. Aresta is Co-Editor of the book “Greenhouse gases utilization” within ACS Series 37 In general, the scientific results are published in Journals of good quality. The choise of the Journal depends on the public the results have to reach. The Unit tends to privilege scientific publications. But, the need to gather funds does not allow to forget contracts with local Authorities. 7.2 Numerical data Category PhD-Dissertations 1997 1998 1999 1 2000 2001 Total 1 Scientific Publications 6 8 3 9 9 35 Professional Publications Master’s Theses 12 19 1 8 8 8 28 8 75 17 Please give a quantitative summary of the publication list, presented under Sections 7.3 -7.5 and elaborate on the selection criteria used for the overviews 8 Self-evaluation The Unit has improved with time its position within the University. The leadership in administrative and scientific tasks gives to the Unit a great visibility. has always pursued a policy of balancing various kind of activities, from basic research to applied research, to contracts with local Authorities. Four permanent staff are actually leading the following positions: - Pro-Rector of the University of Bari for the Taranto seat (five Faculties) - Direction of the METEA Research Centre - Co-ordination of a national research project with six Universities - Co-ordination of a CNR Project with four national partners - Co-ordination of a EU BRITE Project with 35 partners from 12 EU Countries - Contractor for a EU TEMPUS Project, just closed - Direction of the CNR Thalassographic Institute in Taranto - Partnership in two Socrates, two Leonardo, one COST Project - Co-ordination of bilateral Conventions with Russia, Kazakhstan, Brazil - Contracts with the Apulia Region and the Province of Taranto. - Co/ordination of a national Project within INCA - Partnership into two other national INCA Projects - Participation into a National PON project - Participation into three inter-University consortia - Membership in National and International Committees (Inorganic Chemistry Division, Conferences, Panels) - Italy delegates within the International Panel Climate Change, IPCC for the evaluation of the emission factors. - Editors of book with international Publishers - Teaching duties within two Faculties Within the Department of Chemistry, the Unit has a top level size and position. Within the national scientific community the Unit has a high position and consideration. Similarly, the International scientific community highly appreciates the contribution and expertise of the Unit. For the standard of Italian Universities the sum of activities represents a high level. These activities keep the staff full time busy. The number of Projects and Contracts is quite relevant, and not usual for the Italian Universities. The relationship with local and national Authorities is also quite strong. All together, the Unit plays key roles at the University, Regional, National, EU and International level. The integration within the scientific community is also demonstrated by the fact that the Unit is included as partner into four EoI forwarded to the EU, and is co-ordinator of a fifth one. Should financial support come in a more substantial way than at present in the area of carbon dioxide utilisation, the Unit will focus its efforts on this topic, decreasing its engagement into Regional programmes. The Unit considers the EU collaboration as a priority, and will make any effort for strengthening his EU and International role, through new Projects and collaborations. The co-operation with INCA might be important to this end, supposed that INCA is willing to invest into such co-operation and will consider the Unit as a strong operative branch. 38 An evaluative description of the unit’s strengths and weaknesses and of the action taken or to be taken to further improve the quality of the Unit and to strengthen its viability. Appendix I Scientific Output I-1 Overview of Dissertations and Master's Thesis (1997-2001) I.1.1 Dissertations Year Name PhD-student 1998/99 Michele Galatola I.1.2 Master's Thesis Year Name Master’s student Martino Minardi 1997/98 1999/200 0 Giovanni D'Andola 1999/200 0 1999/200 0 1999/200 0 1999/200 0 Valeria Alba Vincenzo Nicastri Nicola Delre Tiziano Pastore 1999/200 0 Ciro Marangell a Antonio Cavallo 1999/200 0 1999/200 0 2000/200 1 2000/200 1 2000/200 1 Title of the Dissertation Supervisor Gestione di sistemi complessi e processi a basso impatto Michele Aresta ambientale Assessment of complex system and processes with low environmental impact Title of the Dissertation Supervisor Trattamento biologico delle acque reflue di cokeria e delle acque di vegetazion e avvio di impianto pilota da banco Biologic treatment of waste water from coke plants and implementation of bench-scale pilot reactor M. Aresta A. Tursi P. Giannoccar o Sintesi, caratterizzazione ed utilizzazione in catalisi di nuovi complessi cationici di palladio M. Aresta (II) E. Quaranta Synthesis, characterization and utilization of new cationi complexes of Pd(II) Sintesi e caratterizzazione di nuovi idruro-complessi di rodio: attività in catalisi M. Aresta Synthesis and characterization of Rh hydrido-complexes and their activity in catalysis E. Quaranta Reattività in fluidi supercritici: utilizzo di SC-CO2 come solvente e reagente M. Aresta Reactivity in supercritical fluids: use of SC-CO2 as solvent and reagent Complessi biomimetici del manganese(II) con fenoli sostituiti M. Aresta Biomimetic Mn(II) complexes whit substituted phenol I. Tommasi Trattamento meccanochimico di terreni contaminati da policlororbifenili (PCBs) M. Aresta Mechanochemical treatment of PCBs contaminated soil C. Tortorella A. Dibenedetto Degradazione microbiologica di derivati del fenolo: influenza della struttura del substrato M. Aresta Micro-biologic phenol derivative degradation: influence of the structure of the substrate Ritenzione di configurazione in reazioni d'inserzione del CO2 in legami epossidici M. Aresta A. Retention of Configuration in insertion reaction of CO2 in epoxide Dibenedetto Michele Sintesi di carbonati organici in reazioni di carbossilazione ossidativa di olefine. Sinthsis of M. Aresta Andriani organic carbonates in the oxidative carboxylation of olefins. A. Dibenedetto Anna Coro Determinazione qualitativa e quantitativa di varietà di amianto in campioni massivi mediante M .Aresta spettrofotometria FT-IR L. DeStefano Qualitative and quantitative determination of asbestous using FT-IR spectrophotometry E. Quaranta supercritico M. Aresta Monica Sintesi di catalizzatori per utilizzo in CO2 Synthesis of catalysts for their utilization in SC-CO2 Distaso Carlo Sviluppo di metodologie innovative per la sintesi di carbonati dialchilici: attivazione di eteri M. Aresta Pastore Development of synthetic methodology for the synthesis of alkyl carbonates: ether activation 39 2000/200 1 Eliana Amodio 2000/200 1 Solidea Marinelli 2000/200 1 Antonella De Vincentis Reazioni di addizione del metil acrilato: influenza del catalizzatore e del solvente M. Aresta Reaction of addition of del metil acrilato: influence of catalysts and solvents A. Dibenedetto Studio sull'utilizzo di due macroalghe del mar piccolo di Taranto per l'estrazione di acidi M. Aresta grassi come fonte di energia alternativa A. Petrocelli Study on the utilization of two macro-algae of the Taranto gulf for fatty acid extraction as G. Alabiso alternative source of energy Ruolo di ferro, nichel e cobalto nel processo di fermentazione anaerobica di rifiuti organici M. Aresta Role of iron, nickel and cobalt on biogas production during the anaerobic fermentation of M-. Minardi I. Tommasi FVG residual biomass 2000/200 1 2000/200 1 Simona Tanzarella Valeria Calò Monitoraggio dell’aria in un’area urbana (Taranto). Analisi statistica dei dati Monitoring of atmosphere in a urban area (Taranto). Statistic and data analysis” Abbattimento di fenoli in acque di vegetazione usando un impianto pilota da banco Abatement of phenol in olive-mill waters by using a continuous bench-scale pilot reactor Please list the PhD-dissertation and Master's thesis supervised by the Unit. If the dissertation or theses title is written in Italian, please add an English translation I-2 Overview of Scientific Publications (1997-2001) per year 1997 1. M. Aresta, E. Quaranta, A. Dibenedetto, P. Giannoccaro, I. Tommasi, M. Lanfranchi e A. Tiripicchio. "Oxidative Addition of Ammonium and Iminium Tetraphenylborates to Low-Valent Metal Complexes. Evidence of Selective N-C and N-H Activation. A New, Easy Route to Cationic Allyl-and Hydrido Nickel Complexes" Organometallics 1997, 16, 834. 2. M. Aresta e E. Quaranta " Carbon Dioxide, a Potential Substitute of Phosgene" ChemTech, 1997, 32, 27. 3. M. Aresta Research for developing carbon dioxide disposal and utilisation World Resource Review, 1997, vol. 9, 248256. 4. M. Aresta, E. Quaranta e I. Tommasi "Tetraphenylborate coordination chemistry and the reactivityof coordinated BPh4-anion. Synthesis, 6 Characterization and Properties of Mono- and Polynuclear Rh(η -BPh4) Complexes"Nouv. Journal de Chimie, 1997, 21, 595. 5. M. Aresta, I. Tommasi "Carbon dioxide utilisation in the chemical industry" Energy Convers. Mgmt., 1997, 38, S373. 6. M. Aresta, I. Tommasi, M. Galatola "Potential of cofiring with biomass in Italy" Energy Convers. Mgmt., 1997, 38, S557. 1998 1. I. Tommasi, M. Aresta, P. Giannoccaro, E. Quaranta and C. Fragale. "Bioinorganic Chemistry of Nickel and carbon dioxide : A Ni-Complex Behaving as a Model System for Carbon Monoxide Dehydrogenase Enzyme" Inorg. Chim. Acta, 1998, 272, 38. 2. M. Aresta, E. Quaranta, R. Liberio, C. Dileo, I. Tommasi "Enzymatic synthesis of 4-OH benzoic acid from phenol and CO2: the first example of a biotechnological application of a carboxylase enzyme" Tetrahedron, 1998, 54, 8841. 3. M. Aresta, A. Dibenedetto, E. Quaranta "Reaction of aromatic diamines with diphenylcarbonate catalyzed by phosphorous acids: a new clean synthetic route to mono- and di-carbamates" Tetrahedron, 1998, 54, 14145-14156. 4. M. Aresta, "Potential of the technological and chemical utilisation of carbon dioxide" La chimica e l'industria, 1998, vol. 80, 1051-1056. 5. M. Aresta “Perspectives of carbon dioxide utilisation in the synthesis of chemicals: coupling chemistry with biotechnology” T. Inui, M. Anpo, K. Izui, S. Yanagida, T. Yamaguchi Eds., "Advanced in Chemical Conversion for mitigating carbon dioxide", Studies in surface science and catalysis, Elsevier Science B.V., Vol. 114, 1998, 65. 6. M. Aresta, E; Quaranta, I. Tommasi, J. Mascetti, M. Tranquille, M. Borowiack M. Aresta M. Aresta 40 "Formation of peroxocarbonates from L3Rh(O2)Cl and L2Ni(CO2) a unique reaction mechanism with carbon dioxide insertin into the O-O bond" T. Inui, M. Anpo, K. Izui, S. Yanagida, T. Yamaguchi Eds., "Advanced in Chemical Conversion for mitigating carbon dioxide", Studies in surface science and catalysis, Elsevier Science B.V., Vol. 114, 1998, 677. 7. M. Aresta, Wojciech Macyk, Zofia Stasicka Photochemistry of [Cu{HB(3,5-Me2pz)3}]2X (X= O2-, CO32-) in non aqueous solvents. Journal of Photochemistry and Photobiology A: Chemistry, 1998, 119, 101-107. 8. J. Cz. Dobrowolski, M; H. Jamroz, J. K. Kazimirski, K. Kajdor, M. A. Borowiack, L. Manna, M.L. Miglietta, M. Aresta The M(O2)X(YH3)3 Dioxigen complexes (M=Rh, Co; X=F, Cl, Br, I; Y=N, P): An Ab Initio, DFT and semiempirical PM3(tm) study. Polish J. Chem., 1998, 72. 1999 1. M. Aresta Dihydrogen influence on Rh(I)-promoted allene-CO2 coupling. Education in advanced chemistry, 1999, Vol 6, pag. 21. 2.M. Aresta, M. Galatola Life Cycle analysis applied to the assessment of the environmental impact of alternative synthetic processes. The dimetilcarbonate case: part 1. Journal of Cleaner Production, 1999, vol. 7 , pag 181. 3. M. Aresta, A. Dibenedetto and Eugenio Quaranta Selective carbomethoxylation of aromatic diamines with mixed carbonic acid diesters in the presence of phosphorous acids. Green Chemistry, 1999, pag. 237. 2000 1. J.Cz. Dobrowolski, M. H. Jamroz, M. A. Borowiak, E. Quaranta, M. Aresta Theoretical IR and Raman spectra of diketene and its 3-methylene isomer. Vibrational spectroscopy, 2000, 22, 19-28. 2. M. Aresta, A. Dibenedetto, I. Tommasi Direct synthesis of organic carbonates by oxidative carboxylation of olefins catalysed by metal oxides: developing green chemistry based on carbon dioxide",Appl. Organometa. Chem., 14, 799-802, 2000. 3. M. Aresta, E. Quaranta, A. Dibenedetto, I. Tommasi and B. Marciniec CO2 catalysed carbamation of aminofunctional silanes. Appl. Organometal. Chem., 14, 871-873, 2000. 4. M. Aresta, A. Dibenedetto, M. Pascale, E. Quaranta and I. Tommasi “New η5– and µ-(O) –Rh(I) phenoxide complexes: synthesis, characterization and unconventional reactivity of η5 complexes towards carbon dioxide”. J. Organomet. Chem., 605, 143-150, 2000. 5. M. Aresta, P: Giannoccaro, I. Tommasi, A. Dibenedetto, A. Manotti, F. Ugozzoli, “Synthesis and Solid State and Solution Characterization of Mono- and Di-(η1-C) Carbamoyl-Palladium Complexes. New Efficient Palladium-Catalysed Routes to Carbamoyl Chlorides: Key Intermediates to Isocyanates, Carbamic Esters, and Ureas. Organometallics. 2000, 19, 3879-3889. 6. M. Aresta, P. Giannoccaro, E. De Giglio, M. Gargano, C. Ferragina "Rh3+ and Rh3+-diamine complexes intercalated in γ-titanium hydrogen phosphate. Synthesis, characterisation and catalytic activity towards aniline oxidative carbonylation processes". J. Mol. Cat. A: Chemical 157, 2000 131-141 7. M. Aresta, D. Ballivet-Tkatchenko, D. Belli Dell'Amico, M.C. Bonnet, D. Boschi, F. Calderazzo, R. Faure, L. Labella, F. Marchetti "Isolation and structural determination of two derivatives of the elusive carbamic acid" Chem. Commun. 2000, 1099-1100. 8. M. Aresta, A. Dibenedetto, E. Quaranta, M. Lanfranchi e A. Tiripicchio “Oxidative Addition of Allylammonium BPh4- to Nickel(0): Synthesis, Crystal Structure, Fluxional Behaviour, and Catalytic Activity of Chiral [(η3-allyl)(NH3)(PCy3)Ni]BPh4”. Organometallics, 2000, 19, 21, 4199-4207. 9. P. Giannoccaro, M. Aresta, S. Doronzo, C. Ferragina "Phenylacetylene carbonylation catalysed by Pd(II) and Rh(III) intercalated in zirconium phosphates" Appl. Organometal. Chem. 14, 581-589, 2000. 2001 1.Aresta M.; Tommasi I.; Dileo C.; Dibenedetto A.; Narracci M.; Ziolkowski J.; Jezierski A. "Synthesis and spectroscopic (1H NMR, ESR) characterization of new aryloxy-Mn(II) complexes: steric control over O- vs phenyl-π-co-ordination of ArO- ligands (ArO- = C6H5O-, 4-methyl-C6H4O-, 3,5dimethyl-C6H3O-, 2,6-di-tert-butyl-C6H3O-, 2,6-dimethyl-C6H3O-) to the "Mn(II)Cp" moiety and their reactivity with carbon dioxide". J. Canad. Chem.79, 570-577, 2001 2. Aresta M.; Dibenedetto A. Tommasi I. 41 "Unique Evidence for a RhIII to RhI Reduction by Deoxygenation of a Carbonate Moiety to CO2 by an Out-ofSphere Phosphane". Eur. J. Inorg. Chem. 2001, 1801-1806. 3. Aresta M.; Dibenedetto A, Tommasi I.;. "Developing Innovative Synthetic Technologies of Industrial Relevance based on Carbon Dioxide as Raw material" Energy&Fuels, 2001, 15, 2, 269-273. 4. Aresta M.; Dibenedetto A. "Key Issues in Carbon Dioxide Utilisation as a Building Block for Molecular Organic Compounds in the Chemical Industry." ACS Book on CO2 Conversion and Utilisation, 2002 54-70. 5.Aresta M.; Dibenedetto, A.; Quaranta E.; Boscolo M.; Larsson R. “The Kinetics and Mechanism of the Reaction between Carbon Dioxide and a series of Amines. Observation and interpretation of an Isokinetic Effect” J. Mol. Catalysis 2001, 174, 7-13. 6. Aresta M; Boscolo M.; Franco D. W. “Copper(II) Catalysis in cyanide Conversion into Ethyl Carbamate in Spirits and Relevant Reactions” J. Agric. and Food Chem. 2001, 49, 6, 2819-2824. 7. Borowiak M. A.; Jamroz M. H.; Dobrowolski J. Cz.; Bajdor K.; Kazimirski J. K.; Mascetti J.; Aresta M.; Tommasi I.; Quaranta E. Application of the impulse oscillation model for modelling the formation of peroxocarbonates via carbon dioxide reaction with dioxygen transition metal complexes. A comparison with the experimental results obtained for Rh(η2-O2)ClP3 [P = phosphane ligand]. J. Mol. Catalysis 2001, 165, 45-54. 8. M. Aresta, M. Minardi, C. Bortone Trattamento integrato in continuo di H2O di vegetazione con impianto pilota Acqua e Aria – Ottobre 2001 9. Arakawa H, Aresta M, Armor JN, et al. Catalysis research of relevance to carbon management: Progress, challenges, and opportunities Chem. Rev. 101 (4): 953-996 APR 2001 I-3 Overview of Professional Publications (1997 - 2001) per year 1997 1. M. Aresta Perspectives in Carbon dioxide Industrial Utilisation. Lecture for the 40th anniversary of ACP, May 19-20, 1997. 2. M. Aresta, M. Galatola Recovery and recycling of plastics Summer School on Waste Management, Rackova dolina, High Tatras, May 19-29, 1997. 3. I. Tommasi, M. Aresta, C. DIleo, R. Liberio Degradation of phenolic and plyphenolic compounds by pseudomonas aeruginosa in anaerobic conditions and potential for biotechnological applications. Workshop on "New challanges for environmental university study", Vienna, Austria, March 20-22, 1997, pag. 203. 4. M. Aresta, M. Galatola Life Cycle analysis approach for the evaluation of the environmental impact of organic carbonates production. Workshop on "New challanges for environmental university study", Vienna, Austria, March 20-22, 1997, pag. 79. 5. M. Aresta Perspectives of carbon dioxide utilisation in the synthesis of chemicals: coupling chemistry with biotechnology Fourth International Conference on Carbon dioxide Utilsation, Kyoto, Japan, September 7-11, 1997, PL 6. 6. M. Aresta, E; Quaranta, I. Tommasi, J. Mascetti, M. Tranquille, M. Borowiack "Formation of peroxocarbonates from L3Rh(O2)Cl and L2Ni(CO2) a unique reaction mechanism with carbon dioxide insertin into the O-O bond" Fourth International Conference on Carbon dioxide Utilsation, Kyoto, Japan, September 7-11, 1997, P 102. 7. M. Aresta, E. Quaranta, I. Tommasi, M. Borowiak, J. Dobrowolski, K. Bajdor, Use of the "Impulse Oscillation Model, IOM" for modelling the reaction of Rh(I)- and Ni(0)-dioxygen complexes with carbon dioxide. Modelling the synthesis and behaviour of peroxocarbonates as monooxigenase-like systems towards olefins and other oxophiles. 4th FGIPS Meeting in Inorganic Chemistry. European mediterranean conference in inorganic chemistry, Corfù, Greece, October 14-18, 1997, ORB 6. 8. M. Aresta Transition metal systems: a bridge between the microbial and industrial chemistry of C1 molecules. 4th FGIPS Meeting in Inorganic Chemistry. European mediterranean conference in inorganic chemistry, Corfù, Greece, October 14-18, 1997, SLB 6. 42 9. M. Aresta Prospettive nella mitigazione delle emissioni di diossido di carbonio. III Congresso nazionale di chimica ambientale, La salvaguardia e la valorizzazione delle risorse, Gallipoli, Lecce, Settembre 24-26, 1997, pag. 22. 10. M. Aresta, M. Galatola L'analisi del ciclo di vita di processi e prodotti come nuovo strumento per la valutazione del loro impatto ambientale: analisi di un caso reale. III Congresso nazionale di chimica ambientale, La salvaguardia e la valorizzazione delle risorse, Gallipoli, Lecce, Settembre 24-26, 1997, pag. 65. 11. M. Aresta Metal ions and life "Education in advanced chemistry", Pollution abatement through cleaner technologies, 1997, vol. 4, 12. M. Aresta, Waste minimization through cleaner production, a must for the chemical industry of the 2000s "Education in advanced chemistry", Pollution abatement through cleaner technologies, 1997, vol. 4, 149. 1998 1. M. Aresta Assessment of of the fixation of carbon dioxide in halophytes. 1rst sectorial meeting of scientists of Santander-Group universities, Seminar Workshop for the identification of problem areas and priorities for the sustainable utilisation of alophytes, Osnabruck, Germany, February 18-19, 1998. 2. M. Aresta, "Process/product performance evaluation as a tool for the assessment of the potential of the utilization of carbon dioxide" Second workshopon Zero-emission power plant, Liège, Belgium, January 26, 1998. 3. M. Aresta, G. Galatola, Life Cycle Analysis (LCA): a methodology for the assessment of the potential of carbon dioxide utilisation. 215 ACS National Meeting, Dallas, Texas, March 29 - April 2, 1998, COLL 051 4. M. Aresta, E. Quaranta, I. Tommasi Mechanism of formation of Rh- and Ni-peroxocarbonates and their utilisation in olefin oxidation and carbonation reactions experimental and theoretical studies. 215 ACS National Meeting, Dallas, Texas, March 29 - April 2, 1998, COLL 086 5. M. Aresta, E. Quaranta, I. Tommasi Selective synthesis of 4-OH benzoic acid from phenol and CO2 under enzymatic catalysis. 215 ACS National Meeting, Dallas, Texas, March 29 - April 2, 1998, COLL 240 6. M. Aresta Allene-CO2 coupling catalysed by Rh(I) complexes. 3rd international school on molecular catalysis. Mechanistic aspects of catalysis. Lagow, Poland, May 20-24, 1998. 7. M. Aresta, M. Capone, E. Quaranta, I. Tommasi Dihydrogen influence on Rh(I)-promoted allene-CO2 coupling. 11 Congresso nazioanle di catalisi, Villasimius (CA), 4-7 giugno 1998, 014. 8. M. Aresta, I. Tommasi, M. L. Miglietta, C. Fragale, Oxidation of two different substrates (L, L') with one dioxygen molecule: the intermediacy of peroxocarbonates. A unique Rh(I)-Rh(III)-Rh(I) cycle and the carbonate deoxygenation to CO2. XXVI Congresso di Chimica Inorganica, Acquafredda di Maratea (PZ), 28 giugno- 2 luglio, 1998, C25. 9. M. Aresta, M. Capone, A. Dibenedetto, C. Fragale, M. L. Miglietta, E. Quaranta, I. Tommasi, A. Tiripicchio, M. Lanfranchi, Oxidative addition of ammonium and imminium tetraphenylborates to low valent complexes. Evidence of a selective N-C and N-H activation. Structure and reactivity of the new cationic Ni- complexes. XXVI Congresso di Chimica Inorganica, Acquafredda di Maratea (PZ), 28 giugno- 2 luglio, 1998, C28 9. P. Giannocaro, M. Aresta, I. Tommasi Palladium carbamoyl complexes key intermediates to isoacyanates or carbamyl chlorides. XXVI Congresso di Chimica Inorganica, Acquafredda di Maratea (PZ), 28 giugno- 2 luglio, 1998, P26. 10. M. Aresta "Chemical utilisation of carbon dioxide" 4th International Conference on Greenhouse Gas Control and Technologies (GHGT4), Interlaken, Switzerland, August 30, September 2, 1998. 11. M. Aresta 43 Coupling the carbon dioxide mitigation strategy with green chemistry. The role of carbon dioxide utilisation option. XXXIII International conference on coordination chemistry, The chemistry of metal ions in everyday life, dedicated to Luigi Sacconi, Firenze, August 30 - September 4, 1998, pag. 31. 12. Michele aresta La gestione dei rifiuti in Italia, ENEA-Trisaia, 30 settembre- 2 ottobre 1998. 13. M. Aresta, M. Galatola, Life Cycle analysis concept applied to new synthetic processes: the DMC case. The third international conference on ECOBALANCE, Progress in LCA for a sustainable society, Tsukuba, Japan, November 25-27, 1998. 14. M. Aresta, E. Quaranta, I. Tommasi, invited Mechanism of formation of Rh- and Ni-peroxocarbonates and their utilisation in olefin oxidation and carbonation reactions experimental and theoretical studies. 215 ACS National Meeting, Dallas, Texas, March 29 - April 2, 1998, COLL 086 15. M. Aresta, E. Quaranta, I. Tommasi Selective synthesis of 4-OH benzoic acid from phenol and CO2 under enzymatic catalysis. 215 ACS National Meeting, Dallas, Texas, March 29 - April 2, 1998, COLL 240 16. M. Aresta, M. Capone, E. Quaranta, I. Tommasi Dihydrogen influence on Rh(I)-promoted allene-CO2 coupling. 11 Congresso nazioanle di catalisi, Villasimius (CA), 4-7 giugno 1998, 014. 17. M. Aresta, I. Tommasi, M. L. Miglietta, C. Fragale, Oxidation of two different substrates (L, L') with one dioxygen molecule: the intermediacy of peroxocarbonates. A unique Rh(I)-Rh(III)-Rh(I) cycle and the carbonate deoxygenation to CO2. XXVI Congresso di Chimica Inorganica, Acquafredda di Maratea (PZ), 28 giugno- 2 luglio, 1998, C25. 18. M. Aresta, M. Capone, A. Dibenedetto, C. Fragale, M. L. Miglietta, E. Quaranta, I. Tommasi, A. Tiripicchio, M. Lanfranchi, Oxidative addition of ammonium and imminium tetraphenylborates to low valent complexes. Evidence of a selective N-C and N-H activation. Structure and reactivity of the new cationic Ni- complexes. XXVI Congresso di Chimica Inorganica, Acquafredda di Maratea (PZ), 28 giugno- 2 luglio, 1998, C28 19. P. Giannocaro, M. Aresta, I. Tommasi Palladium carbamoyl complexes key intermediates to isoacyanates or carbamyl chlorides. XXVI Congresso di Chimica Inorganica, Acquafredda di Maratea (PZ), 28 giugno- 2 luglio, 1998, P26. 1999 1. M. Aresta, A. Dibenedetto, I. Tommasi, A new manganese-depending enzyme phenol carboxylase at work for synthetic purposes and its mimetic systems. th 14 Summer School on Coordination Chemistry, Polanica-Zdroj, Poland, June 6-12, 1999. 2. M. Aresta, A. Dibenedetto, I. Tommasi, E. Quaranta Synthesis and spectroscopic characterization of Mn(II) complexes coordinating phenoxide and mono- and dialkyl substituted phenoxide anions. 14th Summer School on Coordination Chemistry, Polanica-Zdroj, Poland, June 6-12, 1999. 3. M. Aresta, E. Quaranta, A. Dibenedetto, I. Tommasi, M. Lanfranchi, A. Tiripicchio. Oxidative addition of allyl-ammonium and -iminium tetraphenylborates to low valent complexes. II: synthesis, cristal structure and reactivity of chiral [(?3-C3H5)Ni(PCy3)(NH3)]BPh4. XXVII Congresso di Chimica Inorganica, Como, 27 giugno- 1 luglio, 1999. 4. M. Aresta, I. Tommasi, A. Dibenedetto Selective synthesis of 4-OH benzoic acid: potential of the biotechnological utilisation of phenylphosphatecarboxylase enzyme. th 5 International Conference on Carbon Dioxide Utilization, Karlsruhe, Germany, 5-10 September 1999. 5. M. Aresta, P. Giannoccaro, I. Tommasi, A. Dibenedetto, A. Manotti Synthesis, structural characterization and reactivity of Pd-carbamoyl complexes. 5th FGIPS Meeting in Inorganic Chemistry, Toulouse, France, October 26-31, 1999. 6. M. Aresta, E. Quaranta, A. Dibenedetto, I. Tommasi Coordination chemistry of phenoxide ligands to Mn(II) and its relevance to the enzymatic activity of phenylphosphate carboxylase. 5th FGIPS Meeting in Inorganic Chemistry, Toulouse, France, October 26-31, 1999. 7. Aesta M.; Dibenedetto A. 44 “Direct Synthesis of Organic Carbonates by Oxidative Carboxylation of Olefin Catalyzed by Metal Oxide: Developing Green Chemistry Based on Carbon Dioxide”. 10° Congresso Brasileiro De Catalise, September 22–24, Salvador, Bahia, 1999. Invited paper, pp. 410-413 8. M. Aresta Enhanced production and utilisation of biomass for energy purposes: a option for carbon dioxide mitigation Education in advanced chemistry, 1999, Vol 5, pag. 145. 2000 1. M. Aresta, A. Dibenedetto, I. Tommasi “Oxidative carboxylation of olefins to afford organic carbonates: the role of metal catalysis under homogeneous and heterogeneous conditions” International symposium on CO2 conversion and utilisation in refinery and chmeical processing. 219th National Meeting, American Chemical Society, San Francisco, CA, March 26-31, 2000. 2. M. Aresta "Key Issues in Carbon Dioxide Utilasation as a Building Block for Molecular Organic Compounds in the Chemical Industry". 219th National Meeting, American Chemical Society, San Francisco, CA, March 26-31, 2000. 3. M. Aresta, A. Dibenedetto "Synthesis of Organic Carbonates based on CO2 as raw Material" GHGT-5, 13-16 August, 2000, Cairns, Australia 4. Michele Aresta, Angela Dibenedetto, Alessandra Magarelli and Antonella Caroppo "Environmental Life Cycle Assessment (E-LCA) Applied to the Synthesis of Methanol and Dimethylcarbonate" GHGT-5, 13-16 August, 2000 Cairns, Australia 5. A. Dibenedetto, M. Aresta, E. Quaranta "Carbon Dioxide Catalysis in Trans-Esterification Reaction for the Carbamation of Amins of Industrial Interest" 220th National Meeting, ACS, Washington, D.C., August 20-24, 2000, p. 681. 6. Michele Aresta and Angela Dibenedetto, "Developing Innovative Synthetic Technologies of Industrial Relevance Based on Carbon Dioxide as raw Material" 220th National Meeting, ACS, Washington, D.C., August 20-24, 2000, p. 698. 7. M. Aresta, E. Quaranta, V. Alba "Synthesis and structural characterization of [RhCl(C2H4)PPri3]2 an example of solid state hydrogenation catalyst". EURO-Hydrides 2000, September, 6-9, 2000, p. P1 8. M. Aresta, E. Quaranta, G. Dandola The evidence of "hydride intermediacy"in the Ni and Pd catalysed dimerization or polymerization of methylacrylate. EURO-Hydrides 2000, September, 6-9, 2000, p. OC7 2001 1. Aresta M.; ; Tommasi I.; Caterina Dileo; Marcella Narracci Role of iron, nickel and cobalt in biogas production during the anaerobic fermentation of sludges 4° Convegno INCA – Santa Maria Ligure 25-28 Febbraio 2001 2. .Aresta M.; Giannoccaro P.; Tommasi I.; Dibenedetto A.; Manotti A.; Ugozzoli F. “New (η1-C) Carbamoyl-Palladium Complexes: Synthesis, Structural Characterisation and Reactivity towards Halogen Donors. New Catalytic Route to Carbamic Esters and Isocyanates ”. 221st National Meeting, American Chemical Society, San Diego - CA, April 1-5, 2001. Inorganic Division. Abstract n°80. 3. Dibenedetto A. and Aresta M. “Nb2O5 as catalyst in the oxidative carboxylation of olefins” 221st National Meeting, American Chemical Society, San Diego - CA, April 1-5, 2001. Fuel Division. Abstract n°66. 4. Dibenedetto A. and Aresta M. “Nb2O5 as Catalyst in the Fixation of Carbon Dioxide into Epoxides to afford Organic Carbonates with Retention of Stereochemistry” 221st National Meeting, American Chemical Society, San Diego - CA, April 1-5, 2001. Organic Division. Abstract n°220. 5. Aresta M.; Dibenedetto, A.; Quaranta, E. “Synthesis and characterization of new Ni and Pd hydride-species: their catalytic activity in the oligomerisation of methylacrilate” 221st National Meeting, American Chemical Society, San Diego - CA, April 1-5, 2001. Inorganic Division. Abstract n°614. 45 6. Aresta M.; Dibenedetto, A. “Carbon Dioxide Utilisation in Developing Innovative Synthetic Methodologies” 221st National Meeting, American Chemical Society, San Diego - CA, April 1-5, 2001. Environmental Division. Abstract n°9. 7. Michele Aresta, Antonella Caroppo, Angela Dibenedetto “Developing Innovative Synthetic Methodologies Based on Carbon Dioxide. Life Cycle Assessment (E-LCA) as a Tool for the Evaluation of the Enviro-Economic and Energetic Performance of new Technologies: Methanol and Dimethylcarbonate as Probe Cases” 221st National Meeting, American Chemical Society, San Diego - CA, April 1-5, 2001. Fuel Division. Abstract n°61. 8. Aresta M, Dileo C, Tommasi I, et al. Biotechnological synthesis of 4-OH benzoate mediated by a phenylphospate-carboxylase enzyme. 221st National Meeting, American Chemical Society, San Diego - CA, April 1-5, 2001 221: 581-INOR Part 1 9. Aresta Michele “Developing Innovative Synthetic Technologies of Industrial Relevance based on Carbon Dioxide as raw Material” Green Chemistry: Sustainable Products and Processes Swansea - UK, April 3-6, 2001, O20. 10. Dibenedetto A., Tommasi I.. Giannoccaro P. “Pd(II)-catalyzed synthesis of chloroformates and carbamoylchloride: Key intermediates for the synthesis of carbonates, carbamates, isocyanates and ureas” Green Chemistry: Sustainable Products and Processes Swansea - UK, April 3-6, 2001, P3. 11. Dibenedetto Angela “Carbon Dioxide Catalysis in Trans Esterification reaction for the Carbamation of Amines of Industrial Interest" Green Chemistry: Sustainable Products and Processes Swansea - UK, April 3-6, 2001, P2. 12. Michele Aresta* and Angela Dibenedetto “Behaviour of homogeneous and heterogeneous catalysts in the oxidative carboxylation of olefins” SHHC10,in Lyon, France, July 2-6 2001 13.Michele Aresta and Angela Dibenedetto “Enantioselective synthesis of organic carbonates from olefins and epoxides” Europacat V, 2-7 September 2001 Limerick. Abstract 15-O-05 14. Gargano M., Aresta M., Doronzo S., Leoci A., Giannoccaro P. “Reductive N-alkylation of amines, nitrobenzenes, amides, carbamates and ureas promoted by copper catalysts” Europacat V, 2-7 September 2001 Limerick. Abstract 8-P-57 15. Michele Aresta, Immacolata Tommasi, Angela Dibenedetto and Caterina Dileo “Reaction of ketals with carbon dioxide in organic solvents and in SC-CO2” 6th Conference on Supercritical Fluids and Their Applications, 9-12 Sept. 2001 Maiori, Italy 16. Michele Aresta*, Angela Dibenedetto “Carbon Dioxide Utilization in Developing Innovative Synthetic Methodologies” ICCDU VI, September 9-14, 2001, Breckenridge – Colorado 17. Michele Aresta and Angela Dibenedetto* “Enantioselective Nb-catalyzed synthesis of organic cyclic carbonates based on carbon dioxide utilisation » ICCDU VI, September 9-14, 2001, Breckenridge – Colorado 18. Michele Aresta, Immacolata Tommasi, Angela Dibenedetto and Caterina Dileo “Reaction of ketals with carbon dioxide in organic solvents and in SC-CO2” ICCDU VI, September 9-14, 2001, Breckenridge – Colorado 19. Michele Aresta and Angela Dibenedetto A new heteroatomic metathesis reaction: use of ketals as alternative substrates for the synthesis of carbonates. Comparison of the reactivity in organic solvents and SC-CO2 XXIX Congresso di Chimica Inorganica, Taormina, 25 - 29 Settembre 2001. Abstract CR14 20. Michele Aresta, Caterina Dileo, Marcella Narracci e Immacolata Tommasi Anaerobic fermentation of sludges: role of iron, nickel and cobalt in biogas production XXIX Congresso di Chimica Inorganica, Taormina, 25 - 29 Settembre 2001. Abstract CB02 21. Michele Aresta, Angela Dibenedetto, Caterina Dileo, Marcella Narracci e Immacolata Tommasi “Biotechnological Synthesis of 4-OH-benzoic acid” XXIX Congresso di Chimica Inorganica, Taormina, 25 - 29 Settembre 2001. Abstract CB06 22. Michele Aresta and Angela Dibenedetto Synthesis of cyclic carbonates based on carbon dioxide utilization under homogeneous and heterogeneous conditions 46 XXIX Congresso di Chimica Inorganica, Taormina, 25 - 29 Settembre 2001. Abstract CR15 23. Michele Aresta and Eugenio Quaranta Reactivity of ammonium and iminium tetraphenylbortes towards low valent palladium complexes. Evidence of formation of the elusive species [H-Pd(dppe)2]BPh4 XXIX Congresso di Chimica Inorganica, Taormina, 25 - 29 Settembre 2001. Abstract CR01 24. Michele Aresta, Caterina Dileo, Marcella Narracci, Immacolata Tommasi “Anaerobic biodegradation of phenols” Environmental Chemistry. E. Lichtfouse (Ed.). ACE, 2001. p. 251 25. Michele Aresta, Tiziano Pastore Solid state technology for the reductive elimination of polychlorobiphenyls (PCBs) from contaminated soils. Environmental Chemistry. E. Lichtfouse (Ed.). ACE, 2001. p. 85 26. Angela Dibenedetto, Michele Aresta Carbon dioxide utilization for the synthesis of organic cyclic carbonates under homogeneous and heterogeneous conditions. Environmental Chemistry. E. Lichtfouse (Ed.). ACE, 2001 p. 49 27. M. Aresta, P. Caramuscio, De Stefano, T. Pastore “Mechanochemical removal of pcbs in contaminated soil” Proceedings del III congresso ed esposizione internazionale “Valorizzazione e riciclaggio rifiuti industriali” Varirei 2001 – L’aquila – (pp. 154-158). 28. M. Aresta, De Stefano, T. Pastore “Detoxification of PCBs polluted soil by high energy milling” 2001 International Conference on Remediation of Contaminated Sediments: 3-Volume. Battelle Press (Marzo 2002 , data di pubblicazione). Appendix 3 Journal Portfolio Analysis Name of the Unit: Research Director: Years included Name of Journal Utilizzazione CO2 Prof. Michele Aresta 1997-2001 Number Articles Chemical review 1 Eur. J. Inorganic Chemistry 2 Organometallics 3 ChemTech 1 New J. Chem. 1 Energy Conv. Management 2 Inorganica Chimica Acta 1 Tetrahedron 2 J. Photochem and Photob. A 1 Energy&Fuels 1 Green Chemistry 1 Vibrational Spectroscopy 1 Appl. Organometal. Chem. 3 J. Organometal. Chem. 1 J. Mol. Catal. A 3 J. Agric. Food Chem. 1 Chem. Commun. 1 Can. J. Chem. 1 of Journal Factor 21.044 2.475 3.182 1.613 2.44 0.459 1.394 2.276 1.038 1.302 2.477 1.167 1.164 1.803 1.520 1.576 3.902 1.144 Impact Field(s) Ranking Chemistry “ “ “ “ Energy Chemistry “ “ Energy Chemistry Theoretical Chemistry Chemistry “ “ “ “ “ Comments on: a) the method: ISI Journal Citation, 2001 JCR Science Edition. b) the results: Papers appeared in 18 different Journals. It is evident that scientific papers that report chemical facts are published in well reputed Journals. Applied results or invited papers appear in apparently less qualified Journals, that reach a more targeted public. The average impact factor is 2.55. 47 BARI 2 Name of the Research Unit Dipartimento di Chimica - Bari Research Leader Curci Ruggero Contact Person Name Curci Ruggero Mailing Address: Dipartimento di Chimica Università di Bari, Via G. Amendola 173, 70126 Bari. Faculty: Facoltà di Scienze Matematiche Fisiche e Naturali/ Faculty Phone: + 39 080 5442068 Fax: +39 080 5442924 of Mathematical Physical and Natural Sciences E-mail: [email protected] Department: Dipartimento di Chimica/ Department of Chemistry University: Università di Bari Thematic area • Sintesi ecosostenibili (solventi, fotochimica, catalisi, riciclo e altre). (a) Oxidative Degradation of Organic Pollutants. (b) Oxidation Systems using Hyperenergetic Peroxides under Mild Conditions. Introduction and Context Introduction to the Self-evaluation Report As a group participant in the INCA activities, we have been actively engaged in research concerning the application of novel along with classical oxidation reagents to developing clean and efficient selective oxidation methods useful in the field of Fine Chemicals production. In parallel, with a view toward practical applications, we have begun to investigate on the degradation of model pollutants by effective oxidation methods of choice. Along with the revisitation of classical methods (such as the Fenton oxidizing systems), we began to explore the efficiency of new hyperenergetic peroxide species (such as the dioxiranes) in the degradation of chlorinated aromatics in waste-waters and soils under mild conditions. We believe that the INCA network of interdisciplinary expertise should provide an excellent chance to develop practical applications. The University, the Faculty and the Department University of Bari has timely activated the complex and sensitive procedure regarding the structure of “curricula studiorum” and courses leding to Degrees, as well as the Departmental activities. The main goal consists in the alignment of its university education to European standards and to gradually achieve a complete autonomy and innivation. In the various fields, the curricula are articulated according to two distint cycles. The first cover three years and leds to a Degree of 1st Level (roughly equivalent to a B.A.), the second ha a minimum duration of two years, and it leads to a more specialized Degree (2nd Level) roughly equivalent to a Master Degree. These cycles will serve to confer to the students in the various disciplines the basic knowledge, and then an appropriate professional skill concerning the professional methods and skills. After the 2nd Level Degree is achieved, a limited number of graduates are admitted to advanced graduate studies (involving a minimum duration of three years) in research specialities, leding to the “Doctorate” Degree (equivalent to a Ph.D.) The variuos curricula (28) are grouped in 11 Faculties, having full organizing authonomy, within the limits dictated by the National and University regulations. Each professor is assignied to a given Faculty according to his teaching duties, and can join the staff of a given Department. The University of Bari counts nowadays ca. 60,000 students, 6,551 enrolled in the Faculty of Sciences; the number of students enrolled in Chemistry curricula amounts to ca. 370. 48 The Department of Chemistry counts 53 Faculty members and 34 among the staff personnel. The Graduate School in “Chemistry Sciences” has at present 15 students (supported by “ad-hoc” fellowships); the yearly input of new graduate students is on average 4-6, depending on availability of funds. Our group consists of five permanent members, with three of them having regular teaching burdens – all in the field of Organic Chemistry (including laboratory courses). The Department provides the basic research support, plus access to some advanced instrumentation. The permanent members of our UdR have also taken part to a CNR Center (“MISO”, now a Section of ICCOM in Florence) assigned to the Department of Chemistry on grounds of an Agreement between CNR and University of Bari. This has favoured a strong interaction among the research personnel of these two formally different administrations. Accordingly, during the last five years, CNR scientists (two) and University personnel assigned to the CNR Centre (three) have been carrying out joint research that is still underway. In this general frame, we have access to several large-scale facilities such as: GC and GC-MS, HPLC, FTIR Spectrometer, as well as a NMR 500 MHz Spectrometer. The Unit Our Research Unit (UdR) in Bari has by long established a recognized knowledge and expertise in the field of peroxide chemistry and selective oxidations. The recent research activity has regarded: (i) generation and reactivity of isolated dioxiranes and their application to selective oxidations; (ii) peroxide reaction mechanisms and biomimetic oxidations; (iii) oxidation of unactivated alkanes and of target molecules (e.g., the C60 buckminsterfullerene ) under mild conditions; (iv) degradation of chlorinated aromatics by suitably modified Fenton systems. The UdR is constituted by the following permanent staff members: — Ruggero Curci. Full Professor at University of Bari (Italy), since 1975; Director, CNR (Italian Research Council) Center "MISO" (New Synthetic Methods), in 1988; Adjunct Professor , Brown University (providence, RI, USA), from 1998 to present. Awarded the SCI (Italian Chemical Society) Gold Medal “Mangini”, Organic Chemistry Division, in 2000. Invited plenary lecturer at a number of International and National scientific Meetings, has presented seminars and lecture series at several foreign Institutions (Brown University, University of PuertoRico, UCLA, University of Chicago, University of Loughborough, etc.). He is on the board of referees of several established scientific journals (JACS, JOC, EJOC, etc.). At University of Bari, he teaches the course of Organic Chemistry One for the Chemistry curriculum. Author of over 110 primary publications, his main research interests regard: (1) synthesis and reactivity of organic and inorganic peroxides; (2) oxidation mechanisms and catalysis; (3) reactive peroxide intermediates. — Michele Fiorentino. Associate Professor at University of Bari (Italy), since 1985. He teaches the course of Organic Chemistry III and Laboratory (Chemistry curriculum) and the course of Organic Chemistry (Food Science and Technologies). His current research interests include the reactivity and synthesis of dioxiranes. He has coauthored of over 40 scientific publications on major journals. — Caterina Fusco. Ph.D. Degree in Chemical Sciences, in University of Bari, 1995. Federchimica Fellow at the Chemistry Department of the University of Bari, 1989 to May 1991. She spent a period of one year at the Chemistry Department of the Brown Univ., Providence, R.I. (USA) in 1993-1994. Since November 16, 1994 she holds a permanent position as Senior CNR Research Fellow of “Centro di Studio sulle Metodologie di Sintesi Organiche (MISO)” - Chemistry Department, University of Bari. Her current research activities are focused on chemistry of dioxiranes; site selective oxidation of non-natural targets and peroxide reaction mechanisms. She is the author of over 23 joint scientific publications on major journals. — Lucia D’Accolti. Doctorate Degree in Chemistry, 1990. She was at the Chemistry Department of the University of Bari as National Academy "Lincei" (Rome, Italy) Fellow (July 1990 - May 1992) and as C.N.R. Fellow (June 1992 May 1993). Since June 1994, she holds a tenured position as University Senior Assistant (Ricercatore). She spent a period of one year at Chemistry Department of the Brown Univ, Providence, R.I.(USA), and a period of 18 months at the Chemistry Department of the UCLA (Los Angeles, CA, USA) carrynig out collaborative research with prof. C. Foote. Her current research interests focused on chemistry of dioxiranes; enantioselective oxidation of natural products; and singlet oxygen chemistry. She has co-authored of over 14 scientific publications on major journals. — Antonia Detomaso. Doctorate Degree in Chemistry (magna cum laude) on July 1992, she earned a Ph.D. Degree in Chemical Sciences in 1996. At the Chemistry Department of the University of Bari as C.N.R. Fellow (May 1996 - April 1997), then as Procter & Gamble Fellow (May 1997 - April 1998). Since January 1999 she holds the position of Senior CNR Research Fellow at “Centro di Studio sulle Metodologie di Sintesi Organiche (MISO)”, Chemistry Dep., University of Bari. Her current research activity regards the chemistry of dioxiranes, selective oxidation of natural products, novel oxidation methods, and organic reaction mechanisms. She is the author of over 7 joint scientific publications on major journals. Programme Description and Evaluation 49 1 Title Oxidation of Organic Substrates Employing Reactive Peroxide Systems. 2 Research Leader Prof. Ruggero Curci 3 Composition of the scientific research staff of the unit per 1 January 2002 Names and Titles Year of Rank Birth Prof. Ruggero Curci 1937 full professor Prof. Michele Fiorentino 1943 associate professor Dr. Caterina Fusco 1957 research (C.N.R.) Dr. Lucia D’Accolti 1964 research Dr. Antonia Detomaso 1967 research (C.N.R.) Dr. Giangiuseppe Lovecchio 1971 INCA fellowship Dr. Maria Rosaria Rella 1974 INCA fellowship Total research input Research Input in fte in 2001 0.5 0.5 0.9 0.9 0.9 0.9 0.9 6.3 Remarks Finish 2002 Finish 2002 Comments The major changes in the composition of the research group during the previous five years are the following. - Dr. Giarnetti Mariagrazia carried out research in our laboratories for a period of 6 months (November 1998 – May 1999). as a Procter & Gamble Fellow, in the framework of a joint project - Dr. Nicoletta Roppo joined our group for a period of one year (May 6, 1999 – May 2000), as recipient of a Procter & Gamble fellowship. - Dr. Giangiuseppe Lovecchio received a fellowship sponsored by INCA in February 2001. In July 2002 he left the group, taking a temporary position at the CNR Institute IRSA (Water Research) in Bari. He continues collaborating with our group in the frame of joint research links established between this Institution and our group. - Dr. Maria Rosaria Rella received a fellowship sponsored by INCA in January 2002. It is foreseen that she will be able to spend a period of higher formation abroad (USA) starting October 2002. We have reason to believe that in the future the number of research of fellowships made available so far (cf., the table above) will not be diminished, and possibly even augmented, thus allowing the formation of new graduates. It is likely that further contribution to the activity our group will result from the research work of undergraduates (at least 2 per year) preparing their master theses in our laboratory (one year duration). 4 Input of Academic Staff in fte Category Full Professors Associated Professors Researchers Researchers (C.N.R.) Fellowship owners Total 1997 0.5 .5 0.9 0.9 1.8 4.6 1998 .5 .5 0.9 0.9 1.5 4.2 1999 .5 .5 0.9 1.8 0.9 4.6 2000 .5 .5 0.9 1.8 3.7 2001 .5 .5 0.9 1.8 0.9 4.6 Total 2.5 2.5 4.5 7.2 5.1 21.8 Comments Over the last two decades, this Research Unit has established a stable framework, with prof. Ruggero Curci serving as group leader and with prof. Michele Fiorentino as senior coworker; an early addition was Dr. Lucia D’Accolti, who 50 progressed to the position of University Research Fellow (equivalent to Assistant Professor) with tenure. Other members of the group with permanent position are Dr. Antonia Detomaso and Dr. Caterina Fusco, both tenured Research Fellow (“Ricercatore”) of the C.N.R. Centre MISO (recently a section of ICOMM), which have engaged in collaborative research at the Chemistry Department of University of Bari in the frame of a Convention between the CNR and University of Bari. The basic size of the group has been periodically implemented by both undergraduate and graduate students working at their thesis, as well as young graduates supported by fellowships coming from the University of Bari, the CNR, or private company (such as Procter & Gamble S.p.A.). More recently, the group was joined by two young graduates, which were recipients of INCA fellowships. The group has authored several book chapters and articles on primary journals, which witness a proficient activity carried out in the area of new oxidation reagents and reaction mechanisms. In recognition, our research received financial support by the University of Bari, the Ministry of Education and Research (MIUR 60 and COFIN), the Italian Research Council (CNR), as well as the European Union (one STEP project in collaboration with Ausimont S.p.A. and the AEC in Winfrith, U.K.), and Procter & Gamble S.p.A.commmon funding for the research. Finally, an effort has been done for obtaining more consistent funding for fellowships by C.N.R., European Union and Industry. 5. Funding 5.1 Personnel (in fte) Source University CNR Other Sponsors 5.2 1998 2.6 0.9 1.5 1999 2.6 1.8 0.9 2000 2.6 1.8 2001 2.7 1.8 0.9 Total 13.1 7.2 5.1 1999 50 10 8 68 2000 35 10 8 53 2001 35 Total 185 50 95 330 Materials and Equipment (in Million Lire) Source University - MURST CNR Other Sponsors Total 5.3 1997 2.6 0.9 1.8 1997 15 15 7 37 1998 50 15 7 72 65 100 Comments Funding made available through University of Bari include: (i) salaries for the permanent staff, funds covering 80% salary of one postdoctoral position (assegno di ricerca); (ii) research grants from the Ministry of Education and Research (formerly MURST 60%”), that were employed to cover costs for equipment, chemicals, and travel to scientific meeting; (iii) in 1998 and 2000, additional funds came in the frame of a COFIN project (national coordinator: Prof. Giorgio Strukul; titles: “Reactive Peroxide Intermediates” and “Selective Oxidations of Target Molecules with Dioxiranes”); they were employed to cover costs for equipment, chemicals, and travel to scientific meeting, as well as to cover 20% salary of the postdoctoral position mentioned above. In 1997 and 1998, funds (ca. 30 million Lit. total) were also made available by the C.N.R. Centre “MISO” at University of Bari to support research in the frame of Line 2 (“Selective Oxidations”); additional C.N.R funds (10 million Lit.) came from the participation to a CNR Coordinated National Project “Agenzia 2000” (title: “Selective Oxidations of Low Environmental Impact employing Peroxides”). All of the CNR funds above were also employed for equipment, chemicals, and to cover basic research costs. Industry funds were made available by Procter & Gamble S.p.A. in the frame of an Agreement (“Convenzione”) between this company and University of Bari specifically devoted to develop Peroxide Applied Research under the guide of Prof. Ruggero Curci. These funds were devoted to support basic applied research by the group (30 million Lit. total) and to cover the costs of 2 annual and 2 half-annual Fellowships (60 million Lit. total) destined to young chemistry graduates or post-doctoral (Ph.D.) fellows. In the year 2000, the INCA sponsored our work by making available funds (65 million Lit.) in the frame of the activities promoted by the Act L. 488/92, P6 WP2 “Soil remediation and removal of toxic pollutants”. These funds were chiefly employed to achieve the formation of two young graduates, as recipients of INCA research contracts. 51 On the funding policy. Since 1997, funds available to our group for research available have remained substantially stationary. A substantial fraction was devoted to formation of young scientists. In the near future, it is hoped that a substantial increase in funds might result from the participation of our group to National Projects (e.g., the PON blueprinted in collaboration with Syremont S.p.A ,University of Lecce, and University of l’Aquila. This should more than compensate a decrease of CNR funding that is foreseen in the coming years. Other funds are expected to reach us in the framework of the “Piano Nazionale INCA” on the “Chemistry of the clean reactions and processes” (responsible: Prof. P. Tundo). Additional efforts will be done in order to secure us grants from “other sponsors”, such as industry and the EU, by promoting an effective co-operation with cultivating research interest that are complementary to our own. 6. Progress Report 1.3Progress analysis The research activity of our unit has continued to revolve around setting up and optimising novel oxidation reagents and processes. The main strategies followed are: - Activation of simple and economical oxidation reagents (such as hydrogen peroxide, potassium caroate, etc.); - Isolation of novel peroxide species that are reactive toward a variety of organic substrates; - Build-up of efficient catalytic cycles allowing oxidation of organic substrates under mild conditions, The final goal is to devise oxidation methods that are: - environment friendly, allowing clean and efficient processes; - highly selective, as to allow biomimetic oxidation of key “targets”, and in conjunction, or alternative, are - highly reactive as to allow the oxidative degradation of organic pollutants. The combination of accurate reaction conditions set-up with a variety of analytical and product identification techniques (GC, HPLC. MS, 1H- and heteronuclear NMR, UV-Vis, isotope labelling, etc) is required in order to bring this investigations to proper fruition. The initial results collected during the short period of activities carried out under the INCA sponsorship are encouraging. For instance, we have applied a modification of the Fenton oxidative system (i.e. H2O2 and Fe2+/Cu2+ catalyst, at 70° C) to model polychlorinated aromatic substrates (including are representative PCB), achieving practically complete removal of the pollutant and extensive mineralization. In parallel, tailored after our pioneering studies in the field, the oxidative system ketone/caroate (generating dioxirane intermediates in situ) appears eminently suited for green chemistry selective oxidations (e.g., epoxidations) involving the synthesis of fine chemicals. In fact, most simple ketones (e.g., acetone) are rather environment friendly, can be employed in aqueous media, and are not appreciably consumed since they merely act as catalysts. Phase-transfer systems (PTC) can be adopted for substrates that are not appreciably soluble in aqueous media (although using acetone co-solvent could remedy the solubility problem). Actually, suitable simple ketones that present only limited solubility in water (e.g., methylethylketone, MEK) could be used as the organic phase in PTC caroate/ketone oxidations. Concerning the practical applications of the systems mentioned above, it is worth of mention that the reduction product of the bulk oxidant (i.e. H2O from H2O2, and potassium sulfate from caroate KHSO5) are no problem for the environment. 6.2 Position within INCA The main purpose of our collaborative efforts within the INCA Consortium is that of expanding our general knowledge of Environmental and green Chemistry and enhancing our drive toward devising practical applications of our research work. Positive developments are expected by further broadening the collaboration and exchange of expertise with other INCA UdRs’. This should allow us to establish an effective network, attracting research grants and funds to cover temporary positions (research fellowships). An additional benefit expected is that of gaining access to sophisticated and advanced equipment at INCA Laboratories. 6.3 Key Publications 1. "Oxidation of Natural Targets by Dioxiranes. 4. A Novel Approach to the Synthesis of N-Hydroxyamino Acids Using Dioxiranes" Detomaso, A.; Curci, R. Tetrahedron Lett. 2001, 42, 755-758. 52 2. "Oxyfunctionalization of Non-Natural Targets by Dioxiranes. 3. Efficient Oxidation of Buckminsterfullerene C60 with Methyl-(trifluoromethyl)dioxirane" Fusco, C.; Seraglia, R.; Curci, R.; Lucchini, V. J. Org. Chem. 1999, 64, 8363-8368. 3. "Fenton Type Activation and Chemistry of Hydroxyl Radical" Edwards, J. O.; Curci, R. in Catalytic Oxidations with H2O2 as Oxidant; Strukul, G., Ed.; Kluwer: Dodrecht, Netherlands, 1992; Chapter 4, pp 97-151. 4. "Dioxiranes, 3-Membered Ring Cyclic Peroxides" Adam. W.; Hadjiarapoglou, L. P.; Curci, R.; Mello, R. in Organic Peroxides; Ando, W., Ed.; Wiley: New York, 1992 ; Chapter 4, pp 195-219. 5. "Oxidations by Methyl(trifluoromethyl)dioxirane. 2. Oxyfunctionalization of Saturated Hydrocarbons", Mello, R.; Fiorentino, M.; Fusco, C.; Curci, R. J. Am. Chem. Soc. 1989, 111, 6749-6757. 7. Scientific Output 7.1 Publication Policy The great majority of the publications listed have appeared on well established scientific journals or books characterized by wide international circulation and high impact factor on the specialized readership. We believe it appropriate that our findings be also circulated to industries and environmental agencies, as this might result in useful applications and fruitful collaborations. 7.2 Numerical data Category Scientific Publications Master’s Theses 8. 1997 2 1 1998 3 4 1999 2 2000 1 1 2001 3 1 Total 11 7 Self-evaluation Our group is actively engaged in research concerning the application of novel along with classical oxidation reagents, aiming to unfold clean and efficient methods of selective oxidation that are useful in the field of Fine Chemicals production. With a view toward practical applications, we initiated to investigate on the degradation of model pollutants by the suitable modifications of choice oxidation methods. Along with optimizing and reviewing key reaction parameters in classical degradation methods (such as the Fenton oxidizing systems) for cleaning wastewaters and soils, we have successfully explored the application of new hyperenergetic peroxide species (such as the dioxiranes) in the degradation of chlorinated aromatics under quite mild conditions. We believe that the INCA network of interdisciplinary expertise should provide an excellent chance to further develop our skills and drive toward practical applications. In order to bring our research to proper fruition, an expansion of resources seem desirable. In particular, an increase of funding seem appropriate. This is necessary in view of the ever increasing costs of basic research expenditures as well as of the burden of specialized equipment purchase and maintenance. Another stringent need for appropriate resources comes from the necessity renewing the expired temporary appointments and even expanding the size of our group by annexing young scientists, in the form of Research Fellows and/or Graduate Students (hired on contracts). In fact, the present national research policy in regard to academic research seems to favour creating temporary rather than permanent positions. This need is made even more stringent by the fact that new positions (either permanent or temporary), traditionally made available by the C.N.R. are now frozen. Since our traditional major sources of funding (i.e., the Ministry of Education and Research and the C.N.R.) are diminishing their output (if not drying down), the lack of appropriate funds for acquiring new instrumentation (or updating and maintaining the existing one) can be counted as another weak point. The strong point consists in the fact that our group — although small — is stably structured (see above) and can count on a steady flush of undergraduate student that spend a ca. 12 months period working experimentally at their thesis on research carried out in our field. The effective network of by long established collaborations (either national and international), enacted by our group under the leadership of prof. Ruggero Curci, could be counted as 53 another point of advantage. Among these, suffice here to mention the collaboration with various groups (prof.s P. Williard, D. Sweigart, G. Carpenter, etc.) at Chemistry Department of Brown University (Providence, RI, USA). In addition, pursuing our studies in this area, we plan on expanding our cooperation with other INCA UdRs’. For instance, the collaboration with the UdR at University of l’Aquila 1 (Prof. G. Cerichelli) might result in interesting applications concerning the reactivity of our oxidation reagents in micellar media. We also foresee to seek collaborative work with the INCA Laboratories in Venice, especially concerning the access to high-level instrumentation suitable for the detection of residual contaminants in trace amount eventually resulting from oxidation processes. In regard to this aspect, in the past two years we have utilized (and shall continue to exploit) the fruitful collaboration with key scientists at the CNR Institute IRSA (Institute for Water Research) in Bari. Appendix I Scientific Output Master's Thesis Year 1997 1998 1998 1998 1998 2000 2001 Name Master’s Title of the Dissertation student Grazia Accoto Ossifunzionalizzazione di molecole target con diossirani – Indagini sui meccanismi di epossidazione Oxyfunctionalization of target molecules using dioxiranes – Epoxidation mechanism studies Centonze Gianluca Ossifunzionalizzazione di sostanze naturali con diossirani – Sintesi diretta di N-idrossi–amminoacidi e derivati Oxyfunctionalization of natural targets using dioxiranes – Direct synthesis of N-hydroxy-amino acids and derivatives Giarnetti Maria Ossidazione di composti organici del Boro con diossirani Grazia Oxidation of Boron organic compounds using dioxiranes Simona Petroni Ossidazione di target non naturali con diossirani – Sintesi di epossidi del buckminsterfullerene Oxidation of non-natural targets using dioxiranes – Synthesis of buckminsterfullerene epoxides Dario A. De Pinto Ossidazione selettiva di molecole target con diossirani Selective oxidation of target molecules using dioxiranes Giangiuseppe Composti perossidici e scissione ossidativa di composti aromatici Lovecchio clorurati – Sistemi tipo Fenton Peroxide compounds and oxidative degradation of chlorinated aromatic compound – Fenton-type systems Maria Rosaria Rella Composti perossidici iperenergetici e ossidazioni selettive Hyperenergetic peroxides and selective oxidations I-2 Supervisor Curci/Fiorentin o Curci Curci Curci Curci Curci/Lopez Curci Overview of Scientific Publications (1993-2001, including accepted papers) per year 1993 "On the Facile Regeneration of Carbonyl Compounds by Oxidative Cleavage of Hydrazones Using Dioxiranes" Altamura, A.; Curci, R.; Edwards, J. O. J. Org. Chem. 1993, 58, 7289-7293. "Selective Oxidation of Tertiary-secondary vic-Diols to α-Hydoxy Ketones by Dioxiranes" Curci, R.; D'Accolti, L.; Detomaso, A.; Fusco, C.; Takeuchi, K.; Ohga, Y.; Eaton, P. E.; Yip, Y. C. Tetrahedron Lett. 1993, 34, 4559-4562. "Selective Oxidation of Optically Active sec,sec-1,2-Diols by Dioxiranes. A Practical Method for the Synthesis of Homochiral α-Hydroxy Ketones in High Optical Purity" D'Accolti, L.; Detomaso, A.; Fusco, C.; Rosa, A.; Curci, R. J. Org. Chem. 1993, 58, 3600-3601. 54 "Regio- and Chemoselective Epoxidation of Fluorinated Monoterpenes and Sesquiterpenes by Dioxiranes" Lluch, A.-M.; Sanchez-Baeza, F.; Messeguer, A.; Fusco, C.; Curci, R. Tetrahedron 1993, 49, 6299-6308. 1994 “Oxidation of Natural Targets by Dioxiranes. 3. Stereoselective Synthesis of (All-R )Vitamin D3 Triepoxide and of its 25-Hydroxy Derivative” Curci, R.; Detomaso, A.; Prencipe, T.; Carpenter, G. B. J. Am. Chem. Soc. 1994, 116 , 8112-8115. "Oxyfunctionalization of Non-natural Targets by Dioxiranes. Selective Oxidation of Centropolyindans" Kuck, D.; Schuster, A.; Fusco, C.; Fiorentino, M.; Curci, R. J. Am. Chem. Soc. 1994, 116, 2375-2381. 1995 "Enantioselective Epoxidation of Unfunctionalized Alkenes using Dioxiranes Generated In Situ" Curci, R.; D'Accolti, L.; Fiorentino, M.; Rosa, A. Tetrahedron Lett. 1995, 36, 5831-5834. "The oxidation of Coordinated Alkynes by Dimethyldioxirane. Conversion to α-Keto Carbene Complexes" Sun, S.; Edwards, J. O.; Sweigart, D. A.; D’Accolti, L.; Curci, R. Organometallics 1995, 14, 1545-1547. "Dioxirane Oxidations. Taming the Reactivity-selectivity Principle" Curci, R.; Dinoi, A.; Rubino, M. F. Pure Appl. Chem. 1995, 67 , 811-822. 1996 "Organosilyl Peroxides", Ricci, A.; Seconi, G. C.; Curci, R.; Larson, G. L. in Advances in Silicon Chemistry; Larson, G. L., Ed.; JAI: Greenwich, CT, 1996; Vol 3, 63-104. "Oxyfunctionalization of Non-Natural Targets by Dioxiranes. 2. Selective Bridgehead Dihydroxylation of Fenestrindane" Fusco, C.; Fiorentino, M.; Dinoi, A.; Curci, R. ; Krause, R. A.; Kuck, D. J. Org. Chem. 1996, 61, 8681-8684. "Oxidation of Natural Targets by Dioxiranes. 4. High Stereo- and Regioselective Conversion of Vitamin D2 to Its (allR) Tetraepoxide and C-25 Hydroxy Derivative" Curci, R.; Detomaso, A; Lattanzio, M. E.; Carpenter. G. B. J. Am. Chem. Soc. 1996, 118, 11089-11092. "On the Triggering of Free Radical Reactivity of Dimethyldioxirane" Curci, R.; Dinoi, A.; Fusco, C.; Lillo, M. A. Tetrahedron Lett. 1996, 37, 249-252. "Selective Oxidation of O-Isopropylidene Derivatives of Diols to 2-Hydroxy Ketones Employing Dioxiranes" Curci, R.; D’Accolti, L.; Dinoi, A.; Fusco, C.; Rosa, A. Tetrahedron Lett. 1996, 37, 115-118. 1997 "Facile Conversion of Sulfilimines into Sulfoximines Using Dioxiranes" Gaggero, N.; D’Accolti, L.; Colonna, S.; Curci, R. Tetrahedron Lett. 1997, 38, 5559-5562. "Dioxirane Epoxidation and Oxygen Insertion into Alkane CH Bonds Do Not Involve Detectable Radical Pathways" Adam, W.; Curci, R.; D'Accolti, L.; Dinoi, A.; Fusco, C.; Gasparrini, F.; Kluge, R.; Paredes, R.; Schulz, M.; Smerz, A. K.; Veloza, L. A.; Weinkötz, S.; Winde, R. Chem. Eur. J. 1997, 3, 99-103. 1998 "Dioxirane Epoxidations of 1,1-Disubstituted Ethylenes. Probing for Radical Pathways by Computations and Experiments" Liu, J.; Houk, K. N.; Dinoi, A.; Fusco, C.; Curci, R. J. Org. Chem. 1998, 63, 8565-8569. "High-yield Synthesis of Nitriles by Oxidation of Aldehyde N,N-dimethylhydrazones with Dimethyldioxirane" Altamura, A.; D’Accolti, L.; Detomaso, A.; Dinoi, A.; Fiorentino, M.; Fusco, C.; Curci, R. Tetrahedron Lett. 1998, 39, 2009-2012. "On the Reaction of Aminoxyls with Dioxiranes" Dinoi, A.; Curci, R.; Carloni, P.; Damiani, E.; Stipa, P.; Greci, L. Eur. J. Org. Chem. 1998, 1, 871-876. 55 1999 "Oxyfunctionalization of Non-Natural Targets by Dioxiranes. 3. Efficient Oxidation of Buckminsterfullerene C60 with Methyl-(trifluoromethyl)dioxirane" Fusco, C.; Seraglia, R.; Curci, R.; Lucchini, V. J. Org. Chem. 1999, 64, 8363-8368. "Chemo- and Diastereoselectivities in the Oxidation of Cyclopentenols with Dimethyldioxirane and Methyl(trifluoromethyl)dioxirane" D'Accolti, L.; Fiorentino, M.; Fusco, C.; Rosa, A. M.; Curci, R. Tetrahedron Lett. 1999, 40, 8023-8027. 2000 "Synthesis and Reactivity of Manganese Tricarbonyl Complexes of the Centropolyindanes 10-Methyltribenzoquinacene and Fenestrindane" Dullaghan C. A,; Carpenter, G. B.; Sweigart, D. A.; Kuck, D.; Fusco, C.; Curci, R.; Organometallics 2000, 19, 22332236. 2001 "Oxyfunctionalization of Non-Natural Targets by Dioxiranes. 4. Efficient Oxidation of Binor S using Methyl(trifluoromethyl)dioxirane" D'Accolti, L.; Fusco, C.; Lucchini, V.; Carpenter, G. B.; Curci, R. J. Org. Chem. 2001, 66, 9063-9066. "On the Hydroxylation of Bicyclo[2.1.0]pentane using Dioxiranes" Curci, R.; D'Accolti, L.; Fusco, C. Tetrahedron Lett. 2001, 42, 7087-7090. "Oxidation of Natural Targets by Dioxiranes. 4. A Novel Approach to the Synthesis of N-Hydroxyamino Acids Using Dioxiranes" Detomaso, A.; Curci, R. Tetrahedron Lett. 2001, 42, 755-758. 2002 “Concerning Synthesis of Ring-A Fluorinated Anthracyclines. The Dioxirane Shunt” D'Accolti, L.; Fusco, C.; Rella. M. R.; Curci, R. Synth. Commun, 2002, submitted. "The Fenton Reaction Revisited for the Oxidative Degradation of 2,4-Dichlorophenol" Detomaso, A.; Lopez, A.; Lovecchio, G.; Mascolo,G.; Curci, R. Environ. Sci. Technol. 2002, submitted. "Dioxiranes as Green Chemistry Reagents” Detomaso, A.; Lovecchio, G.; Rella. M. R.; Curci, R. in Green Chemistry in Italy, Iteruniversity Consortium “Chemistry for Environment”; Albini, A.; Tundo, P., Ed.s.; Spinea, Venice (Italy); Green Chemistry Series 2002, 4, 117-123. "Chemo- and regioselective oxidation of adamantyl derivatives by dioxiranes" D'Accolti, L.; Kang, P.; Khan, S.; Curci, R.; Foote, C. S. Tetrahedron Lett. 2002, 43, 4649-4652. I-4 Other Scientific Output "Process for the Degradation of Lignin by Dioxiranes" I. Wlassics, F. Burzio, R. Curci, European Patent , EP 529326, A1 (1993). "Process for the Degradation of Lignin by Dioxiranes" Wlassics, I.; Burzio, F.; Curci, R. European Patent, EP 529326, A1 (1993). I-5 Comunications 1993 "Ossidazioni Selettive e Intermedi Diossiranici" R. Curci, L. D'Accolti, A. Detomaso, M. Fiorentino, C. Fusco, T. Prencipe, 56 Il Ruolo della Catalisi nella Chimica Industriale e nella Chimica Fine, Giornate di Studio - C.N.R., Progetto Finalizzato C.F., Milano, 14-15 Giugno 1993; Atti.. "Ossidazione Selettiva di Dioli Vicinali Terziari-secondari in α-Idrossi Chetoni con Diossirani", R.Curci, L. D'Accolti, A. Detomaso, C. Fusco, XXI Convegno Nazionale Divisione Chimica Organica, S.C.I., Terrasini (PA), 28 Settembre - 2 Ottobre 1993; Atti, P 14, 82. "Sintesi di α-Idrossi Chetoni Otticamente Attivi per Ossidazione Selettiva di Dioli Vicinali Secondari-secondari con Diossirani", XXI Convegno Nazionale Divisione Chimica Organica, R.Curci, L. D'Accolti, A. Detomaso, C. Fusco, A. Rosa, S.C.I., Terrasini (PA), 28 Settembre - 2 Ottobre 1993; Atti, P 15, 83. "I Diossirani quali Agenti di Ossifunzionalizzazione Selettiva di Steroidi e Derivati della Vitamina D3", R.Curci, T. Prencipe, XXI Convegno Nazionale Divisione Chimica Organica, S.C.I., Terrasini (PA), 28 Settembre - 2 Ottobre 1993; Atti, P 16, 84. "Sistemi Tipo Fenton per il Trattamento di Contaminanti Tossici", F. Burzio, M. Alfieri, I. Wlassics, M. Twissel, J. Wilks, R. Curci, M. F. Rubino, XXI Convegno Nazionale Divisione Chimica Organica, S.C.I., Terrasini (PA), 28 Settembre - 2 Ottobre 1993; Atti, P 182, 174. 1994 "Concerning Dioxirane Reaction Mechanisms", R. Curci, Italian-Israeli Seminar on Physical Organic Chemistry, Alghero (Sassari), Italy; June 27-30, 1994; Abstracts , 57. "Dioxirane Oxidations. Taming the Reactivity-selectivity Pronciple", R. Curci, 12th IUPAC Conference on Physical Organic Chemistry, Padova, Italy; August 28-September 3, 1994; Abstracts , PL 3, 25. "Synthesis of Nitriles by Oxidative Cleavage of Aldheyde Hydrazones using Dioxiranes", A. Altamura, R. Curci, 12th IUPAC Conference on Physical Organic Chemistry, Padova, Italy; August 28-September 3, 1994; Atbstacts , P 122, 229. "Selective Oxidation of Optically Active O-Isopropylidene Derivatives of Diols by Dioxiranes. A Practical Method for the Synthesis of Homochiral α-Hydroxy Ketones in High Optical Purity", R. Curci, A. Bisceglia, L. D'Accolti, C. Fusco, A. Rosa, 12th IUPAC Conference on Physical Organic Chemistry, Padova, Italy; August 28-September 3, 1994; Atbstacts , P 148, 255. "Stereoselective Synthesis of Vitamin D3 Tris-Epoxide All-R and of its 25-Hydroxy Derivative Using Dioxiranes", R. Curci; A. Detomaso, T. Prencipe, G. B. Carpenter, 12th IUPAC Conference on Physical Organic Chemistry, Padova, Italy; August 28-September 3, 1994; Atbstacts , P 184, 291. 1995 "Processi di Ossidazione Altamente Selettivi in Condizioni Blande mediante l’impiego di Intermedi Diossiranici" R. Curci, L. D'Accolti, A. Detomaso, M. Fiorentino, C. Fusco, XVIII Congresso Nazionale Formazione, Ricerca e Innovazione, S.C.I., Milano, 27 Agosto - 1 Settembre 1995; Atti, ST-P127. 1996 "Processi di Ossidazione Selettivi in Condizioni Blande Mediante l’impiego di Diossirani" R. Curci, L.D'Accolti, A. Detomaso, M. Fiorentino, C. Fusco, XIX Congresso Nazionale Ricerca e Tecnologia, S.C.I., Riccione, 9-14 Giugno 1996; Atti, PS1-92. 57 "On the Trapping of Free-radicals Arising in the Reaction of 1,2-Dihydro-2-methyl-2-phenyl-3H-indol-3-one-1-oxyl with Dioxiranes" L. Greci, P. Carloni, E. Damiani, A. Dinoi, P. Stipa, R. Curci, 7h International Symposium on Organic Free Radicals; Bardolino, Italy, June 16-21, 1996; Abstracts, 83. 1997 "Progressi nelle Ossidazione Selettiva di Substrati Organici con Diossirani" R. Curci, XXIV Convegno Nazionale Divisione Chimica Organica, S.C.I., Salerno, 21-25 Settembre 1997; Atti, PL1. 1998 "Probing into Reaction Mechanisms of Selective Hydrocarbon Oxidations with Dioxirane", R. Curci, Binational Italian-Israeli Conference on Physical Organic Chemistry, Maale Hachamisha -Jerusalem, Israel; June 1416, 1998; Abstracts , 18. " Selective Oxidations Using Doxiranes " IASOC -Ischia Advanced School of Organic Chemistry, VIII Session, Ischia, Italy; September 26-October 1, 1998; Abstracts, L9. 2000 "Advances in Dioxiurane Chemistry" R. Curci, VII Joint Meeting on Heterecyclic Chemistry: Millennium Meeting, RSC - S.C.I., Folgaria (Italy) 3 - 7 Maggio 2000; Atti, PL3. "Ossidazioni Selettive e Meccanismi Polari di Reazione di Composti Perossidici:...non solo Diossirani" R. Curci, SCI 2000 -XX Congresso Nazionale, S.C.I., Rimini, 4 - 9 Giugno 2000; Atti, OR-PL002. "Catalisi da Chetoni nella Ossidazione Selettiva di Substati Organici con Caroato" R. Curci, SCI 2000 -XX Congresso Nazionale, S.C.I., Rimini, 4 - 9 Giugno 2000; Atti, ID-C-OR002. Appendix 3 Journal Portfolio Analysis Name of the Unit: Research Director: Years included Name of Journal Dipartimento di Chimica - Bari Curci Ruggero 1993-2002 including papers accepted for publication Chem. Eur. J. Number Articles 1 of Journal Factor 4.698 Environ. Sci. Technol. 1 3.534 Eur. J.Org. Chem. J. Am. Chem. Soc. 1 3 2.150 6.025 J. Org. Chem. Organometallics 7 1 3.689 3.169 Pure Appl. Chem. 1 1.257 Synthetic Commun. 1 0.828 Impact Field(s) Multidisciplinary Chemistry Environmental Engineering and Environmental Sciences Organic Chemistry Multidisciplinary Chemistry Organic Chemistry Organic Chemistry and Inorganic & Nuclear Chemistry Multidisciplinary Chemistry Organic Chemistry Ranking 58 Tetrahedron Tetrahedron Lett. 1 10 2.356 2.558 Organic Chemistry Organic Chemistry Comments a) the method The Citation Index method is adopted as a suitable in order to assess the contribution of our UdR to the knowledge of the international scientific community in our field. b) the results Inspection of the table above reveals that the results of our work were reported just on high-ranking scientific journals, mostly in the field of Organic Chemistry. All regard the field of effective oxidation processes and mechanisms. Two key publications, one appeared on Pure Appl. Chem. and the other on Environ. Sci. Technol., witness that the aspect of practical applications was not neglected. 59 BOLOGNA BOLOGNA 1 Name of the Research Unit INCA BOLOGNA 1 University: Università di Bologna University of Bologna Faculties: Facoltà di Ingegneria Faculty of Engineering Research Leader Prof. Leonardo Marchetti Contact People Prof. Leonardo Marchetti Prof. Fabio Fava Dipartimento di Chimica Applicata e Scienza dei Materiali Facoltà di Ingegneria, Viale Risorgimento, 2. I-40136 BOLOGNA (ITALY) Facoltà di Scienze Matematiche, Fisiche e Naturali Faculty of Mathematical, Physical and Natural Sciences Departments: Phone: +39 051 2093206-2093212 Dipartimento di Chimica Applicata e Scienza dei Materiali Department of Applied Chemistry and Science of Fax: +39 051 2093218 Materials E-mail: [email protected] Centro Interdipartimentale di Ricerca per le Scienze [email protected] Ambientali Interdepartmental Research Centre for Environmental Science Thematic areas 1• Tecnologie biologiche enzimatiche e biomimetiche per le sintesi ecosostenibili e la decontaminazione ambientale. 2• Chimica degli ecosistemi (chimica del suolo, delle acque e dell’aria; impatto dei prodotti di sintesi sull’ambiente). 3•Tecnologie innovative di monitoraggio e di prevenzione e gestione ambientale Introduction and Context Introduction to the Self-evaluation Report General remarks. In the following sections, a description of the scientific activities carried out by two research groups belonging to the INCA Unit “Bologna 1” (i.e., that of Prof. Marchetti, Faculty of Engineering, and that of Prof. Bruzzi of the Faculty of Sciences, both of the University of Bologna), is presented. Almost all of the scientific activities developed by the two teams are focused on the environment restoration, protection, and management and are therefore strictly related to the thematic areas of INCA. Therefore, these activities are presented and discussed in the following sessions of the report, whereas other minor activities not related to the INCA mission will not be presented here. Collaboration between this Unit and other INCA Units of the Bologna University Seven new INCA Units have been recently created at the University of Bologna, which, therefore, currently counts 9 distinct INCA Units. Many complementary expertises and therefore opportunities of collaboration are now available within the local INCA network. However, as such 7 new units have been formally established in March 2002, no significant cooperation between local INCA Units exists at present. Prof. Fava, who belongs to the Unit “Bologna 1” and who currently coordinates the local INCA Units, is actively working in order to integrate such a large number of expertises and knowledge occurring at the Bologna University in order to develop cooperative research plans and to link the local activities to those in progress within the interuniversity INCA network. The group of Prof. Bruzzi has been incorporated by the former “Bologna 1” Unit in March 2002; thus, also in this case, several efforts are making to efficiently integrate the activity of the new group of the Faculty of Science (Prof. Bruzzi) with those currently in progress at the Faculty of Engineering (Prof. Marchetti); the two groups exhibit highly complementary expertises on 60 the fore front of the environment protection and restoration, and therefore an effective integration between the two teams will be reached in a close future. However, as the present report deals with the activities of the INCA Units from 1997 to 2001, the performances of the two teams joining INCA “Bologna 1” Unit are here separately described. Collaboration between this Unit and INCA Units of other Italian Universities Some of the scientific activities of the Unit group of the Faculty of Engineering, such as those carried out within 3 COFIN/PRIN projects, an INCA project for the Agro-industry and the SISIFO project, have been carried out under strict collaboration with other INCA research Units belonging to other Italian Universities, such as those of the Universities of Roma, Viterbo, Milano, Torino, Genova, Napoli, Cagliari e Messina. The activities related to these projects are marked with an asterisks (*) in the present report. Budget obtained by the Unit from INCA Some research activities carried out at the Faculty of Engineering, such as those related to the SISIFO project and the INCA research Agro-industrial project, have been economically supported by INCA; these projects are marked with two asterisks (**) in the present report. The University, the Faculty and the Department The University of Bologna is the oldest in the western world: 1088 may be accepted as conventional date to indicate when teaching became free and independent of ecclesiastic schools. Bologna University is one of the largest universities in Italy and in Europe. It is a state university and it is autonomous with its own “statuto” which indicates how the University governs itself through its various elected bodies. The University government and the main research and teaching activity are located in Bologna, but many new research and teaching activities have been recently dislocated in other Cities of the Emilia Romagna region, such as Cesena, Faenza, Forli’, Ravenna and Rimini. The whole University currently counts about 900 professors, 1,000 associated professors, 1,050 researchers and more than 100,000 students. It is divided in 19 Faculties, 65 Departments, 5 Federated Departments (“Unità Complesse”), 3 Institutes and it currently offers about 65 “laurea” degree courses and 45 “diploma” degree courses in the following subject areas: a)Agriculture; b) Economics; c) Education and Humanities; d) Engineering; e) Industrial Chemistry, f)Law; g) Literature and Philosophy; h) Mathematical, Physical and Natural Sciences; i) Medicine; l) Pharmacy; m) Political Science; n) School of Modern Languages for Interprets and Translators; o) Statistical Sciences; p) Veterinary Medicine; q) Foreign Languages and Literatures. The Faculty of Engineering has more than 12,000 students and about 500 Faculty members and its consists of about 10 independent Departments. A group of people of the Unit belongs to the Department of Applied Chemistry and Science of Materials of this Faculty. This Department counts about 40 people, 29 of which are Researchers and Professors. The research activity of the Department is focused on 3 different fields: Polymer Chemistry, Material Science & Technologies and Environmental Biotechnology. The group of Prof. Marchetti is the only one involved in teaching and reaserch activities related to the field of the Environmental Biotechnology at the the Department of Applied Chemistry and Material Sciences and at the Faculty of Engineering of Bologna. Another group of people joining the Unit belongs to Interdepartmental Research Centre for Environmental Science, dislocated in Ravenna and part of the Faculty of Mathematical, Physical and Natural Sciences. This Faculty is made up of seven Departments devoted not only to the scientific activity but also to education and training of students: Department of Astronomy, Department of Experimental Biology, Department of Chemistry, Department of Mathemathics, Department of Geological and Geominerological Science, Department of Information Technology, and Department of Pathology. In the Academic year 1999/2000, the Faculty had a total of 6547 students and 982 new enrollments. The Unit The Unit consists of two sub-groups: one belonging to the Faculty of Engineering of the University of Bologna and the second one, operating in Ravenna at the Interdepartmental Research Centre for Environmental Science, belonging to the Faculty of Science of the same University. The group operating at the Faculty of Engineering has been specifically involved in research of Environmental Biotechnology (bioremediation of contaminated soils and waste-waters) since 1990; it consists of two professors, two researchers and a PhD student, and it is responsible for the following courses for students of “Environmental Engineering” and “Chemical Engineering” of the Faculty of Engineering of Bologna: 1.Organic Chemistry; 2.Analytical Chemistry for the Environment and the Industry; 3.Industrial Biochemistry; 4.Environmental Biotechnology. 61 The group operating at the Interdepartmental Research Centre for Environmental Science located in Ravenna and belonging to the Faculty of Science, consists of one professor, two post-doctoral researchers, and one post-graduate fellow. The group is involved in the following research activities: Methods for the environmental risk prevention and management; Monitoring of chemical, biological and ecotoxicological parameters in contaminated sites, jointly with the Montecatini Environmental Centre; Measurements of natural and artificial radioactivity in environmental matrices (e.g. soils, sediments, waters); Programme Description and Evaluation 1 Development of biotechnological processes for the bioremediation of soils, sediments and waste-waters contaminated by organic pollutants. 2 Research Leaders Prof. Leonardo Marchetti/Prof. Fabio Fava 2a Sub-programme titles and sub-programme leaders Methods for the environmental risk prevention and management Prof. Luigi Bruzzi Composition of the scientific research staff of the unit per 1 January 2002 Names and Titles Year of Rank Birth Leonardo Marchetti 1940 Full professor Fava Fabio 1963 0.5 Diana Di Gioia 1965 Associated Professor Researcher Lorenzo Bertin 1970 Reseracher 0.9 Giulio Zanaroli 1976 PhD student 1.0 Luigi Bruzzi 1935 Associated Professor 0.4 Serena Righi 1966 Roberta Guerra 1966 Valentina Boragno 1975 Post-doc 0.5 researcher Post-doc 0.8 researcher Post graduate 0.5 fellow 6.0 Total research input Research Input in fte in 2001 0.2 0.9 Remarks He has been joining the Faculty of Engineering since 1963 He has been joining the Faculty of Engineering since 1989 She has been joining the Faculty of Engineering as researcher since 2001 He has been joining the Faculty of Engineering since 2001 He has been joining the Faculty of Engineering since 2001 Research Sub-programme He joined the Faculty of Engineering from ---to …..and he has joining the Faculty of Science since …. Research Sub-programme Research Sub-programme Research Sub-programme Comments Major changes in the composition of the research group’s staff during the previous 5 years. Fabio Fava, who had been University Researcher at the Faculty of Engineering from 1989 to 2000, became Associated Professor of the same Faculty in November 2000. Diana Di Gioia had been research assistant of the Faculty of Engineering from 1991 to 2001; she became University Researcher of the same Faculty on April 1, 2001. Lorenzo 62 Bertin had joined the Faculty of Engineering from 1997 to 2001 as PhD student and he became University Researcher of the same Faculty on October 1, 2001. Luigi Bruzzi had been Associate Professor at the Faculty of Engineering from 1970 to 1994; since then he has been teaching ‘Principles of Environmental Impact Assessment’ at the Environmental Science degree course, located in Ravenna. Serena Righi had joined the Faculty of Engineering as a PhD student from 1996 to 1999, and has been research assistant at the Interdepartmental Research Centre for Environmental Science since 2000; Roberta Guerra joined the Interdepartmental Research Centre for Environmental Science in 1998, and she has been working as reserach assistant since 2000; Valentina Boragno joined the group in 2001 as a post-graduate fellow. Major changes in the composition of the research group’s staff during the next 5 years. No significant changes in terms of number of people and/or positions covered by the above mentioned people within the Research group of the Faculty of Engineering are expected for the next 5 years. The Prof. Bruzzi’s team will be engaged in new projects dealing with the environmental certification of municipalities located on the coastal areas near Ravenna: new collaboration will start with the Region Emilia Romagna, research organizations, namely ENEA (National Organization for Energy, Environment and Innovation), and environmental Agencies such as ARPA (Regional Agency for Environment Protection). This involvement will result in a growth of people working on the projects of the group. 4 Input of Academic Staff in fte Category Full Professor Associated Professors 1997 0.4 0.4 1998 0.4 0.4 1999 0.4 0.4 2000 0.2 .9 2001 0.2 .9 Total 1.6 3 Ricercatori Post-docs PhD-students Borsisti Total 0.8 0.8 0.8 1.5 1.5 0.5 3.6 1.5 0.5 3.6 0.0 1.3 1.0 1.2 1.3 1.0 0.5 5.1 3.6 2.6 6.5 1.5 18.8 3.1 3.4 Comments The research unit of the Faculty of Engineering increased significantly in size and in level of covered positions during the last 2 years. 5 Funding 5.1 Personnel (in fte) Source University CNR European Union Other Sponsors Total 5.2 1997 3.1 1998 3.6 1999 3.6 1 4.1 1 4.6 2 5.6 2000 3.5 2001 5.1 Total 19.4 5.7 1 6.5 1 5 25.4 2000 65 (*) 45 2001 65 (*) 47 30 55 30 30 60 25 (*) (**) 1 Materials and Equipment (in Million Lire) Source University - MURST CNR EU Other Sponsors 1997 25 (*) 55 10 50 30 1998 20 55 30 80 1999 45 (*) 55 30 30 Total 477 70 175 275 63 Total 5.3 170 185 160 225 30 257 997 Comments: On the figures: Personnel listed by the group of the Faculty of Engineering is permanent staff. The PhD student Zanaroli is paid by the University of Bologna. It is probable that he becomes a new staff person in a few years and that another PhD student joins the group. Personnel listed by the group of the Interdepartmental Research Centre for Environmental science is mainly temporary staff. The two post-docs are paid by the University of Bologna and partially by self-fundings. It is probable that they become a new staff person in a few years. On the Unit cooperation with other INCA Units: Funds and activities related to PRIN/COFIN projects (funded by MURST) joined by the team of the Faculty of Engineering are marked with an asterisk (*). Two of them were jointly prepared with INCA research Units belonging to the Universities of Viterbo, Genova, Roma, Napoli and Caserta (II University of Napoli) (see below for further details on the research Units). In 2001, the team of the Faculty of Engineering joined the SISIFO project, within which it is actively collaborating with INCA units belonging to the Universities of Venezia, Cagliari, Milano, Genova, Napoli, Torino, Calabria, Viterbo and Roma (see below for more details on the Units). The team of the Faculty of Engineering also joined the INCA “Piano Nazionale ‘La sostenibilità e la valorizzazione nel comparto dei residui agroindustriali’" in 2001; within this project it is collaborating with the INCA units of the University of Viterbo, Firenze and Messina (see below for more details on the Units). Research projects directly funded by INCA (15 Million Lire, for the Unit Participation in the SISIFO project and 10 Million Lire for the Unit participation in the Agro-industrial Research Plan) are marked with two asterisks (**) The activities carried on by the Bruzzi’s group will develop new approaches to the environmental analysis of coastal areas, with particular attention to the problems connected to the dredged sediments and the restoration of the beaches. This activity will probably involve contacts with other groups of INCA. Funds relative to projects financed by regional, national and european institutions are those underlined. On the funding policy: The main source of budget for the group of the Faculty of Engineering is represented by the Italian Ministry of Research (MURST), which finances research throughout COFIN/PRIN interuniversity projects and CNR projects, and the University of Bologna, which supports research by means of the ex-60% budget. However, a significant part of the 1997 budget was obtained from ENEL SpA (Italian Company for Electricity); another significant budget was collected by the same group through a NATO-Science for Peace project in the years 2000 and 2001. A small budget was also obtained from INCA through the SISIFO project and the Agro-industry INCA research project. The group of the Faculty of Engineering is currently operating in order to prepare applied-research projects jointly with Italian Private Companies and International private Companies; for instance, it is currently interacting with an American company interested in testing some biogenic surfactants in the bioremediation of hydrocarbon and PCBcontaminated soils and it is in contact with some European Companies located in the Eastern Europe interested in submitting a joint project to EU. Thus, the group of the Faculty of Engineering is working in order to implement connections with Companies involved in the field of soil and wastewaters bioremediation to increase the budgets coming from private Companies and private Research Institutions. The group of the Interdepartmental Research Centre for Environmental Research, currently involved in international networks, is planning to prepare joint research projects in the field of Integrated Coastal Management, and has already submitted an Expression of Interest under the VI Programme of the European Union, to establish a network among 20 European and non European partners. On the major sponsors and the character of the liaison with them: Regarding the researches carried out at the Faculty of Engineering, the main sponsors are, as mentioned above, the Italian Ministry of Research (MURST), the University of Bologna and CNR. INCA has recently become another sponsor for the same team. Interactions occurring between the research team and such supporting Institutions are well known; thus, no details on this matter are provided. In 1997, ENEL SpA financed a research project on the application of cyclodextrins in the bioremediation of PCB-contaminated soils. In this case, the research approach and methods were developed at the Bologna University during the first 6 months of the project and then the research activity was transferred to ENEL laboratories, in Brindisi, where a MS student (Advisor: Prof. Fabio Fava) continued the preliminary work carried out at the Faculty of Engineering of Bologna, thus completing the project. The results have been presented (jointly by the University of Bologna and ENEL SpA) at an Italian Conference. About the research 64 project funded by NATO, the research carried out at the Faculty of Engineering as well as the work performed by 2 public Hungarian research Institutions (Technical University of Budapest and Hungarian Academy of Science, Budapest, HU) and 3 private Companies joining the project, has been periodically described in 6 months-scientific reports submitted to a NATO scientific committee, which then decided on the opportunity to continue to finance the research activities planned in the 3-year research project originally submitted to NATO. The same NATO committee visits the Hungarian Facilities mainly involved in the field experiments during the II year of the project. All papers and presentations along with all formative activities for young scientists (such as workshops and summer schools) derived from the joint project have to be submitted to the same NATO scientific committee. The activities carried on by the Bruzzi’s team are mainly supported by the Emilia-Romagna Region (collaboration in a project aimed to define guidelines for environmental management of coastal areas), by the municipality of Cervia (certification based on EMAS regulation), University of Bologna and Ceramic Centre (measurement of natural radioactivity and radon indoor). 6. Progress Report 6.1 Mission Statement The research group of the Faculty of Engineering is mainly involved in research in the field of the Environmental Biotechnology. In particular, this group works along 3 different lines: 1)Isolation and characterization (under biochemical, microbiological and genetic points of view) of aerobic chemoorganotrophic bacteria capable of degrading chlorinated organic xenobiotics, such as polychlorobiphenyls (PCBs), chlorobenzoic acids, chlorophenols, and hydrocarbons, such as polycyclic aromatic hydrocarbons (PAHs) and hydroxylated and/or methoxylated phenyl-acetic and phenyl-propenoic acids. These are in general a fundamental research and therefore its main client is primarily the scientific community. 2) Design and development of laboratory-scale, packed-bed biofilm reactors for the batch and continuous treatment of PCB-contaminated waste-waters, olive mill wastewaters and the effluents of anaerobic digestors fed with olive mill wastewaters. These are applied researches and therefore they potentially interest National Industries (i.e., those producing olive mill wastewaters), or international Companies (interested in developing technologies for the treatment of PCB-contamianted waters). However, contacts with these Companies are only prelimary at the moment. 3) Design and development of laboratory-scale reactors for the bioremediation of soils contaminated by PCBs and polycyclic aromatic hydrocarbons (PAHs). Use of slurry- and solid-phase microcosms along with different types of reactors for determining the biotreatability of contaminated soils and sediments under aerobic and anaerobic conditions and the role of exogenous inocula and pollutant “solubilizing” agents on the process have been developed as reserach topics. These are applied researches; thus, in addition to the scientific community, the clients for the results of these research projects are regional and national authorities (i.e., MURST, the Italian Ministry of Environment, the local Environmental Protection Agencies, that, as an example, are supporting the SISIFO project), national and international industries (such as ENEL SpA and those joining the NATO Science for Peace project) and educational and training programmes (such as the Summer Schools and workshops held within the SISIFO project and the NATO Science for Peace project). The research group of the Interdepartmental Research Centre for Environmental Science is mainly involved in research in the field of Methods for Environmental Prevention and Management, and Environmental Monitoring. 6.2 The Research Programme The group of the Faculty of Engineering started to work in the field of the environmental biotechnology in 1990. It belongs to the Department of Applied Chemistry and Science of Materials and therefore over the years it has purchased instruments and equipments required for running biological, microbiological and genetic analysis on micro-organisms along with reactors suitable for their cultivation. The required know-how has been obtained from other Italian laboratories and throughout several long and short term stays of Fabio Fava in some American laboratories (such as those at the New Jersey Institute of Technology and those at the Rutgers University -NJ, USA-, specialized in the field of the Environmental Microbiology and Biotechnology) and of Diana Di Gioia who spent 2 months in the laboratory of Environmental Microbiology (Ottawa University, Canada) to learn advanced molecular techniques for the genetic characterization of hydrocarbon-degrading bacteria. The research activities carried out by the group during the last five years can be subdivided, as proposed above, in three lines, which also presently represent the main research topics of the team. 65 1) Isolation and characterization of aerobic chemo-organotrophic bacteria capable of degrading chlorophenols, polycyclic aromatic hydrocarbons (PAHs) and hydroxylated and/or methoxylated phenyl-acetic and phenyl-propenoic acids. These isolates have been obtained from contaminated wastewaters and soils through conventional enrichment procedures. In general, they have been characterized for their taxonomy (through conventional approaches and/or via 16S rDNA sequence analysis), biodegradation potential vs. the organic pollutant (in resting- and growing-cell batch conditions), the biochemical routes through which they degrade the xenobiotic compound (by detecting and characterizing specific enzyme activities in the cell crude extract of the strain, by determining the occurrence of specific genes in the total or purified DNA of the isolate through hybridisation experiments or by chemically characterizing intermediate metabolites accumulated in the crude extracts or liquid cultures of the bacterium) and kinetic parameters, such as µmax, Ks, Ki, etc., describing the growth of the isolates on the xenobiotic or the activity of their specific enzymes vs. the xenobiotic (in batch conditions and, for the cultures, in a chemostat; in general, the kinetic models of Monod, Michaelis-Menten, Andrews or Haldane have been used). 2)Development of laboratory-scale packed-bed biofilm reactors for batch and continuous treatment of olive mill wastewaters and the effluents of anaerobic digestors fed with olive-mill wastewaters. In the first case, a consortium of anaerobic bacteria previously developed in an pilot-scale, anaerobic digestor was immobilized in two identical 2-litres anaerobic reactors packed with silica beads or granular activated carbon and used for the bioremediation and valorisation (through methane production) of olive mill wastewaters. The reactors were first employed in batch conditions and compared (in terms of COD and phenolic compound depletion and methane production) and they were then modified, applied and tested for their microbial stability and flexibility under continuous operative conditions. In the second project (that related to the post-treatment of effluents of anaerobic digestor rich in persisting phenolic compounds), 2 identical 1 litre-aerobic reactors packed with silica beads or polyurethane cubes were used to passively immobilize an aerobic bacterial co-culture (previously developed in the laboratory) capable of extensively biodegrading the hydroxylated and/or methoxylated phenyl-acetic and phenyl-propenoic acids persisting in such effluents. The reactors were compared for their depurative performance under batch conditions by using both a synthetic mixture of monocyclic aromatic phenolic compounds and a real effluent of an anaerobic digestor fed with olive mill wastewater. The biotechnological processes developed under the two projects exhibited the required features and performances to be scaled up. The team is currently looking at Companies interested in supporting this stage of the research under economical and technological point of view. 3) Fundamental and applied researches on the bioremediation of contaminated soils and sediments. Several laboratoryscale, aerobic reactors for the biological removal of PCBs and hydrocarbons from freshly-spiked and agedcontaminated soils have been designed, developed and described in the literature. Furthermore, slurry- and solid-phase anaerobic and aerobic microcosms along with slurry-, semisolid- and solid-phase aerobic reactors (including packedbed loop reactors) have been developed and employed to assess the actual “bio-treatability” of some aged-contaminated soils (as it has been done within the SISIFO research project) and PCB-contaminated sediments of the Venice Lagoon (as it has been done within the COFIN/PRIN project entitled “Liquid and gaseous depurative treatments to remove high toxicity pollutants (priority pollutants) with particular reference to environmental recovery of the Venetian industrial area” coordinated by Prof. Volpicelli of the University of Napoli) as well as for determining the effects of the addition of exogenous specialized bacteria or pollutant-“solubilizing” agents, such as synthetic and biogenic surfactants and cyclodextrins, on the bioremediation of PCB-contaminated soils (as it has been done in the project funded by ENEL SpA, in the NATO Science for Peace project and in other related research activities funded by MURST). The use of biogenic “solubizing”-agents in the bioremediation of PCBs contaminated soils has been an original idea developed and extensively investigated by the team of the Faculty of Engineering during the last 5 years. Several international papers derived from this work; thus, a brief description of the objectives, approaches and results of the research described in these papers is provided here. Bioremediation is generally considered as a safer, environmental friendly and significantly less expensive method to remove harmful pollutants from soils when compared to physical and chemical processes. For these reasons, biological treatment of contaminated soils has become dominant during the last decades. However, bioremediation can be time consuming and unsatisfactory when applied to soils historically contaminated by highly-hydrophobic pollutants, such as PAHs and/or PCBs. In fact, these pollutants are generally poorly bioavailable in such soils as, due to their highly hydrophobic nature, they tend to strongly a(d)sorb onto the soil organic matter, thus becoming scarcely available in the soil water-phase, where the specialized microorganisms are generally located and active. The bioavailability and, in turn, the biodegradation of PAHs and PCBs in such contaminated matrixes may be enhanced by amending them with suitable “solubilizing” agents. A number of commercial synthetic surfactants have been tested for this purpose; in general, they resulted to be very effective “solubilizing” agents but often they also resulted to be recalcitrant and toxic compounds in the amended matrixes. Cyclodextrins (CDs), which are anular D-glucose-oligosaccharides extensively used as solubilizing agents for hydrophobic molecules in the food and pharmaceutical industry, and in particular hydroxypropyl-β-CD, γ-CD and randomly methylated-β-CD (RAMEB), have been tested by the team and found to be 66 non-toxic and biodegradable additives capable of significantly enhancing the aerobic biodegradation of PCBs in agedcontaminated soils under solid-, slurry- and fixed-phase laboratory-scale conditions. RAMEB was found to be also effective in the bioremediation of PCB- and PAH-contaminated soils in technological-scale, solid-phase reactors and it is currently applied in the field bioremediation of a contaminated site located in Hungary (within the Science for Peace NATO project; visit web site www.cyclolab.hu/nato for more details). Phytogenic surfactants, such as Quillaya Saponin (QS) and Soya Lecithin (SL), were also tested by the team for the same reasons and found to be very interesting biogenic PCBs solubilizing agents and capable of intensifying the aerobic bioremediation of PCB-contaminated soils. In general, these agents conjugated interesting pollutantsolubilizing effects with a low-toxicity and a good biodegradability. In particular, QS influenced positively the bioremediation of an aged-contaminated soil under slurry-phase conditions , whereas SL strongly enhanced the aerobic biodegradation of PCBs in a model soil spiked with Fenclor42 and treated under slurry-phase conditions. Prof. Fava and Dr. Di Gioia received the “best paper award for 2001” from the American Oil Chemists’Society (AOCS) for the work they did (published in Biotechnology and Bioengineering, 72, 177, 2001) on the SL application in soil bioremediation of PCB-contaminated soils. Future research activities and efforts will be concentrated on the application of other biogenic “solubilizing” agents in the bioremediation of PCB and PAH-contaminated soils during the next 5 years. This research activity will be carried out within the SISIFO project and, in particular for the application of SL, within an agreement with an American Company which has already expressed the interest in testing its SL-based industrial products in the field of bioremediation of hydrocarbon-contaminated sites. Significant efforts will also be made in order to implement the research area related to the detection and characterization (under biochemical, microbiological and ecological point of view) of processes of reductive dechlorination of PCBs and chlorinated organic pesticides in contaminated sediments of Italian and European contaminated lakes, rivers and marine areas and in sludges resulting from biological plants treating industrial wastewaters containing chlorinated organic pollutants. The research group of the Interdepartmental Research Centre for Environmental Science develops and carries on its research projects as follows: 1.Environmental characterization of case-study areas, with the employment of simulation models when required; 2.Assessment of the Environmental Risk associated with contaminated sites, and assessment of the remediation options by laboratory experiments. 6.3 Position in Networks • Intra-university co-operation The team of the Faculty of Engineering is collaborating with research teams belonging to different Departments of the University of Bologna, such as: 1.Department of Chemical Engineering, Mining and Environmental Sciences (Proff. Nocentini, Pinelli, Magelli, Sarti) 2.Department of Biological Sciences (Prof. Zannoni) 3.Department of Agricultural Sciences and Environmental Technologies (Prof. Biavati) 4.National Cancer Research Institute (Genova), Bologna’s Satellite Unit (INCA Unit Bologna 5) (Prof. Grilli; Dr. Colacci) 5.Department of Farmaceutical Sciences (Prof. Matteuzzi) 6.Department of Industrial Chemistry and Sciences of Material (Units INCA Prof. Trifiro’ and Prof. Morselli). The Faculty of Engineering team is running with these teams common research projects, by sharing equipments with them. In addition, several MS theses have been prepared within this local network and students have been often exchanged within the same network. As for the future, the Unit are evaluating collaboration with other INCA research Units of the University of Bologna, in order to develop common research projects and formative local initiatives. 1.Regional co-operation The team of the Faculty of Engineering has collaborated with Area SpA (Ravenna; Ing. Bazzi) and with the Montecatini Environmental Research Center (Marina di Ravenna, Ravenna; Dr. Iacondini; Dr. Serra). Some MS students have prepared their thesis in strict collaboration with these Centers, which represent the main private regional centers where research and other activities on the environmental defence and management are in progress. 2.National co-operation (including INCA) The team of the Faculty of Engineering of Bologna has already completed 2 distinct COFIN/PRIN interuniversity research projects and it is currently involved in other 2 COFIN/PRIN research projects. One of the completed project 67 (entitled “Utilization, stabilization and valorisation of aromatic components of agroindustrial residues”; National Coordinator: Prof. Giovannozzi-Sermanni of the University of Viterbo) and one of those underway (entitled “Set-up of defined and concerted actions to perform an ecocompatible upgrading of olive mill wastewaters”; national coordinator: Prof. Giovannozzi-Sermanni of the University of Viterbo) have been jointly prepared with INCA research Units belonging to other Universities, such as the Unit of Prof. Giovannozzi-Sermanni (University Viterbo), that of Prof. Canepa (University of Genova), that of Prof. Beccari (University of Roma), that of Prof. Piccolo (University of Napoli), that of Prof. Lucio Previterra (University of Napoli) and that of Prof. Aliotta (University of Caserta, II University of Napoli). In the other completed project (entitled “ Liquid and gaseous depurative treatments to remove high toxicity pollutants (priority pollutants) with particular reference to environmental recovery of the Venetian industrial area”; National Coordinator: Prof. Volpicelli of the University of Napoli), the team of the Faculty of Engineering is collaborating with research Units of the University of Roma (the INCA Unit coordinated by Prof. Beccari), University of Verona (the INCA Unit coordinated by Prof. Cecchi), University of Napoli (Prof. Volpicelli), University of Venezia (Prof. Traverso), and the University of Genova (Prof. Veglio’). In the other COFIN/PRIN in progress (entitled “Vanillin production through microbial conversion of agro-industrial residues” coordinated by Prof. Sorlini of the University of Milano), the same unit collaborates with the University of Milan (Proff. Sorlini, Daffonchio and Molinari), University of Viterbo (Prof. Ruzzi) and the University of Genova (INCA Unit of Prof. Del Borghi). In 2001, the team of the Faculty of Engineering joined the SISIFO project, within which it is actively collaborating with the following INCA units (listed in terms of the Unit coordinator’s name): Prof. Baldi (University of Venezia), Prof. Cao (University of Cagliari), Prof. Galli (University of Milano), Prof. Del Borghi (University of Genova), Prof. Piccolo (University of Napoli), Prof. Pramauro (University of Torino), Prof. Zerbinati (University of Torino), Prof. Molinari/Drioli (University of Calabria), Prof. Giovannozzi-Sermanni (Universitry of Viterbo), Prof. Mentasti (University of Torino), Prof. Beccari (University of Roma) and Prof. Canepa (University of Genova). The team of the Faculty of Engineering also joined the INCA “Piano Nazionale ‘La sostenibilità e la valorizzazione nel comparto dei residui agroindustriali’" in 2001; within this project it collaborated with the following INCA Units (listed in terms of Unit coordinator): Prof. Giovannozzi-Sermanni (University of Viterbo), Prof. Mincione (University of Viterbo), Prof. Scozzafava (University of Firenze) and Prof. Micali (University of Messina). The same team contributes to the 1st Summer School on “Ricerca , sperimentazione e sviluppo di tecnologie di bonifica di siti inquinati” organized by a large number of INCA Units joining the SISIFO project in collaboration with the Italian Ministry of the University and the Italian Ministry of the Environment. This extensive collaboration within the INCA network has been of special interest for the scientific growth of the team of the Faculty of Engineering. Indeed, thank to this national network the team could join 3 of the COFIN/PRIN projects mentioned above and has had the chance to join the SISIFO network along with all its strategic initiatives in the field of the soil remediation. Therefore, the team will do its best to intensify the collaboration currently available within the INCA network during the next 5 years. The team of the Faculty of Engineering has also collaborated with ENEL SpA (Brindisi), where MS students of the Faculty of Engineering of the University of Bologna are often sent for preparing their thesis. 3.International co-operation The research Unit of the Faculty of Engineering is collaborating with the following International institutions: A) within the framework of the NATO Science for Peace N.973720 entitled "Decontamination of Hydrocarbon Polluted Military Sites to Decrease Environmental Risks-Low-Cost Cyclodextrin Technology" (web site www.cyclolab.hu/nato), it is collaborating with research Units of the: -Technical University of Budapest, Hungary (Dr. K. Gruiz); -Hungarian Academy of Science of Budapest, Hungary (Dr. A. Muranyi); -Cyclolab Ltd, Budapest, Hungary (Prof. J. Szejtli); -Thermal Desorption Technology Group, Budapest, Hungary (Mr. E. Someus); -Dunaferr/Innopark , Budapest, Hungary. The team of the Faculty of Engineering has been collaborating with these Research Groups since 1998. In collaboration with these research teams, it has published 2 international papers, organized 2 training courses (one in Bologna and the other in Budapest) and exchanged some students and young scientists. This collaboration is of special interest for the team (it allowed the Faculty of Engineering of Bologna to join the NATO Science for Peace project) and therefore it will do its best to intensify these contacts during the next 5 years. B) within an Erasmus Program (of which Prof. Fava is the main coordinator), the Unit is collaborating with the Institute of Chemical Technology, Technika 5 166 28 00 Prague 5 Czech Republic (Prof. K. Demnerova). A MS student of 68 environmental engineering the Faculty of Engineering has been exchanged during the last year and another one will move to Prague at the end of the year in order to prepare his MS thesis in environmental Microbiology. C) The team is collaborating with the New Jersey Institute of Technology (Newark, NJ, USA), Hazardous Substance Management Research Center (Newark, NJ, USA) (Prof. P.M. Armenante), and Rutgers University, both at Newark and in New Brunswick (NJ, USA) (Prof. D. Kafkewitz and Prof. L.Y. Young, respectively). The team of the Faculty of Engineering has been collaborating with these Research Centers since 1993. Seven international papers have published jointly with them, 3 other papers are in preparation and 3 MS students plus 2 PhD students have been already exchanged within this network. This extensive collaboration is of special interest for the team of the Faculty of Engineering and therefore it will do its best to intensify exchanges with these laboratories during the next years. The research group of the Interdepartmental Research Centre for Environmental Science has been and is still involved in the following international projects: 1.UNESCO/UNITWIN Network for ‘Mutual Support for Advancement of Education and Training, and Promotion of Wise Practices for Sustainable Human Development in Coastal Areas (WiCoP)’, among the University of Cadiz (Spain), University of Bologna (Italy), the University of Aviro (Portugal), the Russian State Hydrometeoriological University (RSHU) of S.Petersburg (Russia), and the University of Latvia; 2.EURO-ECORISK project: High-level Scientific Conferences on ‘Environmental Risk Assessment: Advanced Analytical Techniques’ for young researchers from Member and Associated States, jointly organised by the University of Bologna, Environmental Science and the Budapest University of Technology and Economics, 1999-2002 (contract number HPCT-1999-00159), financed by the European Union under the V Programme for Research and Technological Develpment – Human Potential thematic programme (scientific coordinator: Prof. L.Bruzzi, University of Bologna; local organisers: Dr. R.Serra (Montecatini Environmental Research Centre, Italy), and Prof. K.Gruiz (Budapest University of Technology and Economics, Hungary); 3.Italian-Romanian Intergovernmental Agreement for technical and scientific cooperation between the University of Bologna and the University of Bucharest on ‘Long-term risk assessment of mining site exploitation’; financed by the Italian Ministry of Foreign Affairs, 2000-2004; 4.Italian-Hungarian Intergovernmental Agreement for technical and scientific cooperation between the University of Bologna and the Budapest University of Technology and Economics on ‘Long-term risk assessment of contaminated sediments: new methodology and standardisation’; financed by the Italian Ministry of Foreign Affairs, 2000-2002; 5.Socrates-Erasmus exchanging programme between the University of Bologna, Environmental Science (coordinator Prof. L. Bruzzi) and: 5.3The University of Aveiro (Portugal) 5.4The University of Cadiz (Spain) 5.5Tampere University (Finland) 5.6Budapest University of Technology and Economics (Hungary) 6.Inter-University Agreement between the University of Bologna, Environmental Science and the Budapest University of Technology and Economics (Hungary); 7.Italian-Russian Workshops on ‘Environmental Quality in Urban areas’, Ravenna, 23-27 november 1999, and S.Petersburg, 22-27 March, 2000, financed by the Italian Ministry of Foreign Affairs; 6.4 Societal Relevance and Impact The Unit is convinced that bioremediation of contaminated soils and wastewaters will have a growing role in the defence and protection of the environment in the future. Due to the increasing awareness in problems related to the soil and wastewater contamination, there is a need for further optimisation of the existing bioremediation processes. The team of the Faculty of Engineering contributes to this necessity by testing solubilizing agents that may intensify the biological removal of hydrophobic pollutants from contaminated soils and by developing packed-bed biofilm reactors for a more effective removal of pollutants from contaminated wastewaters. Of course, the contribute that the group can give in this area is relatively limited, mostly for its small size and availability of budget; however, it hopes to remain and to increase its role in the fore front of research in this area for the next 5 years. 6.5 Further Indications of Quality and Reputation Fabio Fava is the current coordinator of the INCA research Units (that are 9 since March 2002) of the University of Bologna. Therefore, he is the delegate of the Rector of the University of Bologna in the INCA “Direttivo” . 69 Fabio Fava is co-director of the 1st National Summer School on “Ricerca , sperimentazione e sviluppo di tecnologie di bonifica di siti inquinati” organized by INCA in collaboration with the Italian Ministry of the University and of the Italian Ministry of the Environment. Fabio Fava is the main coordinator of the Research Project Science for Peace NATO N. 973720 titled “Decontamination of Hydrocarbon Polluted Military Sites to Decrease Environmental Risks-Low-Cost Cyclodextrin Technology” (January 1, 2000-Dcember 31, 2002) joined by the team of the Faculty of Engineering of Bologna and along with two public research institutions (Technical University of Budapest and the Hungarian Academy of Science of Budapest, Hungary) and three private Hungarian Companies (Cyclolab Ltd, Budapest, Hungary, Thermal Desorption Technology Group, Budapest, Hungary and Dunaferr/Innopark , Budapest, Hungary) (web site www.cyclolab.hu/nato). Fabio Fava is the coordinator of an ERASMUS exhange program (for the preparation of MS thesis) between the University of Bologna and the Institute of Chemical Technology, Prague 6, Prague, Czech Republic. Prof. Fava is Peer-reviewer of the following international journals: Bioremediation Journal, Research in Microbiology, FEMS Microbiology Letters, Biotechnology & Bioengineering 6.6 Key Publications 1)Fava F., Di Gioia D., Marchetti L. (1998) Cyclodextrins effects on the ex-situ bioremediation of a chronically polychlorobiphenyl-contaminated soil. Biotechnology & Bioengineering 58: 345-355. 2) Di Gioia D., Peel M., Fava F., Wyndham C. (1998) Structure of homologous composite transposons carrying cbaABC genes from Europe and North America. Applied Environmental Microbiology, 64: 1940-1946. 3) Fava F., Bertin L. (1999) Use of exogenous specialised bacteria in the biological detoxifcation of a dump-site polychlorobiphenyl-contaminated soil in slurry-phase conditions. Biotechnology & Bioengineering 64:240-249 4) Fava F., Di Gioia D. (2001) Soya lecithin effects on the aerobic biodegradation of polychlorinated biphenyls in an artificiallycontaminated soil”. Biotechnology & Bioengineering 72:177-184 5) Guerra R.. 2001. Chemical and Ecotoxicological evaluation of phenolic compounds in industrial effluents. Chemosphere, 44 (8):1737-1747. Please give full bibliometric details of 5 of the units best scientific publications. Two hard copies of these publications should be sent to the INCA Secretariat. One of these copies will be sent to the Committee Member that will act a first Reviewer. The second copy will be available for all Committee Members during their meetings in Italy. 7. Scientific Output 7.1 Publication Policy The team of the Faculty of Engineering has a large productivity in MS dissertations, but a low productivity in terms of PhD dissertation. About publication, the team has aimed primarily to basic and applied research, thus publishing in largely read international journals. 7.2 Numerical data Category PhD-Dissertations 1997 1 1998 1999 2000 2001 Total 1 Scientific Publications 4 5 4 2 6 21 Professional Publications Master’s Theses 4 10 7 4 3 28 70 Sub-unit Category PhD-Dissertations 1997 1 1998 1999 Scientific Publications Professional Publications Master’s Theses 1 3 1 1 3 2000 1 2001 Total 2 2 3 5 7 1 2 15 8 Self-evaluation The research team of the Faculty of Engineering would like to stress the consistency of the various research activities and other scientific activities that has been carried out in the last 5 years. In fact, the main contents of the courses taught by the team members are closely related to environmental chemistry, analytical chemistry, and environmental biotechnology, which are the subjects on which they are also strongly involved in research. The scientific production of the team is mostly focused on the “environmental science” and “biotechnology and applied Microbiology” categories, and it is coherent with the Unit’s mission and the INCA research areas selected in the first page of the present report. In addition, the team’s activity is complementary and extensively connected to those of INCA research Units of other Universities. The team is not yet adequately integrated with the other team (that of the Faculty of Sciences) recently (on March 2002) incorporated in the Unit; in addition, the Unit “Bologna1” is not yet sufficiently integrated with the other INCA Research Units of the University of Bologna (7 of which have been formally established on March 2002). However, several complementary researches and expertises have already evidenced within the Unit and between the different INCA Units of Bologna, and an effective integration of the Units will be reached in a close future. Appendix I Scientific Output I-1 Overview of Dissertations and Master's Thesis (1997-2001) I.1.1 Dissertations Year Name PhD-student Title of the Dissertation Supervisor Thesis Year Name of the PhD Title No. Student 1 1997 Francesco Baldoni Development of a biotechnological process for the bioremediation of wastewaters contaminated by lowchlorinated biphenyls 2 1997 Dario Diamanti Validation of mathematical modelling in the assessment of incidents: comparison with experimental results. 3 2000 Serena Righi Environmental Radioactivity in working places: radioprotection measurements and assessment. I.1.2 Thesis No. 1 Supervisor Prof. Marchetti Prof. Trombetti Co-advisor: Prof. Bruzzi Prof. Bruzzi Master's Thesis Year Name of the MS student Title Supervisor 1997 Romina Santarelli Prof. Fava 2 3 1997 1997 Andrea Sanseverino Stefano Gallegat 4 1998 Loredana Quitadamo Role of the exogenous carbon source in the bioremediation ex-situ of an aged PCB-contaminated soil Distruction of polychlorobiphenyls Use of detergents in the aerobic bioremediation of a PCB, chronically contaminated soil Aerobic biodegradation of chlrobenzoic acids by Prof. Fava Prof. Fava Prof. Fava 71 5 1998 6 1998 7 1998 8 1998 9 1998 10 1999 11 1999 12 1999 13 1999 14 1999 15 1999 16 2000 17 2000 18 2000 19 2001 20 2001 21 2001 22 23 1997 1997 1997 24 1.1998 2.1998 Pseudomonas sp., CPE2 strain: biocehmical and genetic analysis of the biodegradation pathways Alessandro Fabbri Role of the slurry-phase reactor configuration in the aerobic bioremediation of a PCB-contaminated soil Lucia Ricci Optimization of the use of beta-cyclodextrins in the slurry-bioremediation of two soils hystorically contaminated by PCBs Melania Frattini Bioremediation of a dump-site PCB contaminated soil through the use of exogenous specialized bacteria: effects of soya lecithin, glucose and cyclodextrin on the process Diego Cirelli Use of hydroxyprophyl-beta-cyclodextrin in the bioremediation of dump-site PCB contaminated soils in slurry-phase conditions Monica Roscini Vitali Role of the exogenous inoculum on the bioremediation of a PCB-contaminated soil Claudia Summa Optimization of the use of an industrial mixture of beta-cyclodextrins in the bioremediation of PCBcontaminated soils Alessandra Franco Role of humic acids and soya lecithin in the biological degradation of PCBs in a contaminated soil Fabio D’Angelo Role of industrial products based on cyclodextrins and Soya lecitin on the bioremediation of dump-site PCB-contaminated soils Lorena Lorenzini Characterization of aerobic bacteria capable of biodegrading the monocyclic aromatic hydrocarbons of the olive mill wastewater Elisabetta Canuti Production of arginate and alginase from Azotobacter vinelandii Denise Galassi Ecotoxicity measurements on PCB-contaminated soils: application and optimization of tests based on the use of Folsomia candida or other vegetal biomarkers Letizia Zanibon Selection and characterization of bacteria capable of biodegrading the toxic monocyclic aromatic fraction of the olive mill wastewater Vincenzo Fabio Role of the randomly-methylated-beta-cyclodextrins in the aerobic biodegradation of PCBs in soils spiked Ciccotosto with a PCB-containing transformer oil Giovanni Gualandi Optimization of the use of cyclodextrin RAMEB in the aerobic bioremediation of two aged PCBcontamianted soils. Marco Pollastri Anaerobic biodegradation of PCBs in sediments of the Venice Lagoon; preliminary attempt to caharacterize the indigenous bacteria responsible for the process Roberta Di Giacomo Biochemical characterization of aerobic bacteria degrading phenolic compounds of the olive mill wastewater Ing. Alice Dall’Ara Prelimnary studies on the biological processes involved in the polline stabilization Pamela Ugolini Salinity effects on the Pinewood of S.Vitale Alberto Righetti Environmental impact study on the harbour Stefano Fucili Management and riusal of dredged materials from the harbour of Ravenna Rosario Antonio Pappa Monitoring of effluents from a treatment plant in Siracusa. Monica Pantaleoni Life Cycle Assessment of fluids substituting CFC. Prof. Fava Prof. Fava Prof. Fava Prof. Fava Prof. Fava Prof. Fava Prof. Fava Prof. Fava Prof. Fava Prof. Fava Prof. Fava Prof. Fava Prof. Fava Prof. Fava Prof. Fava Prof. Fava Prof. Fava Prof. Bruzzi Prof. Bruzzi Prof. Bruzzi Prof. Bruzzi Prof. Bruzzi 72 3.1998 4.1999 Pierina Guiducci Raffaella Baroncelli 5.2000 Daniele Piccolo 6.2000 7.2000 Monica Gigli Marco Neri 8.2000 Michela Valenti 9.2000 Maria Elena Canali 102000 Valentina Caroli 112000 122001 Claudia Magri Valentina Boragno Biomonitoring of wastewaters from a treatment plant. Monitoring and treatment of effluents from a petrochemical complex. Atmospheric pollution effects on monuments deterioration Monuments deterioration due to organic acids. Environmental Impact Assessment of disposal and reuse of wastes. Environmental assessment of a treatment plant for drinking waters. Environmental sustainability of industries with a radiological impact: a case-study Valutazione chimica ed ecotossicologica di matrici ambientali contaminate da metalli pesaanti ed idrocarburi Risk Assessment of Contaminated sites: comparison of methodologies and ecotoxicity testing Heat pumps: assessment of energy saving and environmental effects. Prof. Bruzzi Prof. Bruzzi Prof. Bruzzi Prof. Bruzzi Prof. Bruzzi Prof. Bruzzi Co-advisor: Serena Righi Prof. Bruzzi Co-advisor: Guerra Prof. Bruzzi Co-advisor: Guerra Prof. Bruzzi Roberta Roberta Master's Thesis of which the team members were co-advisors Thesis No. 1 Year Name of the MS student Title 1997 Ferruccio Solinas 2 1998 Petra Inghelbrecht (Katholieke Universiteit Leuven, Belgio) 3 1998 Gori Paola 4 1998 Fiorilla Giuseppe 5 1998 Breviglieri Valeria 6 1999 Ilkay Cam (New Jersey Institute of Technology, Newark, NJ, USA) Supervisor Bioremediation of a PAH-contaminated soil: Prof. F.Magelli isolation and characterization of the microflora (University of involved in the process Bologna) Co-advisor: Prof. Fava ERASMUS PROGRAM THESIS Prof. H. Verachtert Effect van cyclodextrines in de bioremediatie van (Katholieke PCB-gecontamineerde bodem Universiteit Leuven, Belgio) Co-advisor: Prof. Fava Bioremediation of soils contamianted by Prof. M.Nocentini hydrocarbons: effects of the pollutant nature and of (University of soil properties on the pollutant biodegradation rate Bologna) Co-advisor: Prof. Fava Use of gas-cromatography to run taxonomic analysis Prof. B. Biavati (University of Bologna) Co-advisor: Prof. Fava Biodegradation of PAHs in a soilat low-permeability: Prof. M.Nocentini limits due to oxygen availability and effects of (University of humidity on the rate of the process Bologna) Co-advisor: Prof. Fava Master thesis in Environmental Science Prof. P.M. Vitamin effect on the aerobic biodegradation of Armenante Phenanthrene, Antracene, Fluoranthene, and Pyrene (New Jersey Institute in a contaminated soil from an industrial site of Technology, Newark, NJ, USA) Co-advisor: 73 7 2000 I-2 Cristina Matteini Prof. Fava Biodegradation of the mono-cyclic aromatic fraction Prof. L Morselli of the olive mill wasetwater by aerobic bacteria (University of Bologna) Co-advisors: Prof. Fava; Dr. Di Gioia Overview of Scientific Publications (1997-2001) per year Please note that all the following articles are strictly related to the three thematic areas selected in the first page of this report and closely related to the main topics of the Consortium activity 1997 D. Pinelli, F. Fava, M. Nocentini, G. Pasquali (1997) Bioremediation of a polycyclic aromatic hydrocarboncontaminated soil by using different aerobic batch bioreactor systems. Journal of Soil Contamination 6: 243-256. (published by John Wiley & Sons., Inc., New York, USA; printed in USA) Fava F., Marchetti L., Quattroni G (1997). Factors anhancing the bioremediation of a polychlobiphenyl-contaminated soil in slurry- and fixed-phase batch bioreactors. Journal of Analytical and Environmental Chemistry (Annali di Chimica, Roma, Italy) 87: 667-676. Fava F., Di Gioia D., Marchetti L. 1997. Intrinsic bioremediation of a polychlorobiphenyl-contaminated soil in slurry-phase and fixed-phase batch bioreactors. In Proceedings of the International Symposium Environmental Biotechnology, Oostende, Belgium, 21-24 April 1997. Pp 299-302. Nocentini M., Pinelli D., Pasquali G., Fava F., Prandi A. (1997). Biotreatability and feasibility studies for a bioremediation process of a kerosene contaminated soil. In Proceedings of the International Symposium Environmental Biotechnology, Oostende, Belgium, 21-24 April 1997. Pp. 307-310. Kafkewitz, D., Fava, F., Guptapal, P., Armenante P.M. (1997) Effect of vitamins on the aerobic biodegradation of 4chlorobiphenyl and nonane. In Proceedings of the 1st European Congress on Chemical Engineering. Firenze, Italy, 4-7 Maggio, 1997. Volume IV, pp. 2647-2650 1998 Nocentini M., Pinelli D., Pasquali G., Fava F., Prandi A. (1998) Biotreatability and feasibility tests for a bioremediation process: a case srudy for a kerosene contaminated soil. Journal of Analytical and Environmental Chemistry (Annali di Chimica, Roma, Italy) 88: 177-187. Fava F., Di Gioia D., Marchetti L. (1998) Cyclodextrins effects on the ex-situ bioremediation of a chronically polychlorobiphenyl-contaminated soil. Biotechnology & Bioengineering 58: 345-355. (published by John Wiley & Sons., Inc., New York, USA; printed in USA) Di Gioia D., Fava F., Baldoni F., Marchetti L. (1998) Characterisation of the chlorocatechol degrading activity in the ortho-chlorinated benzoic acid degrading Pseudomonas sp. CPE2 strain. Research in Microbiology 149:339-348. (published by the Intitut Pasteur Paris/Elsevier Science Ltd, printed in Great Britain) Di Gioia D., Peel M., Fava F., Wyndham C. (1998) Structure of homologous composite transposons carrying cbaABC genes from Europe and North America. Applied Environmental Microbiology, 64: 1940-1946. (published by the American Society for Microbiology, Washington DC, USA; printed in Washington DC, USA) Fava F., Di Gioia D. (1998) Effects of Triton X-100 and Quillaya Saponin on the ex-situ bioremediation of a chronically polychlorobiphenyl-contaminated soil. Applied Microbiology and Biotechnology 50: 623-630 (published by Springer-Verlag Berlin Heidelberg 1995, Springer-Verlag GmbH & Co. KG, Berlin, Germany; printed in Germany) 1999 74 Fava F., Bertin L., Marchetti L. (1999) Influence of the exogenous carbon source on the ex-situ bioremediation of a chronically PCB-contaminated soil. Journal of Analytical and Environmental Chemistry 89: 771-776 (Annali di Chimica, Roma, Italy) Fava F., Bertin L., Pinelli D., Nocentini M. (1999) Characterisation of the indigenous bacteria involved in the ex-situ aerobic Bioremediation of a polycyclic aromatic hydrocarbon-contaminated soil. Journal of Analytical and Environmental Chemistry 89: 777-782 (Annali di Chimica, Roma, Italy) Fava F., Bertin L. (1999) Use of exogenous specialised bacteria in the biological detoxifcation of a dump-site polychlorobiphenyl-contaminated soil in slurry-phase conditions. Biotechnology and Bioengineering 64:240-249 (published by John Wiley & Sons., Inc., New York, USA; printed in USA) Nocentini M., Pinelli D., Fava F. (1999) In situ bioremediation of a soil contaminated by mineral oil. In: In situ bioremediation of petroleum hydrocarbon and other organic compounds. Proceedings of The fifth International Symposium on in situ and on-site bioremediation. San Diego, California, April 19-22, 1999, pp 313-318. 2000 Fava F., Di Gioia D., Marchetti L. (2000) Role of the reactor configuration in the biological detoxification of a dump site-polychlorobiphenyl-contaminated soil in lab slurry phase conditions. Applied Microbiology and Biotechnology 53: 243-248 (published by Springer-Verlag Berlin Heidelberg 1995, Springer-Verlag GmbH & Co. KG, Berlin, Germany; printed in Germany) Nocentini M., Pinelli D., Fava F. (2000) Bioremediation of a soil contaminated by hydrocarbon mixtures: the residual concentration problem. Chemosphere 41: 1115-1123 (published by Pergamon-Elsevier Science Publ.; printed in Great Britain) 2001 Fava F., Di Gioia D. (2001) Soya lecithin effects on the aerobic biodegradation of polychlorinated biphenyls in an artificially-contaminated soil”. Biotechnology & Bioengineering 72:177-184 (published by John Wiley & Sons., Inc., New York, USA; printed in USA) This articles received the “best paper award for 2001” by the American Oil Chemists’ Society (AOCS) and it has been presented by Prof. Fava at the 93rd AOCS International Conference held in Montréal, Canada (May 5-8, 2002). Villarante, N.R., Armenante P.M., Quibuyen, T.A.O., Fava F., Kafkewitz D. (2001) Dehalogenation of dichloroethene in a contaminated soil: fatty acids and alcohols as electron donors and an apparent requirement for tetrachloroethene. Applied Microbiology and Biotechnology, 55: 239-247 (published by Springer-Verlag Berlin Heidelberg 1995, Springer-Verlag GmbH & Co. KG, Berlin, Germany; printed in Germany). Di Gioia D., Bertin L., Fava F., Marchetti L. (2001) Biodegradation of hydroxylated and methoxylated benzoic, phenylacetic and phenylpropenoic acids present in olive mill wastewaters by two bacterial strains. Research in Microbiology 152:83-93 (published by the Institut Pasteur Paris/Elsevier Science Ltd, printed in Great Britain) Di Gioia D., Fava F., Bertin L., Marchetti L. (2001) Biodegradation of synthetic and natural occurring mixtures of mono-cyclic aromatic compounds present in olive mill wastewaters by two aerobic bacteria. Applied Microbiology and Biotechnology, 55: 619-626. (published by Springer-Verlag Berlin Heidelberg 1995, Springer-Verlag GmbH & Co. KG, Berlin, Germany; printed in Germany). Bertin L., Majone M., Di Gioia D., Fava F. (2001) An aerobic fixed-phase biofilm reactor system for the degradation of the low-molecular weight aromatic compounds occurring in the effluents of anaerobic digestors treating olive mill wastewaters. Journal of Biotechnology, 87:161-177 Fedi S., Carnevali M., Fava F., Andracchio A., Zappoli S., Zannoni D. (2001) Biodegradative activities and hybridization analysis of fifteen aerobic bacterial strains isolated from a chronically polychlorinated biphenyl (PCB) contaminated site. Research in Microbiology 152:583-592 (published by the Institut Pasteur Paris/Elsevier Science Ltd, printed in Great Britain) 75 I-3 Overview of Professional Publications (1997 - 2001) per year 1997 Vesilind P. A., Peirce J. J., Weiner R. F Environmental Engineering, Italian edition, di L. Bruzzi, translation of L. Bruzzi, G. Dominici, D. Manco, R. Mele, L. Mingozzi, E. Nanni, CLUEB 1997 pp. 685. L. BRUZZI, M. Baroni, R. Mele and E. Nanni. Proposal for a method of certification of natural radioactivity in building materials J. Radiol. Prot. 17: 85-94, 1997. 1999 L. Bruzzi, F. Babini, A. Biliotti, M. Castellari, F. Conti, G. Dominici, D. Manco, S. Righi, M. Turroni. Guida alla V.I.A. Aspetti tecnici, normativi e procedurali. Edizione Maggioli, Rimini, 1999. 2000 -L. Bruzzi, M. Baroni, G. Mazzotti, R. Mele, S. RIGHI. Radioactivity in raw materials and end products in Italian ceramic industry. Journal of Environmental Radioactivity, 47/2, 171-181, 2000. S.RIGHI, M.Betti, L.Bruzzi, G. Mazzotti. Monitoring of natural radioactivity in working places. Microchemical Journal, 67/1-3, 119-126, 2000. S. RIGHI, L. Bruzzi, C. Palmonari. L’industria ceramica e la nuova normativa europea in materia di radioprotezione. Ceramica Acta, 12/5-6, 74-84, 2000. 2001 Guerra R.. 2001. Chemical and Ecotoxicological evaluation of phenolic compounds in industrial Chemosphere, 44 (8):1737-1747. effluents. R. Guerra, M. Martignani, S. Righi, C. Rinaldi , A. Righetti e L. Bruzzi. Studio di fattibilità sul riutilizzo dei materiali di dragaggio: applicazione del test di cessione ai sensi del D.M. 05/02/98. RICICLA 2001, Rimini 26-29 Settembre 2001 – Atti dei Seminari, a cura di Luciano Morselli, Maggioli Editore, Rimini. Riba, I., Guerra, R., Iacondini, A., DelValls, T.A., Forja, J.M. Evaluating the impact of the Aználcollar mining spill on sediments from the Guadalquivir estuary using Pseudomonas fluorescens dehydrogenase inhibition assay. International Conference on Remediation of Contaminated Sediments. October 10-12, 2001, Venice, Italy [in press]. R. Guerra, A. Iacondini, F. Abbondanzi,V.Caroli and L. Bruzzi. A new microbial assay for the toxicity dection of contaminated soils. ANNALI DI CHIMICA/Journal of Analytical and Environmental Chemistry [in press]. S. Righi, R. Guerra e L. Bruzzi. Carbon and nitrogen distribution in sediments of an Italian lagoon. Annali di Chimica/ Journal of Analytical and Environmental Chemistry [in press]. I-4 Other Scientific Output Fabio Fava was one of the three organizers of the Advanced Study Institute NATO titled “Innovative Approaches to the On-Site Assessment and Remediation of Contaminated Sites” held in Praga (Czech Republic) from May 24 to June 2, 2001 (web-site:www.prague2001.lsu.edu). This initiative was directed by Prof. Dr. Reible, Danny D., Professor & Director HSRC/S&SW, Louisiana State University, USA, and by Prof. Dr. Demnerova, Katerina, of the Institute of Chemical Technology, Prague, Czech Republic. Prof. Fava has also been chairman of the session of June 2nd entitled “Bioremediation of PCBs”. Fabio Fava organized a 2-days Training course titled “Biological degradation of polychlorinated biphenyls in contaminated soils and sediments” within the project Science for Peace NATO N. 973720 titled “Decontamination of Hydrocarbon Polluted Military Sites to Decrease Environmental Risks-Low-Cost Cyclodextrin Technology”; the course took place in Bologna (Faculty of Engineering) on September 7 and 8, 2001. 76 Appendix 3 Journal Portfolio Analysis Name of the Unit: Research Director: Years included Bologna 1 Prof. Leonardo Marchetti 1997-2001 Name of Journal Applied Microbiology Number Articles Environmental 1 Biotechnology Bioengineering of Journal Factor 3,389 Impact Field(s) Ranking Biotechnology and 15/134 Applied Microbiology & 3 2,081 Biotechnology and 30/134 Applied Microbiology Applied Microbiology and 4 Biotechnology 1,505 Biotechnology and 46/134 Applied Microbiology Journal of Biotechnology 1 1,311 Research in Microbiology 3 Journal of Soil 1 Contamination 1,631 0.538 Biotechnology and 52/134 Applied Microbiology Microbiology 37/83 Environmental Sciences 84/127 Chemosphere 1 Annali di Chimica 4 (Journal of Analytical and Environmental Chemistry) 1.033 0.413 Environmental Sciences Chemistry Analytical Sub-unit: Prof. Luigi Bruzzi Years included 1997-2001 Name of Journal Number Articles Journal of Environmental 1 Radioactivity Microchemical Journal 1 Chemosphere 1 Annali di Chimica 2 (Journal of Analytical and Environmental Chemistry) of Journal Factor 0.726 0.771 1.033 0.413 Impact Field(s) 52/127 60/65 Ranking Environmental Sciences 71/129 Chemistry Analytical Environmental Sciences Chemistry Analytical 47/68 52/127 60/65 Comments on: 1.the method: the ranking data reported above were calculated by using the ISI journal Citation Reports related to 2000. 77 BOLOGNA 2 Name of the Research Unit: Bologna 2 Research Leader Ferruccio Trifirò University: Università di Bologna Bologna University Contact Person Name Ferruccio Trifirò Mailing Address Dipartimento di Chimica Industriale e dei Materiali, viale Risorgimento 4, 40136 Bologna Phone 051-2093682 Fax 051-2093680 E-mail [email protected] Faculty: Chimica Industriale Industrial Chemistry Department: Dipartimento di Chimica Industriale e dei Materiali Department of Industrial Chemistry and Materials Thematic area • Catalisi eterogenea per le sintesi ecosostenibili e la decontaminazione ambientale. • Sintesi ecosostenibili (solventi, fotochimica, catalisi, riciclo e altre). • Tecnologie di depurazione (membrane, sonochimica, fotocatalisi, elettrochimica e altre). Introduction and Context Introduction to the Self-evaluation Report The Core Competencies of the Bologna 2 Unit are: 1. Wide competence in oxidation and hydrogenation catalysts and technologies: • Use of new raw materials • Use of new oxidants • Study of new reactor technology options • Study of air versus oxygen processes 2. Deep Know-How in the design of catalysts for specific reactions and process development 3. Alliances or joint projects with world scale companies for process and catalyst development In particular, the recent research activity has been directed towards solving problems related to pollution control and to the development of processes at low environmental impact. The main points studied at present in the Unit are: • New technologies for pollution reduction • Identification of alternative raw materials al lower environmental impact for existing chemical processes • Green chemistry: development of clean processes for the production of intermediates in fine chemicals and pharmaceuticals On the basis of these consideration all the Unit work will be considered in the self evaluation report. (*) will indicate INCA projects and people of the staff involved on it The University, the Faculty and the Department The University of Bologna is the oldest in the western world: 1088 may be accepted as conventional date to indicate when teaching became free and independent of the ecclesiastic schools. Bologna University is one of the largest universities in Italy and in Europe. It is a state university and it is autonomous with its own "statuto" which indicates how the University governs itself through its various elected bodies. The University government and the main research and teaching activity are located in Bologna, but many new research and teaching activities have been recently dislocated in other Cities of the Emilia Romagna region, such as Cesena, Faenza, Forli’, Ravenna and Rimini. The whole University currently counts about 900 professors, 1,000 associated professors, 1,050 researchers and more than 100,000 students. It is divided in 19 Faculties, 65 Departments, 5 Federated Departments (“Unità Complesse”), 3 Institutes and it currently offers about 65 “laurea” degree courses and 45 “diploma” degree courses in the following subject areas: a)Agriculture; b) Economics; c) Education and Humanities; d) Engineering; e) Industrial Chemistry, f)Law; g) Literature and Philosophy; h) Mathematical, Physical and Natural Sciences; i) Medicine; l) Pharmacy; m) 78 Political Science; n) School of Modern Languages for Interprets and Translators; o) Statistical Sciences; p) Veterinary Medicine; q) Foreign Languages and Literatures. The faculty of Industrial Chemistry has more than 700 students and about 80 faculty members and is divided in three department (Industrial Chemistry and Materials, Physical and Inorganic Chemistry and Organic Chemistry) and one institute (Metallurgy). The unit belongs to the department of Industrial Chemistry and Materials. The Unit The catalysis section of the Department of Industrial Chemistry and Materials is active by more than 25 years in the field of preparation, characterization and catalytic investigation of heterogeneous catalysts and process development. The organizational structure is based on a full professor, two associated professor and two researchers. There are nine Ph. D. students and about fifteen fellow-ships and a variable number of students doing their master thesis. Each Ph. D. student and fellow-ship has his own subject to study. The administrative staff of the department takes care of the administration. The unit takes care of the following courses of Masters in Industrial Chemistry, Materials Chemistry and Ceramic Technologies, and Chemical Technologies for Environmental and Waste Management - Industrial Chemistry (Inorganic) - Catalysis Chemistry and Technology - Laboratory of Catalysis Chemistry and Technology - Petrochemical processes and Technologies - Theory and Development of Processes - Industrial Chemistry and Ceramic Technologies - Laboratory of Industrial Chemistry and Ceramic Technologies Programme Description and Evaluation 1 Title: Alternative processes of low environmental impact 2 Research Leader: Ferruccio Trifirò 2a Sub-programme titles and sub-programme leaders 3 Composition of the scientific research staff of the unit per 1 January 2002 Name and Titles Year of Birth Rank Research Input in fte in1997 Ferruccio Trifirò * Angelo Vaccari * Fabrizio Cavani Giuseppe Fornasari Stefania Albonetti * Francesco Basile * Laura Forni Maria Ferrari Diana Scagliarini Barbara Panzacchi Francesca Pierelli Rino Trabace Luca Dalpi Nicola Ballarini Massimo Cimini Marco Bolognini Simone Albertazzi* Helene Degrand Sonia Blasioli * Massimiliano Livi Valentina Rosetti * Franceschini Silvia 1938 1948 1958 1961 1967 1971 1970 1971 1973 1974 1973 1973 1974 1973 1975 1976 1976 1977 1974 1973 1976 1976 Full professor Assoc. prof. Assoc. prof. Ricercatore Ricercatrice post-Doc-student post Doc student post Doc student PhD-student PhD-student PhD-student PhD-student PhD-student PhD-student PhD-student PhD-student PhD-student Euro-PhD student Borsista Borsista Borsista Borsista 0.2 0.4 0.4 0.5 0.5 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Remarks since 2001 since 1996 since 1996 since 2001 since 1998 since 1998 since 1998 since 1997 since 1999 since 1999 since 1999 since 2000 since 2000 since 2001 since 1998 since1999 since 2001 since 2001 79 Maselli Luca Cristina Felloni Alessandro Ristori Mirco Corrado Total research input 4 5 Funding 5.1 Personnel (in fte) Source University CNR European Union Other Sponsors Total 1.0 1.0 1.0 1.0 23.0 since 2001 since 2001 since 2000 since 2000 1997 0.2 0.4 1.0 1998 0.2 0.4 1.0 1999 0.2 0.8 0.5 8 6 15.5 2000 0.2 0.8 0.5 1 9 7 18.5 2001 0.2 0.8 1 3 10 8 23 Total 1.0 3.2 4.0 4.0 40 34 86.2 6 6 13.6 7 7 15.6 1997 1998 1999 2000 2001 Total 1.0 8.0 9.0 1.0 9 10 0 10 10 1 11 12 3.0 12.5 15.5 1999 125 45 70 300 540 2000 155 45 70 350 620 2001 155 65 160 350 730 Materials and Equipment (in Million Lire) Source University - MURST CNR EU Other Sponsors Total 5.3 Borsista Borsista Borsista Borsista Input of Academic Staff in fte Category Full Professors Associated Professors Ricercatori Post-docs PhD-students Borsisti Total 5.2 1976 1975 1976 1975 1997 40 10 55 200 305 1998 120 0 140 250 510 Total 595 165 495 1450 2705 Comments: Please add a list of major sponsors and the character of the liaison with the major sponsors The major sponsors are national and international chemical and energetical companies such as: Lonzagroup., Air Liquid, Rhodia, Snamprogetti S.p.A.., EniChem S.p.A., Tecnip, Atofina, Ciba, Borregaard, Vanetta, Enitecnologie, Endura, Millennium, Radici, Ausimont/Solvay. The funding are planned by a research contract on a specific topic and with a detailed program of activity. 6. 6.1 Progress Report Mission Statement The research area of the unit includes the following aspects: 1) development of new processes, which make use of new types of raw materials, i.e. light paraffins (natural gas components), as alternative to processes which utilize olefins, aromatics or other compounds as raw materials. In some cases these processes utilize new synthetic routes with respect to industrial established technologies, routes which are characterized by the absence of nocive co-products or by the absence of toxic intermediates or raw materials. In other cases, the direct transformation of light paraffins to the desired compounds makes it possible to overcome the energyintensive endothermal transformation of petroleum cuts to olefins and aromatics; 80 2) improvement of current industrial processes, aimed to lower their environmental impact. For instance, the improvement of selectivity in a reaction which operates with recycle of unconverted reactant makes it possible to considerably decrease the amount of purge stream, and the content of by-products characterized by environmental impact in vent streams (i.e., CO2); 3) catalytic systems for abatement of pollutants contained in flue gas stream of power plants and of chemical plants. In particular, catalytic systems are studied which allow the catalytic removal of NOxand dioxins 4) development of new processes aimed at the production of new products, alternative to those of current application characterized by unsustainable environmental impact. Unit's objectives have origin in the wide experience and knowledge gained along several years of research on the development of heterogeneous catalytic systems able i) to activate and functionalize saturated substrates, ii) to selectively transform unsaturated organic substrates, and iii) to activate nitrogen oxides. It is expected that the research may lead to the discovery of new catalytic systems and formulations, which make it possible to reach results interesting for industrial applications. The character of the research carried out is applicative, since objectives and research targets are planned together with partner industrial companies. "Clients" of the research work are mostly the industrial companies, both national and foreign, national authorities (i.e., national authority for energy supply), educational and training programs developed by CEE. More in general, the results developed are of utility for the scientific community involved in the area of development of new processes characterized by lower environmental impact. 6.2 The Research Programme Design of the programme The programme of research is usually planned as follows: 1) Analysis of the main characteristics which the new process must possess in order to be of industrial relevance, i.e.: a) global enviromental impact, from both the point of view of the reactants, products, intermediates, catalysts. b) analysis of a possible flow-sheet, and of unit operations which may result dangerous. c) analysis of the target performance in terms of productivity, conversion, selectivity, in order to make the process economically interesting for industrial application. 2) Study of the possible "formal" reaction mechanism, in order to identify the different steps which may lead to the selective transformation of the reactant to the final product. Analysis of the possible reaction pathways leading to byproducts. 3) Analysis of the properties which the catalyst must possess in order to be able to activate and selectively functionalize the substrate. Design of a catalyst formulation including main active components to realize the reaction pathway as hypothesized at point 2. 4) Study and development of a preparation procedure for the catalyst which may be easily transferred to the industrial scale, that is development of a preparation without dangerous steps or possibly without the use of toxic raw materials and intermediates. 5) Analysis of the reaction conditions which can possibly lead to the desired conversion and selectivity from both thermodynamic and kinetic point of view. 6) Study of the reactivity of the catalytic systems prepared, analysis of the effect of reaction parameters on catalytic performance, study of the mechanism of reaction under both stationary, non-stationary and in-situ conditions, kinetic studies. 7) Full chemical-physical characterization of catalytic systems both before and after reaction, in order to find relationships between catalytic performance and bulk/surface properties. 8) Improvement of the catalytic systems by modifications in formulations (i.e., addition of dopants) or in preparation procedure. Overview of the most impressive results The research has led to the deposition of the following patents of industrial applications: 1) Patents assigned to Borregaard Italia, which claim the preparation of catalyst based on Al/P/O mixed oxides. 2) Patent assigned to Snamprogetti which claims new catalytic system for the production of acrilonitrile from propylene.. 3) Patent assigned to Lonza which claims a new, improved catalytic system based on V/P/O mixed oxides, to produce maleic anhydride from n-butane. 4) Patent assigned to Radici which claims new process for decomposing Nitrous Oxide (N2O). 5) Patents assigned to Endura which claims the use of aluminosilicated-based catalysts for the synthesis of 2hydroxyphenylalkyl ketones. 6) Patents assigned to C.N.R.S., Universidad Malaga, Repsol Petroleo, INSTM, which claim the use of new porous silicate materials ad their uses as catalytic systems for diesel improvement. 7) Patents assigned to CHEMI which claims the vapour phase synthesis of indole and its derivatives. 81 Overview of programme development During the coming 5 years the research program will continue along the research directions developed in latest years. Special attention will be dedicated to • Design of materials with new synthetic routes allowing control from the molecular up to the macroscopic level (nanostructured materials) • Use of supercritical conditions for developing eco-efficient processes in chemical industry • Development of solid base catalysts as alternatives to homogeneous catalysts to decrease the environmental impact of fine chemical process as alkylations, condensations, isomerizations. Means needed will be the same as those employed in latest 5 years. No mobility of senior staff is expected right now. 6.3 Position in Networks • Intra-university co-operation • Regional co-operation CNR-Lamel di Bologna • National co-operation (including INCA) INSTM Consortium INCA Consortium Reattività e catalisi Consortium Università di Genova Università di Modena Università di Udine Università di Torino Università di Arcavacata di Rende • International co-operation CNRS Villeneuve D’Ascq Universitat de Barcelona CSIC Madrid, Academy of Science of Prague CINDECA La Plata, Pune National Chemical Laboratory Academy of Sciences of Moscow Colorado State University Boreskov Inst. of Catalysis Novosibirsk CNRS di Villeurbanne Cedex University of Liverpool CEA-PILS project (CEE): Universities of: Montpellier, Reading, Athen, Ioannina, Anvers, Louvain-la-Neuve, Copenaghen, Latolsa, Bilbao, Venice, Salamanca, Madrid. Competitive and sustainable growth programme (CEE) project on “Improvement of diesel quality by catalytic processes”(CNRS,Repsol Petroleo, Snamprogetti, Universidad de Malaga, INSTM, UOP). Competitive and sustainable growth programme (CEE) project on “Use of supercritical conditions for developing ecoefficient catalytic processes in chemical industry” ”(INSTM, Air Liquid, Enichem, Lonza, University of Reading, Universitdad Complutense de Madrid). At moment we do not have big collaboration projects with other INCA units but we are highly interested to develop new co-operations. Moreover, we are also interested to work on the INTA and NATO cooperative programmes 6.4 Societal Relevance and Impact The relevance of the area of research is strictly connected to the objectives of the research itself, including the development of new catalytic processes of low environmental impact. Societal Relevance of the research of the Unit inside the area: The societal relevance is evident when considering the output of the group in terms of patents of industrial application. These patents claim the finding of new catalytic systems to be employed in new processes i) of lower environmental impact, ii) less energy-consuming than current industrial processes, iii) able to decrease the concentration of pollutants in flue gas streams. In this view, the publication strategy of the unit is to privilege, when possible, the protection of important findings by patent pendings. 82 6.5 Further Indications of Quality and Reputation Prof. F. Trifirò has been awarded the following titles: a) De Nora Industries Award for students of chemical engineering b) Humboldt Fellowship recipient c) Special award of the Ministry of Czechoslovakia d) Prof. Pino Award of Italian chemical Society He has been Chairman of several International Congress on Catalysis. He has organized different Symposia, including the First World Congress on Selective Oxidation. He is permanent member of the scientific committees of the following recurring congresses: TOCAT (Japan), International Congress on Catalysis, International Congress on Selective Oxidation, Europacat, C1-C3 paraffin activation (Russia), environmental Catalysis. He is currently Chairman of the International Committee for New Developments in Selective Oxidation and has been UNIDO consultant at the Chemical Laboratory in Pune (India). He is founder of the Italian Group of Catalysis and has been chairman of the Italian Group of catalysis. Prof. A. Vaccari, and Prof. F. Cavani have been awarded the Federchimica award for relevant results achieved in the field of "Clean Chemistry". All members in permanent position of the unit are frequent referees for Journals of international relevance in the field of catalysis. 6.6 Key Publications F. Cavani, R. Mezzogori, A. Pigamo, F. Trifirò “Improved catalytic performance of Keggin-type polyoxometalates in the oxidation of isobutane to methacrylic acid under hydrocarbnon-lean conditions using antimony-doped catalysts” Chem. Eng. J.,Special Issue: Frontiers in Chemical reaction Engineering, 82 33-42 (2001). A.O. Bianchi, M. Campanati, P. Maireles - Torres, E. Rodriguez Castellon, A. Jemenez Lopez, A. Vaccari "Si / Zr mesomorphus catalysts for the vapour phase synthesis of alkylindoles" Applied Catalysis A: General, 220, 105 (2001) F. Basile, G. Fornasari, F. Trifirò, A Vaccari "Partial oxidation of methane. Effect of reaction parameters and catalyst composition on the thermal profile and heat distribution" Catalysis Today, 64, 21 (2001) (*) F. Cavani, S. Ligi, T. Monti, F. Pierelli, F. Trifirò, S. Albonetti, G. Mazzoni "Relationship between structural / surface characteristics and reactivity in n-butane oxidation to maleic anhydride. The role of the V3+ species" Catalysis Today, 61, 203 (2000) F. Trifirò "The chemistry of oxidation catalysts based on mixed oxides" Catalysis Today, 41, 21 (1998) 7. Scientific Output 7.1 Publication Policy The publication policy of the Unit is aimed at: 1) protection of relevant results achieved within the framework of contracts with industrial companies by deposition of patents for industrial application; 2) publication in journals of significant scientific relevance, in the field of heterogeneous catalysis and environmental protection; 3) communications at some important national and international Congress and Symposia on Heterogeneous Catalysis, with preference for restricted Symposia devoted to specific tematics. Thesis dissertations and PhD dissertations constitute the fundamental background of the scientific production of the unit, when the results are not to be protected by patent deposition. The publications of dissertation works allows the discussion and rationalization of scientific results. 7.2 Numerical data Category PhD-Dissertations 1997 1 1998 0 1999 1 2000 2 2001 2 Total 6 Scientific Publications 23 22 8 18 23 94 Professional Publications 83 Master’s Theses 15 15 14 14 19 77 8 Self-evaluation Appendix I Scientific Output I-1 Overview of Dissertations and Master's Thesis (1997-2001) I.1.1 Dissertations 1997 – A. Galli “Conversione catalitica di ossidi di azoto a N2 - Catalytic conversion of nitrogen oxides to N2” (Prof. Vaccari) 1998 – 1999 – S. Masetti “Ossidazione di o-xilene/naftalina ad anidride ftalica – Oxidation of o-xilene/naftaline to phtalic anhydride (Prof. Trifirò) 2000 – F. Basile “Processi innovativi per l’attivazione del gas naturale - New processes for natural gas activation” (Prof. Vaccari) S. Ligi “Catalizzatori a base di V/P/O per l’ossidazione selettiva di paraffine leggere – Catalysts based on V/P/O mixed oxides for the selective oxidation of light paraffins” (Prof. Trifirò) 2001 – L. Forni “Transposizione di ossime in fase gas su catalizzatori a base di ossidi misti – Vapour phase oximes transposition over mixed oxide catalysts” (Prof. Trifirò) I.1.2 Master's Thesis List of Mater’s thesis will be given divided for general argument: 1) “Processi catalitici per la sintesi dei HFC” - Heterogeneous catalysts for the synthesis of HydroFluoroCarbons (HFC’S) Supervisor F. Trifirò 1998 – Emma Zappellini 2000 - Monia Monari 2001 – Francesca Baschieri 2001 – Valentina Giammetta 2) “Ossidazione parziale catalitica del metano a gas di sintesi” - Catalytic partial oxidation of methane to syngas (*) Supervisor A. Vaccari 1997 Matteo Galli 1997 E. Poluzzi Supervisor G. Fornasari 1998 Elisabetta Veggetti 1999 Alessandro Musti 1999 Nicola Zagni 2000 Francesca Facchini 2001 Simone Albertazzi 2001 Alessandro Ristori 3) “Catalizzatori acidi per la trasposizione di Beckmann in fase vapore” Acid catalyst for the vapour phase oximes transposition Supervisor - G. Fornasari 1998 Chiara Faenza 1998 Rino Trabace 1999 Emanuele Miserazzi 1999 Guido Montanari 2000 Chiara Tosi 2001 Luca Guerrini Supervisor F. Trifirò 1997 L. Forni 84 4) “Ammossimazione del cicloesanone in fase liquida con catalizzatori eterogenei” - Liquid phase ammoximation of cyclohexanone over heterogeneous catalysts Supervisor G. Fornasari 2000 Luca Dal Pozzo 2001 Michela Medri 5) “Sintesi in fase gas di composti eterociclici” - Vapor phase synthesis of heterocyclic compounds . Supervisor A. Vaccari. 1997 M. Campanati. 1997 Alberto Carloni 1998 Anna Valentini 1999 Federica Donati 1999 Alessandra Olga Bianchi 2000 Andrea Aiardi 2001 Ivan Fagiolino 2001 Silvia Franceschini 6) “Sviluppo di catalizzatori eterogenei per l’ossidazione selettiva di alchilaromatici” –Development of heterogeneous catalysts for the selective oxidation of alkylaromatics. Supervisor: A. Vaccari. 1997 S. Niccolini 1998 Stefano Tonini 1998 Stefano Gardi 7) ”Sviluppo di catalizzatori per lo storage-reduction of NOx” – Development of catalyst for NOx storage reduction. Supervisor A. Vaccari. 1997 Paolo Vitali 1998 Alessia Bianchini 1999 Massimiliano Livi 2000 Andrea Calciolari 2001 Carlotta Gobbi 2001 Valentina Rossetti 8) Sviluppo di catalizzatori per la sintesi di combustibili diesel a minor impatto ambientale – Development of catalysts for the synthesis of diesel fuels at lower envirmental impact. Supervisor A. Vaccari 1999 Monica Mandreoli 2000 Federico Ghelfi 2000 Simona Lolli 2001 Marco Morisi 9) Decomposizione catalitica di N2O – Catalytic decomposition of N2O Supervisor A. Vaccari 1998 A. Barbara Panzacchi 10) “Ossidazione selettiva di n-butano ad anidride maleica” – anhydride. Supervisor F. Cavani 1997 Tiziana Monti. 1998 Giorgia Bignardi 1999 Francesca Pierelli 1999 Stefano Cortesi 2000 Mirko Bacchini 2001 Federica Gasparini Supervisor F. Trifirò 1997 T. De Lucia Selective oxidation of n-butane to maleic 11) Sviluppo di catalizzatori per l’ossidazione ed ammonossidazione di propano e prolilene Development of catalysts for propane and propene oxidation and ammoxidation Supervisor F. Cavani 1997 Tania Spimpolo 1998 Leandro Capponi 1998 Elisa Frontoni 1999 Gian Maroc Mascanzoni 1999 Nicola Ballarini 85 2000 Chiara Giunchi Supervisor F. Trifirò 1997 E. Arcozzi 1998 Andrea Del Bianco 2001 Francesca Zappoli 12) Sviluppo di catalizzatori per l’ossidazione di isobutano ad acido metacrilico Development of catalysts for the oxidation of isobutane to methacrylic acid Supervisor F. Cavani 1997 Marco Margotti 2000 Fabio Candiracci Supervisor F. Trifirò 1997 R. Gurioli 1998 Roberto Mezzogori 13) Nuove vie di sintesi per la produzione di intermedi per l’industria alimentare mediante processi a basso impatto ambientale. - New synthesis routes for the production of intermediates for food industry with low environmental impact processes. Supervisor: F. Cavani 1998 Daniele Paoli. 1999 Lorenzo Calzolari: 2000 Mirco Corrado 2001 Luca Maselli 14) Studio di nuovi catalizzatori eterogenei con caratteristiche basiche - Study of new heterogeneous basic catalysts. Supervisor: F. Cavani 2001 Marco Bolognini 2001 Cristina Felloni 15) Deidrogenazione ossidativa di propano a propilene – Oxidative dehydrogenation of propane to propene. 2001 Paola Nobili 16) “Ossidazione selettiva di o-xilene ad anidride ftalica” – Selective oxidation of o-xylene to phtalic anhydride. Supervisor F. Trifirò 2000 Massimo Cimini 2001Alberto Guerrini 17) Decomposizione catalitica NOx - “Catalytic decomposition of NOx”. Supervisor F. Trifirò (*) 1997 Stefano Martelli 1998 Diana Scagliarini 1999 Sonia Blasioli 2000 Enrico Randi 2001 Marco Biaggi I-2 Overview of Scientific Publications (1997-2001) per year 2001 M. Campanati, F. Donati, A. Vaccari, A. Valentini, O. Piccolo "Vapour phase synthesis of indole and its derivatives" in Catalysis of organic reactions, M.E. Ford Ed., Marcel Dekker, New York, pp. 157 (2001) F. Basile, G. Fornasari, F. Trifirò, A Vaccari "Partial oxidation of methane. Effect of reaction parameters and catalyst composition on the thermal profile and heat distribution" Catalysis Today, 64, 21 (2001) (*) F. Basile, G. Fornasari, M. Gazzano, A. Vaccari Thermal evolution and catalytic activity of Pd / Mg / Almixed oxides obatined from a hydrotalcite -. type precursor" Applied Clay Science, 18, 51 (2001) (*) G. Cristallo, E. Roncari, A. Rinaldo, F. Trifirò "Study of anatase - rutile transition phase in monolithic catalyst V2O5 / TiO2 and V2O5 - WO3 / TiO2" Applied Catalysis A: General, 209, 249 (2001) (*) 86 A.O. Bianchi, M. Campanati, P. Maireles - Torres, E. Rodriguez Castellon, A. Jemenez Lopez, A. Vaccari "Si / Zr mesomorphus catalysts for the vapour phase synthesis of alkylindoles" Applied Catalysis A: General, 220, 105 (2001) S. Miertus, F. Trifirò "Catalysis for cleaner industrial technologies. A survey" United nations, Industrial Development Organization, Trieste (2001) F. Cavani, R. Mezzogori, A. Pigamo, F. Trifirò “Improved catalytic performance of Keggin-type polyoxometalates in the oxidation of isobutane to methacrylic acid under hydrocarbnon-lean conditions using antimony-doped catalysts” Chem. Eng. J.,Special Issue: Frontiers in Chemical reaction Engineering, 82 33-42 (2001). S. Albonetti, F. Budi, F. Cavani, S. Ligi, G. Mazzoni, F. Pierelli, F. Trifirò “ALMAX catalyst for the selective oxidation of n-butane to maleic anhydride: a highly efficient V/P/O system for fluidized-bed reactors” in "Natural Gas Conversion VI", J.J. Spivey et al. (Eds.), Elsevier Science, Amsterdam, Stud. Surf. Sci. Catal. 136, p. 141-146 (2001) N. Ballarini, R. Catani, F. Cavani, U. Cornaro, D. Ghisletti, R. Millini, B. Stocchi, F. Trifirò “New catalysts based on rutile-type Cr/Sb and Cr/V/Sb mixed oxides for the ammoxidation of propane to acrylonitrile” in "Natural Gas Conversion VI", J.J. Spivey et al. (Eds.), Elsevier Science, Amsterdam, Stud. Surf. Sci. Catal. 136, p. 135-140 (2001) N. Ballarini, F. Cavani, C. Giunchi, S. Masetti, F. Trifirò, D. Ghisletti, U. Cornaro, R. Catani “Rutile-type Cr/Sb mixed oxides as heterogeneous catalysts for the ammoxidation of propane to acrylonitrile” Topics Catal., 15, 111119( 2001) F. Cavani, E. Etienne, R. Mezzogori, A. Pigamo, F. Trifirò “Improvement of catalytic performance in isobutane oxidation to methacrylic acid of Keggin-type phosphomolybdates by preparation via lacunary precursors: nature of active sites” Catal. Letters, 75, 99-105 (2001) F. Cavani, F. Pierelli, F. Ghelfi, G. Mazzoni “Microcristalli a base di ossidi misti di V e P. Controllo della morfologia” La Chimica e l’Industria, 83, 56-59 (2001) F. Cavani, R. Mezzogori, A. Pigamo, F. Trifirò “Modification of redox and catalytic properties of Keggin-type, Sbdoped P/Mo polyoxometalates in the selective oxidation of isobutane to methacrylic acid: control of preparation conditions” Stud. Surf. Sci. Catal., 140, 141-152 (2001) F. Cavani, R. Mezzogori, A. Pigamo, F. Trifirò, E. Etienne “Main aspects of the selective oxidation of isobutane to methacrylic acid catalyzed by Keggin-type polyoxometalates” Catal. Today, 71, 97-110 (2001) P. Arpentinier, F. Cavani, F. Trifirò “The Technology of Catalytic Oxidations” Editions Technip, Paris, 2001, ISBN 2-7108-0777-7 G. Centi, F. Cavani, F. Trifirò “Selective Oxidation by Heterogeneous Catalysis” Kluwer Academic/Plenum Publishers, New York, 2001, ISBN 0-306-46265-6 F. Trifirò, F. Cavani, F. Gennari "Trends in catalysis for industrial applications” in “Catalysts for Cleaner Industrial Tchnologies. A Survey”. Eds. S. Miertus e F. Trifirò, Unido, Trieste 2001, p.1-19. F. Trifirò, F. Cavani, F. Gennari “Selective oxidation of paraffins in the gas phase with heterogeneous catalysis” in “Catalysts for Cleaner Industrial Technologies. A Survey”. Eds. S. Miertus e F. Trifirò, Unido, Trieste 2001, p. 21-73. F. Trifirò, F. Cavani, F. Gennari “Catalytic oxidations with H2O2 and alternative processes with molecular oxygen” in “Catalysts for Cleaner Industrial Technologies. A Survey”. Eds. S. Miertus e F. Trifirò, Unido, Trieste 2001, p. 75-103. L. Balduzzi, F. Prinetto, G. Ghiotti, A. Bianchini, M. Livi, A. Vaccari "FT - IR study of Pt, Cu and Pt-Cu phases supported on hydrotalcite - derived mixe oxide" in "Studies in surface Science and Catalysis", Eds. A. Gamba, C. Colella, S. Coluccia, Elsevier, Vol. 140 (2001) S. Masetti, F. Trifirò, G. Blanchard "Fluid - bed tin - based catalyst for propane ammoxidation" Applied Catalysis A: General, 217, 119 (2001) 87 S. Blasioli, E. Roncari, D. Scagliarini, F. Trifirò "Etudes des techniques de stabilisation de catalyseurs DENOx" Ann. Chim. Sci. Mat., 26, 245 (2001) (*) F. Basile, A. Vaccari "Applications of hydrotalcite - type anionic clays (layered double hydroxide) in catalysis" in Layered Double Hydroxides: Present and Future, Nova Science Publisher, Inc., New York (2001), cap. 10 2000 F. Basile, G. Fornasari, M. Gazzano, A. Vaccari "Synthesis and thermal evolution of hydrotalcite - type compounds containing noble metals" Applied Clay Science, 16, 185 (2000) G.L. Castiglioni, G. Minelli, P. Porta, A. Vaccari "Synthesis and properties of spinel-type Co-Cu-Mg-Zn-Cr mixed oxides" Journal of Solid State Chemistry,152, 526 (2000) L. Forni, G. Fornasari, R. Trabace, F. Trifirò, A. Vaccari, L. Dalloro "Beckmann rearrangement over anionic clays" Studies in surface Science and Catalysis, Vol. 130, Proceeding of the 12th International Congress on Catalysis, Granada July (2000), Elsevier, p. 3513 F. Basile, G. Fornasari, F. Trifirò, A. Vaccari "Reactivity and thermal profile of methane partial oxidation at very short residence time" Studies in surface Science and Catalysis, Vol. 130, Proceeding of the 12th International Congress on Catalysis, Granada July (2000), Elsevier, p. 449 (*) M. Campanati, A. Vaccari, O. Piccolo "Environment - friently synthesis of nitrogen - containing heterocyclic compouds" Catalysis Today, 60, 289 (2000) M. Campanati, F. Donati, A. Vaccari, O. Piccolo "Vapour phase synthesis of heterocyclic compounds" In “Actas XVII Simp. Iberoamericano de Catalise”, J.M. Orfao, J.L. Faria, J.L. Figueredo, Eds., FEUP ediçiones, Porto, (2000) . M. Campanati and A. Vaccari "Acidic clays" In “Fine Chemicals through Heterogeneous Catalysis” (R. Sheldon and H. van Bekkum, Ed.s), VCH, Weinheim, pp. 61 (2000). R. Catani, F. Cavani, u. Cornaro, A. Del Biaco, E. Frontani, D. Ghisletti, A. Tasso, F. Trifirò "Ammoxidation of propylene to acrylonitrile catalyzed by multimetal molibdate- and iron antimonate - based active compounds dipersed in oxidic matrixes: the effect of the dipsersing oxide on the catalytic performance" In "Studies in Surface Science and Catalysis", A. Corma, F.V. Melo, S. Mendioroz, J.L.G. Fierro (Editors), vol. 130, pp. 1691 (2000) F. Cavani, T. Monti, D. Paoli "Charaterization and reactivity of supported and unsupported B / P / O catalysts in the O-alkylation of diphenols with methanol" In "Studies in Surface Science and Catalysis", A. Corma, F.V. Melo, S. Mendioroz, J.L.G. Fierro (Editors), vol. 130, pp. 2633 (2000) F. Cavani, S. Ligi, T. Monti, F. Pierelli, F. Trifirò, S. Albonetti, G. Mazzoni "Relationship between structural / surface characteristics and reactivity in n-butane oxidation to maleic anhydride. The role of the V3+ species" Catalysis today, 61, 203 (2000) L. Forni, G. Fornasari, E. Miserazzi, R. Trabace, F. Trifirò, A. Vaccari, L. Dalloro "Vapour phase beckmann rearrangement over ht-like matierials" Heterogeneous Catalysis, Proceedings of the 9th International Symposium, l. Petrov, Ch. Bonev, G. Kadinov (Editors), pp. 507 (2000) F. Cavani, D. Scagliarini "Catalizzatori solidi basici" La Chimica e L'Industria, 6, 665 (2000). F. Cavani, T. Monti "Reactivity of B/P/O-based heterogeneous catalysts in gas-phase O-alkylation of diphenols with methanol" in "Catalysis of Organic Reactions", M.E. Ford (Ed.), Marcel Dekker, New York, 2000, p. 123 G.L. Castiglioni,. F. Cavani, C. Fumagalli, S. Ligi, F. Trifirò "Synthesis of methylmaleic anhydride (citraconic anhydride) by heterogeneous selective oxidation of isoprene with V/Ti/O catalysts" in "Catalysis of Organic Reactions", M.E. Ford (Ed.), Marcel Dekker, New York, 2000, p. 371 L. Calzolari, F. Cavani, T. Monti "Heterogeneous catalysts based on B / P /O for the monoetherification of 1,2dihydroxybenzene in the gas phase" C. R. Acad. Sci. Paris, Série IIc, Chimie, 3, 533 (2000) 88 F. Cavani, R. Mezzogori, A. Pigamo, F. Trifirò "Synthesis of methacrylic acid by selective oxidation of isobutane, catalysed by Keggin - type polyoxometalates: relationship between catalytic performance, reaction conditions and chemical - physical features of the catalyst" C. R. Acad. Sci. Paris, Série IIc, Chimie, 3, 523 (2000) M.S.M Mujeebur Rahuman, L. Pistone, F. Trifirò, S. Miertus "Destruction technologies for polychlorinated biphenyls (PCBs)" ICS proceedings expert group meeting on POPs and Pesticides contamination: Remediation Technologies, Trieste, 17 - 19 Aprile 2000, p.9 S. Albonetti, L. Dal Pozzo, F. Trifirò "Catalysis in clean technologies for fine chemicals" Proceedings of the Workshop on Catalytic processes for clean chemistry and water and air depollution, A. Ghorbels, S. Miertus, Eds., 159 (2000) 1999 A. Vaccari "Hydrotalcite - type anionic clays (layer double hydroxides) as precursors of both catalysts and catalysts supports" 9th Cimtec - World Ceramic Congress, Ceramics: Getting into the 2000 - Part D, P. Vincenzini (Editor), Techna srl 1999, p. 571 A. Vaccari "Clays and catalysis: a promising future" Applied Clay Science, 14, 161 (1999) R. Angelucci, A. Poggi, L. Dori, G.C. Cardinali, A. Parisini, A. Tagliani, M. Mariasaldi, F. Cavani "Permetated porous silicon for hydrocarbon sensor fabrication" Sensors and Actuators, 74, 95 (1999) S. Albonetti, F. Cavani, S. Masetti, F. Trifirò "Mixed oxides with rutile type structure active in ammoxidation to acrylonitrile" Science and Technology in Catalysis, Kodansha Ltd. (1998) p. 79 C.I. Cabello, G.L. Castiglioni, F. Cavani, C. Fumagalli, L. Grasso, S. Ligi, F. Trifirò "Oxidation of isoprene to methylmaleic anhydride (citraconi anhydride) over vanadium oxide - based catalysts"Science and Technology in Catalysis, Kodansha Ltd. (1998) p. 359 F. Cavani, F. Trifirò "Selective oxidation of light alkanes: interaction between the catalyst and the gas phase on different classes of catalytic materials" Catalysis Today, 51, 561 (1999) B. Ballarin, R. Seeber, D. Tonelli, A. Vaccari "Electrocatalytic properties of nickel (II) hydrotalcite-type anionic clay: application to methanol and ethanol oxidation" Journal of Electroanalytical Chemistry, 463, 123 (1999) F. Cavani "Ammonossidazione di propano in fase gas per la sintesi dell'acrilonitrile" La Chimica e l'Industria, 81, 1285 (1999) 1998 F. Basile, L. Basini, M. D' Amore, G. Fornasari, D. Matteuzzi, F. Trifirò, A. Vaccari "Ni/Mg/Al anionic caly derived catalyst for the catalytic partial oxidation of methane: contact time dependence of the reactivity features" J. Catal., 173, 247 (1998) (*) B. Ballarin, M. Gazzano, F. Gulmanelli, R. Seeber, D. Tonelli, A. Vaccari "Electodes coated by hydrotalcite-like clays. Effects of the metals and the intercalated anions on ion accumulation and retention capability" J. Electroanal. Chem., 445, 27 (1998) A. Vaccari "Preparation and catalytic properties of cationic and anionic clays" Catalysis Today, 41, 53 (1998) F. Cavani "Heteropolycompounds-based catalysts: A blend of acid and oxidizing properties" Catalysis Today, 41, 73 (1998) G. Fornasari, F. Trifirò "Oxidation with no-redox oxides: ammoximation of cyclohexanone on amorphous silicas" Catalysis Today, 41, 443 (1998) 89 F. Cavani, A. Tanguy, F. Trifirò, M. Koutrev "Effect of antimony on the chemical-physical features and reactivity in isobutyric acid oxidehydrogenation of Keggin-type hetheropolycompounds" Journal of Catalysis, 174, 231 (1998) S. Albonetti, G. Blanchard, P. Burattin, S. Masetti, A. Tagliani, F. Trifirò "A new ternary mixed oxide catalyst from ammoxidation of propane: Sn / V / Sb" Catalysis Letters, 50, 17 (1998) M. Sanati, R. Akbari, S. Masetti, F. Trifirò "Kinetic study of propane ammoxidation to acrylonitrile over V - Sb O / TiO2 (B)" Catalysis Today, 42, 325 (1998) F. Basile, L. Basini, G. Fornasari, A. Guarinoni, F. Trivirò, A. Vaccari "Catalytic behaviour of Ni- and Rhcontaining catalyst in the partial oxidation of methane at short residence times" in Natural Gas Conversion V, Studies in Surface Science and Catalysis, Vol. 119, A. Parmaliana, D. Sanfilippo, F. Frusteri, A. Vaccari, F. Arena, Eds., Elsevier, Amsterdam, 1998, 693 G.L. Castiglioni, C. Fumagalli, E. Armbruster, M. Messori, A. Vaccari "Cu / Zn / Zr catalysts for the production of environmentally friendly solvents" in Catalysis of Organic Reactions, F. E. Herkes Ed., Dekker, New York, 1998, 391 M. Campanati, F. Fazzini, G. Fornasari, A. Tagliani, A. Vaccari "Environmentally friendrly catalysts for acylation reactions" in Catalysis of Organic Reactions, F. E. Herkes Ed., Dekker, New York, 1998, 307 F. Basile, L. Basini, G. Fornasari, M. Gazzano, F. Trifirò, A. Vaccari "Anionic clays as precursors of noble metal based catalysis for methane activation" in Preparation of catalysts VII, B. Delmon, P.A. Jackobs, R. Maggi, J.A. Martens, P. Grange, G. Poncelet Eds., Elsevier, Amsterdam, 1998, 31 (*) S. Albonetti, G. Blanchard, P. Burattin, F. Cavani, S. Masetti, F. Trifirò "Propane ammoxidation to acrylonitrile over a tin-based mide-oxide catalyst" Catalysis Today, 42, 283 (1998) M. López Granados, J.L.G. Fierro, F. Cavani, A. Colombo, F. Giuntoli, F. Trifirò "Study by XPS and TPD of the interaction of n-pentane and n-butane with the surface of 'non-equilibrated' and 'equilibrated' V-P-O catalysts" Catalysis Today, 40, 251 (1998) F. Cavani, S. Ligi, S. Masetti, F. Trifirò "SbVO4: the chemistry of preparation" in "Preparation of Catalysts VII",B. Delmon et al., Eds., Elsevier Science, Amsterdam, 1998, 377-384 C. Cabello, F. Cavani, S. Ligi, F. Trifirò "Oxidation of n-butane and n-pentane over V/P/O-based catalysts: comparison between fresh and "equilibrated" catalysts" in "Natural gas Conversion V", A. Parmaliana et al. (Eds.), Elsevier Science, Amsterdam, 1998, 925 F. Cavani, F. Trifirò "Paraffins as raw materials for the petrochemical industry" in "Natural gas Conversion V", A. Parmaliana et al. (Eds.), Elsevier Science, Amsterdam, 1998, 561 A. Bottino, G. Capannelli, A. Comite, F. Ferrari, O. Monticelli, D. Romano, A. Servida, F. Cavani, V. Chiappa "Hydrocarbons catalytic combustion in membrane reactors" in "Natural gas Conversion V", A. Parmaliana et al. (Eds.), Elsevier Science, Amsterdam, 1998, 435 G. Capannelli, A. Bottino, D. Romano, O. Monticelli, A. Servida, F. Cavani, A. Bartolini, S. Rossini "Oxydehydrogenation of propane to propylene in catalytic membrane reactor: a model for the interpretation of experimental data" in "Natural gas Conversion V", A. Parmaliana et al. (Eds.), Elsevier Science, Amsterdam, 1998, 423 F. Trifirò "The chemistry of oxidation catalysts based on mixed oxides" Catalysis Today, 41, 21 (1998) F. Basile, G. Fornasari, E. Poluzzi, A. Vaccari "Catalytic partial oxidation and CO2 - reforming on Rh- and Nibased catalysts obtained from hydrotalcite - type precursors" Applied Clay Science, 13, 329 (1998) J. Pasel, P. Kabner, B. Montanari, M. Gazzano, A. Vaccari, W. Makowski, T. Lojewski, R. Dziembaj, H. Papp "Transition metal oxide suported on active carbon as low temperature catalysts for the selective catalytic reduction (SCR) of NO with NH3" Applied Catalysis B:Environmental, 18, 199 (1998) 90 1997 L. Basini, M. D’Amore, G. Fornasari; D. Matteuzzi, D. Sanfilippo, F. Trifirò, A. Vaccari "Syngas production by methane partial oxidation: Reactivity dependance on catalyst properties and contact time" In "Natural Gas Conversion IV" (M. de Pontes et al., Eds), Elsevier Science, Amsterdam, 1997, pp. 429-434 G. Centi, A. Galli, B. Montanari, S. Perathoner, A. Vaccari "Catalytic decomposition of N2O over noble and transition metal containing oxides and zeolites. Role of some variables on reactivity" Catal. Today, 35, 113 (1997) S. Perathoner, A. Vaccari "Catalysts based on pillared interlayed clays for the selective catalytic reduction of NO" Clay Minerals, 32, 119 (1997) B. Montanari, A. Vaccari, M. Gazzano, P. Kabner, H. Papp, J. Pasel, R. Dziembaj, W. Makowski, T. Lojewski "Characterization and activity of novel copper-containing base catalysts for selective catalitic reduction of NO with NH3" Appl. Catal. B:Environmental, 13, 205 (1997) M. Gazzano, W. Kagunya, D. Matteuzzi, A. Vaccari "Neutron diffraction studies of polycrystalline Ni/Mg/Al mixed oxides obtained from hydrotalcyte-like precursors" J. Phys. Chem., 101, 4514 (1997) F. Basile, L. Basini, G. Fornasari, A. Guarinoni, L. Piovesan, A. Vaccari, F. Trifirò "Short residence time partial oxidation of methane: it is an heterogeneous and kinetically controlled processe?" In "Proc. 1st European Congress on Chemical Engineering", AIDIC, Milano, 1997, vol. 1, pp. 349-352 F. Basile, L. Basini, G. Fornasari, M. Gazzano, F. Trifirò, A: Vaccari "New rhodium and ruthenium based anionic clay catalysts for the partial oxidation of methane to syngas" in "Proc. 1st European Congress on Chemical Engineering", AIDIC, Milano, 1997, vol. 1, pp. 381-384 M. Trombetta, G. Ramis, G. Busca, B. Montanari, A. Vaccari "Ammonia adsorption and oxidation on Cu/Mg/Al mixed oxide catalysts prepared via hydrotalcite-type precursors" Langmuir, 13, 4628 (1997) F.M. Cabello, D. Tichit, B. Coq, A. Vaccari, N.T. Dungù "Hydrogenation of acetonitrile on nickel based catalysts prepared from hydrotalcite-like precursors" J. Catal., 167, 142 (1997) M. Campanati, P. Savini, A. Tagliani, A. Vaccari, O. Piccolo "Environmentally friendly vapour phase synthesis of alkyl-quinoline" Catal. Letters, 47, 247 (1997) T. Loiewski, R. Dziembaj, R. Chyzy, A. Vaccari, B. Montanari "Characterization of the DeNOX catalysts derived from impregnated and co-precipitated hydrotalcyte-type precursors" Polish J. Environm. Studies, 6, 71 (1997) A. Vaccari "Vapour phase synthesis of g-butyrolactone: an example of environmentally-friendly processes of industrial relevance" In "Actas 26° Riun, Bienn. Real Soc. Española de Quimica" (C. Mira, Ed.), Univ. de Cadiz, Cadiz (E), 1997, vol. 1, pp. 89 S. Albonetti, G. Blanchard, P. Burattin, S. Masetti, F. Trifirò "Propane ammoxidation over Sn/V/Sb mixed oxide: preparation method and calcination effect" In "Proc. of the 1st International Workshop Reactivity of Oxide Materials Theory and Experiment" (A. Gamba and S. Coluccia, Eds), Il Nuovo Cimento, Bologna, 1997, pp. 1631 S. Albonetti, G. Blanchard, P. Burattin, S. Masetti, F. Trifirò "A new catalyst for propane ammoxidation: the Sn/V/Sb mixed oxide" In "3rd World Congress On Oxidation Catalysis", Stud. Surf. Sci. Catal., Vol. 110 (R.K. Grasselli et al. Eds.), Elsevier, Amsterdam, 1997, pp. 403 S. Albonetti, G. Blanchard, P. Burattin, T.J. Cassidy, S. Masetti, F. Trifirò "Mechanism of Ammoxidation of Propane on Sb/V/O System" Catal. Lett., 45. 119 (1997) F. Cavani, A. Colombo, F. Trifirò, M.T. Sananes Schulz, J.C. Volta, G.J. Hutchings "The effect of cobalt and iron dopants on the catalytic behavior of V/P/O catalysts in the selective oxidation of n-pentane to maleic and phthalic anhydrides" Catal. Lett., 43, 241 (1997) 91 R. Angelucci, A. Poggi, L. Dori, G.C. Cardinali, A. Parisini, G. Pizzochero, F. Trifirò, F. Cavani, C. Critelli, L. Boarino "Porous silicon layer permeated with Sn-V mixed oxides for hydrocarbon sensor fabrication" Thin Solid Films, 297, 43 (1997) F. Cavani, A. Lucchi, A. Tanguy, F. Trifirò "The gas phase oxidation of isobutane to methacrylic acid catalyzed by Keggin-type P/Mo/W heteropolycompounds" In "Proc. DGMK-Conference, C4 Chemistry-Manufacture and Use of C4 Hydrocarbons", (W. Keim et al. Eds.), Tagungsbericht 9705, Hamburg, 1997, p.173 M. Lòpez Granados, J.M. Coronado, J.L.G. Fierro, F. Cavani, F. Giuntoli, F. Trifirò "TPD, XPS and ESR Studies of the Surface Processes Involved in the Oxidation of n-Pentane on a (VO)2P2O7 system" Surf. Interface Anal., 25, 667 (1997) F. Cavani, F. Trifirò "The characterization of the surface properties of V-P-O-based catalysts by probe molecules" Appl. Catal. A: General, 157, 195 (1997) F. Cavani, F. Trifirò "Some aspects that affect the selective oxidation of paraffins" Catal. Today, 36, 431 (1997) F. Cavani, F. Trifirò "The multifunctional properties of heterogeneous catalysts, active and selective in the oxidation of light paraffins" In "3rd World Congress on Oxidation Catalysis", (R.K. Grasselli et al. Eds.), Elsevier Science, Amsterdam, 1997, p. 19 M.R. Cramarossa, L. Forti, M.A. Fedotov, L.G. Detusheva, V.A. Likholobov, L.I. Kuznetsova, G.L. Semin, F. Cavani, F. Trifirò "Reactivity of transition-metal-modified, Keggin-type heteropolycomplexes in the homogeneous oxidation of cyclohexane and adamantane" J. Mol. Catal. A: Chemical, 127, 85 (1997) F. Basile, L. Basini, G. Fornasari, E. Poluzzi, F. Trifirò, A. Vaccari "Nuovi sistemi catalitici contenenti metalli nobili per l' attivazione del metano" in "Materiali, ricerca e prospettive tecnologiche alle soglie del 2000", Vol. 2, FAST (Milano) p. 1441 (1997) S. Albonetti, G. Blanchard, P. Burattin, S. Masetti, F. Trifirò "A new catalyst for propane ammoxidation: the Sn/V/sb mixed oxide" 2rd World Congress on Oxidation Catalysis, R.K. Grasselli, S.T. Oyama, A.M. Gaffney, J.E. Lyons Editors, Elsevier Science V.B. 403 (1997) S. Albonetti, G. Blanchard, P. Burattin, S. Masetti, F. Trifirò "Propaneammoxidation over Sn / V / Sb mixed oxide: preparation method and calcination effects" Il Nuovo Cimento, 19, 1631 (1997) F. Cavani, F. Trifirò "Classification of industrial catalysts and catalysis for the petrochemical industry" Catalysis Today, 34, 269 (1997) T.J. Cassidy, M. Pollastri, F. Trifirò "Ammoxidation of propane on nickel antimonates" Journal of Catalysis, 172, 55 (1997) I-3 Overview of Professional Publications (1997 - 2001) per year I-4 Other Scientific Output Patents F. Cavani, T. Monti, P. Panseri, B. Castelli, V. Messori “Ossido misto di alluminio e fosforo: procedimento per la sua preparazione e suo impiego come catalizzatore” Domanda di Brevetto Italiano A00685 (2000). Assegnato a Borregaard Italia. Milano, 31/03/2000 U. Cornaro, R. Catani, D. Sanfilippo, F. Cavani “Sistema catalitico per la produzione di acrilonitrile da propilene” Domanda di Brevetto Italiano 02603 (2000). Assegnato a Snamprogetti SpA. Milano, 20/12/2000 V. Borzatta, E. Poluzzi, M. Tozzi, A. Vaccari "Processo per la sintesi di 2-idrossifenilalchilchetoni" Italian Patent MI99 A002038 (1999), WO Patent 01/23,339 A1 (2001), Assegnato a Endura. S. Ligi, F. Cavani, S. Albonetti, G. Mazzoni “Vanadium/Phosphorus mixed oxide catalyst precursor” Domanda di Brevetto Italiano A01233 (1999); WO Patent 00/72,963 (2000). Assegnato a Lonza SpA Milano, 01/06/1999 92 O. Piccolo, A.. Vaccari, M. Campanati, P. Massardo Procedimento per preparare composti indolici" Italian Patent MI98 A002,397 (1998) Assegnato a CHEMI A. Vaccari, S. Alini, A. Bologna, F. Basile, T. Montanari, "Process for decomposing nitrous oxide (N2O)" EP Patent 183354 (2001), , Assigned to Radici. Appendix 2 Ranking Scientific Journals Appendix 3 Journal Portfolio Analysis Name of the Unit: Bologna 2 Research Director: Trifirò Years included 1997-2001 Name of Journal Catalysis Today Number Articles 15 Applied Catalysis A Applied Catalysis B Catal. Letters Applied Clay Science J Catal J ELECTROANAL CHEM Topics Catal. Altri 4 2 5 4 4 2 1 57 of Journal Impact Field(s) Factor (2001) 2.333 Engineering, chemical Chemistry, physical 2.258 Chemistry, physical 3.643 Chemistry, physical 1.852 Chemistry, physical 2.095 Mineralogy 3.293 Chemistry, physical 1.96 Chemistry, analytical 2.136 Chemistry, physical Ranking 4/123 25/93 27/93 13/93 33/93 3/24 17/93 16/68 29/93 93 BOLOGNA 3 Name of the Research Unit (In Italian and English) Bologna 3 Bologna 3 University: (In Italian and English) Alma Mater Studiorum - Università di Bologna Alma Mater Studiorum - University of Bologna Faculty: (In Italian and English) Facoltà di Chimica Industriale Faculty of Industrial Chemistry Department: (In Italian and English) Dipartimento di Chimica Industriale e dei Materiali Department of Industrial Chemistry and Materials Research Leader (The name of the person in charge of the research programme of the unit) Prof. Luciano Morselli Contact Person (The name and address of the person who will act as liaison between the unit and the INCA-Secretariat) Please specify: Name Phone Fax E-mail Luciano Morselli Mailing Address Department of Industrial Chemistry and Materials, viale Risorgimento 4, 40136 Bologna Italy +39 051 2093668 +39 051 2093863 [email protected] Thematic area • Tecnologie innovative di monitoraggio • Chimica degli ecosistemi (chimica del suolo, delle acque e dell’aria; impatto dei prodotti di sintesi sull’ambiente). Introduction and Context Introduction to the Self-evaluation Report The University, the Faculty and the Department The University of Bologna is the oldest in the western world: 1088 may be accepted as conventional date to indicate when teaching became free and independent of the ecclesiastic schools. Bologna University is one of the largest universities in Italy and in Europe. It is a state university and it is autonomous with its own "statuto" which indicates how the University governs itself through its various elected bodies. The University government and the main research and teaching activity are located in Bologna, but many new research and teaching activities have been recently dislocated in other Cities of the Emilia Romagna region, such as Cesena, Faenza, Forli’, Ravenna and Rimini. The whole University currently counts about 900 professors, 1,000 associated professors, 1,050 researchers and more than 100,000 students. It is divided in 19 Faculties, 65 Departments, 5 Federated Departments (“Unità Complesse”), 3 Institutes and it currently offers about 65 “laurea” degree courses and 45 “diploma” degree courses in the following subject areas: a)Agriculture; b) Economics; c) Education and Humanities; d) Engineering; e) Industrial Chemistry, f)Law; g) Literature and Philosophy; h) Mathematical, Physical and Natural Sciences; i) Medicine; l) Pharmacy; m) Political Science; n) School of Modern Languages for Interprets and Translators; o) Statistical Sciences; p) Veterinary Medicine; q) Foreign Languages and Literatures. The Faculty of Industrial counts about 125 teaching and researching staff units, including full professors, associated professors and researchers and about 500 students. The unit is formed by groups which belong to two Departments of the same Faculty, Inorganic and Physical Chemistry Dep. and Industrial Chemistry and Material Dep. The Unit The Unit consists of 3 members of University Staff, a Full Professor (since 2001), an Associated Professor (since 2001) and a Researcher. The disciplinary areas they belong to are “Environmental Chemistry”, “Analytical Chemistry” and “Chemistry and Biotechnology” respectively. The Faculty offers three different degree courses (“Industrial Chemistry”, “Environmental and Waste Management Chemical Technologies”, “Material Chemistry and Ceramic Technologies”) and a specialistic course (“Products, Materials and Processes for the Industrial Chemistry). The teaching load can be estimated in about 38 credits, corresponding to about 400 hours, including lectures and laboratory experiences of Environmental Chemistry, Analytical Chemistry and Industrial Biochemistry. 4 Post-doc and 4 PhD students (2 at the third year, 2 at the first year) are presently co-operating with the research group. 94 Programme Description and Evaluation 1 Title Integrated Environmental Monitoring System applied to Pollutant Chemistry and Control. 2 Research Leader Prof. Luciano Morselli 2a Sub-programme titles and sub-programme leaders Title: Applied chemistry and biochemistry for the valorisation of industrial and agro-food wastes, environmental control and remediation of polluted sites. Leaders: Prof. Luciano Morselli, Dr. Leonardo Setti 3 Composition of the scientific research staff of the unit per 1 January 2002 Names and Titles Year of Rank Birth Prof. Luciano Morselli Prof. Sergio Zappoli 1943 1958 Prof. Leonardo Setti Dr. Antonella Andracchio Dr. Silvia Giuliani Dr. Fabrizio Passarini Dr. Roberto Mezzogori Dr. Elena Badiali Dr. Chiara Piana Dr. Michele Bartoli Dr. Elena Bernardi Total research input 1963 1965 1969 1972 1974 1970 1974 1975 1977 Full Professor Associated Professor Ricercatore Post-doc Post-doc Post-doc Post-doc PhD-student PhD-student PhD-student PhD-student Research Input in fte in 2001 .5 .5 0.5 1.0 1.0 1.0 1.0 1.0 0.5 1.0 1.0 10.0 Remarks He joined the unit in 2001 He joined the institute in 1999 He joined the unit in 2001 She joined the institute in 2000 She graduated in 2000 He graduated in 2001 She graduated in 2001 Comments The group is constituted by 3 members of the structured personnel and 8 of the unstructured personnel. These last members are all Post-doc or PhD students, and almost all joined the group only in the last 2 years. A great investment by the unit is made on research formation, considering the PhD-courses as the most suitable way to reach the competences in programming and leading research projects. Many young graduated people followed one another, since 1997; someone worked in the unit for a few months, to carry out short range projects, while others stayed for some years, after the graduation, achieving PhD and Post-doc positions or finding a job outside the University. The unit is expected to increase in number in the next 5 years. In particular, an expansion in structured personnel is predicted, in technical and research positions, due to the growing importance achieving in Industrial Chemistry Faculty the environmental subjects. Such a change can be accompanied by the replacement of PhD and Post-doc positions. 4 Input of Academic Staff in fte Category 1997 Full Professors 0.0 Associated Professors .5 Ricercatori 1 Post-docs 2.0 PhD-students 0.0 Borsisti 2.5 Total 6 1998 0.0 .5 1 2.0 1.0 2.5 7 1999 0.0 .5 1 2.0 2.0 2.5 8 2000 0.0 .5 1 1.0 2.5 2.0 7 2001 .5 .5 0.5 3.0 2.5 2.5 9.5 Total .5 2.5 4. 10.0 8.0 11.5 37 95 The Academic Staff increased from 1997 to 2001. As to the structured personnel, a Full Professor and an Associated Professor were appointed in 2001. Post-docs, PhD students and Borsisti have increased in number, thanks to more funds supplied by many agencies or private concerns. These funds allowed many just graduated students to continue the research training in the University and to attend PhD courses. A PhD student leaved the course in 2000, while attending the second year. In the next 5 years the unit could still further increase in number, aiming to a growing research formation of young investigators, by means of PhD courses. 5 Funding 5.1 Personnel (in fte) Source University CNR European Union Other Sponsors Total 5.2 * * 1998 0.5 0.0 1.0 4.0 5.5 1999 1.0 0.0 1.0 4.5 6.5 2000 1.0 0.0 1.0 3.5 5.5 2001 0.8 0.5 0.0 6.7 8.0 Total 3.5 0.5 4.0 22.0 30 1999 22 0 13 37 72 2000 47 0 6 75 128 2001 25 15 0 400 440 Total 118 20 79 672 889 Materials and Equipment (in Million Lire) Source University - MURST CNR EU Other Sponsors Total 5.3 1997 0.2 0.0 1.0 3.3 4.5 1997 10 4 30 112 156 1998 14 1 30 48 93 Comments: On the figures On the funding policy Please add a list of major sponsors and the character of the liaison with the major sponsors A sharp increase in funding can be observed in 2001, which is not a occasional trend, but is going to be confirmed also in the next years. The percentage of institutional financing (University, CNR and EU) reached the maximum in 1998 and 1999 (about 50%). It can be seen that both personnel and materials are supported mainly by private sponsoring. This observation underlines that these subjects have a great social importance and find growing favour with private business. Major sponsors: ENEL Brindisi Procedures for the extraction and analysis of PCB congeners in real matrices, by Supercritical Fluid Extraction (SFE) technology have been set up. A particular attention has been paid to the recovery efficiency of PCB from soil matrices in different analytical conditions. Emilia Romagna Region An overview on Incineration Plant in the Region has been conducted, in order to compare technological and ecological efficiencies. A report has been published, including technological description, mass and energy balances, factor emissions of macro and micro-pollutants. Tetra Pak Italiana S.p.A. A research on the possibility of recycling beverage cartons, made of cellulose, polyethylene and, for long-life food, aluminium, in a paper mill process has been conducted. The technological feasibility, the paper quality and the characterisation of wastes have been studied. 96 AMIA S.p.A. The application of an Integrated Environmental Monitoring System has been carried out to an incineration plant, to evaluate its environmental impact. Process and natural matrices, collected in the vicinity, have been compared for the investigation of cause-effect relationships. ANPA (National Environmental Protection Agency) A deep investigation of critical loads and exceedances of atmospheric pollutants has been effected. Critical loads have been calculated with a progressively more accurate methods. Exceedances of different Italian sites are compared to estimate environmental risks. ARPA Emilia Romagna (Regional Environmental Protection Agency) The same investigation strategy used in the research sponsored by AMIA S.p.A. has been applied to another case study, regarding two incineration plants sited near an industrial and residential area. Le.Se.Pi.Da.Do. S.r.l. Development of new inks for ink-jet technology, in order to reduce the problems linked to the deinking processes into the paper mills both for the whiteness of the paper and for the disposal of the waste waters from the deinking. 6. Progress Report 6.1 Mission Statement The Unit’s mission is to investigate the environmental diffusion, reactions and fate of pollutants. In particular, innovative methodologies and strategies of sampling are defined, in order to assess the environmental quality of a given site, describing the pollutant load which undergo natural matrices and other materials. An Integrated Environmental Monitoring System is defined and used as an innovative approach that allows a remarkable understanding of impacts due to a contamination source. The determination of contaminants is carried out from the source to the final sink, investigating the correlations existing between the content in process effluents and in natural matrices. Suitable procedure are studied and adopted, for each type of environmental compartment affected by contamination. A particular study is addressed in the sampling, treatment and analysis of wet and dry depositions. The research is also bent on the comparison of environmental impact due to different waste treatment activities (incineration, composting, different types of recycling processes), in order to outline a management strategy which supports the most eco-sustainable industrial technologies, improving the recovery of material and energy, considering the different merceological categories of waste. A sub-programme mission consists in achieving technological innovations for the valorisation of industrial and agrofood wastes, for the decontamination of different matrices and sites, and for the planning of new eco-sustainable processes, by means of chemical and biological plants and technologies. Particular interest has the development of new integrated biological processes using enzymes and microorganisms. The industrial interest is focused on the design of novel reactors for the bioprocesses in non-conventional systems using immobilized enzymes and microorganisms; in particular, a study has developed immobilized cell bioreactor for fuel biodesulfurization processes. The research can be considered essentially applied, even if more fundamental studies are conducted on the reactions of chemical species in the atmospheric compartment and on the improvement of analytical techniques for the determination of organic and inorganic pollutants. The principle client of research results is the international scientific community, within which they are diffused by means of scientific publications and congress presentations. However, due to the environmental relevance of these studies, also Regional and National Environmental Protection Agencies, as well as other public authorities or institutions (Region, city-owned enterprises) are interested and involved in them. Furthermore, private business provides financial support to attain product or process environmental certification, or to assess and improve the ecosustainability of its processes. Finally, the scientific content of the research is quite innovative and is a matter of educational and training programmes, consisting in a degree course and in a national school. 6.2 The Research Programme A proper Environmental Monitoring strategy becomes more and more crucial, in order to provide a reliable estimation of the state of the environment and of the condition of ecosystems. Furthermore, it’s in the interest of private business to exhibit an environmental care, which is the basic idea supporting the certification of products and processes. Thus, a particular attention must be paid to those sites which are affected by a diffuse or punctual contamination, due to the presence of highly contaminating industrial plants, or to the widespread distribution of small industrial or handicraft activities, or to the existence of a dense road traffic network. 97 The first step of an Integrated Environmental Monitoring System consists in the characterisation of contamination sources, using all the instruments that can be put together with analytical emission monitoring, such as (in the case of a punctual origin) Life Cycle Inventory, calculation of Mass and Energy Balance, determination of pollutant Mass Fluxes and Emission Factors. These results become important when an Environmental Monitoring takes place, because the immission of contaminants must be correlated to their content in natural matrices. Organic or inorganic macro and micropollutants can be chosen as Environmental Indicators, depending on the primary sources that have to be investigated. Generally, also a diffusion model has to be applied, in order to predict the zones of maximum deposition and the minimally invested areas. In this way, a monitoring network can be arranged, and the collection of a significant number of environmental matrix samples, sited in different affected zones, can be carried out. Atmospheric environment is especially studied, because of its importance in the transport of pollutants and in the interaction with plants and animals. The monitoring of gaseous pollutants, atmospheric aerosol and wet and dry atmospheric depositions are conducted. Innovative procedures are set up in order to characterise, fractionate and isolate macromolecular organic compounds in the aerosol. In the suspended particulate the organic component is isolated and characterised and the inorganic component is determined even with speciation techniques. The oxidative capacity of the multiphase atmospheric system is also investigated, with a particular attention to the couple Fe(II)/Fe(III). Because of the lack of official methods for the monitoring of atmospheric depositions, in particular for the collection of dry contribution, devoted studies have been carried out. Both types of deposition are collected using a modified sampler, for the collection of dry deposition on a thin layer of water surface, which performs a more effective recovery than the solid-surface ones. The content of each vessel is then filtered, for the determination of a soluble (or dissolvable) fraction and an insoluble one. Heavy metals contained in the soluble fraction can be considered the most dangerous, due to their higher availability. However, the determination of organic micropollutant deposition (as PCB, PAH and PCDD/F) is conducted using a bulk sampler, because of their very low absolute concentration in the atmosphere. An evolution of these studies, concerning the pollution load on a given site, is the calculation of critical loads, which are defined as a quantitative estimate of exposure to one or more pollutants below which significant harmful effects on sensitive elements of the environment do not occur, according to present knowledge. Exceedances represent the difference between the real deposition flux and the calculated Critical Load. The knowledge of the whole fluxes, from wet and dry deposition, of different contaminants allows an evaluation of the environmental quality of a site, through a comparison with the Critical Load value of the territory itself, for each pollutant. The Critical Loads of a given area are defined on the base of territorial characteristics, as geological nature, type of soil, and vegetation cover, and express the territorial sensitivity to the different pollutants. Static methods (Level 1) for the determination of Critical Loads were used: they are identified as SSMB method (Steady State Mass Balance). An important result was obtained in the determination of critical loads and of exceedances in the Province of Bologna. A more punctual knowledge of the territory characteristics and the monthly determination of wet and dry atmospheric depositions allowed an ever-growing precision in the determination of this important parameters. The critical load was calculated for different chemical species, as acidity, nutrient N, and heavy metals, in the different geographical zones, represented in maps, subdivided in suitably dimensioned grids. The outlook of this research will focus on the improvement of critical load calculation and on the extension also to other atmospheric parameters. A deeper environmental investigation can be accomplished extending the determination of pollutant content to soil and vegetation species collected in the same sites constituting the monitoring network. For these matrices, official standard methods can be used, except for vascular plants (a method for the determination of the superficially deposited trace contaminants has also been used). A biomonitoring campaign, using mosses as bioaccumulators, has been started since the second half of 2001, in order to compare chemical results to the response of biological receptors. An important results obtained by our group is the definition of a methodological approach for the recognition of causeeffect relationship between the emissions from a contamination source and the environmental contamination observed in the vicinity. This approach, which was successfully applied to incineration plants sited in Emilia-Romagna Region, can be considered a reference point useful for the assessment of environmental impacts caused by industrial plants. It is characterised by the application of many different knowledge and procedures, thus resulting a highly interdisciplinary strategy. In studying incinerators, heavy metals were chosen as preferential contamination tracers, and the results were elaborated using multivariate techniques for data treatment. Similar variable correlations were noticed both in process and in nearest natural matrices, while the farthest monitoring site displayed quite different patterns. Furthermore, natural samples’ contamination, in particular in soil, differed mostly due to the year of collection, rather than the position with respect to the plant (except for the farthest site), and variable fluctuations accorded well with those observed in emissions from incinerators. The continuation of the research will be focused on the better knowledge of particulate atmospheric interaction and deposition, to distinguish more precisely the different sources of atmospheric pollutants. An ongoing project has been opened about the study of the interaction of common atmospheric pollutants with materials, and in particular with cultural assets, in which Italian historical cities are very rich. An assessment of the 98 corrosion of bronze materials exposed to natural acid rain collected in Bologna, compared to artificial rain, is conducted. Monitoring of the soil constitutes an important instrument for the application of remediation technologies. A new possibility to use the supercritical fluid extraction for investigate the fate of pollutants in the soil structure is in progress. The recovery of the analyte from the soil matrix depends on the mass transfer. This includes the desorption of the analyte from the soil surface, its diffusion through the interior of the soil structure, and its transport within the bulk flow of supercritical fluid through the interstitial pores of the soil. The mass transfer can be expected to depend on both the different types of soil and the different location of the analyte in the soil structure. Thermodynamic factors, desorption and diffusion control the extraction rate of the analyte from soil. On this basis, a mathematical model based on the supercritical fluid extraction conditions (viz, temperature, pressure, fluid flow, modifier,...), which are directly linked to the status of the analyte in the soil, is developed. The elaboration of the kinetical results using our model would permit to approximate the distribution of the contaminant to a non porous- or to a deep porous-soil structure model. Supercritical fluid extraction could represent an interesting instrument for investigating the fate of pollutants in the soil structure in order to establish criteria to choose the appropriate remediation technology. The sub-program research is aimed to the specific study of management, environmental control and valorisation of municipal and industrial waste. Indeed, a growing interest in national and European policy is addressed to this issue. The most recent laws governing waste management in the context of sustainable development, have laid down precise guidelines in order of priority, namely: prevention of waste production and of hazardous waste; recovery and recycling of matter from waste; recovery of energy from waste; safe landfilling of inert waste and inert residues derived from other waste treatments. The recycling of the beverage cartons from Tetra Pak Italiana SpA (Rubiera, RE) shows an increasing interest in Italy for both an environmental point of view and the valorisation of residue with high value. Generally beverage cartons are divided in: 1) long conservation bricks constituted by carton (75%), aluminium (5%) and polyethylene (20%), and 2) short conservation brick constituted by carton (85-90%) and polyethylene (10-15%) with an annual production around 120000 tons. The high percentage of carton as well as the high quality of cellulose makes this product of great interest for the ordinary process of the paper recycling. One of the most realistic scenery could be the harvesting of these beverage cartons together with journals and reviews. The aim of these research is to get data for the development of a LCI/LCA of the complete process of recycling in the framework of the Integrated Product Policy (IPP). Our tests, performed in an Italian paper mill processing about 10 tons/hour of cellulose materials, have shown that is possible the recycling of the beverage cartons when they are diluted in the pulp paper (Type A2). No significant problem was observed in tests performed in the usual operative conditions where the presence of the beverage cartons was 2.5% in the feedstock. The paper produced was in conformity of the required regulations. About the recycling of pulp paper, our group in cooperation with Lesepidado srl (Bologna) and Olivetti Tecnost (Ivrea) has been realizing a project for the development of new inks for ink-jet technology in order to reduce the problems linked to the deinking processes into the paper mills both for the whiteness of the paper and for the disposal of the waste waters from the deinking. This project is focused on the increase of the recycling of the graphic paper that is actually estimated in 7.3% against 91% of the cartons for packaging, even if the graphic paper represents the 50% of the produced paper. Ink jet technology has rapidly diffused for office and photographic application as a consequence of the high quality printed images, so that a correct IPP is necessary in order to obtain an easier recycling of the cartridges and on the printed papers. This project is actually developed at industrial scale with the realization of two plants for the ink production located in Baraldi Lubrificanti srl (Bologna) and for the cartridge production located in Olivetti I-Jet SpA (Aosta). A particular interest of the group is the development of new integrated chemical and biological processes using enzymes and microorganisms (e.g white rot fungi) for the valorisation of agricultural and industrial waste-waters and solid residue. Different processes were studied for the production of edible biomass or for the recovery of antioxidants from the olive milling waste-waters. The basic purpose of our technical approach is to remove the phenolic compounds with a selective adsorption process and their recover with a desorption step in order to obtain on one side the dephenolization of OMWW to be used for ferti-irrigation and on the other side antioxidant biomolecular compounds. This project was developed during the works of the European Project FAIR CT 97 3039 in which the technical choose was oriented to the adsorption/desorption extraction because of logistic, technical and environmental questions. Today, an industrial plant by Tuyap (Istanbul, Turkey) is going to be working which previews the direct treatment of the olive milling waste waters for the adsorption of the biophenols on specific sorbents using a very economical process. Subsequently the sorbents, saturated with biophenols, are carried away toward a central plant for the recovery of the antioxidants and the regeneration of the sorbent material. The regenerated sorbent is then sent back to the single olive mill for a new adsorption process. The biophenols are recovered in a specific ethanolic extract having a final concentration of 10 g/l in which 40% is constituted by hydroxityrosol. This phenol was demonstrated to have a high antioxidant power both in vitro than in vivo with human tests. The plant at regime will be capable to work 30 m3/day of olive milling waste waters with a production estimated in 63 kg/day of biophenols for 100 working days per season. The products were presented at VITAFOODS 2002 (Geneve) and represent the second industrial source of biophenols from agrofood after those from grape seeds. 99 Microbial desulfurization of heavy oil and crude oil has been studied extensively in order to reduce the SOx emission during the burning of fuels. Fundamental studies are carried out on the physico-chemical limiting factors of sulfur aromatic microbial uptake in organic media. The group has also suggested a technology for immobilized cell reactors for oil biodesulfurization processes which overcomes some “bottle-necks” hindering the industrial application of the typical continuous stirred tank bioreactor. Today, our group in cooperation with Lesepidado srl (Bologna) and API Refinery (Falconara, AN) are planning a large scale plant of 0.1 m3/h for the biodesulfurization of middle-distillates with the aim to obtain a sulfur concentration under 50 ppm (upper limit at 2005). Other research fields are the Life Cycle Assessment applied to products and processes of recycling, as in wood and leather tanning industries. 6.3 Position in Networks • Intra-university co-operation The most significant intra-university co-operation have been achieved between the Departments of Industrial Chemistry and Materials, in which a group of Environmental Chemistry is operating, and of Analytical and Inorganic Chemistry. • Regional co-operation In Emilia-Romagna Region many co-operations are actuated. In particular, close collaborations exist with the Regional Environmental Protection Agency (ARPA) and its Provincial Sections (Rimini, Forlì-Cesena, Ravenna), in order to integrate technical and methodological competences in performing environmental monitoring campaigns. A collaboration with the Environmental Councillorship of Regional Government has also been accomplished, concerning the inventory of emissions from regional incinerators and comparison of the Emission Factors. Some city-owned enterprise and some private business, in particular those which deal with waste disposal, has been cooperating with our research Unit, allowing the use of their monitoring instruments and financing the environmental assessment in the vicinity of the plants. A co-operation with the University of Ferrara has also been established, in the field of the monitoring of cultural heritage degradation due to the atmospheric pollution. Particular co-operation is in progress with Lesepidado srl (Bologna) for the development of industrial project and for the mobility/formation of young researchers. • National co-operation (including INCA) The most important co-operation has been established with the National Environmental Protection Agency (ANPA), for the subject of atmospheric wet and dry depositions and calculation of Critical Loads and Exceedances. At an industrial point of view, important co-operations are with Tetra Pak Italia SpA (Reggio Emilia), Unione Conciaria SpA (Milan) and Olivetti Tecnost SpA (Ivrea) for the development of strategic industrial projects as well as with Tecnoalimenti (Milano) for the menagement of some national and European projects. The group presents also co-operations with several Universities such as: Milan, Verona and Florence, INCA represents for our Unit a useful network for the exchange of information and knowledge with other research groups dealing with environmental monitoring issue. Furthermore, we benefit from the convention with some Italian laboratory associated to INCA, to perform the collection and analysis of ultratrace contaminants (e.g., PCDD/F in soil, atmospheric deposition and atmospheric particulate). For the future, we suggest that INCA start a specific, new thematic area, which could be named “Waste: Management, Environmental Control and Valorisation”, including LCA methodologies, an Integrated Environmental Monitoring System, clean technologies for waste disposal. This issue could interest many institutions, as Italian Environmental Protection Agency (ANPA), local authorities and, at international level, in agreement with Italy, North African Countries (Maghreb), as proposed during the 5th Congress of INCA Consortium in Tunis (26-28 June 2002). • International co-operation A co-operation with the German Federal Environmental Agency has been started for the definition of a standard analytical procedure, at European level, for PBDE (polybrominated diphenyl ethers) in different environmental matrices (watercourses, landfills, contaminated industrial sites). Several co-operations with research units are in progress such as: University of Madrid, Institute of Food Research (Norwich, UK), Istituto Superior Tecnico (Lisbon, PG),… At an industrial point of view, an important co-operation is with Tuyap (Turkey) for the recovery of the biophenols from the olive milling waste waters. 6.4 Societal Relevance and Impact The environmental monitoring is assuming a ever growing importance, because of the diffusing awareness of the close link between environmental quality and human health. 100 The research of our Unit presents a great societal relevance, in particular because it is aimed to the assessment of the environmental impact from possible hazardous processes, which is an issue of increasing concern for the public opinion. A particular attention has been turned to the impacts of municipal waste management (especially incineration plants), because it is an ever growing problem in our consumer society, even if all the valid alternatives to landfilling are not sufficiently been practised or stimulated by Italian policy. The Strategies of Sustainable Development promoted since Rio ’92 focus on the improvement of prevention actions, on the increase of resource efficiencies and on the passage to more sustainable consumer models, by means of the V and the VI Environmental Action Programmes (1993-2000; 2000-2010). Aims about waste production are to reach a condition able to reintroduce the most wastes in the economic cycle, particularly through recycling, or to return them to the environment in a useful or at least not harmful form. This goal can be achieved through a targeted action, as awakening public opinion, but in particular suggesting technological solutions which answer to an economical-industrial feasibility. Waste recycling becomes then a valorisation process, and waste turns from a worthless reject to a resource. 6.5 Further Indications of Quality and Reputation Prof. Luciano Morselli is member of the Editorial Board of Annali di Chimica - Journal of Analytical and Environmental Chemistry. Dott. Leonardo Setti is the scientific responsible of TUYAP industrial plant for the recovery of antioxidants from olive mining waste waters sited in Istanbul (Turkey). He is the scientific responsible of Baraldi Lubrificanti s.r.l. industrial plant for the production of low environmental impact inks and of OLIVETTI I-JET industrial plant for the production of the ink-jet cartridges. 6.6 Key Publications S. Zappoli, A. Andracchio, L. Morselli, “Dissolved organic matter and pH affect the extraction efficiency of PCBs from aqueous samples”, Chemosphere, 35(8), 1729-1736 (1997). S. Zappoli, A. Andracchio, S. Fuzzi, M. C. Facchini, A. Gelencsér, G. Kiss, Z. Krivácsy, Á. Molnár, T. Barcza, E. Mészáros, H-C. Hansson, K. Rosman, Y. Zebühr, “Organic components and chemical mass balance of fine aerosol in different areas of Europe”, Journal of Aerosol Science, 29, S731-S732 (1998). L. Morselli, L. Setti, A. Iannuccilli, S. Maly, G. Dinelli, G. Quattroni, “Supercritical-fluid extraction for the determination of petroleum hydrocarbons in soil”, Journal of Chromatography, A, 845, 357-363 (1999). L. Morselli, M. Cecchini, E. Grandi, A. Iannuccilli, L. Barilli, P. Olivieri, “Heavy metals in atmospheric surrogate dry deposition”, Chemosphere, 38(4), 899-907 (1999). L. Morselli, M. Bartoli, B. Brusori, F. Passarini, “Application of an Integrated Environmental Monitoring System to an Incineration Plant”, The Science of the Total Environment, 289(1-3), 177-188 (2002). 7. Scientific Output 7.1 Publication Policy As it can be seen in Appendix 1, a steady production of international publication has been maintained in these 5 years, both in the thematic area of the Unit and in other research field, the management and valorisation of waste products. Although the research about innovative monitoring technologies and methodologies allowed us to obtain results more suitable to find the interest of international scientific community, the study of environmental control in waste management has been more limited to national case studies, although favourably received by international congresses (as those organised by International Solid Waste Association or those on Integrated Resources Management). However, the results coming from more applied researches, i.e. those bound to the confidential nature of industrial results, could not be published. Because of the innovation of this research area, a greater effort will be necessary to attain a better communication within national researchers and toward international scientific community. New international co-operations could result in even more interesting and appreciable solutions. 7.2 Numerical data Category PhD-Dissertations 1997 0 1998 0 1999 0 2000 0 2001 1 Total 1 Scientific Publications 8 19 19 15 30 91 101 Professional Publications Master’s Theses 8 0 0 0 0 0 0 0 0 0 0 0 0 Self-evaluation The heterogeneity of the competences of the unit personnel can be surely considered a necessity in a field like the environmental monitoring, due to the stimulating knowledge exchange, even if it implies a significant coordination effort. The good and growing results obtained since 1997 in terms of publications, funding and patents demonstrate the importance of the synergy in the unit’s group and supply good indication about the future. Because of the increasing interest of these environmental subjects and the greater concern felt by the public opinion, a number of activities has been promoted in the last years to know better the interactions between pollutants, environment and human health. Likewise, a growing interest, also by private business, is focused on the improvement of industrial process ecoefficiency. The knowledge acquired by a multidisciplinary research group in the field of environmental science, as ours, becomes necessary to meet the requirements of many public institutions or environmental agencies, who want to have a clear description of problems and possible solutions. Thus, another strength of the group consists in having achieved the competences for a qualified research and education on environmental issues. Due to the multidisciplinary nature of the unit and to the mostly applicative researches conducted, the environmental monitoring has been seen not only as an analytical exercise, but also as an instrument for the subsequent development of novel, economically and ecologically sustainable technologies. This approach can be applied in particular to the management of waste from different sources. The logical scheme can be described as follows: -) Environmental Monitoring; -) Study of the environmental impact of the most concerning industrial processes or waste streams (LCA, Integrated Product Policy); -) Investigation of new technologies for waste valorisation, to turn discards to resources. A useful contribution can be supplied by INCA Consortium, if a specific thematic area dealing with waste management, environmental monitoring and valorisation will be created. Appendix I Scientific Output I-1 Overview of Dissertations and Master's Thesis (1997-2001) I.1.1 Dissertations Year Name PhD-student Title of the Dissertation Supervisor 2001 Antonella Andracchio La componente organica macromolecolare nell'aerosol atmosferico: Isolamento, caratterizzazione dimensionale e interazione con la componente inorganica (The organic macromolecular component of atmospheric aerosol: isolation, dimensional characterisation and interaction with inorganic component) Prof. S. Zappoli I.1.2 Master's Thesis I-2 Overview of Scientific Publications (1997-2001) per year 1997 Area: ENVIRONMENTAL MONITORING M. C. Pietrogrande, C. Beneventi, F. Dondi, L. Morselli, “Environmental analysis by GC. Estimation of error in quantitative determination from multicomponent chromatograms”, Annali di Chimica, Journal of Analytical and Environmental Chemistry, 87, 753-763 (1997). L. Morselli, E. Sbaffi, “Environmental control in Municipal Solid Waste Incineration. A survey of the plants operating in the Emilia Romagna region”, Annali di Chimica, Journal of Analytical and Environmental Chemistry, 87, 721-731 (1997). 102 S. Zappoli, A. Andracchio, L. Morselli, “Dissolved organic matter and pH affect the extraction efficiency of PCBs from aqueous samples”, Chemosphere, 35(8), 1729-1736 (1997). L. Morselli (ed. by), “Progetto di Monitoraggio Ambientale della Tenuta Presidenziale di Castelporziano. Creazione di un Sistema Informativo Territoriale Ambientale Castelporziano (SITAC)”, Edizione a cura di ENEA, Unità Comunicazione e Informazione, Report 1997. Area: WASTE MANAGEMENT L. Morselli, A. Valentini, C. Galli, “Analisi delle classi merceologiche e dei flussi dei RSU nella Provincia di Rimini”, Gea, 1, gennaio-febbraio 1997. L. Morselli, A. Valentini, “Elementi di ecobilancio nella termodistruzione dei pneumatici usati”, Rifiuti Solidi, 2, marzo-aprile 1997. A. Valentini, L. Morselli, “Analisi dei flussi dei RSU in funzione delle caratteristiche merceologiche dei rifiuti e degli imballaggi”, Gea, 3, maggio-giugno 1997. L. Morselli, A. Riva (ed. by), “Siti contaminati da rifiuti. Bonifica e riuso.”, Fondazione Flaminia Ravenna, Longo Editore, Ravenna 1997. 1998 Area: ENVIRONMENTAL MONITORING L. Morselli, L. Setti, A. Iannuccilli, G. Spinozzi, G. Dinelli, G. Quattroni, “PBCs and hydrocarbons in soil matrix controlled by supercritical fluid extraction (SFE). Preliminary studies”, Annali di Chimica, Journal of Analytical and Environmental Chemistry, 88, 545-553 (1998). L. Morselli, A. Iannuccilli, L. Barilli, P. Olivieri, R. Francaviglia, R. Aromolo, V. Di Carlo, “A methodological proposal for the monitoring of atmospheric depositions and evaluation of critical loads exceedances”, Annali di Chimica, Journal of Analytical and Environmental Chemistry, 88, 645-655 (1998). V. Andrisano, H. Makamba, E. Bovina, S. Zappoli, V. Cavrini, “HPLC analysis of basic organic compounds in a multicomponent ion interaction system: a mechanistic study”, Chromatographia, 47, 493-508 (1998). D. Tonelli, S. Zappoli, B. Ballarin, “Dye-coated stationary-phases: a retention model for anions in ion-interaction chromatography”, Chromatographia, 48, 190-196 (1998). S. Zappoli, A. Andracchio, S. Fuzzi, M. C. Facchini, A. Gelencsér, G. Kiss, Z. Krivácsy, Á. Molnár, T. Barcza, E. Mészáros, H-C. Hansson, K. Rosman, Y. Zebühr, “Organic components and chemical mass balance of fine aerosol in different areas of Europe”, Journal of Aerosol Science, 29, S731-S732 (1998). L. Morselli, A. Iannuccilli, L. Barilli, P. Olivieri, “Deposizioni acide umide: flussi di deposizioni di specie chimiche in due siti di tipo rilievo appenninico e area urbana”, Inquinamento, 1 (gennaio 1998). L. Morselli (ed. by), “Progetto Di Monitoraggio Ambientale Della Tenuta Presidenziale Di Castelporziano. Creazione di un Sistema Informativo Territoriale Ambientale Castelporziano (SITAC)”, Edizione a cura di ENEA, Unità Comunicazione e Informazione, Report 1998. Area: WASTE MANAGEMENT A. Riva, L. Morselli, M. Furini, “LCA and LCI for the management of Municipal Solid Waste (MSW)”, Annali di Chimica, Journal of Analytical and Environmental Chemistry, 88, 915-924 (1998). F. Finzi, R. Laraia, L. Morselli, “Dalla strategia dei flussi prioritari dei rifiuti all’attuazione del recupero. Casi studio”, Proceedings of “RICICLA ’98”, Rimini, 16-19 October 1997, 146-157, Maggioli Ed. (1998). L. Morselli, C. Ranieri, S. Poletti, “Ricognizione sugli impianti di termodistruzione in Italia”, Proceedings of “RICICLA ’98”, Rimini, 16-19 October 1997, 293-300, Maggioli Editore (1998). L. Morselli E A. Valentini, “Dal ciclo di vita integrato per la gestione dei rifiuti al ruolo del riciclo, riuso, recupero”, Proceedings of “RICICLA ’98”, Rimini, 17-20 September 1998, 122-127, Maggioli Ed. (1998). L. Morselli, F. Grassi, “L’incenerimento dei rifiuti. Ricognizione sulla realtà regionale in Emilia Romagna. Avanzamento della Ricerca”, Proceedings of “RICICLA ’98”, Rimini, 17-20 September 1998, 153-162, Maggioli Ed. (1998). L. Morselli, A. Riva, V. Bonora, “Le ricerche applicate al riciclo dei rifiuti: indagine bibliografica”, Proceedings of “RICICLA ’98”, Rimini, 17-20 September 1998, 376-380, Maggioli Ed. (1998). L. Morselli, M. Furini, A. Riva, “Destino ambientale dei prodotti e dei rifiuti. Il caso delle lastre cinelitioradiografiche”, Proceedings of “RICICLA ’98”, Rimini, 17-20 September 1998, 411-415, Maggioli Ed. (1998). L. Morselli, F. Grassi, A. Riva, “Il recupero energetico nel sistema di incenerimento in Emilia Romagna”, 8° Convegno Nazionale Inquinamento dell'aria e tecniche di riduzione, Padova, 30 November-2 December 1998, 491-503 (1998). Area: BIOREMEDIATION AND BIOTECHNOLOGY L. Setti, S. Scali, I. Degli Angeli P. G. Pifferi, “Horseradish peroxidase-catalyzed oxidative coupling of 3-methyl 2benzothiazolinone hydrazone and methoxyphenols”, Enzyme and Microbial Technology 22, 656-661 (1998). L. Setti, S. Maly, A. Iacondini, G. Spinozzi, P. G. Pifferi Biological treatment of olive milling waste waters by Pleurotus ostreatus. Annali Chimica - J. Anal. Environ. Chem. 88, 201-210 (1998). 103 S. Frassinetti, L. Setti, A. Corti, P. Farinelli, P. Montevecchi, G. Vallini, “Biodegradation of dibenzothiophene by a nodulating isolate of Rhizobium meliloti”, Canadian Journal of Microbiology, 44, 289-297 (1998). P. G. Pifferi, G. Spagna, L. Morselli, I. Manenti, M. Bertuccioli, “Rimozione di fitofarmaci da bevande con derivati della cellulosa”, Industrie delle Bevande – XXVII, 9-13, febbraio 1998. 1999 Area: ENVIRONMENTAL MONITORING L. Morselli, M. Cecchini, E. Grandi, A. Iannuccilli, L. Barilli, P. Olivieri, “Heavy metals in atmospheric surrogate dry deposition”, Chemosphere, 38(4), 899-907 (1999). L. Morselli, L. Setti, A. Iannuccilli, S. Maly, G. Dinelli, G. Quattroni, “Supercritical-fluid extraction for the determination of petroleum hydrocarbons in soil”, Journal of Chromatography, A, 845, 357-363 (1999). B. Ballarin, R. Seeber, D. Tonelli, S. Zappoli, “High-performance size exclusion chromatography in the evaluation of molecular size distributions of humic acids fractionated by ultrafiltration”, Annali di Chimica, Journal of Analytical and Environmental Chemistry, 89, 211 (1999). L. Morselli, L. Barilli, P. Olivieri, M. Cecchini, R. Aromolo, V. Di Carlo, R. Francaviglia, L. Gataleta, “Heavy metal determination in Dry surrogate Depositions. Characterization of urban and natural site”, Annali di Chimica, Journal of Analytical and Environmental Chemistry, 89, 739-746 (1999). S. Zappoli, A. Andracchio, S. Fuzzi, M. C. Facchini, A. Gelencsér, G. Kiss, Z. Krivácsy, Á. Molnár, T. Barcza, E. Mészáros, H-C. Hansson, K. Rosman, Y. Zebühr, “Inorganic, organic and macromolecular components of fine aerosol in different areas of Europe in relation to their water solubility”, Atmospheric Environment, 33, 2733-2743 (1999). M. C. Facchini, S. Fuzzi, S. Zappoli, A. Andracchio, A. Gelencsér, Gy. Kiss, Z. Krivácsy, E. Mészáros, H-Ch. Hansson, T. Alsberg, Y. Zebühr, “Partitioning of the organic aerosol component between fog droplets and interstitial air”, Journal of Geophysical Research - Research – Atmospheres, 104, 26821-26832 (1999). G. Pastorelli, R. De Laurentis, P. De Stefanis, L. Morselli, G. Viviano, “PCDD/PCDF from municipal solid waste incinerators in Italy: an inventory of air emission”, 19th International Symposium on Halogenathed Environmental Organic Pollutantsand POPs, Vol 41, 495-498, Venice, September 12-17, 1999 (1999). L. Morselli (ed. by), “Progetto Di Monitoraggio Ambientale Della Tenuta Presidenziale Di Castelporziano. Creazione di un Sistema Informativo Territoriale Ambientale Castelporziano (SITAC)”, Edizione a cura di ENEA, Unità Comunicazione e Informazione, Report 1999. D. Tonelli, S. Zappoli, P. L. Buldini, “L’applicazione della cromatografia ionica all’analisi dei composti organici di rilevanza ambientale”. In: “La cromatografia ionica nell’analisi ambientale”; S. Cavalli, C. Sarzanini Eds.; SCI, Divisione Chimica Ambientale, Milano, 1999. Area: WASTE MANAGEMENT L. Morselli, L. Ramponi, “Sistema Integrato: l'altra versione dei rifiuti”, Energia blu. Periodico delle fonti energetiche rinnovabili. N. 5 26-32 (settembre/ottobre 1999). L. Morselli, “LCI Applied to municipal Solid Waste Incinerator. A survey of the plants operating in the Emilia Romagna Region and correlation with national statistics”, RECYCLING ’99 Congress Proceedings, I, 404 – 409 (1999). L. Morselli, A. Riva, L. Ramponi, “Il contributo della combustione nella gestione integrata dei rifiuti”, Secondo Convegno Nazionale Utilizzazione Termica Dei Rifiuti, Abano Terme, 20-21 May 1999 (1999). L. Morselli, “A European harmonization in the field of waste and a more punctual evaluation of the reality of the mediterranean area”, Proceedings of “RICICLA ’99”, Rimini, 21-24 October 1999, 12-14, Maggioli Ed. (1999). R. Cioffi, G. Genon, L. Morselli, L. Musmeci, L. Santoro, “Approccio metodologico al riciclo e recupero dei rifiuti pericolosi”, Proceedings of “RICICLA ’99”, Rimini, 21-24 October 1999, 358-363, Maggioli Ed. (1999). L. Morselli, L. Ramponi, G. Benedetti, S. Sacchetti, “Ricognizione sul sistema incenerimento in Emilia Romagna. Aspetti emergenti di ricerca e valutazione ambientale”, Proceedings of “RICICLA ’99”, Rimini, 21-24 October 1999, 388-395, Maggioli Ed. (1999). Area: BIOREMEDIATION AND BIOTECHNOLOGY L. Setti, S. Giuliani, G. Spinozzi, P. G. Pifferi, “Laccase-catalyzed oxidative coupling of 3-methyl 2-benzothiazolinone hydrazone and methoxyphenols”, Enzyme and Microbial Technology 25, 285-289 (1999). L. Setti, S. Mazzieri, P.G. Pifferi, “Enhanced degradation of heavy oil in an aqueous system by a Pseudomonas sp. in the presence of natural and synthetic sorbents”, Bioresource Technology, 67, 191-199 (1999). L. Setti, P. Farinelli, S. Di Martino, S. Frassinetti, G. Lanzarini, P.G. Pifferi, “Developments on destructive and nondestructive pathways for selective desulphurizations in oil biorefining processes”, Applied Microbiology and Biotechnology, 52, 111-117 (1999). J. Klein, D.E.A. Catcheside, R. Fakoussa, L. Gazso, W. Fritsche, M. Hofer, F. Laborda, I. Margarit, H.J. Rehm, M. Reich-Walber, W. Sand, S. Schacht, H. Schmiers, L. Setti, A. Steinbuchel, “Biological processing of fossil fuels” – Resume of the bioconversion session of ICCS’97. Applied Microbiology and Biotechnology, 52: 2, (1999). 104 2000 Area: ENVIRONMENTAL MONITORING L. Morselli, F. Passarini, E. Zamagni, B. Brusori, “Methodological approach for an integrated environmental monitoring system relative to heavy metals from an incinerator plant”, Annali di Chimica, Journal of Analytical and Environmental Chemistry, 90, 723-732 (2000). Z. Krivácsy, Gy. Kiss, B. Varga, I. Galmbos, Zs. Sarvari, A. Gelencsér, S. Fuzzi, M. C. Facchini, S. Zappoli, A. Andracchio, T. Alsberg, H-Ch. Hansson, L. Persson, “Study of humic-like substances in fog and interstitial aerosol by size-exclusion chromatography and capillary electrophoresis”, Atmospheric Environment, 34, 4273-4281 (2000). L. Morselli, “Sistema Integrato di Monitoraggio Ambientale applicato alla gestione dei rifiuti”, Inquinamento, 21, 6067 (November 2000). L. Morselli, B. Brusori, M. Cecchini, F. Passarini, P. Olivieri, “Soluble and Insoluble Fractions of Heavy Metals in Wet and Dry Atmospheric Depositions”, 7th FECS Conference on Chemistry and the Environment, Porto (Portogallo), 2730 Agosto 2000. L. Morselli, M. Cecchini, L. Barilli, P. Olivieri, L. Moretti, S. Valcher, G. Pulcini, “Deposizioni atmosferiche: applicazioni ai carichi critici di acidità ed azoto nutriente e relative eccedenze”, Proceedings of “AIR QUALITY ’98. 5° Convegno Nazionale”, Ravenna, 25-28 Ottober 1998, ARPA Emilia–Romagna (2000). L. Morselli, M. Cecchini, P. Olivieri, “Il monitoraggio delle deposizioni atmosferiche secche e umide. Controllo e calcolo dei carichi critici ed eccedenze”, In: “Il Monitoraggio Ambientale. Metodologie Analitiche – Biomonitoraggio – Monitoraggio Ecosistemi”, by N. Cardellicchio and S. Cavalli, 283-312, Nuova Poligrafica Milanese Ed., Milano (2000). Area: WASTE MANAGEMENT L. Morselli, “I rifiuti: verso un sistema integrato di gestione sostenibile”, L’ambiente. Periodico tecnico–scientifico di cultura ambientale, 5, 8-11 (settembre/ottobre 2000). L. Morselli, A. Riva, L. Ramponi, F. Passarini, “Characterisation of incinerator residues for their possible re-use”, 5th World Congress and Envirotech Trade Show, “R’2000”, June 5-9, 2000, Toronto, Ontario, Canada (2000). P. Masoni, L. Morselli, L. Ramponi, P. Azzurro, E. Maldini, F. Sacchetto, “Integrated Waste Management Life Cycle Assessment for prevention, recovery and recycling. An Italian case study: application of WisardTM to IWM in the Province of Ravenna”, ISWA World Congress 2000, July 3-9, 2000, Paris, France (2000). P. Azzurro, P. Masoni, L. Morselli, L. Ramponi, “Life Cycle Assessment applicata al sistema incenerimento: caso studio dell’inceneritore di Bologna”, Proceedings of “RICICLA 2000”, Rimini, 8-11 November 2000, 362-373, Maggioli Ed. (2000). A. Bassoni, L. Morselli, “Aspetti innovativi nel trattamento termico dei rifiuti”, Proceedings of “RICICLA 2000”, Rimini, 8-11 November 2000, 500-508, Maggioli Ed. (2000). L. Ramponi, L. Morselli, T. Coleman, P. Masoni, “Applicazione della metodologia LCA a sistemi di gestione integrata dei rifiuti in ambiti territoriali regionali e nazionali. Caso studio in Inghilterra e Galles, riferimento alla realtà italiana”, Proceedings of “RICICLA 2000”, Rimini, 8-11 November 2000, 531-543, Maggioli Ed. (2000). E. Zamagni, C. Galli, L. Morselli, F. Cappelli, “Dismo, una nuova tecnologia a basso impatto ambientale per il trattamento dei rifiuti”, Proceedings of “RICICLA 2000”, Rimini, 8-11 November 2000, 666-672, Maggioli Ed. (2000). L. Morselli, L. Ramponi, R. Cioffi, M. Marroccoli, L. Musmeci, E. Beccaloni, L. Santoro, “Approccio metodologico al riciclo e recupero dei rifiuti pericolosi”, Proceedings of “RICICLA 2000”, Rimini, 8-11 November 2000, 699-712, Maggioli Ed. (2000). G. Pastorelli, R. De Lauretis, P. De Stefanis, R. Fanelli, C. Martines, L. Morselli, L. Pistone, G. Viviano, “Italian dioxin inventory of air emissions from MSW incinerators: use of filed-based PCDD/F emission factors”, Proceedings of “SIDISA 2000 – International Symposium on Sanitary and Environmental Engineering”, Trento, 18-23 September 2000, III, 467-475 (2000). 2001 Area: ENVIRONMENTAL MONITORING L. Morselli, B. Brusori, M. Cecchini, P. Olivieri, D. Silingardi, F. Passarini, “Long term atmospheric deposition wetdry fluxes. Critical load exceedances in an urban area”, Annali di Chimica, Journal of Analytical and Environmental Chemistry, 91, 459-469 (2001). L. Setti, L. Morselli, “Supercritical-fluid extraction as a method for investigating the fate of the organic contaminants in soil”, Annali di Chimica, Journal of Analytical and Environmental Chemistry, 91, 503-515 (2001). L. Morselli, F. Passarini, S. Lorusso, F. Prestileo, L. C. Lorusso, “La qualità dell’aria nei centri storici e la tutela dei manufatti di interesse storico artistico”, Scienza e Tecnica, 367, 10-12 (Marzo 2001). L. Morselli, F. Passarini, L. Ramponi, “Il contributo delle emissioni gassose da impianti di incenerimento di rifiuti al degrado dell’atmosfera”, Proceedings of “ARIE DI CITTÀ. La qualità dell’aria in ambiente urbano. Convegno Nazionale, Bologna, 28-30 November 2000”, 593-599 (2001). 105 L. Morselli, B. Brusori, M. Cecchini, P. Olivieri, F. Passarini, “La strategia delle deposizioni atmosferiche secche e umide; la strategia dei Carichi Critici”, Proceedings of “ARIE DI CITTÀ. La qualità dell’aria in ambiente urbano. Convegno Nazionale, Bologna, 28-30 November 2000”, 623-630 (2001). L. Bettini, G. R. Gramolini, R. Maltoni, C. Nizzoli, C. Ravaioli, P. Rossini, L. Morselli, C. Regazzi, V. Rumberti, S. Tugnoli, “Studio ambientale e territoriale di un’area industriale urbana”, Proceedings of “ARIE DI CITTÀ. La qualità dell’aria in ambiente urbano. Convegno Nazionale, Bologna, 28-30 November 2000”, 461-464 (2001). L. Morselli, B. Brusori, F. Passarini, “Nuove acquisizioni sul Sistema Integrato di Monitoraggio Ambientale. Applicazione ad un Impianto di Incenerimento di RSU”, Proceedings of “Convegno Nazionale. Terzo Millennio: Il Futuro della Chimica Analitica nel Controllo Alimentare ed Ambientale”, 22-24 February 2001, Roma (2001). L. Morselli, M. Bartoli, F. Passarini, “Sistema Integrato di Monitoraggio Ambientale applicato ad un impianto di incenerimento di RSU”, Proceedings of “RICICLA 2001”, Rimini, 26-29 September 2001, 149-159, Maggioli Ed. (2001). L. Morselli, S. Lorusso, F. Paccagnella, F. Passarini, B. Brusori, L. Lorusso, “Guidelines for an environmental monitoring in urban areas to a right prevention of Cultural Heritage deterioration”, 3rd International Congress on “Science and Technology for the safeguard of Cultural Heritage in the Mediterranean Basin”, 9-14 July 2001, Alcalá de Henares, Spain (2001). L. Morselli, B. Brusori, R. Francaviglia, F. Manes, L. Lepore, S. Merolli, “The Atmospheric Monitoring To Prevent Natural Heritage Degradation”, 3rd International Congress on “Science and Technology for the safeguard of Cultural Heritage in the Mediterranean Basin”, 9-14 July 2001, Alcalá de Henares, Spain (2001). L. Morselli, F. Passarini, B. Bartoli, “Il destino dei metalli pesanti nell’ambiente da un impianto di incenerimento di rifiuti”, Proceedings of “III Congresso ed Esposizione Internazionale. Valorizzazione e Riciclaggio dei rifiuti industriali – VARIREI 2001”, 25-29 June 2001, L’Aquila, 200-204 (2001). L. Morselli, B. Brusori, R. Francaviglia, L. Gataleta, M. Marchionni, R. Aromolo, A. Benedetti, P. Olivieri, “Caratterizzazione integrata della contaminazione da metalli pesanti in matrici ambientali della Tenuta Presidenziale di Castelporziano”, In: Il sistema ambientale della Tenuta Presidenziale di Castelporziano. Accademia Nazionale delle Scienze detta dei XL, Collana “Scritti e Documenti”, Vol. XXVI, 303-314, Roma (2001). L. Morselli, L. Barilli, P. Olivieri, M. Cecchini, R. Aromolo, V. De Carlo, R. Francaviglia, L. Gataleta, “Heavy metals determination in dry surrogate depositions. Characterization of an urban and a natural site”, Il sistema ambientale della Tenuta Presidenziale di Castelporziano. Accademia Nazionale delle Scienze detta dei XL, Collana “Scritti e Documenti”, Vol. XXVI, 319-329, Roma (2001). R. Francaviglia, R. Aromolo, L. Gataleta, L. Morselli, B. Brusori, F. Passarini, A. Novo, P. Olivieri, “Monitoraggio delle deposizioni atmosferiche umide e secche presso la Tenuta Presidenziale di Castelporziano”, Il sistema ambientale della Tenuta Presidenziale di Castelporziano. Accademia Nazionale delle Scienze detta dei XL, Collana “Scritti e Documenti”, Vol. XXVI, 331-341, Roma (2001). L. Morselli, B. Brusori, M. Cecchini, P. Olivieri, R. Francaviglia, R. Aromolo, L. Gataleta, “La strategia dei carichi critici nello studio della vulnerabilità del territorio”, Il sistema ambientale della Tenuta Presidenziale di Castelporziano. Accademia Nazionale delle Scienze detta dei XL, Collana “Scritti e Documenti”, Vol. XXVI, 343-354, Roma (2001). R. Francaviglia, L. Gataleta, M. Marchionni, R. Aromolo, A. Benedetti, L. Morselli, B. Brusori, P. Olivieri, “Valutazione della vulnerabilità all’acidificazione e della degradazione microbiologica dei suoli della Tenuta Presidenziale di Castelporziano”, Il sistema ambientale della Tenuta Presidenziale di Castelporziano. Accademia Nazionale delle Scienze detta dei XL, Collana “Scritti e Documenti”, Vol. XXVI, 377-395, Roma (2001). Area: WASTE MANAGEMENT G. Pastorelli, R. De Laurentis, P. De Stefanis, R. Fanelli, C. Martines, L. Morselli, L. Pistone, G. Viviano, “Sviluppo di fattori di emissione da inceneritori di rifiuti urbani lombardi e loro applicazione all’inventario nazionale delle diossine”, Ingegneria Ambientale, 1, 32-43 (Gennaio 2001). L. Morselli, “Crescita elevata. Nuovo Paradigma europeo per creare ricchezza e competitività sulla base dei prodotti più ecologici”, Inquinamento, 367, 56-63 (Settembre 2001). L. Morselli, “Ciclo di vita. Strumento di valutazione e pianificazione nella Gestione Integrata dei Rifiuti”, Proceedings of “1° Convegno Nazionale. Rifiuti: Aspetti Innovativi”, 21 February 2001, Milano, 3-10 (2001). L. Morselli, F. Passarini, B. Brusori, “Gestione dei rifiuti e Sistema Integrato di Monitoraggio Ambientale”, Proceedings of “1° Convegno Nazionale. Rifiuti: Aspetti Innovativi”, 21 February 2001, Milano, 39-50 (2001). P. Azzurro, P. Masoni, L. Morselli, L. Ramponi, “Life Cycle Assessment applicata al sistema incenerimento mediante codice di calcolo Wisard”, Proceedings of “1° Convegno Nazionale. Rifiuti: Aspetti Innovativi”, 21 February 2001, Milano, 51-62 (2001). P. Azzurro, P. Masoni, L. Morselli, J. Luzi, “Analisi comparativa di sistemi di trattamento rifiuti attraverso la metodologia LCA (Life Cycle Assessment)”, Proceedings of “1° Convegno Nazionale. Rifiuti: Aspetti Innovativi”, 21 February 2001, Milano, 63-70 (2001). L. Setti, L. Morselli, S. Tomasin, F. Passarini, M. Bartoli, S. Giuliani, “Inchiostri per stampa ink-jet a basso impatto ambientale all’interno del ciclo di lavorazione di una cartiera”, Proceedings of “RICICLA 2001”, Rimini, 26-29 September 2001, 324-331, Maggioli Ed. (2001). 106 D. P. Serrano, J. Aguado, J. M. Escola, E. Garagorri, L. Morselli, G. Palazzi, S. De Dea, “Riciclo chimico delle plastiche residuali di uso agricolo”, Proceedings of “RICICLA 2001”, Rimini, 26-29 September 2001, 535-540, Maggioli Ed. (2001). L. Morselli, L. Setti, F. Passarini, M. Bartoli, M. Monaci, M. Mastrobuono, E. Scalia, “Riciclo di contenitori per bevande in materiale poliaccoppiato all’interno del ciclo di lavorazione di una cartiera”, Proceedings of “RICICLA 2001”, Rimini, 26-29 September 2001, 582-592, Maggioli Ed. (2001). L. Morselli, F. Passarini, M. Bartoli, E. Beccaloni, L. Musmeci, L. Santoro, R. Cioffi, “Rifiuti pericolosi, i test di eluizione. Trattamenti e stabilizzazione/solidificazione di ceneri da inceneritori. LCA applicato al sistema incenerimento per il recupero dei residui solidi”, Proceedings of “RICICLA 2001”, Rimini, 26-29 September 2001, 882-894, Maggioli Ed. (2001). L. MORSELLI, R MARASSI (ed. by), “I RIFIUTI. La chimica, il ciclo di vita, la valorizzazione, lo smaltimento, il controllo ambientale”, Franco Angeli Ed., Milano (2001). Area: BIOREMEDIATION AND BIOTECHNOLOGY P. G. Pifferi, G. Spagna, R. N. Barbagallo, L. Morselli, I. Manenti, C. Ranieri, “Use of food industry by-products for the removal of fungicides from white wine”, Ital. J. Food Sci, XIII, 173-188 (2001). S. Fedi, M. Carnevali, F. Fava , A. Andracchio, S. Zappoli, D. Zannoni, “A polychlorobiphenyl-degrading aerobic bacterial community from an actual site contaminated soil: a metabolic and genetic study”, Research in Microbiology, 152, 583-592 (2001). S. Giuliani, C. Piana, L. Setti, A. Hochkoeppler, P. G. Pifferi, G. Williamson, C. B. Faulds, “Synthesis of pentylferulate by a feruloyl esterase from Aspergillus niger using water-in-oil microemulsions”, Biotechnology Letters, 23(4), 325330 (2001). I-4 Other Scientific Output Brunetti P., Cagnazo D., Cocchi D.,Samoggia S. and Setti L., Sistema per la gestione informatica di prodotti alimentari. Italian Patent BO99A000139 Setti L., Pifferi P.G., Bordado J., Impianto per il trattamento di acque reflue, le rigenerazione di adsorbenti naturali o sintetici ed il recupero di sostanze di interesse industriale. Italian Patent BO2001/A/000419 Setti L., Giuliani S., Metodo per ottimizzare i processi industriali di rifinizione e di stampa a getto d’inchiostro sulle pelli naturali e sintetiche. Italian Patent BO2001A000464 Setti L., Giuliani S., Metodo per decorare superfici vetrose con una stampante a getto d’inchiostro. Italian Patent BO2001A000438 Setti L., Metodo per predisporre l’epidermide a ricevere decorazioni eseguite con inchiostri alimentari. Italian Patent BO2001A000633 Setti L., Giuliani S., Metodo per predisporre una superficie lignea a ricevere decorazioni eseguite con inchiostri a base d’acqua. Italian Patent BO2001A000634 Appendix 3 Journal Portfolio Analysis Name of the Unit: Research Director: Years included Name of Journal Bologna 3 Prof. Luciano Morselli 1997-2001 Number Articles Journal of Geophysical 1 Research– Atmospheres Journal of Chromatography A 1 Chromatographia 2 Journal of Aerosol Science 2 Atmospheric Environment 2 Chemosphere 2 Annali di Chimica, Journal of 11 Analytical and Environmental Chemistry Italian Journal Food Science 1 of Journal Factor 2.680 2.551 1.619 2.071 1.942 1.033 0.413 0.812 Impact Field(s) Geosciences, Interdisciplinary Chemistry, Analytical Chemistry, Analytical Environmental Science Environmental Science Environmental Science Environmental Science Food Science Technology Ranking 6/117 10/65 22/65 11/127 12/127 52/127 101/127 & 36/95 107 Research in Microbiology Applied Microbiology and Biotechnology Enzyme and Microbial Technology Canadian Journal of Microbiology Biotechnology letters 1 2 1.631 1.505 2 1.411 1 1.105 1 0.967 Bioresource technology 1 0.700 Microbiology Biotechnology Microbiology Biotechnology Microbiology Biotechnology Microbiology Biotechnology Microbiology Biotechnology Microbiology 37/83 & Applied 46/134 & Applied 50/134 & Applied 61/134 & Applied 68/134 & Applied 86/134 Comments on: This evaluation method can be the most appropriate in order to assess the quality of a research which is devoted only to a scientific diffusion. It is less suitable for the assessment of more applied researches, which deal with specific problems or which are bound to the confidential nature of industrial results. Even if our group is strongly occupied in applied researches, most international publications are in journals ranked in the first half of the respective fields. 108 BOLOGNA 4 Name of the Research Unit Bologna 4 Research Leader Prof. Aldo Roda University: Università degli Studi di Bologna University of Bologna, Italy Contact Person Prof. Aldo Roda Dipartimento di Scienze Farmaceutiche Via Belmeloro 6 40126 Bologna Tel e fax: +39 051 343398 e-mail: [email protected] Faculty: Facoltà di Farmacia Faculty of Pharmacy Department: Dipartimento di Scienze Farmaceutiche Department of Pharmaceutical Sciences Thematic area • 1 Chimica degli ecosistemi (chimica del suolo, delle acque e dell’aria; impatto dei prootti di sintesi sull’ambiente). • 2 Tecnologie innovative di monitoraggio. Introduction and Context Introduction to the Self-evaluation Report The Research Unit has 9 components with different background culture: chemistry, biology, pharmacy, and biotechnology. Moreover, it is a tradition of the Research Unit to collaborate with various private companies (in the pharmaceutical and alimentary fields), public institutions (other Universities, local administrations, or research institutions) and researchers belonging to other fields (medicine, veterinary, etc). This produces a stimulating environment and leads to very productive interaction of different cultural inputs and interests. As a consequence, the research topics of the Unit are various and not all of them concern the INCA research area. However, we chose to report all the research activity of the Unit in this Self-evaluation Report, particularly stressing the topics relevant for the INCA activity. The University, the Faculty and the Department The University of Bologna is the oldest in the western world: 1088 may be accepted as conventional date to indicate when teaching became free and independent of the ecclesiastic schools. Bologna University is one of the largest universities in Italy and in Europe. It is a state university and it is autonomous with its own "statuto" which indicates how the University governs itself through its various elected bodies. The University government and the main research and teaching activity are located in Bologna, but many new research and teaching activities have been recently dislocated in other Cities of the Emilia Romagna region, such as Cesena, Faenza, Forli’, Ravenna and Rimini. The whole University currently counts about 900 professors, 1,000 associated professors, 1,050 researchers and more than 100,000 students. It is divided in 19 Faculties, 65 Departments, 5 Federated Departments (“Unità Complesse”), 3 Institutes and it currently offers about 65 “laurea” degree courses and 45 “diploma” degree courses in the following subject areas: a)Agriculture; b) Economics; c) Education and Humanities; d) Engineering; e) Industrial Chemistry, f)Law; g) Literature and Philosophy; h) Mathematical, Physical and Natural Sciences; i) Medicine; l) Pharmacy; m) Political Science; n) School of Modern Languages for Interprets and Translators; o) Statistical Sciences; p) Veterinary Medicine; q) Foreign Languages and Literatures. The Faculty of Pharmacy, to which the Research Unit belongs, has a total of about 100 teachers (among Full professors, Associate professors and “ricercatori”) and more than 2,000 students. The Unit At the moment (July 2002) the Research Unit has 9 components: one full professor who is the Research Leader, one associate professor, two “ricercatori”, one technician, one Post-Doc, two PhD students, and one “borsista”; in addition six Bachelor students are doing research in the context of the Research Unit as part of their thesis. 109 Out of the components of the research Unit, four (one full professor, one associate professor and two “ricercatori”) have a consistent teaching load. In particular, the Research Unit is responsible for a total of seven courses, as follows: Analytical Chemistry, Environmental Chemistry, Laboratory of Instrumental Analytical Chemistry, Clinical Analytical Chemistry (for the Master Degree in Pharmaceutical Chemistry and Technology), Analytical Chemistry, Laboratory of Analytical Chemistry (for the Master Degree in Biotechnology), Analytical Chemistry (for the Bachelor Degree in Botanic Techniques). The Department of Pharmaceutical Sciences administers the funding of the Research Unit. Since the beginning of the ’90, the research activity of the Unit deals with the development of analytical and bioanalytical methods (including chromatography coupled with mass spectrometry, immunoassays, biosensors, enzyme assays, in situ hybridization, immunohistochemistry) applied to the clinical, pharmaceutical, environmental and food analysis fields. Programme Description and Evaluation 1 Title Ultrasensitive analytical and bioanalytical methods for the detection of pollutants in environmental matrices 2 Research Leader Prof. Aldo Roda 2a Sub-programme titles and sub-programme leaders 3 Composition of the scientific research staff of the unit per 1 January 2002 Names and Titles Year of Rank Birth Aldo Roda Massimo Guardigli Mario Baraldini Patrizia Pasini Patrizia Simoni Mara Mirasoli Laura Sabatini Elisa Michelini Barbara Marcaccio Total research input 1949 1964 1948 1963 1957 1971 1971 1978 1972 Full professor Associate professor Ricercatore Ricercatore Technician Post-Doc PhD-student PhD-student Borsista Research Remarks Input in fte in 2001 0.2 0.4 Part of the Unit since 1998 0.6 0.6 0.6 0.8 0.8 Part of the Unit since 1998 0.8 Part of the Unit since 2000 0.8 Part of the Unit since 2001 5.6 Comments Since 1997 four components of the staff joined the Research Unit: one associate professor, two PhD students and one “borsista”. No major changes in the composition of the research group’s staff are expected during the next 5 years. 4 Input of Academic Staff in fte Category Full Professors Associated Professors Ricercatori Post-docs PhD-students Borsisti Total Comments 1997 0.2 1998 0.2 1999 0.2 2000 0.2 0.6 1.2 0.8 0.8 2.4 1.6 1.6 4.6 1.8 0.8 1.6 0.8 5.2 1.8 0.8 2.4 0.8 6.0 2001 0.2 0.4 1.2 0.8 2.4 0.8 5.8 Total 1.0 0.4 6.6 2.4 8.8 4.8 23.2 110 In the period under scrutiny, four components joined the Research Unit, moreover various components changed their academic rank, thus causing variations in the total ftes dedicated to research. However, the trend of the Research Unit is an increase of the total ftes dedicated to research, also thanks to young people joining as PhD students and “borsisti”. 5 Funding 5.1 Personnel (in fte) Source University CNR European Union Other Sponsors Total 5.2 1998 4.6 1999 5.2 2000 6.0 2001 5.8 Total 23.2 0.6 3.0 0.6 6.2 0.6 5.8 0.6 6.6 0.6 6.4 3.0 26.2 Total 488 40 5 370 903 Materials and Equipment (in Million Lire) Source University - MURST CNR EU Other Sponsors Total 5.3 1997 2.4 1997 28 30 1998 60 5 1999 140 5 2000 145 2001 115 30 88 55 120 55 200 115 260 5 115 235 Comments: * On the figures A rough estimation of the figures is reported. Please add a list of major sponsors and the character of the liaison with the major sponsors The major sponsors are pharmaceutical companies (e.g. Giuliani) or public institutions (e.g. Istituto Zooprofilattico Sperimentale dell’Abruzzo e del Molise). In the context of these collaboration projects, the Research Unit has the task to undertake both basic science research (in order to explore innovative analytical techniques and develop new methods), and applied research (in order to study a particular analytical problems in the clinical, environmental, pharmaceutical and food quality fields). 6. Progress Report 6.1 Mission Statement In the context of INCA activity, the research of this Research Unit deals with the development and optimization of the following analytical and bio-analytical methods: 1.Colorimetric and chemiluminescent immunoassays for the quantitative analysis of pollutants in environmental samples. Application to real samples and screening activity. 2.Luminescent whole-cell biosensors, based on engineered microorganisms (bacteria and yeasts) and mammalian cells. The cells are engineered in order to be able to produce a measurable protein (reporter protein) in response to the presence of a particular analyte or class of analytes. 3.Chemiluminescent enzymatic tests for the detection of pollutants (e.g. pesticides). 4.Chromatographic methods, coupled with mass spectrometry for the quantitative analysis of contaminants, drug residues, and pollutants in environmental and alimentary matrices. Moreover, the Research Unit is involved in the following fields: development of ultrasensitive bio- and chemiluminescent methods based on the use of immobilized enzymes for several analytes, including bile acids, ethanol, aminoacids, lactate, oxalate, antioxidants; study of drug activity and bioavailability in vitro and in vivo; ultrasensitive chemiluminescence imaging for quantitative localization of analytes in tissue and single cells using immunocytochemistry and in situ hybridization technology: applications in biochemistry, immunology and drug screening; development of immunological methods for drugs and molecules of clinical and pharmacological interest; development of innovative clinical tests (e.g. homogeneous immunoassays, multi-analyte methods, breath tests); 111 development of chromatographic methods including HPLC-mass spectrometry with electrospray interface, C13/C12 isotope ratio mass spectrometry. In the context of INCA, the Research Unit has the goal to develop and optimize ultrasensitive and rapid analytical methods that can be easily automated and applied to the screening of environmental samples. The Unit deals prevalently with basic research in the context of the international scientific community. However, the Unit deals also with practical and applicative aspects, by means of consultancy activity and collaborations with private industries and local and national public institutions. 6.2 The Research Programme • Design of the programme (scientific problem formulation, objectives, subject matter, research methods and anticipated results; The Research Unit will select, among the analytes of environmental interest, those for which rapid and ultrasensitive screening methods are needed and not available at the moment. In this context, the nature and composition of the environmental matrices of interest will be studied, with particular attention to the presence of molecules able to interfere with the quantification of the analyte. The most suitable analytical or bio-analytical method will be chosen, by taking into account the characteristics of the analyte and of the matrices, but also practical aspects, like the possibility of automation, field application. If needed, suitable pre-analytical methods will be developed and optimized. The analytical method will be developed and optimized in terms of analytical performances (sensititity, accuracy, precision, robustness, and rapidity). • A substantive overview of the most impressive results over the past five years In the context of environmental analysis, the research activity of the Unit deals with the development of analytical methods for the detection of pollutants in environmental matrices, in particular freshwater, sea water and wastewater. The developed methods belong to three main classes: (a) ultrasensitive colorimetric or chemiluminescent immunoassays; (b) luminescent whole-cell biosensors based on engineered microorganisms or mammalian cells; (c) separative techniques coupled with mass spectrometry. In particular, the following methods were developed and optimized: 1.A colorimetric immunoassay for the determination of polycyclic aromatic hydrocarbons, that was applied to the analysis of smoked meat samples. 2.A bacterial luminescent biosensor for mercury, based on the use of genetically engineered E. coli cells that express the reporter protein firefly luciferase in the presence of mercury. The method was optimized for the analysis of urine matrices and applied to the screening of urine samples collected from subjects exposed to mercury. The optimized method was found to be highly sensitive (4.0x10-18 mol/tube), selective accurate and precise and the matrix effect was found to be low. This analytical performance suggests that the biosensor can be successfully applied in the future to the analysis of environmental samples, e.g. water samples. 3.A whole-cell biosensor for endocrine disrupting compounds (EDCs), based on the use of genetically engineered yeast cells (S. cerevisiae) that express the reporter protein ?-galactosidase?in the presence of compounds able to bind and activate the human estrogen receptor (hER). The use of chemiluminescent substrate for ?-galactosidase activity allowed reaching a limit of detection of 10 pmoli/L for 17?-estradiol with a reduced incubation time (24 h), with respect to the incubation time (72 h) required when a colorimetric detection is used. The biosensor was applied to the analysis of environmental samples (i.e. wastewater samples collected for influents and effluents of urban activated sludge sewage treatment plants). In inlet samples some endocrine activity was detected (average 50 ng/L of 17?-estradiol equivalents), while no endocrine activity was detected in outlet samples. 4.A bioluminescent whole-cell biosensor for polyhalogenated aromatic hydrocarbons (like dioxins, furans, and polychlorurated biphenils), based on the use of genetically engineered mammalian cells (mouse hepatoma cell line) that express the reporter protein firefly luciferase?in the presence of compounds able to bind and activate the aromatic hydrocarbons receptor (AhR). The biosensor, which showed a limit of detection of 1 pmol/L for dioxin, was optimized for the analysis of milk samples. However, thanks to its analytical performances, it can be successfully applied in the future to the analysis of environmental samples, e.g. water samples, after a suitable pre-analytical extraction step. 5.Application of microscopy techniques (optical, electronical, laser confocal, and differential scanning calorimetry) for investigating the localization and the modifications induced by butyl benzyl phtalate (BBP) and di-butyl phtalate (DBP) in cell lines and in the gastrointestinal tract of various animal species. 6.An analytical method for the quantification of methyl tert-butyl ether (MTBE) in water samples, based on solid phase micro extraction (SPME) of the analyte and the quantification by means of gaschromatography coupled with mass spectrometry. The method was applied to the determination of MTBE in surface and deep water samples. 112 • A short overview of the programme development in the future (the coming 5 years) including the means needed for realising the programme's mission. In the future, the research activity of the Unit will pursue the same objective: the development of ultrasensitive analytical and bioanalytical methods suitable for environmental screening. In addition, innovative concepts will be explored: new labelling strategies will be developed, based on the use of lanthanide chelates (for time-resolved fluorescence detection) or fluorescent compounds (for fluorescence polarization detection). This will allow the development of highly sensitive multi-analyte, or homogeneous immunoassays, respectively. Moreover, the expertise in luminescence imaging of the Unit will be exploited to study the localization of pollutants of interest in tissues and cells and to study their effect in exposed marine organisms. 6.3 Position in Networks • Intra-university co-operation CIRB, Centro Interdipartimentale Ricerche Biotecnologiche (Inter-department Center for Biotechnology Research) CRBA, Centro per le Ricerche Biomediche Applicate (Center for Applied Biomedical Research) The collaboration with these structures is very important for the activity of the Research Unit concerning the development of whole-cell biosensors for environmental screening. In fact, since this is a rather new field of research for the Unit, most of the instrumentation is made available thanks to these collaborations and, in addition, exchange of information and ideas with long-term experienced researchers in biotechnological, medical, biological, biochemical, and microbiological fields is possible. Moreover, the new mass spectrometry instrumentation (MALDI-TOF and nanoHPLC coupled with Q-TOF) was purchased in the context of these collaborations. • Regional co-operation • National co-operation (including INCA) Consorzio INCA The collaboration with other Research Units belonging to INCA is important for various reasons. One of them is the possibility to find representative environmental samples, necessary for the validation of the developed analytical methods. Moreover, it is crucial for defining the most interesting environment-related research topics to be explored. In the future, the expectations of our Research Unit concerning the function and role of INCA is mainly the possibility to interact with the other Research Units, in order to find new projects that can involve the activity of various Units and establish new collaboration relationships. In particular, we expect that our innovative analytical methods for environmental screening will be useful for assessing environmental impact of synthesis procedures, waste management, etc. “Istituto Zooprofilattico Sperimentale dell’Abruzzo e del Molise”, Teramo This long-term collaboration is important for the development of immunoassays. Various immunoassays for food analysis were developed in collaboration with this structure; furthermore, the “Istituto Zooprofilattico Sperimentale dell’Abruzzo e del Molise” supplies our Research Unit with the specific polyclonal antibodies for molecules of environmental interest, when these are not commercially available. • International co-operation 1.“Galileo” Project– University of Strasbourg (France) This collaboration is important for the development of analytical methods based on time-resolved fluorescence measurements, since the synthesis of appropriate chelates for lanthanide ions is performed in collaboration with this University. 2.INTAS – Biochemical Department, Wageningen Agricultural University (The Netherlands); Institute of Biophysics, SB RAS (Russia); Departmentof Enzymology, Moscow State University (Russia) 3.British Council/CRUI – University of Leeds 4. 5.Department of Analytical Chemistry, University of Kentucky, Lexington, KY, USA 6.Department of Biotechnology, University of Turku, Turku, Finland In particular, the collaborations with the Department of Analytical Chemistry, University of Kentucky and with the Department of Biotechnology, University of Turku are important for the development of luminescent whole-cell biosensors. In fact, since this is a rather new research topic for the Unit, few components of the Unit had the 113 opportunity to work in those laboratories for the time necessary to acquire experience in the field of genetical engineering. 6.4 Societal Relevance and Impact The research of the Unit will make available highly sensitive analytical methods suitable for rapid analysis of a large number of samples. This will allow performing screening studies on the environmental distribution and persistence of pollutants of interest, thus to assess the potential risk for humans and environment and consequently to establish suitable intervention strategies. In addition, the developed methods will be useful for assessing the environmental impact of new synthesis methods or waste management systems. 6.5 Further Indications of Quality and Reputation Prof. Aldo Roda is: 1.IUPAC Delegate for Italy: Clinical Chemistry Division 2.Member of the following scientific societies: 2.3Italian Society of Clinical Chemistry and Molecular Biology (SIBIOC) 2.4Italian Society of Chemistry (SCI) :Analytical Chemistry Division. 2.5Italian Association for the Liver Studies (Associazione Italiana per lo Studio del Fegato, AISF) 2.6Italian Society of Gastroenterology (Società Italiana di Gatroenterologia, SIGE) 2.7European Association for Clinical Investigation 2.8American Association of Clinical Chemistry 3.Member of the Advisory Board of the Biliary Club. 4.President (2000-2002) and Past President (2002-2004) of the International Society for Bioluminescence and Chemiluminescence (ISBC) 4.3In 1998 he organized the 10th International Symposium on Bioluminescence and Chemiluminescence. 5.European Editor of Luminescence, John Wiley and Sons eds. 6.Member of the Editorial Board of Analytical and Bioanalytical Chemistry (merger of Fresenius’ Journal of Analytical Chemistry and Analusis) 6.6 Key Publications Roda A., Simoni P., Ferri E.N., Girotti S., Ius A., Rauch P., Poplstein M., Pospisil M., Pipek P., Hochel I., Fukal L.: Determination of PAHs in various smoked meat products and different samples by enzyme immunoassay. J. Sci. Food. Agric., 79, 58-62, 1999. Sabbieti M.G., Marchetti L., Curini R., Menghi G., Roda A., Russo M.V., Nugnes C., Materazzi S.: Evidence of butyl benzyl phtalate induced modifications in a model system developed in vitro. Analusis, 28, 843-846, 2000. Roda A., Pasini P., Mirasoli M., Guardigli M., Russo C., Musiani M., Baraldini M.: Sensitive determination of urinary mercury(II) by a bioluminescent transgenic bacteria-based biosensor. Anal. Lett., 34(1), 29-41, 2001. Piazza F., Barbieri A., Violante F., Roda A.: A rapid and sensitive method for methyl tert-butyl ether analysis in water samples by use of solid phase microextraction and gas chromatography-mass spectrometry. Chemosphere, 44, 539-544, 2001. Pasini P., Gentilomi G., Guardigli M., Baraldini M., Musiani M., Roda A.: A chemiluminescent whole cell biosensor for assessing estrogenic activity. In: “Bioluminescence and Chemiluminescence 2000”, J.F. Case, P.J. Herring, B.H. Robison, S.H.D. Haddock, L.J. Kricka, P.E. Stanley, eds., World Scientific Publishing Company, Singapore, 327-330, 2001. 7. Scientific Output 7.1 Publication Policy Since, as stated above, the components of the Research Unit have different background culture (chemistry, biology, pharmacy, and biotechnology) the research activity spans to various fields. In particular, the activity mainly concerns the development of analytical and bioanalytical methods to be applied in various fields: environmental screening, toxicology, medicine, veterinary, etc. This is reflected to the publication fields of the Unit. The Unit's publication policy pursues the following goals: 114 1.publication of relevant scientific results on journals of national and international relevance in the analytical and bioanalytical chemistry and medicine fields, with particular interest to applications in environmental, diagnostic, pharmaceutical, and toxicological analysis. 2.presentation of the most relevant results at national and international Conferences in the fields of analytical and bioanalytical chemistry, bio- and chemiluminescence. 7.2 Numerical data Category PhD-Dissertations Scientific Publications Professional Publications Master’s Theses 8 1997 17 1998 1 17 7 4 1999 15 2000 2 10 2001 10 Total 3 69 4 6 5 26 Self-evaluation The coordinator of the Research Unit, Prof. Aldo Roda, is a member of the Faculty of Pharmacy and Biotechnology of the University of Bologna, where he is professor of Analytical Chemistry. The components of Research Unit have different background culture: chemistry, biology, pharmacy, and biotechnology. This is one of the main strength point of the Unit, that is able to join expertise in various fields related to analytical and bioanalytical chemistry, medicine and environmental studies. The group of Prof. Aldo Roda published more than 70 articles since 1997 in International Journals and book chapters (monograph) related to bio- and chemiluminescence, immunoassays, biosensors and chromatographic methods. One of the main strength points is the fact that the components of the Research Unit have different background culture (chemistry, biology, pharmacy, and biotechnology), thus the research activity spans to various fields. In particular, the activity mainly concerns the development of analytical and bioanalytical methods to be applied in various fields: environmental screening, toxicology, medicine, veterinary, etc. This Moreover, it is a tradition of the Research Unit to collaborate with various private companies (in the pharmaceutical and alimentary fields), public institutions (other Universities, local administrations, or research institutions) and researchers belonging to other fields (medicine, veterinary, etc). produces a very stimulating environment that further and leads to very productive interaction of different cultural inputs and interests. The laboratory is equipped with modern analytical instrumentation, including mass spectrometers and a series of instruments for chemiluminescence studies — including highly sensitive imaging devices, also connected to microscopes for microsamples analysis— and bio- and chemiluminescence immunoassays. In this context, it is important to note that the field of mass spectrometry analysis (also coupled to chromatography) has been recently powered thanks to the acquisition of new high-tech and modern instrumentation: a MALDI-TOF (matrix assisted laser desorption ionization - time of flight) spectrometer and a Q-TOF (quadrupole - time of flight) spectrometer coupled to nano-HPLC have been recently acquired, in the context of intra-university collaborations with CRBA and CIRB. As a consequence, one weakness of the Research Unit was the need of highly trained personnel in this field, and therefore the Unit acquired the collaboration of a long-term experienced expert in mass spectrometry techniques. For what concerns environmental analysis, one main weakness of the Unit is the difficulty in obtaining a large number of environmental samples, necessary for the validation of the developed analytical methods. With this respect, the collaboration with other research groups (also belonging to INCA) is crucial for finding a representative number of samples. Furthermore, it is worth noting that few research groups in Italy develop immunoassays for environmental screening purposes, thus our Research Unit fills an unmet need for rapid and low-cost screening methods to be applied in this field. However, since reagents (immunogens, antibodies, and enzymatic labels) necessary for the development of immunoassays are seldom commercially available for analytes of environmental interest, the Research Unit needs to produce them in-house. One weakness of the Research Unit in this context is the lack of total independence. In fact, while the Unit has the expertise and instrumentation necessary for the synthesis of enzymatic labels and immunogens, it does not have the facilities necessary for antibodies production. However, the Unit collaborates with the “Istituto Zooprofilattico Sperimentale dell’Abruzzo e del Molise” where antibodies are produced using the immunogens synthesized by the Unit. The Research Unit develops analytical methods based on the use of luminescent whole-cell biosensors. This requires engineering microorganisms or mammalian cells in order to insert reporter genes. Since this is a rather recently 115 undertaken research topic for the Unit, one of its weakness is the partial lack of components with specific background and of necessary instrumentation. In order to improve the quality of the Unit in this field, new personnel with biotechnology background was enrolled and, in addition few components had the opportunity to work in the Department of Analytical Chemistry of the University of Kentucky and in the Department of Biotechnology of the University of Turku for the time necessary to acquire experience in the field of genetical engineering. In addition, thanks to the collaboration relationship with CRBA and CIRB, the Unit has access to high-tech and updated instrumentation for genetical engineering. Appendix I Scientific Output I-1 Overview of Dissertations and Master's Thesis (1997-2001) Dissertations and Master’s Theses marked with a star deal with subjects particularly related to INCA activity. I.1.1 Dissertations Year Name PhD-student Title of the Dissertation Supervisor 1998 F. Piazza, Sviluppo di metodi immunoenzimatici ultrasensibili per la determinazione quantitativa e rapida di βagonisti in matrici biologiche (Development of ultrasensitive immunoenzymatic methods for the quantification of βagonists in biological samples) (A. Roda) 2000 M. Mirasoli, Sviluppo di metodi bio- e chemiluminescenti per l’analisi quantitativa e l’identificazione di residui di farmaci, fitofarmaci ed additivi alimentari in matrici biologiche (Development of bio- and chemiluminescent methods for the identification and quantification of drugs, alimentary additives in biological matrices) (A. Roda) 2000 K. Afandi, Sviluppo e messa a punto di metodi bioanalitici immunologici quantitativi per l’analisi e controllo di residui di farmaci in matrici alimentari (Development and optimization of immunoassays for the analysis and control of drug residues in food samples) (A. Roda) I.1.2 Master's Thesis Year Name Master’s student Title of the Dissertation Supervisor 1997 M. Di Falco, Valutazione delle proprietà antiossidanti di acidi biliari in soluzione micellare mediente un metodo chemiluminescente (A. Roda) 1997 M. Mirasoli, Isolamento, attività antiossidante in vivo e metabolismo dell’oleuropeina da Olea europaea L. (A. Roda) 1997 E. Di Matteo, Messa a punto di una metodica analitica ultrasensibile per la determinazione dell’ureasi nella mucosa gastrica (A. Roda) 1997 M. Malaguti, Prestazioni analitiche della tecnica HPLC-elettrospray-spettrometria di massa per l’analisi ed identificazione di composti biologicamente attivi (A. Roda) 1997 C. Boldrini, Sviluppo di un metodo chemiluminescente per la rivelazione e localizzazione di radicali liberi dell’ossigeno in fegato di ratto isolato e perfuso (A. Roda) 1997 M. Lotierzo, Distribuzione spaziale dell’acetilcolinesterasi immobilizzata in sistemi modello mediante microscopia ottica-chemiluminescenza: screening ad alta produttività di vari inibitori 1997 M. Rinaldi, Metodologie analitiche per lo studio del metabolismo degli acidi biliari nell’uomo (A. Roda) 1998 C. Russo, Sviluppo di modelli in vitro ed in vivo per la epatotossicità degli acidi biliari (A. Roda) * 1998 A. Ferrante, Messa a punto di un immunosensore luminescente per la determinazione rapida ed ultrasensibile del benzo[a]pirene in matrici ambientali (Development of a luminescent immunosensor for the rapid and highly sensitive detection of benzo[a]pyrene in environmental samples) (A. Roda) 1998 B. Cicero, Sviluppo di una nuova via di somministrazione dell’UDCA – Studio chimico analitico tossicologico nel cane mediante metodo immunoenzimatico (A. Roda) 116 1998 M. Di Annunzio, Determinazione immunoenzimatica degli anticorpi anti-HCV sierici: studio epidemiologico di prevalenza e di incidenza su una popolazione campione di 1600 soggetti (A. Roda) * 1999 L. N. Cambareri, Determinazione ultrasensibile di mercurio (II) mediante biosensore basato su batteri transgenici luminescenti (Highly sensitive determination of mercury(II) by a bioluminescent transgenic bacteria-based biosensor )(A. Roda) 1999 L. Mudrea, Determinazione immunoenzimatica chemiluminescente del clenbuterolo in matrici biologiche (A. Roda) 1999 D. Longobardo, Identificazione di acidi biliari solfati mediante HPLC elettrospray-spettrometria di massa (A. Roda) 1999 V. Ruvolo, L’impiego della gas cromatografia-spettrometria di massa nella determinazione di cocaina, oppiacei e loro metaboliti nei capelli (A. Roda) * 2000 M. Targa, Sviluppo di un biosensore chemiluminescente basato su cellule di lievito transgeniche per il monitoraggio ambientale di modulatori endocrini (Development of a chemiluminescent yeast-based whole cell biosensor for assessing estrogenic activity in environmental samples) (A. Roda) *2000 M. Pisani Sviluppo di un metodo di analisi d’immagine in bioluminescenza per la determinazione della distribuzione spaziale di ATP come bioindicatore di attività microbica nella conservazione e recupero di beni culturali (Development of a bioluminescenlt low-light imaging techniques for the assessment of ATP spatial distribution, as biomarker of microbial activity: application in the protection and recovery of cultural heritages) (A. Roda) * 2000 A. Fiumana, Determinazione immunoenzimatica simultanea del Benzo[a]pirene atmosferico e dell’Idrossipirene urinario come markers di esposizione-effetto a idrocarburi policiclici aromatici (Immunoenzymatic simultaneous detection of atmospheric benzo[a]pyrene and urinary 1-hydroxypyrene as markers of exposition-effect relationship to aromatic polycyclic hydrocarbons) (A. Roda) * 2000 L. Mazzini, Messa a punto di un microscopio ad alta sensibilità per analisi dell’immagine mediante luminescenza: caratteristiche analitiche utilizzando fluorescenza risolta nel tempo e chemiluminescenza (Development and optimization of a highly sensitive microscope for imaging analysis by means of time-resolved fluorescence and chemiluminescence) (A. Roda ) * 2000 M. Malaguti, Sviluppo e covalida di un metodo per la determinazione del carbonio organico totale mediante tecnica di permeazione e misure di conducibilità (Development and validation of a method for quantification of total organic carbon by means of XXX and conductivity measurements) (A. Roda) 2000 R. Ruscelli, Determinazione dell’attività di inibitori della cicloossigenasi mediante un metodo chemiluminescente ad alta produttività (HTS) (A. Roda) 2001 L. Cremonini, Significato fisiopatologico del contenuto di nitriti e nitrati nella bile umana (A. Roda) * 2001 E. Michelini, Sviluppo di un biosensore batterico fluorescente mediante tecniche di ingegneria genetica utilizzando forme mutanti della Green Fluorescent Protein (Development of a fluorescent bacterial biosensor, by means of genetical engineering techniques, using two mutants of the Green Fluorescent Protein (A. Roda) * 2001 C. Ricciardelli, Determinazione di estrogeni in campioni di acque reflue prime e dopo trattamento di depurazione (Estrogens quantification in samples collected from influents and effluents of sewage treatment plants) (A. Roda) 2001 B. Marcaccio, Determinazione del 7aidrossi-4colesten-3one nel siero umano mediante HPLC-ES-Spettrometria di massa quale biomarker della sintesi di acidi biliari * 2001 P. Colizzi, Monitoraggio ambientale di idrocarburi aromatici polialogenati mediante un biosensore luminescente recettoriale che utilizza cellule ricombinanti di epatoma di topo (Environmental monitoring for polyalogenated aromatic hydrocarbons by means of a receptor-based bioluminescent whole-cell biosensor using a genetically engineered mouse hepatoma cell line) (A. Roda) I-2 Overview of Scientific Publications (1997-2001) per year Scientific Publications marked with a star deal with subjects particularly related to INCA activity. 1997 Gatti R., Roda A., Cerrè C., Bonazzi D., Cavrini V.: HPLC-fluorescence determination of individual free and conjugated bile acids in human serum. Biomed. Chromatogr., 11, 11-15, 1997. 117 Musiani M., Zerbini M., Venturoli S., Gentilomi G., Gallinella G., Manaresi E., La Placa M., D’Antuono A., Roda A., Pasini P.: Sensitive chemiluminescence in situ hybridization for the detection of human papillomavirus genomes in biopsy specimens. J. Histochem. Cytochem., 45 (5), 729-735, 1997. Feroci G., Fini A., Fazio G., Roda A., Zuman P.: Reactions of small aggregates of taurine conjugates of dihydroxy bile salts with divalent transition metal ions. Microchemical Journal, 55, 382-391, 1997. Rauch P., Ferri E.N., Girotti S., Rauchova H., Carrea G., Bovara R., Fini F., Roda A.: A chemiluminescent flow sensing device for determination of choline and phospholipase D activity in biological samples. Anal. Biochem., 245, 133-140, 1997. Klein P.D., Logan R.P., Amarri S., Andriulli A., Iaquinto G., Luzza F., Pajares Garcia J.M., Pazzi P., Perri F., Pozzato P., Roda A., Vaira D., Zagari R.M.: Update on Helicobacter pylori research. Diagnosis. Eur. J. Gastroenterol. Hepatol., 9, 617-618, 1997. Lucisano E., Solazzo M., Roda A., Zanarini D., Cristino R., Tonini V., Cervellera M.: Emergency surgery in colorectal cancer. J. Chemother., 9, 142-143, 1997. * Roda A., Pasini P., Musiani M., Robert C., Baraldini M., Carrea G.: Chemiluminescence imaging as a bioanalytical tool. In: Bioluminescence and Chemiluminescence: Molecular Reporting with Photons, 307-310, J.W. Hastings, L.J. Kricka and P.E. Stanley Editors, Wiley and Sons, Chichester, UK, 1997. Roda A., Pasini P., Russo C., Baraldini M., Feroci G., Kricka L.J., Gioacchini A.M.: Evaluation of bile acids antioxidant activity using enhanced chemiluminescent assay. In: Bioluminescence and Chemiluminescence: Molecular Reporting with Photons, 361-364, J.W. Hastings, L.J. Kricka and P.E. Stanley Editors, Wiley and Sons, Chichester, UK, 1997. Pasini P., Musiani M., Roda A., Zerbini M., Gentilomi G., Baraldini M., Gallinella G., Venturoli S: Chemiluminescence in situ hybridization for the detection of viral genomes. In: Bioluminescence and Chemiluminescence: Molecular Reporting with Photons, 509-512, J.W. Hastings, L.J. Kricka and P.E. Stanley Editors, Wiley and Sons, Chichester, UK, 1997. Pasini P., Gasbarrini A., De Notariis S., Nardo B., Bernardi M., Roda A.: Oxygen free radical detection in isolated and perfused rat liver by chemiluminescence imaging. In: Bioluminescence and Chemiluminescence: Molecular Reporting with Photons, 505-508, J.W. Hastings, L.J. Kricka and P.E. Stanley Editors, Wiley and Sons, Chichester, UK, 1997. Roda A., Pasini P., Russo C., Baraldini M., Feroci G., Kricka L.J., Gioacchini A.M.: Antioxidant properties of bile acids evaluated with enhanced chemiluminescent assay: a possible physiological role. In: Bile Acids in Hepatobiliary Disease. Basic Research and Clinical Application, 246-253, G. Paumgartner, A. Stiehl and W. Gerok Editors, Kluwer Academic, Lancaster, UK, 1997. Roda A., Gioacchini A.M., Seraglia R., Montagnani M., Baraldini M., Pedrazzini S., Puricelli M., Traldi P.: A comparison of the analytical performance of sodium dodecyl sulfate-polyacrylamide gel electrophoresis, electrospray and matrixassisted laser desorption/ionization mass spectrometry in the study of the protein extract from Bothrops jararaca snake venom. Rapid Commun. Mass Spectrom., 11, 1297-1302, 1997. Gioacchini A.M., Carrea G., Secundo F., Baraldini M., Roda A.: Electrospray mass spectrometric analysis of poly(ethylene glycol)-protein conjugates. Rapid Commun. Mass Spectrom., 11, 1219-1222, 1997. * Girotti S., Ferri E.N., Ghini S., Fini F., Musiani M., Carrea G., Roda A., Rauch P.: Luminescent techniques applied to bioanalysis. Chem. Listy, 91, 477-482, 1997. * Girotti S., Ferri E., Ghini S., Roda A., Pasini P., Carrea G., Bovara R., Lodi S., Lasi G., Navarro J., Rauch P.: Luminescent techniques applied to food analysis. Quimica Analitica, 16 (1), S111-S117, 1997. Tonelli D., Gattavecchia E., Mazzella G., Roda A.: Bile acid kinetics in man studied by radio thin-layer chromatography and densitometry coupling. Journal of Chromatography B, 700, 59-66, 1997. Gentilomi G., Musiani M., Roda A., Pasini P., Zerbini M., Gallinella G., Baraldini M., Venturoli S., Manaresi E.: Colocalization of two different viral genomes in the same sample by double-chemiluminescence in situ hybridization. BioTechniques, 23 (6), 1076-1083, 1997. 1998 Musiani M., Pasini P., Zerbini M., Roda A., Gentilomi G., Gallinella G., Venturoli S., Manaresi E.: Chemiluminescence: a sensitive detection system in in situ hybridization. Histology and Histopathology, 13, 243-248, 1998. 118 * Roda A., Pasini P., Baraldini M., Musiani M., Gentilomi G., Robert C.: Chemiluminescent imaging of enzymelabeled probes using an optical microscope-videocamera luminograph. Analytical Biochemistry, 257, 53-62, 1998. Chieco P., Romagnoli E., Aicardi G., Suozzi A., Cantelli Forti G., Roda A.: Apoptosis induced in rat hepatocytes by in vivo exposure to taurochenodeoxycholate. Histochemical Journal, 29, 875-883, 1998. Gasbarrini A., Pasini P., Nardo B., De Notariis S., Simoncini M., Cavallari A., Roda E., Bernardi M., Roda A.: Chemiluminescent real time imaging of post-ischemic oxygen free radicals formation in livers isolated from young and old rats. Free Radic. Biol. Med., 24 (2), 211-216, 1998. Ventrucci M., Cipolla A., Ubalducci G.M., Roda A., Roda E.: 13C labelled cholesteryl octanoate breath test for assessing pancreatic exocrine insufficiency. Gut, 42 (1), 81-87, 1998. Roda A., Piazza F., Baraldini M., Speroni E., Guerra M.C., Cerrè C., Cantelli Forti G.: Taurohyodeoxycholic acidinduced cholestasis in the rat. Hepatology, 27 (2), 520-525, 1998. Roda A., Russo C., Pasini P., Piazza F., Feroci G., Kricka L.J., Baraldini M.: Antioxidant properties of bile salt micelles evaluated with different chemiluminescent assays: a possible physiological role. J. Biolumin. Chemilumin., 13, 327-337, 1998. Speroni E., Guerra M.C., Minghetti A., Crespi-Perellino N., Pasini P., Piazza F., Roda A.: Oleuropein evaluated in vitro and in vivo as an antioxidant. Phytother. Res., 12, S98-S100, 1998. Bazzoli F., Zagari M., Pozzato P., Varoli O., Fossi S., Ricciardiello L., Alampi G., Nicolini G., Sottili S., Simoni P., Roda A., Roda E.: Evaluation of short-term low-dose triple therapy for the eradication of Helicobacter pylori by factorial design in a randomized, double-blind, controlled study. Aliment. Pharmacol. Ther., 12, 439-445, 1998. Roda A., Piazza F., Pasini P., Baraldini M., Zambonin L., Fossi S., Bazzoli F., Roda E.: Development of a chemiluminescent urease activity assay for Helicobacter pylori infection diagnosis in gastric mucosa biopsies. Anal. Biochem., 264, 47-52, 1998. * Pasini P., Musiani M., Russo C., Valenti P., Aicardi G., Crabtree J.E., Baraldini M., Roda A.: Chemiluminescence imaging in bioanalysis. J. Pharm. Biomed. Anal., 18, 555-564, 1998. Montagnani M., Aldini R., Roda A., Roda E.: New insights in the physiology and molecular basis of the intestinal bile acid absorption. Ital. J. Gastroenterol. Hepatol., 30, 435-440, 1998. Roda A., Piazza F., Baraldini M.: Separation techniques for bile salts analysis. J. Chromatogr. B, 717, 263-278, 1998. * Roda A., Pasini P., Mirasoli M., Guardigli M., Russo C., Musiani M., Mazzeo C.: Chemiluminescent imaging in immunoassays and DNA detection. J. Clin. Lig. Assay, 21, 365-376, 1998. * Roda A., Piazza F., Simoni P., Afandi K., Ruffini F., Cantagalli D., Fini F., Girotti S.: I metodi immunometrici quantitativi nell’analisi ambientale tossicologica. (The use of quantitative immunometric methods for environmental and toxicological analysis) Ligandassay, 3 (4), 243-249, 1998. * Girotti G., Ruffini F., Cantagalli D., Fini F., Piazza F., Simoni P., Afandi K., Roda A.: Recenti applicazioni dei saggi immunologici negli alimenti. (Recent applications of immunoassays in food analysis) Ligandassay, 3(4), 250-258, 1998. * Roda A., Pasini P., Mirasoli M., Guardigli M., Russo C., Musiani M., Mazzeo C.: Metodologie analitiche di imaging in chemiluminescenza nei metodi immunologici e nella localizzazione del DNA. (Chemiluminescent imaging in immunoassays and DNA detection) J. Clin. Lig. Assay (Ed. Italiana), 21(4), 377-388, 1998. 1999 * Ranalli G., Pasini P., Roda A.: Bioluminescent low-light imaging technique as a rapid method to detect spatial distribution and activity of biodeteriogen agents in cultural heritages. In: Bioluminescence and Chemiluminescence: Perspectives for the 21st Century, A. Roda, M. Pazzagli, L.J. Kricka and P.E. Stanley Editors, Wiley and Sons, Chichester, UK, 153-156, 1999. Pasini P., Baraldini M., Russo C., Guardigli M., Mirasoli M., Piazza F., Afandi K., Musiani M., Roda A.: Bioanalytical challenges of chemiluminescence immunohistochemistry and in situ hybridization. In: Bioluminescence and Chemiluminescence: Perspectives for the 21st Century, A. Roda, M. Pazzagli, L.J. Kricka and P.E. Stanley Editors, Wiley and Sons, Chichester, UK, 191-194, 1999. Mirasoli M., Pasini P., Russo C., Lotierzo M., Valenti P., Guardigli M., Roda A.: Chemiluminescence in high throughput screening for drug developmnet on 384 well microtiter format. In: Bioluminescence and 119 Chemiluminescence: Perspectives for the 21st Century, A. Roda, M. Pazzagli, L.J. Kricka and P.E. Stanley Editors, Wiley and Sons, Chichester, UK, 524-527, 1999. * Roda A., Simoni P., Ferri E.N., Girotti S., Ius A., Rauch P., Poplstein M., Pospisil M., Pipek P., Hochel I., Fukal L.: Determination of PAHs in various smoked meat products and different samples by enzyme immunoassay. J. Sci. Food. Agric., 79, 58-62, 1999. Musiani M., Pasini P., Zerbini M., Gentilomi G., Roda A., Gallinella G., Manaresi E., Venturoli S.: Prenatal diagnosis of Parvovirus B19-induced hydrops fetalis by chemiluminescence in situ hybridization. J. Clin. Microbiol., 37, 23262329, 1999. Manaresi E., Pasini P., Gallinella G., Gentilomi G., Venturoli S., Roda A., Zerbini M., Musiani M.: Chemiluminescence Western blot assay for the detection of immunity against parvovirus B19 VP1 and VP2 linear epitopes using a videocamera based luminograph. J. Virol. Methods, 81, 91-99, 1999. Paolini M., Pozzetti L., Piazza F., Cantelli-Forti G., Roda A.: Bile acids structure modulation of murine hepatic cytochrome P450-linked enzymes. Hepatology, 30(3), 730-739, 1999. Azzaroli F., Mazzella G., Mazzeo C., Simoni P., Festi D., Colecchia A., Montagnani M., Martino C., Villanova N., Roda A., Roda E.: Sluggish small bowel motility is involved in determining increased biliary deoxycholic acid in cholesterol gallstone patients. Am. J. Gastroenterol., 94(9), 2453-2459, 1999. Lucisano E., Roda A., Cristino R., Negri L., Vittimberga G., Solazzo M.: Lymphadenectomy in gastric cancer: our experience with 180 cases. J. Chemother., 11(3), 227-229, 1999. Gioacchini A.M., Calonghi N., Boga C., Cappadone C., Masotti L., Roda A., Traldi P.: Determination of 4-hydroxy-2nonenal at cellular levels by means of electrospray mass spectrometry. Rapid Commun. Mass Spectrom., 13(15), 15731579, 1999. Roda A., Paolini M., Piazza F., Baraldini M., Speroni E., Guerra M.C., Pozzetti L., Cantelli-Forti G.: Taurohyodeoxycholic acid prevents taurochenodeoxycholic acid-induced cholestasis in rat: modulation of cytochrome P450 system. In: Bile Acids and Cholestatsis (XV International Bile Acids Meeting), G. Paumgartner, A. Stiehl, D. Keppler, W. Gerok and U. Leuschner Editors, Kluwer Academic, Dordrecht, Germany, 184-190, 1999. Aldini R., Montagnani M., Russo C., Roda A.: Basi molecolari del trasporto epatico degli acidi biliari. In Acidi Biliari 2000: aggiornamento per il futuro, E. Roda, A. Roda ed A.F. Hofmann Editori, Masson, Milano, Italia, 335-348, 1999. Montagnani M., Aldini R., Roda A., Russo C., Roda E.: Fisiologia dell’assorbimento intestinale degli acidi biliari. In Acidi Biliari 2000: aggiornamento per il futuro, E. Roda, A. Roda ed A.F. Hofmann Editori, Masson, Milano, Italia, 387398, 1999. Roda A., Piazza F.: Nuovi acidi biliari sintetici farmacologicamente attivi. In Acidi Biliari 2000: aggiornamento per il futuro, E. Roda, A. Roda ed A.F. Hofmann Editori, Masson, Milano, Italia, 149-187, 1999. Piazza F., Roda A, Simoni P.: Metodiche analitiche estrattive e separative per l’analisi di sali biliari in fluidi biologici. In Acidi Biliari 2000: aggiornamento per il futuro, E. Roda, A. Roda ed A.F. Hofmann Editori, Masson, Milano, Italia, 93124, 1999. 2000 Roda A., Guardigli M., Russo C., Pasini P., Baraldini M.: Protein microdeposition using a conventional ink-jet printer. BioTechniques, 28(3), 492-496, 2000. Paolini M., Pozzetti L., Piazza F., Guerra M.C., Speroni E., Cantelli-Forti G., Roda A.: Mechanism for the prevention of cholestasis involving cytochrome P4503A overexpression. J. Investig. Med., 48(1), 49-59, 2000. * Roda A., Pasini P., Guardigli M., Baraldini M., Musiani M., Mirasoli M.: Bio- and chemiluminescence in bioanalysis. Fresenius J. Anal. Chem., 366, 752-759, 2000. * Roda A., Musiani M, Pasini P., Baraldini M., Crabtree J.E.: In situ hybridization and immunohistochemistry with enzyme-triggered chemiluminescent probes. Methods Enzymol., 305, 577-590, 2000. * Roda A., Pasini P., Musiani M., Baraldini M.: Chemiluminescence imaging systems for the analysis of macrosamples: microtiter format, blot membrane, and whole organs. Methods Enzymol., 305, 120-132, 2000. * Ranalli G., Pasini P., Roda A.: Rapid diagnosis of microbial growth and biocide treatments on stone materials by bioluminescent low-light imaging technique. In: Proceedings of the 9th International Congress on Deterioration and Conservation of Stone, V. Fassina Editor, Elsevier, Amsterdam, 499-505, 2000. 120 Roda A., Manetta AC, Piazza F., Simoni P., Lelli R.: A rapid and sensitive 384-microtiter wells format chemiluminescent enzyme immunoassay for clenbuterol. Talanta, 52, 311-318, 2000. Piazza F., Montagnani M., Russo C., Azzaroli F., Aldini R., Roda E., Roda A.: Competition in liver transport between chenodeoxycholic acid and ursodeoxycholic acid as a mechanism for ursodeoxycholic acid and its amidates protection of liver damage induced by chenodeoxycholic acid. Digest. Liver Dis., 32, 318-328, 2000. Floreani A., Molaro M., Mottes M., Sangalli A., Baragiotta A., Roda A., Naccarato R., Clementi M.: Autosomal dominant benign recurrent intrahepatic cholestasis (BRIC) unlinked to 18q21 and 2q24. Am. J. Med. Genet., 95, 450453, 2000. * Sabbieti M.G., Marchetti L., Curini R., Menghi G., Roda A., Russo M.V., Nugnes C., Materazzi S.: Evidence of butyl benzyl phtalate induced modifications in a model system developed in vitro. Analusis, 28, 843-846, 2000. 2001 * Charbonniére L., Ziessel R., Guardigli M., Roda A., Sabbatini N., Cesario M.: Lanthanide tags for time-resolved luminescence microscopy displaying improved stability and optical properties. J. Am. Chem. Soc., 123, 2436-2437, 2001. * Roda A., Pasini P., Mirasoli M., Guardigli M., Russo C., Musiani M., Baraldini M.: Sensitive determination of urinary mercury(II) by a bioluminescent transgenic bacteria-based biosensor. Anal. Lett., 34(1), 29-41, 2001. * Roda A., Pasini P., Musiani M., Baraldini M., Guardigli M., Mirasoli M., Russo C.: Bioanalytical applications of chemiluminescent imaging. In: “Chemiluminescence in Analytical Chemistry”, A.M. GarcÍa-Campaña, W. Baeyens, eds., Marcel Dekker, New York, 473-495, 2001. Bacigalupo M.A., Ius A., Simoni P., Piazza F., Roda A., Setchell K.D.R.: Analytical performance of luminescent immunoassays of different format for serum daidzein analysis. Fresenius J. Anal. Chem., 370, 82-87, 2001. Addolorato G., Di Campli C., Simoncini M., Pasini P., Nardo B., Cavallari A., Pola P., Roda A., Gasbarrini G., Gasbarrini A.: Oxygen free radical production in rat liver: dose-related effect of ethanol on reperfusion injury. Dig. Dis. Sci., 46, 1057-1066, 2001. Nardo B., Caraceni P., Pasini P., Domenicali M., Catena F., Cavallari G., Santoni B., Maiolini E., Grattagliano I., Vendemiale G., Trevisani F., Roda A., Bernardi M., Cavallari A.: Increased generation of reactive oxygen species in isolated rat fatty liver during postischemic reoxygenation. Transplantation, 71, 1816-1820, 2001. * Piazza F., Barbieri A., Violante F., Roda A.: A rapid and sensitive method for methyl tert-butyl ether analysis in water samples by use of solid phase microextraction and gas chromatography¯mass spectrometry. Chemosphere, 44, 539-544, 2001. Musiani M., Pasini P., Roda A., Zerbini M.: In situ detection of viral nucleic acids by chemiluminescence. In: “FISH Technology. Springer Lab Manuals”, B. Rautenstrauss, J. Liehr, eds., Springer Verlag, Heidelberg, 346-359, 2001. * Pasini P., Gentilomi G., Guardigli M., Baraldini M., Musiani M., Roda A.: A chemiluminescent whole cell biosensor for assessing estrogenic activity. In: “Bioluminescence and Chemiluminescence 2000”, J.F. Case, P.J. Herring, B.H. Robison, S.H.D. Haddock, L.J. Kricka, P.E. Stanley, eds., World Scientific Publishing Company, Singapore, 327-330, 2001. * Roda A., Guardigli M., Pasini P., Baraldini M.: development of a time-resolved fluorescence microscope for imaging analysis. In: “Bioluminescence and Chemiluminescence 2000”, J.F. Case, P.J. Herring, B.H. Robison, S.H.D. Haddock, L.J. Kricka, P.E. Stanley, eds., World Scientific Publishing Company, Singapore, 493-496, 2001. Andreani A., Cavalli A., Granaiola M., Guardigli M., Leoni A., Locatelli A., Morigi R., Rambaldi M., Recanatini M., Roda A.: Synthesis and screening for antiacethylcholinesterase activity of (1-benzyl-4-oxopiperidin-3-ylidene)methyl indoles and pyrroles related to donepezil. J. Med. Chem., 44, 4011-4014, 2001. I-4 Other Scientific Output In the period 1997-2001, more than 50 presentations (oral or posters) were presented at National and International Congresses in the fields of analytical and bioanalytical chemistry, bio- and chemiluminescence. Appendix 3 Journal Portfolio Analysis 121 Name of the Unit: Research Director: Years included Bologna 4 Prof. Aldo Roda 1997-2001 Name of Journal Chemosphere Rapid Commun Mass Spectrom Anal Biochem J Chromatogr B Fresenius J Anal Chem Talanta J Pharmaceut Biomed Anal Lett Microchem J Analusis Quim Anal J Am Chem Soc Chem Listy J Sci Food Agr J Med Chem Phytother Res BioTechniques Methods Enzymol Biomed Chromatogr J Clin Lig Assay Number of Journal Articles Impact Factor 1 1.181 3 2.478 3 2.019 2 1.911 2 1.649 1 1.587 1 1.177 1 1.000 1 0.771 1 0.502 1 0.303 1 6.079 1 0.317 1 1.160 1 4.139 1 0.603 2 1.955 2 1 1 1.793 1.432 0.308 Free Radical Bio Med 1 5.082 J Biolumin Chemilumin 1 1.111 J Histochem Cytochem Histol Histopathol Histochem J Transplantation J Invest Med Hepatology 1 1 1 1 1 2 2.718 1.859 1.169 4.184 2.527 8.096 Gut 1 6.170 Aliment Pharm Therap 1 3.900 Am J Gastroenterol 1 3.549 Ital J Gastroenterol 1 1.594 Field(s) Ranking Environmental Sciences Chemistry, Analytical Chemistry, Analytical Chemistry, Analytical Chemistry, Analytical Chemistry, Analytical Chemistry, Analytical Chemistry, Analytical Chemistry, Analytical Chemistry, Analytical Chemistry, Analytical Chemistry, multidisciplinary Chemistry, multidisciplinary Chemistry, Applied Chemistry, Medicinal Chemistry, Medicinal Biochemical research methods Biochemistry and molecular biology Biochemical research methods Biochemistry and molecular biology Biochemical research methods Biochemistry and molecular biology Biochemical research methods Medical Laboratory technology Biochemistry and molecular biology Biochemistry and molecular biology Cell Biology Cell Biology Cell Biology Transplantation Medicine, General & Internal Gastroenterology and Hepatology Gastroenterology and Hepatology Gastroenterology and Hepatology Gastroenterology and Hepatology Gastroenterology and Hepatology 43/129 9/68 14/68 18/68 22/68 23/68 35/68 40/68 47/68 53/68 64/68 5/118 95/118 18/58 6/36 31/36 18/43 151/308 21/43 164/308 28/43 190/308 42/43 21/24 53/308 219/308 54/147 84/147 113/147 1/16 16/112 2/47 4/47 5/47 8/47 23/47 122 Name of Journal Eur J Gastroen Hepat Digest Dis Sci Digest Liver Dis Am J Med Genet J Chemotherapy J Virol Methods J Clin Microbiol Number of Journal Field(s) Articles Impact Factor 1 1.580 Gastroenterology and Hepatology 1 1.516 Gastroenterology and Hepatology 1 0.696 Gastroenterology and Hepatology 1 2.378 Genetics and Heredity 2 1.256 Pharmacology and Pharmacy 1 1.768 Virology 1 3.965 Microbiology Ranking 24/47 25/47 38/47 51/113 106/186 18/25 12/81 Comments on: a) the method The most recent version of the ISI Journal Impact Factor Index was used (2001). b) the results The Research Unit has published, since 1997, more than 50 articles in National and International Scientific Journals in the fields of analytical and bioanalytical chemistry, environmental research, and medicinal chemistry. Out of the total, 17 articles were published in journals belonging to the top 25 percent of their fields. 123 BOLOGNA 5 Analisi luminescenti e cromatografiche per il monitoraggio ambientale Luminescent and chromatographic analysis in environment monitoring Name of the Research Unit BOLOGNA (Stefano Girotti) University Università degli Studi di Bologna University of Bologna Faculty Farmacia Pharmacy Research Leader Prof. Stefano Girotti Contact Person Stefano Girotti U.C.I. Sc. Chim. Radioch. e Metall. Via San Donato 15 I-40127 Bologna Phone 051 251147 Fax 051 6443680 E-mail: [email protected] Department U.C.I. Scienze Chimiche, Radiochimiche e Metallurgiche Institute of Chemical Sciences Thematic Area • Tecnologie innovative di monitoraggio • Tecnologie biologiche enzimatiche e biomimetiche per le sintesi ecosostenibili e la decontaminazione ambientale. Introduction and Context Introduction to the Self-evaluation Report The Unit research activity mainly concerns the development and the application of analytical techniques in the environmental monitoring of several analytes. At present can be pointed out both the monitoring by using honeybees, that required the development ad hoc of new techniques, and the application of toxicity bioassays based on bioluminescent bacteria and “musselmonitor”. The fundamental thematic area is the first one, but exist interesting applications even in the second one. The collaboration with an enterprise to develop a bioremediation procedure using bacteria grown and checked in this Unit is in progress. It is our wish to emphasize that the character of the research carried on at the Unit is definitely that of applied one. Moreover, formally the Unit is composed by the scientific research staff reported in the tables but, thanks to national and international collaborations, the range of available skills is much more broad, including, behind chemistry, the biological, entomologic, veterinary knowledges needed to deal with the environment problems. The continuous and effective collaboration is proved by the several exchanges, often at international level, among the Unit and its partners, involving both researchers and experts. A part of the funds are awarded by enterprises collaborating with the Unit, even if not within the consortium. . The University, the Faculty and the Department The University of Bologna is the oldest university in western civilizations. The exact beginning is uncertain, but the 1088 is accepted as the conventional starting date of the period during which, in Bologna, was possible to identify free teachers, giving lessons independent from ecclesiastical school. Nowadays the University of Bologna is among the greater universities in Italy. It is a government university, as the most part of Italian universities, independent, its own statute settles the rules of the self-government. The University government and the main research and teaching activity are located in Bologna, but many new research and teaching activities have been recently dislocated in other Cities of the Emilia-Romagna region, such as Cesena, Faenza, Forlì, Ravenna and Rimini. The whole University currently counts about 900 professors, 1,000 associated professors, 1,050 researchers and more than 100,000 students. The University of Bologna includes 20 faculties, 65 Departments, 5 Federated Departments (“Unità Complesse”), 3 Institutes that offer more than 100 courses, both short degrees (45, three years) and specialistic degrees (65, five years) in the following disciplines: 124 Agriculture, Architecture, Industrial Chemistry, Preservation of Cultural Heritage, Economics, Pharmacy, Law, Engineering, Arts and Philosophy, Foreign Languages and Literatures, Medicine, Veterinary Medicine, Psychology, Mathematics Physics and Natural Science, Motory Sciences, Training Sciences, Political Science, Statistics Science, High School of modern languages for interpreters and translators The Faculty of Pharmacy enrols about 3000 students and includes 100 of teachers and researchers. The members of teaching staff belong to 12 different Research Departments and one UCI (Complex Unit of Institutes). According to the data of a report conducted by CENSIS and by the newspaper “La Repubblica”, the information of a group of deans and of the Professional Associations in 2001 the Faculty of Pharmacy of Bologna was the top among about 30 faculty in Italy, taking into account various parameters such as: teaching activities, research, productivity, the interest aroused and international relations. The Unit belongs to the UCI of Chemical Science. The Unit The Unit of Analytical Chemistry at the UCI of Chemical Science is engaged since about 20 years in the development of analytical methods suitable in monitoring several analytes in the environment, in foods, in clinical and pharmacological samples. The revealing techniques are based, mainly but not only, on bio and chemiluminescent reactions. The staff of the Unit includes an Associated Professor, two researchers, a PhD graduate, four fellows and various students carrying out the degree thesis work. The teachers of this unit are, or were, charged with the courses of Analytical Chemistry and Clinical Analytical Chemistry for the degree courses of Pharmacy (Bologna and Rimini branches), Pharmaceutical Chemistry and Technology, Technologies for Herbalists. The Unit was responsible of the organisation and carrying out of the following Specialization Courses: “Quality management: Principles and applications in the analytical laboratories”. “Analytical Microbiology of foods and water”. “Advanced Analytical Techniques in clinical, environmental, foods and industrial assays”. Moreover, the teachers of the Unit did: theoretical and practical classes for the Specialization Courses in “Synthesis and Application of Radiopharmaceuticals” and “Digestion of Toxic, Harmful and Special Wastes: Analysis, Identification and Classification”; theoretical lesson of Environmental Toxicology and Precautionary Measures for the Specialization School of Toxicology, University of Bologna. Program Description and Evaluation 1.Title: Analisi luminescenti e cromatografiche per il monitoraggio ambientale Luminescent and chromatographic analysis in environment monitoring 2.Research Leader: Stefano Girotti 3.Composition of the scientific research staff of the unit Name and title Girotti Stefano Ghini Severino Ferri Elida Nora Fini Fabiana Bolelli Luca Setti Ilaria Camprini Giovanni Giardini Denise Total research input Year of birth 1950 1949 1957 1971 1971 1976 1974 1974 Rank Associated Professor Researcher Researcher Post-doc Fellow Fellow Fellow Fellow Research Input 0.4 1.0 0.5 1.0 1.0 1.0 1.0 1.0 6.9 Remarks Since 1996 Since 2000 Since 2000 Since 2001 Since 2001 Comments The research activity of the Unit is widening its field of interest and application, but because the well known, chronic situation of Italian universities makes extremely difficult to be officially employed it is necessary to involve several fellows. Their salaries often are paid directly from enterprises funding. For example, the fellowship of Dr. Bolelli for last year was a “Spinner” fellowship to develop a Research, Development and know-how transfer to enterprises Project. The aim of this project was to set up a bioassay kit based on bioluminescent bacteria. This fellowship, as well as all the other ones, fits perfectly the mission statement of the Unit and is of fundamental importance for the development and quality of the research work. 1.Input of Academic Staff in fte 125 Category 1997 1998 1999 2000 2001 Total Full Professor Associated professor Researchers Post-docs PhD-students Fellows Total 0 0.4 1.5 0 1.0 0 2.9 0 0.4 1.5 0 1.0 0 2.9 0 0.4 1.5 0 1.0 0 2.9 0 0.4 1.5 0 1.0 2.0 4.9 0 0.4 1.5 1.0 0 4.0 6.9 0 2.0 7.5 1.0 4.0 6.0 20.5 5. Funding 1.3Personnel (in fte) Source 1997 1998 University-MURST 2.9 1.9 CNR EU 1 Other Sponsors Total 2.9 2.9 1.3Materials and Equipment (in million lire) Source University-MURST CNR EU Other Sponsors Total 1999 1.9 2000 3.9 1 1 2001 5.9 Total 16.5 3 1 20.5 2.9 4.9 1 6.9 1997 18 1998 22 1999 24 2000 22 2001 25 Total 111 55 25 98 42 60 124 24 80 128 14 120 156 97 122 135 382 628 5.3 Comments: On the figures: The size of the academic staff involved in this research is increasing, as well as the amount of the funds allocated for the personnel. On the funding policy: The financial resources are obtained from several sponsors: this is a clear proof of the good management quality in preparing and submit the fund requests and, on the other hand, of the quality of proposed researches and obtained results. During the 2001 the total amount of funds seems reduced, because the end of the triennial European projects. Actually, the amount of funds given to monitoring analysis projects is increasing and the policy of the Unit in the future is to continue to increase it, both involving new local organisation besides those now collaborating with the unit, and turning to this research part of inner resources. Concerning this we want to point out that in this report are not included the funds, employed in this research, obtained as sub-unit partners in project administered by other departments or research groups, i.e. the National Interest Project ”Endocrine disrupting compounds in aqueous and biological systems: new analytical methodologies and toxicological impact” and the research project “Honeybees, Honey, Environment” funded by the Agricultural Policies Ministry, coordinated by the Institute of Entomology and the Institute of Apiculture. The major sponsors are: - National enterprises: Busi Impianti S.p.A., Le Rocche Malatestiane, Azienda Liofilchem Diagnostici, “La Carlina”, a cooperative society. - Some communes in the district of Bologna (Ozzano, Granarolo, Castenaso) - The Emilia-Romagna region. The research aim and activity funded by each one of this sponsor is defined in advance by the signature of a specific contract. - The European Community: The themes developed in our Research Projects till now approved and funded by the EC during the 5th Framework Project concerned environmental problems. We were able to reach the foreseen results and the Final Reports obtained 126 the enthusiastic approval of the EU Scientific Committee. The scientific responsibles underlined the good quality of the drawing up of the Reports but mainly the high level of effective collaboration reached among the researchers and between scientific research and enterprises. One of these Reports was chosen as advertising material for the INCOCOPERNICUS programme. 6. Progress Report 6.1 Mission Statement The main topics of the research activity of the Unit are: 1) The development of bioluminescent and chemiluminescent analytical methods to be used in complex matrices. 2) The application of the developed assays, together with other fundamental analytical methods, to the analysis of environmental, food and pharmacological samples. 3) The use of honeybees in the environmental monitoring of pesticides in agroecosystems, in the monitoring of heavy metals pollution in cities and industrial areas and for the detection of radionuclides in several other environments. 4) The use of honeybees for the detection of phytopatogen bacteria, like Erwinia amylovora. The application of bio and chemiluminescent revealing systems is greatly useful in all cases the sample contain just traces of the analyte or when a rapid screening procedure on several samples is requested. The chromatographic and spectroscopic methods can be used to determine pesticides and heavy metals. The radiochemical instruments available at the Unit allow to perform no destructive assays of honeybees to monitor radioactive pollution in the environment. The expected results include: the set up of new methods and assays useful in the monitoring of environment and food. The character of the research is mostly applied. “Clients” of our research work can be both enterprises (like Busi S.p.A. or Granarolo S.p.A.) and public bodies, like the Regione Emilia-Romagna. Generally speaking the results obtained in this research are useful for the whole scientific community interested in analytical chemistry. 6.2 The Research (*) Star marks the items concerning INCA Consortium ¾ The research work of the Unit continues developing the topics under study since a number of years, during which were developed several kinds of bio and chemiluminescent (BL and CL) assays: involving flow sensors, in batch, immunological, using DNA or RNA probes labelled by BL or CL tracers, using directly the luminescent microorganisms to set up biotoxicologic assays. The main lines of the research will be the development of new BL and CL analytical and new applications of assays already well validated. It is foreseen to continue following 6 lines already active in the Unit: 1)*Synthesis and application of new luminescent molecules and luciferines to develop immunoluminescent methods both for microbiological and viral assays by using DNA probes and immunoenzymatic assays on microplates. More in details these assays will be used to determine pesticides and pathogenic bacteria like Erwinia amylovora, detected by a PCR-ELISA assays in pollen and honeybees 2) *The use of honeybees as bioindicators to perform an accurate monitoring and control of the environment, setting up and optimising chromatographic methods to detect pesticides. 3) Development of continuous flow systems to determine substrates and enzymatic activities, also employing antibodies; optimisation of the enzymatic reactions already prepared. 4) Determination of microorganisms content in complex matrices and in *bioaerosol by using the ATP content measurement. 1) Chemiluminescent determination of the antioxidant properties of food and antioxidant activity *in treatment plants for wastewaters and sludges of civil and industrial origin (Petrochemical). 2) *Evaluation of the toxic potential of compounds present in milk and in the sea water by measuring their inhibitory effects on the light emission of BL bacteria. This activity will be connected to the molluscs rearing. (clams, mussels, etc.). ¾ The studies performed during the period 1997-2001 concerned various aspects of the application of BL and CL assays. 127 Employing both monoclonal antibodies, produced expressly for this research, and polyclonal antibodies commercially available were developed chemiluminescent assays for pesticide (DDT and endosulfan families), benzo[a]pyrene (BaP), PHAs and pathogenic bacteria (Salmonella and Listeria) determination. A batch system including the enzymes Horseradish Peroxidase (HRP), Choline Oxidase (ChOX) and Acetylcholine Estherase (AChE) and the chemiluminescent mixture Hydrogen peroxide/Luminol was used as a preliminary test to determine the presence of pesticide residual in honeybees extracts. This system is based on the inhibition of AChE activity by several pesticide families and is able to detect in various matrices (soil and vegetables) 0,75 µg/L of Paraoxon and 4 µg/L of Aldicarb, with recovery between 81 and 108 %. A flow sensor was already developed, using HRP and ChOX immobilized on Eupergit-C, AChE and the luminescent mixture in the flowing solution. It was employed to determine Paraoxon and Aldicarb in extracts of environmental samples and the idea was to use it for a large screening of honeybees samples. The positive samples can be further analysed by Gas Chromatography (GC) to assess which pesticides are present. By using this couple of assays is possible to control a large territory testing samples of dead honeybees or of their products, honey and pollen. The GC method was improved performing a pre-analytical treatment of the sample, that was purified by GPC (Gel Permeation Chromatography). This procedure is very effective, quite rapid, and the chromatograms are very clear. Moreover, this allow a reduction of the cost per sample and the use of toxic solvents, an advantage for the environment and technicians health. To compare the validity of the method the samples were tested by using Liquid Chromatography Atmospheric Pressure Ionization Mass Spectrometry (LC-APCI-MS) with ionisation in positive and negative ions method (PI) (NI). By this method was possible to identify 22 pesticides on the 25 under investigation. A microextraction on solid phase (SPME) technique was also studied to obtain purified samples to measure directly in the Gas Chromatograph equipped with a N-P detector. Using this method the number of pesticides isolated from honeybees was 18. Two different probes, as solid phase, were tested, made by polyacrylate and polydimethylsiloxane, respectively and the first one shown itself more effective in absorbing the pesticides. The extraction was performed in water/acetone mixture; in samples added with standard solutions of pesticides (0.2 mg /kg) the CV resulted between 1 and 13% and detection limit of 10 µg/kg. Erwinia amylovora (Ea) is a phytopathogenic bacteria, the causal agent of “fire blight” the most destructive bacterial disease of Rosaceous plants. A PCR-ELISA assay with chemiluminescent end-point detection allowed to reach a detection limit of 30 cells in pure cultures and of 380 cells in pollen samples. The colorimetric detection is of two order of magnitude less sensitive. This assay has been applied to environment control analysing pollen samples collected by honeybees. This avoid the need to test a sample per each pear or apple tree in the field to discover the presence of an infected plant. Various strains of luminescent bacteria are employed since several years in the environmental monitoring. The light emission of these microorganisms is a biochemical process very sensitive to the presence and toxicity of most xenobiotics. When toxic compounds and bacteria are brought into contact the luminescent emission decreases proportionally to the xenobiotic concentration. Various methods based on luminescent bacteria were set up to analyse heavy metals, antibiotics, BTEX present in solutions, biological matrices and extracts from bivalve molluscs. Moreover, the bioluminescent determination of ATP content is, and was, employed in the control of surfaces hygiene and of the microorganisms amount in air (museums and indoor rooms), in wastewater and food. ¾ During next five years will be continued the research lines till now followed. Particular care will be given to the environmental monitoring using honeybees, developing tests for other analytes, and to the bio-toxicological assays based both on BL bacteria and sensors as the “musselmonitor“. The last one allow to evaluate the toxicity of the compounds directly on the mussels. It is foreseen to involve more graduated or post-doc student offering various fellowships, sponsored by enterprises, too and probably another “Spinner” fellowship. 6.3 Position in network The Institution marked by the star (*) are essential to continue the collaborations needed to develop new analytical technologies in environmental monitoring, especially those based on honeybees, concerning Thematic area No. 1. During last years has been created a wide network of collaborations and contacts both at national and international level, that enable the Unit to face the problems of environmental monitoring from several point of view and to propose global solutions, thanks to the possibility to connect research groups with different skills. 128 Intra-university co-operation • *Dipartimento di Medicina Clinica Specialistica e Sperimentale (Erwinia amylovora PCR-ELISA assays, bioluminescent bacteria) • *Dipartimento di Medicina e Sanità Pubblica (microbiological analysis in wastewater treatment plants). • Clinica Medica III, Istituto di Microbiologia, Università di Bologna (biosensors and flow systems). • Dipartimento Scienze Farmaceutiche, Università di Bologna (biosensors and flow systems). • *Dipartimento Scienze e Tecnologie Agroambientali, Università di Bologna • Regional co-operation - *SEABO, Laboratorio Analisi Ambientali, Bologna. - *ARPA, Agenzia Regionale per la Protezione Ambientale, Laboratorio Analisi Ambientali, Bologna. - *Busi Impianti, S.p.A. (luminescent sensor for microorganisms in air). - *Regione Emilia-Romagna, in particolare Osservatorio delle Malattie delle Piante - Le Rocche Malatestiane, Società Cooperativa a R.L., Rimini (food analysis). - *Comuni di Granarolo, Castenaso ed Ozzano. - *Cooperativa “La Carlina” – Bologna. - *Centro Studi Ambientali (CSA), Rimini. National Co-operation (including INCA) - *Istituto di Biocatalisi e Riconoscimento Molecolare (ex Chimica Ormoni), CNR, Milano (flow systems) - Laboratorio Centralizzato e Servizio Immunoematologia e Trasfusionale, Ospedale S. Orsola, Bologna (nucleotides analysis). - Granarolo S.p.A., Laboratorio Analisi Qualità, Bologna (food analysis and quality system). - *Istituto Zooprofilattico Sperimentale Abruzzo-Molise, Teramo (“musselmonitor ” and biotoxicological analysis) - *Istituto Nazionale di Apicoltura, Bologna. - *IAS - Industria Acqua Siracusana SpA, Priolo Gargallo, Siracusa International co-operation - *Teaching Project Tempus II (S JEP- 07599-94): University of Chemical Technology Prague, Brno e Olomouc, Czech Republic; Luton e Norwich, U.K.; Salamanca, Spain; Lyngby, Denmark; Bayreuth, Germany; Lund, Sweden. - R&D Project UE Copernicus CIPA CT 94-0147;, University of Chemical Technology Prague; Pilsen Breweries, Pilsen; Granarolo Felsinea SpA, Bologna; Dairy Research Institute, Prague; Golden Pheasant Brewery, Urbanovo, Slovak Republic. - *R&D Project UE Copernicus ERBIC15CT961001; Universidad Politecnica de Valencia, Spain; University of Chemical Technology, Prague; Moscow State University “Lomosov”, Moscow, Russia. - Joint Project CNR/JNICT (132.21.1); Universidade Nova, Departamento de Quimica, Lisboa, Portugal. - *R&D Project UE Copernicus IC15-CT96-1013; The Robert Gordon University, Aberdeen, UK, University of Chemical Technology, Prague; Food Research Institute, Bratislava, Slovakia; Boneco Ltd., Benesov, Czech Republic. - Teaching Project Tempus II (S JEP-12325-97, Joint European Project); University of Chemical Technology and Charles University Prague, Brno (Masaryk, Veterinary and Pharmaceutical Sciences e Mendel Agricultural and Forestry Universities), Pardubice e Olomouc, Czech Republic; Luton e Norwich, UK; Salamanca, Spain; Lyngby, Denmark. - *Research Project- Integrated Action Italia/Spagna; Universidad de Cordoba, Spain. - *Scientific Exchange Project Italy/Czech Republic; University of Chemical Technology, Prague. - Teaching Project Tempus -Phare Compact Measures Grant (CME-03617-97); University of Chemical Technology, Czech University of Agriculture e Charles University, Brno (Masaryk, Veterinary and Pharmaceutical Sciences e Mendel Agricultural and Forestry Universities), Pardubice e Olomouc, Czech Republic; Lyngby, Denmark; Luton e Norwich, U.K.; Salamanca, Spain. - UE "Socrates/Erasmus" Programme of the Faculty of Pharmacy, Bologna: in the context of this programme were established further scientific collaborations with: *Facultad de Ciencias del Mar, Universidad de las Palmas de Gran Canaria, España, *Department of Biotechnology, *University of Lund, Sweden, *Departement de Chimie-Biochimie, Universitè Claude Bernard, Lyon, France, *Department of Environmental Sciences, University of Plymouth, UK, *Departamento de Quimica Analitica, Universidad de Cordoba, España. The exchanges concerned the performance of common researches and of master thesis works. - Department Chemistry and Medicine, University of California, USA (development of nanotechnologies). School of Chemistry, Hull University, UK (flow sensors). - *Department of Biochemistry and Microbiology, University of Chemical Technology, Praha, Czech Republic (development of pesticides immunoassays). 129 - UNIASA SPA, Granada, España (food analysis). - Istituto de Nutricion y Tecnologia de Alimentos, Universidad de Granada, España (food analysis ). - *Departamento de Medicina Preventiva, Facultat de Farmàcia, Universitat de València, España Part of the research activity concerned some National projects, i.e.: The Project: “Production of the bioluminescent recombinant phytopathogen Erwinia amylovora, causative agent of Rosacee “Fire Blight”, for epidemiological study” funded by the Interuniversitary Centre for Biotechnologies (CIB); The National Project: “Endocrine disrupting compounds in aqueous and biological systems: new analytical methodologies and toxicological impact” and the Research Project “Chemiluminescent assays of antioxidant properties of wines” sponsored by Le Rocche Malatestiane, Società Cooperativa a r.l., Rimini. In the context of INCA we were involved again very recently (2002), then the only one collaboration is with the Unit of Prof. Roda, Bologna 4. One of the reasons because we started again the collaboration with INCA is that in the immediate future we could undertake several collaborations with other Units, since many research topics are common. My expectations on the function and role of INCA in the future concern its ability to coordinate and aggregate the similar Project both at local-regional and at national level, together with a deep interest in preparing European Project proposals. 6.4 Societal Relevance and Impact The social relevance of the research is connected to the objectives of the projects. The pollutants detected by the analytical methods developed by the Unit are wide spread in land and sea environment and a timely detection can avoid serious damages to human health and to the environment. This research work is of fundamental importance, since is devoted to the development of methods suitable to be effectively applied to real problems, as it is demonstrated by the collaboration between the Unit and the Region Emilia-Romagna or with other laboratories engaged in environmental monitoring (ARPA, SEABO). In the specific case of the application of honeybees monitoring and of the phytopathogenic organism the results of this research can have a great social, environmental and economic impact. To disclose timely the presence of the microorganism reduces the damages on fruit-threes. The method developed in our laboratory will became an official method in Emilia-Romagna Region to test the presence of . Erwinia amylovora infections. *Employing honeybees has been performed too the monitoring of pesticides, radionuclides and heavy metals. This service is requested by some communes of Bologna district (Granarolo, Castenaso ed Ozzano) in which the presence and distribution of pesticide is recorded and data processed to prepare “month risk maps” To the researches in progress on other microorganisms some enterprises are interested with the aim to prepare Pate4nts on them. Comparing the funds obtained (see pag. 4), the publications (see pag. 14-16) and the interest displayed by Public bodies and enterprises (see pag. 7-8) it is possible to see clearly that the research results of this Unit has good application to real problems. 6.5 Further indication of Quality and Reputation Il Prof. Girotti has been International European Referee Ph.D. Thesis commissions at the University of Chemical Technology, Prague, Czech Republic; the University of Valencia, Spain; the Palacky University of Olomouc, Czech republic and the Universidad Jaume I di Castellon, Spain. Professor Girotti audited and reviewed some Fellowship Research Grant proposals of the Grant Agency September 1994, August 1995, August 1998, August 1999, August 2001.He audited and reviewed a Research Grant proposal of the "Fonds zur Förderung der Wissenshaftlichen Forshung", Austria., March 1999. He audited and reviewed Research Grant proposals of the "Grant Agency" of the Czech Republic: June 2001 and June 2002. He has reviewed papers for "Analytica Chimica Acta"; "Journal of Bioluminescence and Chemiluminescence"; "Talanta"; "Mikrochimica Acta", "Annali di Chimica-Rome", "Il Farmaco", "Journal of Immunological Methods" and "Journal of Chromatography". He has been Visiting Professor at the Departamento de Quimica, Universidade Nova, Lisboa, Portugal, at the PULEVA s.a. in Granada, Spain, and he lectured on invitation in Czech and Spanish Universities. Consultant in the Project "Application of Biological Markers" at IAS-Industria Acqua Siracusana SpA, Priolo Gargallo, Siracusa, for the coordination of the research which involves also the Siracusa ASL 8 Laboratory, using biotoxicological biosensors based on Bioluminescent Bacteria and Mussels. May 2001 - May 2002 Consultant in the Project for the standardisation of bioluminescent bacteria assay in the "Misura 2" of the Research Project "Qualificazione del prodotto Chamelea gallina (vongola comune) della fascia costiera Molise-Alta Puglia (Termoli) finalizzata al riconoscimento di un marchio di qualità”. December 1999 - November 2001. 130 Consultant in the Project "Evaluation of a research concerning the development of a bioluminescent sensor for bioaerosol measurement", a research performed at Busi Impianti SpA, Bologna.Consultant in the Project "Development and marketing of a biotoxicological analytical kit employing bioluminescent bacteria I" with the Liofilchem SpA, Roseto degli Abruzzi (TE).He is author of the European n. 02425030.0 Patent entitled “Detection of Listeria monocytogenes by the polymerase chain reaction”, granted and supported by University of Bologna, registered on 28 January 2002. Member of the scientific committee of the II Meeting of the Italian Section of the International Society of Bioluminescence and Chemiluminescence and co-ordinator of the scientific session: "Applications of ATP measurement in bioluminescence ". Florence, 16–17th June 1997. Member of the organising committee of the 10th International Symposium on Bioluminescence and Chemiluminescence and co-ordinator of the session: "ATP-Based assay for rapid microbiology and toxicology". Bologna, 4 – 8th September 1998 6.6 Key Publications *S.Rossi, A.P.Dalpero, S.Ghini, R.Colombo, A.G.Sabatini, S.Girotti. “Multi residual method for Gas Chromatography analysis of pesticides in honeybees cleaned by gel permeation chromatography”. Journal of Chromatography A, 905 (1-2), 223-232, 2001. *I.Hochel, G.Jenikova, C.F.Dursi, J.Pazlarova, S.Girotti, K.Demnerová. “Application of Mouse Antibodies to Somatic Antigen for Detection of Salmonella enteritidis by Competitive ELISA”: Food and Agricultural Immunology, 13, 115-126, 2001. *M.Merighi, A.Sandrini, S.Landini, S.Ghini, S.Girotti, S.Malaguti, C.Bazzi. "Chemiluminescent and colorimetric detection of Erwinia amylovora by immunoenzymatic determination of PCR amplicons (PCR-ELISA) from plasmid pEA29". Plant Disease, 84, 49-54, 2000. *M.Fernández, Y.Picó, S.Girotti, J.Mañes. “Analysis of organophosphorus pesticides in honeybee by liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry”. Journal of Agricultural and Food Chemistry, 49, 3540-3547, 2001. *S.Girotti, E.N.Ferri, L.Bolelli, G.Sermasi, F.Fini. "Applications of bioluminescence in analytical chemistry". In: “Chemiluminescence in Analytical Chemistry”, A.M.Garcia-Campaña, W.R.G.Baeyens, Editors, Marcel Dekker, New York, 247-284, 2001. 1.Scientific Output 7.1 Publication Policy Concerning publications, the policy of the Unit is: - To publish in the most important journals of Analytical Chemistry and Luminescence. - To communicate the research results at national and international conferences The number and the quality of the Journal that accepted our papers (see Appendix 1) is increasing; many publications are in the top category (AO) according to the “Osservatorio della Ricerca/Research Watch” of Bologna, based on the Impact Factor values. The collaborations under way allow to publish in several Journals that differ in quality and area of interest. This offer the possibility of a wider spread of the obtained results. One of the aims is to prepare Patents, directly in collaborations with enterprises or ready to be acquired by them, like the Patent prepared in 2001 and registered in the January 2002. 7.2 Numerical Data Category PhD Dissertation Scientific publications Professional Publications Master’s Thesis 1997 1998 1999 2000 5 2001 1 14 Total 1 37 5 7 6 1 7 6 12 5 31 131 8 Self-evaluation As strengths of the Unit are to mention the scientific skills, the wide network of contacts and collaborations both at national and international level, the ability to coordinate groups that can offer completely different skills. This allow to reach actually applicative results that lead to another strength of this group, the collaboration with Enterprises and Public bodies, doing not only academic research, but really applicative. The collaboration network allow to overcome one of the weaknesses of the group, the need to involve several fellows, PhD or Post-doc students because the deep lack of people officially employed by the University. The total absence of technicians creates another point of weakness: all technical and bureaucratic problems must be solved by the research staff members. This is, of course, time consuming, reducing the possibilities to start new collaborations, then to obtain new funds. Moreover, is reduced the time devoted to research and specialization stages, abroad or in Italy, very important to increase the skills of the group. We hope that in the future the Unit will have the possibility to engage more researchers than students, to obtain sponsorisation to research ideas already positively assessed at national or international level, overcoming the established power of the lobbies present in the research field. Appendix I Scientific Output I.1.1 Dissertations Year Name PhD-student * 2001 Fini Fabiana Title of the Dissertation Supervisor Development and application of luminescent methods (Stefano Girotti) for the analysis of complex matrices I.1.2 Master’s Thesis (*) Star marks the items concerning the topics of INCA Consortium 1997 * 1998 * 1998 Danila Trampetti Anna Paola Dalpero Annalisa Sandrini 1998 1998 Mattia Muratori Daniele Cantagalli * 1998 Serena Landini 1998 1998 * 1999 Luca Bolelli Francesca Ruffini Simona Rossi 1999 Giovanni Maglia 1999 Di Leo Debora * 1999 Sermasi Gloria * 1999 Granetto Francesca 1999 Naio Elena 2000 Valerio Spinosi Luminescent determination of superoxide dismutase Extraction and determination of pesticides in honeybees In vitro amplification of genomic sequences of Erwinia amylovora and chemiluminescent detection of hybridised DNA (PCR ELISA) Luminescent analysis in the quality control of beer Determination of the antioxidant capacity of complex matrices using a bioluminescent assay Analytical methods for Erwinia amylovora monitoring in pollen: BIO-ELISA, DOT-BLOT PCR, and PCRELISA with chemiluminescent detection Bioluminescent assay of micro-organisms in milk Enzymatic determination of nitrites in beer Methodological extraction problem in the determination of pesticides in the honeybee matrix Amplified chemiluminescence: study of the effects of 4bromophenyl-boronic-acid Comparison of manual and automated method for the total bacterial count in raw and pasteurized milk Development of an immunochemiluminescent assay for pesticides determination The pollen in Erwinia amylovora monitoring: official methods and immunoenzymatic advanced assay (PCRELISA) with chemiluminescent detection Optical and electrochemical sensors for the determination of ammonium and nitrites Electrochemiluminescence for codeine determination in biological fluids (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) 132 * 2000 2000 * 2000 * 2000 2000 * 2000 * 2000 * 2000 2000 * 2000 * 2000 * 2001 * 2001 * 2001 2001 * 2001 D'Aurizio Mariangela Maccagnani Luana Bacteria bioluminescence: study of inhibitors Validation of chemiluminescent methods for the determination of antioxidant capacity in complex matrix Marconi Luciana Solid phase microextraction for pesticides determination in the honeybee matrix: application to environmental monitoring Scurti Piero Pesticides residues in fruit and vegetable: comparison of analytical data to estimate possible cumulative and synergetic effects Tsafack Takouking Study of new bioactive layers for the development of a Valerie Carine optical fibre based biosensor: application to electrochemiluminescent and chemiluminescent detection of choline Dursi Cinzia- Development of a chemiluminescent method for the Francesca detection of pathogenic bacteria Dallamotta Francesca Comparison of different Quality Control criteria for the analytical performances of primary water samples Lisa Zeri Improvement of immunoenzymatic advanced systems (PCR-ELISA) with chemiluminescent detection for the detection of Erwinia amylovora in pollen and application to precocious monitoring of fire blight Raffaelli Simonetta Quality Control in milk: comparison of different Sabine methods for the determination of alkaline phosphatase Silvia Luppi Application of chemiluminescent methods for the determination of antioxidant capacity in complex matrices Gaspari Giorgia Development of an immunochemiluminescent technique for the determination of organochlorine pesticides Adriana Vannella Numerical simulations of bioluminescent reactions for analytic purposes Cristina Borrini Pesticides determination in honeybees with solid phase extraction techniques Denise Giardini Flow analysis with chemiluminescent detection for lubricants determination in diesel fuels Francesca Osti: Development of miniaturised systems in analytic chemistry: applications to protein determination Ilaria Setti Development of immunochemiluminescent assay for carbamates pesticides determination (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) (Stefano Girotti) (Stefano Girotti). (Stefano Girotti) I-2 Overview of Scientific Publications (1997-2001) per year (*) Star marks activities concerning the topics of INCA consortium. 1997 P.Rauch, E.Ferri, S.Girotti, H.Rauchova, G.Carrea, R.Bovara, F.Fini, A.Roda. "A chemiluminescent flow sensing device for determination of choline and phospholipase D activity in biological samples". Analytical Biochemistry, 245, 133-140, 1997. S.Girotti, E.Ferri, S.Ghini, A.Roda, P.Pasini, G.Carrea, R. Bovara, S.Lodi, G.Lasi, J.Navarro, P.Rauch. "Luminescent techniques applied to food analysis". Quimica Analitica, 16, Supplement I, S111-S117, 1997. S.Girotti, E.N.Ferri, F.Fini, S.Righetti, L.Bolelli, R.Budini, G.Lasi, P.Roubal, L.Fukal, I.Hochel, P.Rauch. “Determination of microbial contamination in milk by ATP assay”. Potravinárské Vêdy (Czech Journal of Food Sciences), 15 (4), 241-248, 1997. * S.Girotti, E.N.Ferri, S.Ghini, F.Fini, M.Musiani, G.Carrea, A.Roda, P.Rauch. “Luminescent techniques applied to bioanalysis”. Chemické Listy, 91 (7), 477-482, 1997. 133 * S.Girotti, E.Ferri, F.Fini, F.Zanetti, S.Stampi, A.Roda, R.Budini. "ATP bioluminescence for the rapid assessment of wastewater and sludges microbial content". In: A Practical Guide to Industrial Uses of ATP-Luminescence in Rapid Microbiology (Stanley, P. E., Smither, R. and Simpson, W. J., Eds.), pp. 41-47, Cara Technology Ltd, Lingfield, Surrey, 1997. 1998 * A. Dvoráková, K. Demnerová, M. Macková, J. Pazlarová, P.Rauch, E.Ferri, S.Girotti. “Microbial Nitrate Reductase: Classification and Determination. Chemické Listy, 92 (1), 128-132, 1998. * S.Girotti, F.Zanetti, E.Ferri, S.Stampi, F.Fini, S.Righetti, A.Roda, R.Budini. "Wastewater and sludges: the rapid determination of microbial content by ATP bioluminescence". Annali di Chimica, Journal of Analytical and Environmental Chemistry, 88 (3-4), 291-298, 1998. * F.Zanetti, S.Girotti, S.Stampi, F.Fini, G.De Luca, E.Ferri. "Valutazione della contaminazione microbica dei fanghi mediante la determinazione chemiluminescente di ALP". Annali di Igiene, 10 (4, Supplemento 2), 229, 1998. * A.Roda, F.Piazza, P.Simoni, K.Afandi, F.Ruffini, D.Cantagalli, F.Fini, S.Girotti. "I metodi immunometrici quantitativi nell'analisi ambientale tossicologica". Ligand Assay, 3 (4), 155-166, 1998. S.Girotti, F.Ruffini, D.Cantagalli, F.Fini, F.Piazza, P.Simoni, K.Afandi, A.Roda. "Recenti applicazioni dei saggi immunologici negli alimenti". Ligand Assay, 3 (4), 167-175, 1998. * M.Merighi, A.Sandrini, S.Landini, S.Malaguti, C.Porrini, A.G.Sabatini, S.Girotti, S.Ghini, C.Bazzi. "Automated detection of the plant pathogen Erwinia Amylovora by chemiluminescent immunoenzymatic determination of PCR amplicons from pEA29: applications to diagnosis and epidemiology". In: "Bioluminescence and Chemiluminescence: Perspectives for the 21st Century" p. 504-507, A.Roda, M.Pazzagli, L.J.Kricka and P.E.Stanley Editors, Wiley and Sons, Chichester, UK, 1998. * A.P.Dalpero, S.Ghini, S.Girotti, C.Porrini, A.G.Sabatini. "Detection of organophosphorous and carbamate pesticide residues by chemiluminescent enzymatic determination". In: "Bioluminescence and Chemiluminescence: Perspectives for the 21st Century" p. 540-543, A.Roda, M.Pazzagli, L.J.Kricka and P.E.Stanley Editors, Wiley and Sons, Chichester, UK, 1998. 1999 * A.Roda, E.N.Ferri, S.Girotti, A.Ius, P.Rauch, M.Poplstein, M.Pospisil, P.Pipek, I.Hochel, L.Fukal. “Determination of PAHs in various smoked meat products and different samples by enzyme immunoassay". Journal of the Science of Food and Agriculture, 79, 58-62, 1999. * T.Kuchta, I.Hapala, M.Mariássyová, D.Cantagalli, S.Girotti, (in Slovak). "Luminometric determination of the antioxidative activity of natural colour concentrates-Luminometrické stanovenie antioxidacnej aktivity koncentrátov prírodných farbív". Bulletin of Food Research - Bulletin potravinarskeho vyskumu, 38 (2), 103-108, 1999. S.Girotti, S.Lodi, E.Ferri, G.Lasi, F.Fini, S.Ghini, R.Budini. "Chemiluminescent determination of Xanthine Oxidase activity in milk". Journal of Dairy Research, 66, 441-448, 1999. S.Girotti, E.N.Ferri, F.Fini, F.Ruffini, R.Budini, I.Moura, G.Almeida, C.Costa, J.J.G.Moura, G.Carrea. "Enzymatic spectrophotometric determination of nitrites in beer". Analytical Letters, 32 (11), 2217-2227, 1999. F.Fini, G.Gallinella, S.Girotti, M.Zerbini, M.Musiani. "Development of a chemiluminescence competitive PCR for the detection and quantification of Parvovirus B19 DNA using a microplate luminometer". Clinical Chemistry, 45 (9), 1391-1396, 1999. 134 * M.Merighi, S.Malaguti, C.Bazzi, A.Sandrini, S.Landini, S.Ghini, S.Girotti. "Specific detection of Erwinia amylovora by immunoenzymatic determination of PCR products". Acta Horticulturae, 489, 39-42, 1999. 2000 S.Girotti, M.Muratori, F.Fini, E.Ferri, G.Carrea, M.Korac, P.Rauch. "Luminescent enzymatic flow sensor for D- and L-lactate assay in beer". European Food Research and Technology - Zeitschrift für Lebensmittel-Untersuchung und -Forshung A, 210 (3), 216-219, 2000. * M.Merighi, A.Sandrini, S.Landini, S.Ghini, S.Girotti, S.Malaguti, C.Bazzi. "Chemiluminescent and colorimetric detection of Erwinia amylovora by immunoenzymatic determination of PCR amplicons (PCR-ELISA) from plasmid pEA29". Plant Disease, 84, 49-54, 2000. S.Girotti, F.Fini, E.Ferri, R.Budini, S.Piazzi, D.Cantagalli. "Determination of superoxide dismutase in erythrocytes by a chemiluminescent assay". Talanta, 51 (4) 685-692, 2000. * M.Bancirova, S.Girotti, J.Lasovský. “Determination of reactive oxygen species based on chemiluminescence of CLA, FCLA and MCLA”. CLSAC, Chemické Listy, 94 (9) 761, 2000. * B.Micková, L.Karasová, L.Fukal, I.Hochel, P.Rauch, P.Gregor, J.Hajšlová, F.Fini, S.Girotti, A.Abad, J.J.Manclus, J.V.Mercader, A.Montoya. “Immunoassay of Organochlorine Pesticides”. Proceedings of “Chemical Reactions in Foods IV, 20-22 September 2000, Prague, Czech Republic, FECS-Event No.245. Potravinárské Vêdy (Czech Journal of Food Sciences), 18, Special Issue, 266-267, 2000. 2001 * S.Girotti, F.Fini, P.Rauch, B.Micková, A.Abad, J.J.Manclus, A.Montoya. “Development and application of chemiluminescent immunoassays in analytical chemistry” Workshop “Environmental Biotechnology in Europe”, September, 30 - October 2, 2000, Salamanca, Spain, Tempus/Phare Project Compact Measures Grant (CME-03617-97) “Environmental Issues in University Education”. J. Káš and P Jenč, Eds., ICT Press Praha, CZ, page 9, 2001. * L.Bolelli, F.Fini, S.Girotti, E.Carpenè, M.Musiani, G.Gentilomi. “Bioluminescent bacteria: a versatile tool for environmental monitoring”. Workshop “Environmental Biotechnology in Europe”, September, 30 - October 2, 2000, Salamanca, Spain, Tempus/Phare Project Compact Measures Grant (CME-03617-97) “Environmental Issues in University Education”. J. Káš and P Jenč, Eds., ICT Press Praha, CZ, page 10, 2001. * S.Girotti, S.Ghini, F.Fini, C.Porrini, A.G.Sabatini. “Honey bees as bioindicators in environmental monitoring”. Workshop “Environmental Biotechnology in Europe”, September, 30 - October 2, 2000, Salamanca, Spain, Tempus/Phare Project Compact Measures Grant (CME-03617-97) “Environmental Issues in University Education”. J. Káš and P Jenč, Eds., ICT Press Praha, CZ, page 11, 2001. * P.Rauch, B.Micková, L.Karasová, L.Fukal, A. P.Gregor, J.Hajšlová, F.Fini, S.Girotti, A. Abad, J.J. Manclus, J.V. Mercader, Montoya. “Development of enzyme immunoassay for organochlorine pesticides”. Workshop “Environmental Biotechnology in Europe”, September, 30 - October 2, 2000, Salamanca, Spain, Tempus/Phare Project Compact Measures Grant (CME-03617-97) “Environmental Issues in University Education”. J. Káš and P Jenč, Eds., ICT Press Praha, CZ, page 19, 2001. * S.Rossi, A.P.Dalpero, S.Ghini, R.Colombo, A.G.Sabatini, S.Girotti. “Multi residual method for Gas Chromatography analysis of pesticides in honeybees cleaned by gel permeation chromatography”. Journal of Chromatography A, 905 (1-2), 223-232, 2001. 135 * S.Girotti, E.N.Ferri, L.Bolelli, G.Sermasi, F.Fini. "Applications of bioluminescence in analytical chemistry". In: “Chemiluminescence in Analytical Chemistry”, A.M.Garcia-Campaña, W.R.G.Baeyens, Editors, Marcel Dekker, New York, 247-284, 2001. * S.Girotti, F.Fini, P.Rauch, B.Micková, L.Karasová, L.Fukal, A.Abad, J.J.Manclus, J.V.Mercader, A.Montoya. “Chemiluminescent immunoassays for the detection of organochlorine pesticides”. In: "Bioluminescence and Chemiluminescence2000" J.F.Case, P.J.Herring, B.H.Robison, S.H.D.Haddock, L.J.Kricka and P.E.Stanley Editors, World Scientific Publishing Co., Singapore, 349-352, 2001. * S.Girotti, E.Errani, P.Scurti. “Esposizione dei consumatori della provincia di Bologna ai residui di fitofarmaci presenti con maggiore frequenza nella dieta alimentare nel quadriennio 1996-1999”. Bollettino Chimici Igienisti, 52, 43-49, 2001. * I.Hochel, G.Jenikova, C.F.Dursi, J.Pazlarova, S.Girotti, K.Demnerová. “Application of Mouse Antibodies to Somatic Antigen for Detection of Salmonella enteritidis by Competitive ELISA”: Food and Agricultural Immunology, 13, 115-126, 2001. * M.Fernández, C.Padrón, L.Marconi, S.Ghini, R.Colombo, A.G.Sabatini, S.Girotti. “Determination of organophosphorus pesticides in honeybees using SPME”. Journal of Chromatography A, 922, 257-265, 2001. * M.Fernández, Y.Picó, S.Girotti, J.Mañes. “Analysis of organophosphorus pesticides in honeybee by liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry”. Journal of Agricultural and Food Chemistry, 49, 3540-3547, 2001. D.Di Leo, S.Girotti, G.Lasi, S.Lodi. “Una metodica automatizzata per un’analisi microbiologica”. Qualificazione Industriale, Giugno, 55-57, 2001. S.Rossi, R.Serra, R.Badiello, S.Girotti. “Rischi degli studenti nei laboratori didattici di una Facoltà di Farmacia”. Atti 7° Convegno di Igiene Industriale AIDII, Corvara, 21-23 Marzo 2001, R.Vistocco Editore, pag. 175-178, 2001. * S.Girotti, L.Bolelli, F.Fini, M.Musiani, G.Gentilomi, G.Andreani, E.Carpené, G.Isani. “I batteri bioluminescenti: uno strumento versatile per l'analisi dell’inquinamento marino”. ATTI del XVI CONGRESSO NAZIONALE DI CHIMICA ANALITICA “Chimica Analitica e Scienze del Mare”, Portonovo (AN) ,24-28 Settembre 2001, pag 260-261. I-4 Other Scientific Output * European Patent n. 02425030.0 entitled “Detection of Listeria monocytogenes by the polymerase chain reaction”, developed in the 2001, funded by the University of Bologna, registered on 28 January 2002 and granted to a Company. Appendix 3 Journal Portfolio Analysis Name of the Unit: Bologna 7 Research Director: Stefano Girotti Years included: 1997-2001 Name of Journal Number articles Analytical Letters 1 Talanta 1 Journal of Agricultural and Food 1 Chemistry of Journal Impact Field(s) Factor 1.000 Chemistry, Analytical 1.587 Chemistry, Analytical 1.576 Agriculture, Multidisciplinary Chemistry, Applied Ranking 40/68 23/68 9/94 136 Food Science and Technology Food Science and Technology Chemistry, Applied Food Science and Technology Immunology Toxicology Biochemical Research Methods Chemistry, Analytical Chemistry, Multidisciplinary Agriculture, Multidisciplinary Chemistry, Applied Food Science and Technology Medical Laboratory Technology Food Science and Technology Journal of Dairy Research 1 Food and Agricultural 1 Immunology 1.374 0.825 Journal of Chromatography A 2 2.793 Chemické Listy 3 Journal of the Science of Food 1 and Agriculture 0.317 1.160 Clinical Chemistry 1 European Food Research and 1 Technology Plant Disease 1 Analytical Biochemistry 1 4.371 0.791 Quimica Analitica 1 0.303 Plant Sciences 48/134 Biochemical Research Methods 14/68 Biochemistry and Molecular Biology Chemistry, Analytical Chemistry, Analytical 64/68 Annali di Chimica-Rome 1 0.394 Chemistry, Analytical 1.163 2.019 12/94 38/94 6/68 95/118 22/94 1/24 41/94 60/68 Comments on: a) the method: We used the JCR Science Edition 2001 b) the results: Several fields were interested according to the publication policy: Analytical Chemistry –Plant Science – Food Science and Technology – Medical Laboratory Technology – Environmental Science – Multidisciplinary Chemistry 137 BOLOGNA 6 Name of the Research Unit BOLOGNA6 Research Leader Prof. Claudio Trombini University: Università degli Studi di Bologna University of Bologna Contact Person Claudio Trombini Dipartimento di Chimica “G. Ciamician” Università degli Studi di Bologna via Selmi 2, I-40126, Bologna (Italy) Phone: 051 2099513 Fax: 051 2099456 E-mail: [email protected] Faculty: Scienze Matematiche Fisiche e Naturali Mathematical, Physical and Natural Science Department: Dipartimento di Chimica “G. Ciamician” Department of Chemistry “G. Ciamician” Thematic area • Sustainable chemistry (solvents, catalysis, recycling and others). photochemistry, • Chemistry of the Ecosistems (soil, water and air chemistry; environmental impact of synthetic chemicals). Introduction and Context Introduction to the Self-evaluation Report The whole research activities of our unit will be reported. Emphasis will be given on aspects related to thematic areas of INCA (italics). The University, the Faculty and the Department The University, the Faculty and the Department The University of Bologna is the oldest in the western world: 1088 may be accepted as conventional date to indicate when teaching became free and independent of the ecclesiastic schools. Bologna University is one of the largest universities in Italy and in Europe. It is a state university and it is autonomous with its own "statuto" which indicates how the University governs itself through its various elected bodies. The University government and the main research and teaching activity are located in Bologna, but many new research and teaching activities have been recently dislocated in other Cities of the Emilia Romagna region, such as Cesena, Faenza, Forli’, Ravenna and Rimini. The whole University currently counts about 900 professors, 1000 associated professors, 1050 researchers and more than 100000 students. It is divided in 19 Faculties, 65 Departments, 5 Federated Departments (“Unità Complesse”), 3 Institutes and it currently offers about 65 “laurea” degree courses and 45 “diploma” degree courses in the following subject areas: a)Agriculture; b) Economics; c) Education and Humanities; d) Engineering; e) Industrial Chemistry, f) Law; g) Literature and Philosophy; h) Mathematical, Physical and Natural Sciences; i) Medicine; l) Pharmacy; m) Political Science; n) School of Modern Languages for Interprets and Translators; o) Statistical Sciences; p) Veterinary Medicine; q) Foreign Languages and Literatures. The Faculty of Mathematical, Physical and Natural Sciences is one of the most complex Faculty of the entire Athenaeum since it embraces scientific disciplines going from mathematic to chemistry, from physic to computer science, from geology to biology and biotechnologies, from natural sciences to astronomy, from environmental sciences to the technologies for the conservation and the restoration of the cultural heritage. The Faculty supplies therefore a wide didactic offer, justified by the numerous competences that in it operate and in it are developed. The didactic activity is developed totally in the Departments, structures devoted to the organization of the scientific activity, but which carry out a fundamental role in the education of the students. There are seven Departments in the Faculty of Sciences: the Department of Astronomy, of Biology, the Department of Chemistry "G. Ciamician", the Department of Physics, the Department of Mathematics, the Department of Geological Sciences, the Department of Sciences of the Information, the Department of General Pathology. In addition, in Ravenna is active the Interdepartmental Center of Environmental Science. 138 The Department of Chemistry “G. Ciamician” derives from the same Institute which, in turn, can be ascribed to the first Chemistry chair in Italy, founded in Bologna in 1737. The Course of Bachelor in Chemistry of the Faculty of Mathematical, Physical and Natural Sciences of the University of Bologna offers to its own students the proper instruments in order to gain access to the various fields of Chemistry: from new materials to bioactive compounds, from fundamental research to the environmental control. The Course of Bachelor in Environmental Sciences - the first in Italy – was founded in Ravenna by the University of Bologna in 1989/90. The student graduated in Environmental Sciences has a deep knowledge of classic scientific disciplines (mathematics/informatics, physics, chemistry, biology/ecology, earth sciences). In its curriculum are present courses in law, economics, assessment of environmental impact as well as experimental trans-disciplinar activities. He is an expert who, beyond possessing an excellent environmental sistemic culture, is in the position to estimate or manage environmental processes and ecosystems. Professional and research training of graduates may be further on completed via: 1.PhD Course in “Environmental Science: control and management of natural resources” (3 years). 2.Master in “Marine pollution management” (1 year) 3.Master in “Law of the environmental and cultural heritage” (1 year) The Unit The research unit is composed by Professors and Researchers of the Chemistry Department “G. Ciamician”, working in the Course of Bachelor in Chemistry and of Environmental Sciences (Ravenna). In detail, the research unit is composed by two Full Professors, one Associate Professor and three Researchers. The research activity of the unit has been centered in the last decade on organometallic chemistry and, particularly, on the field of catalysis and reaction mechanism. The administrative staff of the Department of Chemistry will take care of the administrative part. The components of the research unit are in charge of the following courses of the Degree in Chemistry and in Environmental Sciences: 1.Organic Chemistry III (Chemistry) 2.Applied Organic Chemistry (Chemistry) 3.Organic Chemistry Lab III (Chemistry) 4.Organic Chemistry (Environmental Sciences) 5.Green Chemistry (Environmental Sciences) 6.Chemistry of Marine Natural Substances (Environmental Sciences) 7.Organic Chemistry (Cultural heritage preservation diagnostics) Moreover, the unit is involved in the teaching activity of Masters and Ph.D. courses. Programme Description and Evaluation 1 Title New methodologies for the development of eco-compatible processes and for the study of natural processes. 2 Research Leader Prof. Claudio Trombini 2a Sub-programme titles and sub-programme leaders Organometallic chemistry applied to the development of sustainable processes. (Leader: Prof. A.Umani-Ronchi) Atmospheric processes of the organic fraction (Leader: Prof. E. Tagliavini) 3 Composition of the scientific research staff of the unit per 1 January 2002 Names and Titles Claudio Trombini Year Birth 1949 of Rank Full Professor Research Input Remarks in fte in 2001 0.2 Research Leader 139 Achille Umani-Ronchi Emilio Tagliavini Marco Bandini Paola Galletti Marco Lombardo Total research input 4 1936 1954 1973 1969 1969 0.2 0.2 0.4 0.4 0.4 1.8 Sub-programme leaders Sub-programme leaders Input of Academic Staff in fte Category Full Professors Associated Professors Ricercatori Post-docs PhD-students Borsisti Total 5 Funding 5.1 Personnel (in fte) Source University CNR European Union Other Sponsors Total 5.2 Full Professor Associate Professor Researcher Researcher Researcher 1997 0.4 0.2 1.2 1998 0.4 0.2 1.2 1999 0.4 0.2 1.2 2000 0.4 0.2 1.2 2001 0.4 0.2 1.2 Total 2.0 1.0 6.0 1.8 1.8 1.8 1.8 1.8 9.0 1997 1.8 1998 1.8 1999 1.8 2000 1.8 2001 1.8 Total 9.0 1999 256000000 5000000 4000000 265000000 2000 55000000 10000000 65000000 2001 63000000 10000000 73000000 Total 606000000 50000000 60000000 716000000 Materials and Equipment (in Million Lire) Source University - MURST CNR EU Other Sponsors Total 6. Progress Report 6.1 Mission Statement 1997 185000000 20000000 13000000 218000000 1998 47000000 25000000 23000000 95000000 The research unit is primarly involved in: 1) the development of new synthons and catalysts in order to improve the stereocontrol and the efficiency in the preparation of useful intermediates for the synthesis of bioactive compounds. 2) The development of new synthetic eco-friendly methodologies through the use of less hazardous procedures, of alternative solvents, including water, and of different energy sources. 3) The stereoselectivity optimisation through a deep analysis of its dependance from temperature and from the solvent, or mixture of solvents, composition. 4) Atmospheric chemistry studies on the volatile or suspended organic component. The results will be used by the international scientific community active in the field of synthetic chemistry, fine chemicals and pharmaceuticals on one hand, and by the locals government authorities and public environmental managers, responsible of the urban air quality control. 6.2 The Research Programme 140 The interests of the research unit focus on two main topics: A) process development and optimization in organic synthesis according to the main strategies of green chemistry; B) studies of environmental processes. As refers to the field of organic synthesis (section A), the unit efforsts are centered on: 1.optimization of catalytic processes and/or transformation of stoichiometric processes based on ecotoxic metals into catalytic processes, particularly in the field of enantioselective reactions; 2.integration of multistep sequences into one-pot multicomponent processes; 3.development of clean routes to new organometallic reagents; 4.analysis of the effect of temperature and of solvent on stereo and regiochemistry for optimization purposes. As refers to the topic of environmental chemistry, the efforts of the unit have been focused on: 1.the role of mono, di and polycarboxylic acids in determining the formation of cloud droplets in the atmosphere; 2.the interaction of semivolatile organic compounds, particularly of polycyclic aromatic hydrocarbons, with particulate matter (PM10 and PM2.5) and with vegetation. Examples of the most important recent achievements on the previous activities by the research unit are here summarized: 1.development of an enantioselective catalytic version of the Nozaki-Hiyama-Kishi reaction for the asymmetic synthesis of homoallylic alcohols via allyl chromium complexes and carbonyl compounds. Stoichiometric Cr(II) has been replaced by a catalytic amount of Cr(III) by the in situ generation of the active species exploiting the redox couple Cr(III)-Mn°. Carrying out the reaction in the presence of chiral ligands, such as Jacobsen’s salen, an excellent control of absolute configurations of the newly formed stereogenic centers has been obtained. 2.Three new synthetic protocols based on boron chemistry have been developed which allow the synthesis of substituted, noncrotylic, homoallylic alcohols by the integration in a one-pot sequence of five different steps; 3.Two new synthetic protocols to 1-en-3,4-diols have been developed starting from 3-halo-enolesters, indium or zinc under Barbier conditions. Particularly, water replaces aprotic solvents, thus fulfilling one of the main principles of green chemistry which calls for reducing toxic or dangereous wastes. 4.A number of systematic studies on model reactions have been carried out in order to carefully evaluate both the effect of temperature on a large range of values and the effect of solvent or solvent composition on the regio and stereochemical outcome of nucleophilic addition to carbonyl compounds and their azomethyne derivatives. v) a complete picture of the biogeochemical study of mercury released in 20 years of industrial activity into a coastal lagoon, in the sediment and in the biota of this aquatic ecosystem. 6.3 Position in Networks • Intra-university co-operation C.I.N.M.P.I.S. “Consorzio Interuniversitario Nazionale per le Metodologie e Processi Innovativi di Sintesi” • Regional co-operation Comune di Ravenna, Assessorato all’Ambiente Provincia di Ravenna • National co-operation (including INCA) CNR-ISAO, Enichem, INCA, RIBBON s.r.l. Pharmaceutical and Chemical Products, PHARMABIOS Pavia. • International co-operation COST D12 6.4 Societal Relevance and Impact The relevance of the unit research area is on one hand strictly connected to the general principles of green chemistry and to their applications to organic synthesis (catalysis, low environmental impact processes, integration one-pot of multistep sequences, optimization studies), on the other hand is determined by the importance of gain information on atmospheric transformations and processes. 141 The impact of the research unit activity is clearly demonstrated by the exam of its scientific production which allows to emphasize both the strategic goals and the results of clear interest for the scientific community. Within the frame of our strategic guidelines are represented by optimization of economic factors (yield, stereocontrol, integration one-pot of multistep processes, molecular design of new and more effiecient synthons and catalysts), emphasis is also directed to the development of low-energy consuming processes with minimum environmental externalities. On the environmental side, a relevant contribution was offered by an innovative study on the mechanisms of formation of clouds droplets in the atmosphere, promoted by carboxylic and polycarboxylic acids. Furthermore, an almost complete description of the environmental status of a coastal lagoon impacted by severe inductrial pollution (particularly mercury) has been obtained, which represents a fundamental knowledge basis for planning future remediation projects. 6.5 Further Indications of Quality and Reputation Major scientific honours: Prof. Achille Umani-Ronchi: 2001. Premio alla Ricerca awarded from the Division of Organic Chemistry of the Italian Chemical Society. Dr. Marco Bandini: 2002. GICO Prize for young scientists awarded from the Italian Chemical Society. 6.6 Key Publications 1) R. Girotti, M. Lombardo, S. Morganti, C. Trombini “The First Zinc-Promoted, Environmentally Friendly, and Highly Efficient Acetoxyallylation of Aldehydes in aq Ammonium Chloride” Chem. Comm., 2001, 2310-2311. 2) Bandini, Pier Giorgio Cozzi, Paolo Melchiorre, Achille Umani Ronchi "The first catalytic enantioselective nozaki-hiyama reaction" Angew. Chem. Int. Edit Eng, 1999, 38, 3357-3359 3) G. Cainelli, D. Giacomini, P. Galletti, P. Orioli “Solvation of the Carbonyl Compound as a Predominant Factor in the Diastereofacial Selectivity of a Nucleophilic Addition” Angew. Chem. Int. Edit Eng, 2000, 39, 523-527. 4) C. McRae, C. E. Snape, C.-G. Sun, D. Fabbri, D. Tartari, C. Trombini, A. E. Fallick “Use of compound-specific stable isotope analysis to source anthropogenic natural gas-derived polycyclic aromatic hydrocarbons in a Lagoon sediments” Environmental Science and Technology, 2000, 34, 4684-4686. 5) Decesari, S; Facchini, MC; Matta, E; Lettini, F; Mircea, M; Fuzzi, S; Tagliavini, E; Putaud, JP ”Chemical features and seasonal variation of fine aerosol water-soluble organic compounds in the Po Valley, Italy” Atmospheric Environment, 35(21), 2001, pp. 3691 – 3699 7. Scientific Output 7.1 Publication Policy The research unit publication policy aims to: 1.publish the research results on high rank (impact factor) international journals, in the field of synthetic organic chemistry, applied chemistry, catalysis and environmental chemistry. 2.Present the research results on the most qualified national and international symposia, particularly in the field of synthetic organic chemistry, organometallic chemistry, catalysis and environmental chemistry. 7.2 Numerical data Category PhD-Dissertations 1997 - 1998 - 1999 2 2000 2 2001 2 Total 6 Scientific Publications 16 15 13 17 20 81 Professional Publications Master’s Theses 4 7 3 8 2 24 142 8 Self-evaluation The scientific output is charactyerized by a high quali and quantitative standard, and most of the publications may be located in frontier areas of modern chemistry. Future potential will further on improve when the unit will move to new modern buildings which are expected to be ready in a few years, thus leaving the disconfort of the present condition. Appendix I Scientific Output I-1 Overview of Dissertations and Master's Thesis (1997-2001) I.1.1 Dissertations Year Name PhD-student Title of the Dissertation Supervisor 1999, Paola Galletti, “Stereoselective Synthesis of Biological Active Molecules” (Prof. G. Cainelli) 1999, Marco Lombardo, “Isoxazolidines as Latent Functionalities: Synthesis and Applications” (Prof. C. Trombini) 2000, Sonia Casolari, “Nucleophilic Additions Catalysed by Chiral Lewis Acids: High Efficiency in the Stereocontrolled Synthesis of C-C Bonds“ (Prof. E. Tagliavini) 2000, Marco Bandini, “Asymmetric Reactions Promoted by Chiral Catalysers” (Prof. A. Umani-Ronchi) 2001, Stefano Decesari, “Studies on the Atmospheric Organic Aerosol: Composition, Sources and Chemical-Physical Properties”, (Prof. E. Tagliavini) 2001, Ivano Vassura, , “Studies on the Industrial Pollution in a Industrial Lagoon Area of Ravenna” (Prof. C. Trombini) I.1.2 Master's Thesis Year Name Master’s student Title of the Dissertation Supervisor 1997-1998, Emiliano Castiglioni, “Synthesis of Nitrogen Containing Heterocycles Starting from Nitrones”, Prof. Claudio Trombini 1997-1998, Lorenzo Gaddoni, “Hydroboration of Propargylic Compounds: a New Synthesis of Allylboranes”, Prof. Claudio Trombini 1997-1998, Michelangelo Marsili, “Optimization of a Protocol for the Biomonitoring of Incinerator Emissions”, Prof. Claudio Trombini 1997-1998, Meri de Angelis, “Boranes Enantioselective Reduction of Carbonyl Compounds Promoted by Chiral BisOxazolines”, Prof. Achille Umani-Ronchi 1998-1999, Milena Stracquadanio, “Studies on Polycyclic Aromatic Hydrocarbons Atmospheric Pollution in an Industrial Site of Ravenna”, Prof. Claudio Trombini 1998-1999, Serena Fabbroni, “Synthesis and Application of Optically Active Polyhydroxylated Pyrrolidines”, Prof. Claudio Trombini 1998-1999, Andrea Neri, “Theoretical and Experimental Studies on Reactivity of Quaternary Borate Ions”, Prof. Claudio Trombini 1998-1999, Cristian Soncini, “Synthesis of New Cephalosporins”, Prof. Achille Umani-Ronchi 1998-1999, Alfonso Melloni, “Use of New Chiral Catalysts for the Carbon-Carbon Bond Formation”, Prof. Achille Umani-Ronchi 1998-1999, Roberta Tino, “Enantioselective Formation of Carbon-Carbon Bonds Using Cr-Salen”, Prof. Achille Umani-Ronchi 1998-1999, Stefano Morganti, “Stereoselctive Studies on Pinacolic Reaction of Carbonyl Compounds”, Prof. Achille Umani-Ronchi 1999-2000, Laura Sgreccia, “Catalytic Oxidoreduction Reactions Promoted by Titanium Complexes”, Prof. Achille Umani-Ronchi 1999-2000, Barbara Roda, “Addition Reactions of Allylchromium to Imines Using Chiral Ligands”, Prof. Achille Umani-Ronchi 1999-2000, Arianna Quintavalla, “Enantioselective Addition of Crotylhalides and Bromoesters to Carbonyl Compounds in the Presence of Chiral Chromium Complexes”, Prof. Achille Umani-Ronchi 143 2000-2001, Rugiada Girotti, “Organic Chemistry Applications of Heterofunctionalized Indium and Zinc Allylic Compounds”, Prof. Claudio Trombini 2000-2001, Massimo Tozzi, “New Applications of Organoboron Compounds in Organic Synthesis”, Prof. Claudio Trombini 2000-2001, Massimo Giacobini, “Formation of New Carbon-Carbon Bonds Catalyzed by Indium Salts”, Prof. Achille Umani-Ronchi 2000-2001, Sebastiano Licciulli, “Enantioselective Addition of Functionalized Allylhalides to Aldehydes Using CrSalen”, Prof. Achille Umani-Ronchi 2000-2001, Paolo Angelucci, “Additive Effect On Facial Diastereoselectivity”, Dott. Paola Galletti 2000-2001, Giancarlo Trani, “Lewis Acids Mediated Syntheses of 4-Alkyliden-Azetidin-2-Ones”, Dott. Paola Galletti 2000-2001, Elisa Bertoletti, “Synthesis Of Novel Azetidin-2-Ones For The Development Of Enzymatic Inhibitors”, Dott. Paola Galletti 2000-2001, Ilaria Giordano, “Solvent And Temperature Dynamic Effects On Diels-Alder Reactions”, Dott. Paola Galletti 2001-2002, Francesca D’Ambrosio, “Study on the Acetoxyallylation of Carbonyl Compounds”, Prof. Claudio Trombini 2001-2002, Rosa Prati, “Temperature and Solvent Effect in Chemical and Enzymatic Reactions”, Dott. Paola Galletti I-2 Overview of Scientific Publications (1997-2001) per year 1997 F. Degiorgis, M. Lombardo, C. Trombini “Synthesis of 3-O-Benzyl-3,7-imino-1,3,6,7-tetradeoxy-L-manno-heptitol and of 3-O-Benzyl-3,7-imino-1,3,6,7tetradeoxy-D-gluco-heptitol” Organic Preparations & Procedures International 1997, 29, 485-488. D. D. Dhavale, V. N. Desai, M. D. Sindkhedkar, R. S. Mali, C. Castellari, C. Trombini “A new route to aminosugars from sugar nitrones: synthesis of 6-deoxynojirimycin” Tetrahedron: Asymmetry 1997, 8, 1475-1486. A. Fiumana, M. Lombardo, C. Trombini “Synthesis and Iodocyclization of Homoallylic Hydroxylamines” Journal of Organic Chemistry 1997, 62, 5623-5626. F. Degiorgis, M. Lombardo, C. Trombini “A Nitrone Based Route to Polyhydroxylated Lactams and Piperidines: An Expeditious Synthesis of rac-Fagomine” Synthesis, 1997, 1243-1245. F. Degiorgis, M. Lombardo, C. Trombini “Synthesis of Four Stereoisomers of 5-Amino-2,5-dideoxy-heptono-1,5-lactams” Tetrahedron, 1997, 53, 11721-11730. P.G. Cozzi, P. Orioli, E. Tagliavini, A. Umani-Ronchi. "Enantioselective Allylation of Aldehydes Promoted by Chiral Zinc Bis(Oxazoline) Complexes." Tetrahedron Letters 1997, 38, 145-148. C.M. Bellucci, A. Bergamini, P.G. Cozzi, A. Papa, E. Tagliavini, A. Umani-Ronchi. "Catalytic Asymmetric Synthesis of Secondary Alcohols Using Chiral cis-1-Amino-2-Hydroxy-1,2,3,4-Tetrahydronaphthalene as Chiral Ligand." Tetrahedron:Asymmetry 1997, 8, 895-902. P.G. Cozzi, E. Tagliavini, A. Umani-Ronchi. "Enantioselective Addition of Allylic Silanes and Stannanes to Aldehydes mediated by Chiral Lewis Acid" Gazzetta Chimica Italiana 1997, 127, 247-253. P.G. Cozzi, G.P. Prati, A. Umani-Ronchi "New Easily Accesible Chiral Indole Ligands" Gazzetta Chimica Italiana, 1997, 127, 403-405. 144 S. Casolari, P.G. Cozzi, P. Orioli, E. Tagliavini, A. Umani-Ronchi. "Chiral-achiral ligand synergy: activation of a Zirconium-BINOL Lewis acid Complex by Addition of a tertButylcalix[4]arene" Chemical Communications, 1997, 2123-2124. E. Tagliavini, C. Trombini, A. Umani-Ronchi "Stereoselective Synthesis Based on Zinc and Boron Enolates", in Advances in Carbanion Chemistry, JAI Press Inc, London , 1997, Vol.2, vol. pp 111-146, G. Cainelli, D. Giacomini, P. Galletti, M. DaCol “Penicillin G Acylase mediated Synthesis of the Enantiopure (S)-3-Amino-Azetidin-2-one” Tetrahedron: Asymmetry 1997, 8, 3231-3235 G. Cainelli, M. DaCol, P. Galletti, D. Giacomini “Ruthenium Catalyzed Oxidation of 3-amino-?-Lactams” SynLetters 1997, 8, 923. G. Cainelli, D. Giacomini, P. Galletti “Synthesis of N-(Tri-i-propylsilyl)-and N-(t-Butyldimethylsilyl)aldimines and Their Application in the Synthesis of ?Lactams ” Synthesis 1997, 8, 886-890. Braga D; Angeloni A; Grepioni F; Tagliavini E Organic-Organometallic Crystal Synthesis .2. Organic Frameworks Constructed Around [(eta(5)-C5H5)(2)Co](assisted O-H-Center-Dot-Center-Dot-Center-Dot-O and C-H-Center-Dot-Center-Dot-Center-Dot-O Hydrogen-Bonds() via Charge) Organometallics, 1997, 16, 5478 – 5485. A. Bottoni; A. Costa; D. Ditommaso; I. Rossi; E. Tagliavini New Computational And Experimental-Evidence For The Mechanism Of The Sakurai Reaction Journal of the American Chemical Society, 1997, 119, 12131 – 12135. 1998 M.Gianotti, M.Lombardo, C.Trombini “Trimethylsilyl Triflate Promoted Addition of Allyltributylstannane to Aldonitrones; One-pot Synthesis of 5Iodomethylisoxazolidines.” Tetrahedron Letters, 1998, 39, 1643-1646. D.Fabbri, O.Felisatti, M.Lombardo, C.Trombini, I.Vassura “The Lagoon of Ravenna (Italy): Characterisation of mercury-contaminated sediments” The Science of the Total Environment, 1998, 213, 121-128. M. Lombardo, C. Trombini “One-pot multicomponent reactions” Seminars in Organic Synthesis, XXIII Summer School “A.Corbella”, S.C.I.. 1998, pp.7-32. M. Lombardo, S. Spada, C. Trombini “A route to (2α,3?,4?)-(±)-(hydroxymethyl)3,4-pyrrolidinediol based on the ?-silyloxy-allylation of a glycolaldehydederived nitrone” European Journal of Organic Chemistry 1998, 1, 2361-2364. L. Gaddoni, M. Lombardo, C. Trombini “One-pot three-component route to anti-homoallylic alcohols based on the hydroboration of propargyl bromide” Tetrahedron Letters, 1998, 39, 7571-7574. D. Fabbri, C. Trombini, I. Vassura “Analysis of polystyrene in polluted sediments by pyrolysis-gas chromatography/mass spectrometry” Journal of Chromatographic Science, 1998, 36, 600-604. 145 P.G. Cozzi, E. Tagliavini, A. Umani-Ronchi. "Enantio and diastereoselective addition of organometallic reagents to aldehydes and imines." Proceedding of the ICOS conference., Plenum Press. 1998, 230-238 M. Contento, M. Da Col, P. Galletti, S. Sandri, A. Umani-Ronchi "A facile synthesis of Chephem side chains by Palladium catalyzed cross-coupling of 3-substituted-??-chephems with dialkylzinc or vinyltributyl tin" Tetrahedron Letters, 1998, 42, 8743-8749 M. Bandini, P.G. Cozzi, L. Negro, A. Umani-Ronchi "Enantioselective reduction of ketones with triethoxysilane catalized by chiral bis-oxazoline titanium complexes" Chemical Communications, 1998, 2115-2116 G. Cainelli, D. Giacomini, P. Galletti “N, N-Dibenzyloxycarbonyl-glycylchloride as useful Ketene Equivalent in the Synthesis of Azetidin-2-one” SynLetters 1998, 6, 611. D. Giacomini, P. Galletti “Enantioselective Reductions by Chiral Hydride Reagents” in Seminars in Organic Synthesis, Summer School “A. Corbella”, S. C. I. 1998. G. Cainelli, D. Giacomini, P. Galletti “Practical Synthesis of a Key Intermediate to Produce ?-Lactam Antibiotics” Tetrahedron Letters 1998, 42, 7779. D. Braga; F. Grepioni; E. Tagliavini; Jj. Novoa; F. Mota C-H-Center-Dot-Center-Dot-Center-Dot-O Hydrogen-Bonds In The Mixed-Valence Salt [(Eta(6)-C6h6)(2)Cr](-) And The Breakdown Of The Length()[Cro3(Och3)]()Strength Analogy/ New Journal of Chemistry, 1998, 22, 755 – 757. D. Braga; A. Angeloni; E. Tagliavini; F. Grepioni Crystal engineering via negatively charged o-h-center-dot-center-dot-center-dot-o- and charge-assisted c-h-delta-dotcenter-dot-center-dot-o(delta-) hydrogen bonds from the reaction of [co(eta(5)-c5h5)(2)][oh]with polycarboxylic acids(center) Journal of the Chemical Society. Dalton Transactions, 1998, 1961 – 1968. C. Alvisi; S. Casolari; A. Costa; M. Ritiani; E. Tagliavini Addition of Dialkylzinc to Ketones in the Presence of Silylating Agents - Synthesis of Functionalized Tertiary Silyl Ethers Journal of Organic Chemistry, 1998, 63, 1330 – 1333. 1999 O. Cattani, D. Fabbri, M. Salvati, C. Trombini, I. Vassura “Active biomonitoring in a coastal mercury-polluted wetland by traslocation of bivalve molluscs” Environmental Toxicology and Chemistry, 1999, 18, 1801-1805. Marco Bandini, Pier Giorgio Cozzi, Achille Umani Ronchi "Highly diastereoselective Pinacol coupling of aldehydes catalyzed by Titanium-Schiff base complexes" Tetrahedron Letters, 1999, 40, 1997-2000 Marco Bandini, Pier Giorgio Cozzi, Lucia Negro, Achille Umani Ronchi "Enantioselective reduction of ketones with triethoxysilane catalyzed by chiral bis-oxazoline titanium complexes" Chemical Communications, 1999, 39-40 Marco Bandini, Pier Giorgio Cozzi, Paolo Melchiorre, Achille Umani Ronchi "The first catalytic enantioselective Nozaki-Hiyama reaction" 146 Angew. Chem. Int. Ed. Eng. 1999, 38, 3357-3359 Marco Bandini, Pier Giorgio Cozzi, Achille Umani Ronchi, Marzia Villa "Diastereoselective addition of higher order cuprates and zinc-copper reagents to imines derived from (S)-1phenylethylamine" Tetrahedron, 1999, 55, 8103-8110 Marco Bandini, Pier Giorgio Cozzi, Achille Umani Ronchi "Asymmetric synthesis with "Privileged Ligands" - The challenge to realize the synthesis of enentiomeric pure compounds on industrial scale" La Chimica e L'Industria, 1999, 81, 201-211 Pier Giorgio Cozzi, Emilio Tagliavini and Achille Umani Ronchi "Enantio and diastereoselective addition of organometallic reagents to aldehydes and imines" Kluwer Academic - Plenum Publishers, 1999,239-246 G. Cainelli, D. Giacomini, P. Galletti “Reversal Diastereofacialselectivity in the n-Butyllithium Addition to O-protected N-trimethylsilylimines of (2S)Lactal: Enthalpic versus Entropic Contributions” European Journal of Organic Chemistry 1999, 61. G. Cainelli, D. Giacomini, P. Galletti “Temperature and Solvent Effects in Facial Diastereoselectivity of Nucleophilic Addition: Entropic and Enthalpic contribution ” Chemical Communications, Feature Article, 1999, 567. G. Cainelli, D. Giacomini, P. Galletti "Synthesid of ?-lactams via[2+2] cycloaddition reactions" in Seminars in Organic Synthesis, Summer School “A. Corbella”, S. C. I. 1999. S. Casolari, D. D'Addario, E. Tagliavini BINOL-Ti-catalyzed synthesis of tertiary homoallylic alcohols: The first catalytic asymmetric allylation of ketones Organic Letters, 1999, 1, 1061 – 1063. D. Braga, F. Paganelli, E. Tagliavini; S. Casolari, G. Cojazzi, F. Grepioni The remarkable behavior of crystalline [Fe(eta(5)-C5H4CHO)(2)]: Two solid-to-solid phase transitions and a solidstate reaction Organometallics, 1999, 18, 4191 – 4196 2000 M. Lombardo, C .Trombini “Trimethylsilyltriflate-promoted addition of 2-trimethylsilyloxyfuran to a chiral cyclic nitrone; a short synthesis of 1S(1?,2?,7?,8?,8a?)]-1,2-di(t-butyldiphenylsilyloxy)-indolizidine-7,8-diol” Tetrahedron, 2000, 56, 323-326. M. Lombardo, C. Trombini “Nucleophilic additions to nitrones” Synthesis, 2000, 759-774. D. Fabbri, D. Tartari, C. Trombini “Analysis of poly(vinyl chloride) and other polymers in sediments and suspended matter of a coastal lagoon by pyrolysis-gas chromatography-mass spectrometry” Analytica Chimica Acta, 2000, 413, 3-11. M.Lombardo, S. Morganti, C.Trombini “The hydroboration of propargyl bromide. Simple one-pot three-component routes to (Z)-1-bromo-alk-1-en-4-ols and to anti-homoallylic alcohols” 147 Journal of Organic Chemistry, 2000, 65, 8767-8773. C. McRae, C. E. Snape, C.-G. Sun, D. Fabbri, D. Tartari, C. Trombini, A. E. Fallick “Use of compound-specific stable isotope analysis to source anthropogenic natural gas-derived polycyclic aromatic hydrocarbons in a Lagoon sediments” Environmental Science and Technology, 2000, 34, 4684-4686. M. Bandini, P.G. Cozzi, M. de Angelis and A. Umani-Ronchi "Zinc triflate-bis-oxazoline complexes as chiral catalysts: enantioselective reduction of ?-alkoxy-ketones with catecholborane" Tetrahedron Letters, 2000, 41, 1601-1605 M. Bandini, S. Casolari, P.G. Cozzi, G. Proni, E. Schmohel, G.P. Spada, E. Tagliavini, A. Umani-Ronchi "Synthesis and characterization of new enantiopure 7,7'-disubstituted 2,2'-dihydroxy-1,1'binaphthyls: useful ligands for the asymmetric allylation reaction of aldehydes" European Journal of Organic Chemistry, 2000, 491-497 M. Bandini, P.G. Cozzi and A. Umani-Ronchi "Salens chiral activator: anti versus syn switchable diastereoselection in the enentioselective addition of crotyl bormide to aromatic aldehydes" Angewandte Chemie. Int. Ed. Eng, 2000, 39, 2327-2330 M. Bandini, P.G. Cozzi and A. Umani-Ronchi "The first catalytic enantioselective Nozaki-Hiyama-Kishi reaction" Polyhedron, 2000, 19, 537 G. Cainelli, D. Giacomini, P. Galletti “A Total Synthesis of (1R, 5R)-3-phenylmethyl-4-thia-2,6-diazabicyclo[3.2.0]hept-2-en-7-one, a Useful Intermediate for the preparation of Penem and Cepham Derivatives” Synthesis, 2000, 2, 289-294. G. Cainelli, P. Galletti, D. Giacomini, P. Orioli “Carbonyl Compound Solvation as a Predominant Factor in Diastereofacial Selectivity of Nucleophilic Addition” Angewandte Chemie, Int. Ed.Eng. 2000, 39, 523-527. G. Cainelli, D. Giacomini, P. Galletti, P. Orioli “Solvent and Temperature effects on facial diastereoselectivity” in "The Chemistry at the beginning of the III millenium" Springer-Verlag Ed. 2000, 139-160. G. Cainelli, P. Galletti, D. Giacomini, P. Orioli, M. A. Polidoro, M. C. Righetti "Bulyllithium addition to ?-chiral compounds: solvent mixture effects on diastereofacial selectivity" Helvetica Chimica Acta, 2000, 83, 1951-1961 G. Cainelli, D. Giacomini, P. Galletti, P. Orioli, F. Paradisi "Diastereofacial Selectivity of O-Protected ?-Hydroxy Aldehydes: Temperature and Solvent Effect" European Journal of Organic Chemistry, 2000, 3619-3626. G. Cainelli, V. De Matteis, P. Galletti, D. Giacomini, P. Orioli "Temperature and solvent effects on enzyme stereoselectivity: inversion temperature in kinetic resolutions with lipases" Chemical Communications 2000, 2351-2352. S. Decesari, M.C. Facchini, S. Fuzzi, E. Tagliavini Characterization of water-soluble organic compounds in atmospheric aerosol: A new approach Journal of Geophysical Research - Atmospheres, 2000, 105(D1), 1481 – 1489 F. Bernardi, A. Bottoni, S. Casolari, E. Tagliavini Zirconium tetrachloride-formaldehyde sigma-complexes: A computational and spectroscopic investigation Journal of Organic Chemistry, 2000, 65, 4783 – 4790 148 2001 M. Lombardo, S. Fabbroni, C. Trombini “Entropy-Controlled Selectivity in the Vinylation of a Cyclic Chiral Nitrone. An Efficient Route to Enantiopure Polyhydroxylated Pyrrolidines” Journal of Organic Chemistry, 2001, 66, 1264-1268. M. Marsili, M. Stracquadanio, C. Trombini, I. Vassura “The epicuticular wax of Laurus nobilis leaves as a passive sampler of polycyclic aromatic hydrocarbons in ambient air” Fresenius Environmental Bulletin, 2001, 10, 26-30. D. Fabbri, S. Gemelli, L. Langone, S. Miserocchi, C. Trombini, I. Vassura “Anthropogenically Derived Mercury in Sediments of Pialassa Baiona, Ravenna, Italy” Annali di Chimica 2001, 91, 563-575. D. Fabbri, C. Trombini, I. Vassura “Reading the Chronicle of Past Industrial Pollution in the Sediments of a Coastal Lagoon (Pialassa Baiona, Ravenna)” Chimica & Industria (Milano), 2001, 83(3), e2/1-e2/4, 2001. M. Lombardo, S.Morganti, C.Trombini, “The Hydroboration of Propargyl Chloride: a Flexible One-pot Three Component Process easily Directed towards the Synthesis of (E)-homoallylic alcohols or anti-homoallylic alcohols” SynLetters, 2001, 601-604. D. Fabbri, M. Lombardo, C. Trombini, I. Vassura, E. Zavoli, M. Horvat “Mercury Contamination of a Coastal Lagoon (Pialassa Baiona, Ravenna, Italy)” RMZ-Materials & Geoenvironment, 2001, 48, 186-192. D. Fabbri, G. Gabbianelli, C. Locatelli, D. Lubrano, C. Trombini, I. Vassura “Distribution of Mercury and Other Heavy Metals in Core Sediments of the Northern Adriatic Sea” Water, Air, and Soil Pollution, 2001, 129, 143-153. R. Girotti, M. Lombardo, S. Morganti, C. Trombini “A New Protocol for the Acetoxyallylation of Aldehydes Mediated by Indium in THF” Organic Letters, 2001, 3, 2981-2983. R. Girotti, M. Lombardo, S. Morganti, C. Trombini “The First Zinc-Promoted, Environmentally Friendly, and Highly Efficient Acetoxyallylation of Aldehydes in aq Ammonium Chloride” Chemical Communications, 2001, 2310-2311. M. Bandini, P.G. Cozzi and A. Umani-Ronchi "Enantioselective catalytic addition of allyl organometallic reagents to aldehydes promoted by [Cr(Salen)]: the hiden role played by weak Lewis acids in metallo-Salen promoted reactions" Tetrahedron, 2001, 57, 835. M. Bandini, P. G. Cozzi, P. Melchiorre, S. Morganti, A. Umani-Ronchi "Cr(Salen) Catalyzed Addition of 1,3-Dichloropropene to Aromatic Aldehydes. A Simple Access to Optically Active Vinyl Epoxides" Organic Letters., 2001, 3, 1153 M. Bandini, P.G. Cozzi, P. Melchiorre, A. Umani-Ronchi "Indium Tribromide: a Highly Effective Catalyst for the Addition of Trimethylsilyl Cyanide to alpha-HeteroSubstituted Ketones" Tetrahedron Letters, 2001, 42, 3041 M. Bandini, P.G. Cozzi, M. Monari, R. Perciaccante, S. Selva, A. Umani-Ronchi “Design of Boron bis-oxazolinate (B-BOXate) complexes: a new class of stable organometallic catalyst” 149 Chemical Communications., 2001, 1318-1319 M. Bandini, P.G. Cozzi, M. Gazzano, A. Umani-Ronchi “An effective and useful synthesis of enantiomerically enriched arylglycinols” European Journal of Organic Chemistry, 2001, 1937-1942 M. Bandini, P.G. Cozzi, P. Melchiorre, R. Tino, A. Umani-Ronchi “Chemo- and enantioselective catalytic addition of propargyl chloride to aldehydes promoted by [Cr(Salen)] complexes” Tetrahedron: Asymmetry, 2001, 12, 1063-1069 G. Cainelli, D. Giacomini, P. Galletti, P. Orioli “Dynamic solvation effects in ethylmagnesium bromide addition to (2S)-O-tert-butyldimethylsilyl-lactal” European Journal of Organic Chemistry, 2001, 4509-4515. G. Cainelli, D. Giacomini, P. Galletti, P. Orioli “Solvent and Temperature Effect in Aldol Condensation between the Lithium Enolate of tert-Butyl Acetate and 2Phenyl propanal: Enthalpy and Entropy Contribution” Tetrahedron Letters, 2001, 42, 7383-7385. S. Decesari, M. C. Facchini, E. Matta, F. Lettini, M. Mircea, S. Fuzzi, E. Tagliavini, J. P. Putaud ”Chemical features and seasonal variation of fine aerosol water-soluble organic compounds in the Po Valley, Italy” Atmospheric Environment, , 2001, 35, 3691 – 3699 S. Fuzzi, S. Decesari, M. C. Facchini, E. Matta, M. Mircea, E. Tagliavini A simplified model of the water soluble organic component of atmospheric aerosols Geophysical Research Letters, 2001, 28, 4079 – 4082 Braga, D; Maini, L; Paganelli, F; Tagliavini, E; Casolari, S; Grepioni, F Organometallic building blocks for crystal engineering. Synthesis, structure and hydrogen bonding interactions in [Fe(eta(5)-C5H4-CH2(CH3)OH)(2)], [Fe(eta(5)-C5H3(CH3)COOH)(2)], [Fe(eta(5)-C5H4CH(CH3)NH(eta(5)C5H4CH(CH3))] and in the diaminecyclohexane salt [Fe(eta(5)-C5H4COO)(2)](2-) [(1S,2S)(NH3)(2)C6H10](2+)center dot 2[H2O] Journal of Organometallic Chemistry, 2001, 637, 609 – 615 Appendix 3 Journal Portfolio Analysis Name of the Unit: Research Director: Years included Bologna6 Claudio Trombini 1997-2001 Name of Journal ANGEW CHEM INT EDIT Number Articles 3 of Journal Factor 8.547 J AM CHEM SOC 1 6.025 CHEM COMMUN 7 3.695 JOC 5 3.689 ORG LETT 3 3.367 ORGANOMETALLICS 2 3.169 TETRAHEDRONASYMMETR SYNLETT 4 2.797 3 2.763 Impact Field(s) CHEMISTRY, MULTIDISCIPLINARY CHEMISTRY, MULTIDISCIPLINARY CHEMISTRY, MULTIDISCIPLINARY CHEMISTRY, ORGANIC CHEMISTRY, ORGANIC CHEMISTRY, ORGANIC CHEMISTRY, ORGANIC CHEMISTRY, Ranking 5/118 7/118 11/118 5/48 7/48 8/48 9/48 10/48 150 TETRAHEDRON LETT 9 2.558 J CHEM SOC DALTON 1 2.502 TETRAHEDRON 4 2.356 SYNTHESIS-STUTTGART 4 2.193 J ORGANOMET CHEM 1 1.632 HELV CHIM ACTA 1 2.209 EUR J ORG CHEM 6 2.150 ENVIRON SCI TECHNOL 1 3.035 ENVIRON TOXICOL 1 CHEM SCI TOTAL ENVIRON 1 2.091 FRESEN ENVIRON BULL 1 0.277 ANAL CHIM ACTA 1 1.849 J CHROMATOGR SCI 1 1.247 1.252 ORGANIC CHEMISTRY, ORGANIC CHEMISTRY, INORGANIC & NUCLEAR CHEMISTRY, ORGANIC CHEMISTRY, ORGANIC CHEMISTRY, ORGANIC CHEMISTRY, MULTIDISCIPLINARY CHEMISTRY, ORGANIC ENVIRONMENTAL SCIENCES ENVIRONMENTAL SCIENCES ENVIRONMENTAL SCIENCES ENVIRONMENTAL SCIENCES CHEMISTRY, ANALYTICAL CHEMISTRY, ANALYTICAL 13/48 11/38 15/48 16/48 23/48 18/118 18/48 3/127 10/127 35/127 112/127 18/65 33/65 151 BOLOGNA 8 Bologna-8 University: Alma Mater Studiorum- Università di Bologna Faculty: Chimica Industriale Department: Chimica Organica “A. Mangini” dell’Università Viale del Risorgimento n.4 40136 BOLOGNA Research Leader Goffredo ROSINI Contact Person Goffredo Rosini Please specify: Goffredo Rosini Phone +39.0512093640 Fax+39.0512093654or+39.0512093630 E-mail; [email protected] Thematic area • Processi chimici e tecnologie pulite. Introduction and Context The University. The Studium at Bologna is the oldest in the world: 1088 may be accepted as a conventional date indicating when teaching became free and independent of the ecclesiastical schools in Bologna. The University of Bologna was formed between the eleventh and twelfth centuries, mainly around Roman Law as laid down in Justinian Code. Centuries passed through and nowaday we have Alma Mater Studiorum –Università di Bologna. In recent years has set up Faculties and courses at Cesena, Forlì, Ravenna, Reggio Emilia and Rimini. On the occasion of the Ninth Centenary in 1988, the University and City of Bologna promoted several cultural events and activities in order to address the many problems of research, training and qualification, professionalism and the labour market arising from the new international context of learning. The aim of the University is to promote the advancement of knowledge and to provide the training and skills required to practise a wide range of professions. Bologna University is a State institution, like the vast majority in Italy, and with 100,000 students it is one of the largest in the country. On the basis of the principle of university independence, Bologna has established its own code of rules and regulations enshrined in the “Statute”. The Rector is the legal representative of the University and chairs the Academic Senate and the Board of Governors. The Rector is elected every five years by the academic staff. The Registrar, who is in charge of all the central services and departments, is appointed by the Board of Governors and serves as secretary to the Senate and the Board of Governors. Alma Mater Studiorum- Università di Bologna is organized in 22 Faculties, 67 Departments, 4 Complex Units, and 2 Institutes. In these structures are involved 770 Full Professors, 976 Associate Professors and 1024 Researchers. Faculty of Industrial Chemistry. Founded in 1935, until 2001 the Faculty of Industrial Chemistry awarded a five-year degree in Industrial Chemistry and a three-year diploma in Chemistry and Technology of Ceramic Materials. The five-year degree is intended to provide a sound knowledge of basic chemistry as well as the principle of unit operations, chemical reaction engineering, process design and industrial chemistry. The theoretical work is accompanied by laboratory training. Courses are taught on a semester basis, for a total of 10 semesters. The first six semesters consists of introductory courses in organic, inorganic, analytical, industrial and physical chemistry and chemical engineering, all of them compulsory. In addition, students are required to pass an English language test. In the remaining four semesters, advanced courses on the same topics may be taken, some compulsory and some optional. The fifth year is also used for the preparation of a dissertation on an original topic. This is done by each student by carrying out experimental work under the supervision of a Faculty member within a research group, sometimes in conjunction with industry. Both degree train students for positions in industry (R&D, production, etc.), government agencies (environmental monitoring and protection), and private and governmental research centres. Although there are no restrictions on students numbers, the staff-student ratios are in line with European standards, and the Faculty is active in EU student mobility programmes. Teaching and research take place in Bologna for the degree course and in Faenza for the diploma course. In the academic year 1999-2000 there were 21 Full Professors, 44 Associate Professors and 29 Researchers, while 78 Students were registered at the first year (478 as total number) and 104 took the degree in Industrial Chemistry. 152 Recently, another Course is active in Rimini: the Course of “Chemical Technologies for the Environmental Preservation and Waste Management”. In addition, there are several Doctoral Research Programs (3 years) in a variety of fields: Chemical Sciences, Industrial Chemistry, Industrial Fermentation and Applied Biocatalysis, Metallurgy, Tribology. Department of Organic Chemistry “A. Mangini” of the University. This Department hosts 11 Full Professors (6 of the Faculty of Industrial Chemistry and 5 of the Faculty of Pharmacy), 15 Associate Professors (14 of the Faculty of Industrial Chemistry and 1 of the Faculty of Pharmacy) and 14 Researchers (9 and 5 respectively) in two distinct buildings. see The research groups in Department are active in several arguments. In particular: synthesis of naturally occurring substances, the study of reaction mechanisms, free radical reactions and their mechanisms, spectroscopy (NMR, Mass, IR, UV), synthesis of fine chemicals pharmaceuticals, synthesis of key intermediates, synthesis of enantiopure compounds to be used as a catalyst, etc. Main instrumentations and facilities of Dipartimento di Chimica Organica “A. Mangini” dell’Università di Bologna: NMR Spectrometers Gemini 200 e 300 MHz- Mass spectrometer VG Analitica- UV Spectrometer Jasco.- ESR Spectrometer Varian E-104.- IR Spectrometer Perkin Elmer 257 e 1600 FT- EPR Spectrometer Bruker ESP 300- GasMassa HP 5970- Polarimeter Jasco- DIP 360- Polarimeter Perkin Elmer 341-Dicrograph Jasco J 500- Preparative HPLC Varian Prostar- PROLABO Synthewave 402. The Unit Bologna 8 This group is active since 1984 in Dipartimento di Chimica Organica “A. Mangini” – University of Bologna and is located in Viale del Risorgimento n.4 in the same building where the Faculty of Industrial Chemistry-University of Bologna is. The research group have focused the main interests and activities in organic synthesis dealing with several themes: (a) Research and development of innovative methodologies to prepare fine chemicals and specialities; (b) Synthesis of products having commercial interest through eco-friendly processes, (c) Optimization and automation of reactions and processes. In particular we are seeking efficiency and practicality in synthesis, making available desired substances useful to solve some important problem. The components of our research group are: one Full Professor, three Researchers and one Post Dct Position (Assegnista). Presently one PhD Student and three owners of post doctor positions are involved in our group. These latter positions are available by research agreements with several Companies, such as ENDURA S.p.A.; FATRO S.p.A.; NEWCHEM S.rl.; GSK S.p.A. Students of the Faculty of Industrial Chemistry as well as students of other Faculties are involved in the activities of our laboratory to prepare their thesis. The laboratory of this Unit is equipped with: two Agilent GCs (chiral columns available); one Agilent 1100 HPLC (chiral columns available); one Gilson liquid chromatography with fraction collector; an automatic synthesis reactor, by SYSTAG AG, where fully automatic running recipes can be executed, with dosage, temperature, pH, and distillation control. The group have participated in several Erasmus and Socrates Projects with other European Universities. Courses taken by teachers of our group in the Faculty of Industrial Chemistry of the University of Bologna: Organic Chemistry II; Complements of Organic Chemistry; Organic Chemistry, Laboratory I; Organic Chemistry, Laboratory II; Industrial Organic Chemistry, Laboratory. Programme Description and Evaluation 1 Title: Eco-friendly and innovative methodologies in synthesis to achieve high efficiency and selectivity. 2 Research Leader: Goffredo ROSINI 2a Sub-programme titles and sub-programme leaders: No subprogram title 3 Composition of the scientific research staff of the unit per 1 January 2002 Names and Titles Year of Rank Birth Goffredo ROSINI Emanuela MAROTTA 1940 1957 Research Input in maRerks ftein 1997 Prof. Ord 0.4 Ricercatore 0.5 153 Paolo RIGHI Claudio PAOLUCCI Francesca PERI Noemi SCARDOVI Alessandro LORENZI Alberto GUERRINI Micaela VANNINI Total research input 1963 1950 1971 1975 1975 1975 1975 Ricercatore Ricercatore Post-Doc PhD-Stud Borsista Borsista Borsista 0.5 0.5 1.0 1.0 1.0 1.0 1.0 6.9 Since ----2001 Since January 2000 Since September 2001 Since January 2002 Since February 2001 Comments: it is the first year: no comment 4 Input of Academic Staff in fte Category Full Professors Associated Professors Ricercatori Post-docs PhD-students Borsisti Total 5 Funding 5.1 Personnel (in fte) Source University CNR European Union Other Sponsors Total 5.2 * * 1998 0.4 -1.5 ---3.0 4.9 1999 0.4 --1.5 ---3.0 4.9 2000 0.4 --1.5 --1.0 3.0 5.9 2001 0.4 --1.5 1.0 1.0 3.0 6.9 Total 2.0 --1.5 1.0 2.0 15.0 1997 1998 1999 2000 2001 1.0 Total 1.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 15.0 Materials and Equipment (in Million Lire) Source University - MURST CNR EU Other Sponsors Total 5.3 1997 0.4 -1.5 --3.0 4.9 1997 70 16 1998 70 15 1999 70 9 2000 75 9 2001 76 10 Total 350 59 60 146 75 160 75 154 75 159 75 161 210 780 Comments: On the figures: no comment On the funding policy: no comments Major sponsors and the character of the liaison: Sponsor of the Unit are several national and international Companies and Firms. Among them: Alfa-Wassermann S.p.A- Bologna, ENDURA S.p.A.-Bologna NEWCHEM S.r.l.-Verona, GSK S.p.A.-Verona, FATRO S.p.A. Ozzano dell’Emilia (BO) active in the fields of: fine chemicals, pharmaceuticals, agrochemicals and so on. Funding is currently performed trough contracts between Department and Society. In general Companies provide the unit of some bursary too, and the recipients devote their activity exclusively to the theme of the agreement. All the results are considered and treated as confidential matter. 6. Progress Report 154 6.1 Mission Statement We consider efficiency and practicality two main aspects relevant requirements of any synthetic scheme devised to make available desired compounds useful to solve some important problem. Our efforts are focused in devising new and efficient methodologies in the synthesis of fine chemicals and pharmaceuticals. Once the route is defined, initial scale up, development and the transition to process equipment proceed, followed by process optimization and refinement for manufacturing operations for each synthetic step. As a unit of the Faculty of Industrial Chemistry of the University of Bologna, our research group works in close collaboration with a variety of industrial partners particularly in fields such as pharmaceutical, fine chemical, and agriculture chemical industries. The activity of this Unit is mainly oriented to provide our students with a good preparation in chemistry together with a peculiar sensibility for the problems of the production of chemicals in a modern society being aware of the problems of environment. 1.3The Research Programme The activity of the Unit is mainly focused to: 1.Design of synthetic schemes for achieving fine chemicals or any useful compound. The procedure must be more effective and practical when compared with those ones already reported in the literature. In some case we attempt to start from a more convenient and commercially available starting material. 2.In our approach we attempt to perform compacted synthetic operations such as: tandem reactions, domino reactions and cascade reactions taking advantage of the simplification of all the synthetic operations included the work-up with a view to a possible scale-up and a possible industrialization. 3.In our projects a particular care will also dedicated to the optimization and automation of the procedures by using software and hardware apt to minimize the utilization of reagents as well as to know the more safe and efficient conditions of any synthetic step of the process. 4.The building up of the target compounds is to be performed to achieve the best chemo, regio, and stereo selectivity together with an high atom economy. 5.When is suitable we attempt to develop the solid-phase synthesis and combinatorial technologies. 6.Recently we are developing the utilization of “obsolete” enantiomerically pure pharmaceutical intermediates and precursors as new and convenient catalysts in synthesis. The more significant results: (a) -ENICHEM S.p.A.-Istituto Guido Donegani S.p.A. Goffredo Rosini, Rossella Serra, Franco Rama, Giovanni Confalonieri Procedure for the preparation of bicyclo[3.20]hept-3-en-6-ones. EP521571B1-09/13/1995; US5191125-March 2, 1993. This procedure has been published on Organic Syntheses 1997, 64, 185. More recently, the procedure has been studied in terms of optimization and automation of the process: Alessandro Lorenzi, Paolo Righi, Goffredo Rosini- Ottimizzazione e automazione di un processo su scala per la sintesi di intermedi di Prostaglandine- Dal laboratorio all’impianto pilota- CLUEB, 2001- Bologna. ISBN 88-491-1852-X. An innovative and practical approach to the synthesis of a variety of pheromones and other naturally occurring substances particularly useful in agriculture (control of pests) stems on the utilization of this preparation of bicyclo[3.2.0]hept-3-en-6-ones. For a Review, see: Marotta, E.; Righi, P.; Rosini, G. “The Bicyclo[3.2.0]heptan-endo2-ol and Bicyclo[3.2.0]hept-3-en-6-one Approaches in the Synthesis of Grandisol: The Evolution of an Idea and Efforts to Improve Versatility and Practicality” Org. Proc. Res. & Devel. 1999, 3, 206. (b) -Alfa-WASSERMANN S.p.A. Goffredo Rosini, Claudia Baldazzi, Eleonora Romagnoli, Stefano Saguatti, Silvano PianiLactones with antioxidising and hypolipidaemic activity useful in the therapy of the atherosclerosis. US Patent N. 5,608, 084 (1997). This study has been published in 1999: Baldazzi, C.; Calderoni, F.; Marotta, E.; Piani, S.; Righi, P.; Rosini, G.; Saguatti, S.; Tiozzo, R.; Calandra, S.; Venturelli, F. “Medium Sized Lactones with Hypolipidaemic and Antioxidant Activity: Synthesis end Biological Evaluation of Promising Dual-action Anti-atherosclerosis Drugs” Bioorg. Med. Chem. 1999, 7, 411. (c) -Alfa-WASSERMANN S.p.A. Goffredo Rosini, Claudia Baldazzi, Silvano Piani3,4-Dihydro-2-iodomethyl-2,5,7,8-tetramethyl-2H-1-benzopyrans. US Patent N. 5,608, 084 (1997). 155 (d)- An innovative approach to the stereo controlled synthesis of 2-aminopolyols and poly hydroxylated amino acids through the utilization of heterotricyclic intermediates obtained by an efficient three component domino process with a high atomic economy. For an in deep illustration of the approach, see: Righi, P.; Marotta, E.; Rosini, G.- Linear Aminopolyhydroxylated Structures Through Rapid Domino Assembly of a Highly Functionalized Heterotricyclic System and Its Selective Cleavage.- Chem. Eur. J. 1998, 4, 2501. More recently, the procedure has been further developed by using reagents supported on solid polymers and N-tosyl2,3-aziridine alcohols (P. Righi, N. Scardovi, E. Marotta, P. Ten Holte, B. Zwanenburg – Solution and solid phase synthesis of 4-hydroxy-4,5-isoxazole derivatives from enantiomerically pure N-tosyl-2,3-aziridine alcohols Org. Lett. 2002, 4, 497). Moreover, an efficient procedure to prepare nitroacetic acid esters and amides has been devised (N. Scardovi, Andrea Casalini, Francesca Peri, Paolo Righi- Domino Processes as a Tool for Recovering Substandard Reactions, Org. Lett. 2002, 4, 965). (e)-Several other methodologies have been devised and developed to perform the synthesis of important intermediates and to prepare desired compounds in an eco-friendly manner. See: (i) Ballini, R.; Bosica, G.; Maggi, R.; Ricciutelli, M.; Righi, P.; Sartori, G.; Sartorio, R. “Clay-catalysed Solventless Synthesis of trans-Chalcones” Green Chem. 2001, 3, 178; (ii) Ballini, R.; Bosica, G.; Conforti, M. L.; Maggi, R.; Mazzacani, A.; Righi, P.; Sartori, G. “Three-component process for the synthesis of 2-amino-2-chromenes in aqueous media” Tetrahedron 2001, 57, 1395; (iii) Demicheli, G.; Maggi, R.; Mazzacani, A.; Righi, P.; Sartori, G.; Bigi, F. “Supported organic catalysts: synthesis of (E)-nitrostyrenes from nitroalkanes and aromatic aldehydes over propylamine supported on MCM-41 silica as a reusable catalyst” Tetrahedron Letters 2001, 42, 2401; (iv) Ballini, R.; Bosica, G.; Maggi, R.; Mazzacani, A.; Righi, P.; Sartori, G. “Amberlyst® 15 as a Mild, Chemoselective and Reusable Heterogeneneous Catalyst for the Conversion of Carbonyl Compounds to 1,3-Oxathiolanes” Synthesis 2001, 1826. (f)- In what concerns our cooperation with Companies and Firms (ENDURA S.p.A, GSK S.p.A., NEWCHEM S.p.A.) several procedures we have devised are presently under patenting and we cannot treat here these results for a due confidentiality. 6.3 Position in Networks • Intra-university co-operation: (a) National Project “Stereoselezione in Sintesi Organica: Metodologie ed Applicazioni” jointly supported by University of Bologna and MIUR is a cooperative project with a several Units of other Universities (included other Units of INCA, such as Parma). (b) Local Project “Nuove Strategie di assemblaggio molecolare selettive e a basso impatto ambientale- Applicazione alla sintesi di molecole bioattive e di intermedi organici di interesse industriale (1997)” supported by the University of Bologna. • Regional co-operation: Several co-operations with units of the University of Camerino and of University of Parma are active upon important themes. • National co-operation (including INCA) Some people of this unit participate to the activity of Consorzio Internuniversitario “Metodologie e Processi Innovativi di Sintesi”- CINMPS- Bari. International co-operation- Our group have had an interchange of several students through Erasmus and Socrates Projects, in particular with the University of Nijmegen. Dr. Noemi Scardovi is spending one year in the Laboratory of Prof. Philip Paul Garner- Department of Chemistry, Case Western Reserve University, Cleveland (USA). 6.4 Societal Relevance and Impact. 1.3Further Indications of Quality and Reputation. Goffredo Rosini has been Director of Dipartimento di Chimica Organica “A. Mangini” dell’Università di Bologna (1992-1995); Vice-Dean of the Facoltà di Chimica Industriale dell’Università di Bologna (1998-2001). Presently is “Coordinatore del Dottorato in Scienze Chimiche dell’Università di Bologna per i Cicli XV, XVI e XVII (2000, 2001, 2002). Goffredo Rosini has been member in many Commissions for the evaluation of both national and international PhD thesis in Chemical Sciences as well as peer in the evaluation of national research projects. While G.R, E.M., P.R., C.P., F.P. and N.S. are members of the Italian Chemical Society- Division of Organic Chemistry, Dr. Paolo Righi and Dr. Claudio Paolucci are members of the American Chemical Society too. Since 1996 Dr Paolo Righi regularly attended Gordon Conferences in USA. Since 2002, Paolo Righi is member of the Advisory Subcommittee of the IUPAC Chemical Nomenclature and Structure Representation Division (VIII). 156 1.3Key Publications: It is really very difficult to make a choice. The titles here reported are those where, in our opinion, the aim and the development of some arguments of our research are presented in a more detailed and global form. Righi, P.; Marotta, E.; Rosini, G.- Linear Aminopolyhydroxylated Structures Through Rapid Domino Assembly of a Highly Functionalized Heterotricyclic System and Its Selective Cleavage.- Chem. Eur. J. 1998, 4, 2501. Marotta, E.; Righi, P.; Rosini, G. “The Bicyclo[3.2.0]heptan-endo-2-ol and Bicyclo[3.2.0]hept-3-en-6-one Approaches in the Synthesis of Grandisol: The Evolution of an Idea and Efforts to Improve Versatility and Practicality” Org. Proc. Res. & Devel. 1999, 3, 206. Marotta, E.; Righi, P.; Rosini, G. “A Bicyclo[3.2.0]hept-3-en-6-one Approach to Prostaglandin Intermediates” Org. Lett. 2000, 2, 4145. Marotta, E.; Micheloni, L. M.; Scardovi, N.; Righi, P. “One-pot direct conversion of 2,3-epoxy alcohols into enantiomerically pure 4-hydroxy-4,5-dihydroisoxazole 2-oxides.” Org. Lett. 2001, 3, 727. Ballini, R.; Bosica, G.; Maggi, R.; Ricciutelli, M.; Righi, P.; Sartori, G.; Sartorio, R. “Clay-catalysed Solventless Synthesis of trans-Chalcones” Green Chem. 2001, 3, 178. 7. Scientific Output 1.3Publication Policy. All the activities we have performed have been inspired by the aim already declared in 6.1 Mission Statement, therefore we consider the publications, patents, divulgation articles and invited lectures etc. all pertinent the mission statements of INCA. The publication policy is oriented towards: (a) Protection of the more important results obtained in the collaborations with Companies and Firms through research contracts by deposit and extension of patents. (b) Publication in international journals of the results of base research and applicative research performed by using funds for institutional activities included those devoted to the formation of Laureate and PhD students. (c) Participation to local, national and international Congresses and Schools where the results obtained are presented and shared with components of other research groups. Frequently, the results obtained with the involvement of students (laureandi and PhD) during their thesis are published after their presentation to the Commission. 7.2 Numerical data Category PhD-Dissertations 1997 1998 1999 2000 2001 Total Scientific Publications 2 4 3 1 6 16 Professional Publications 1 2 1 2 6 Master’s Theses 4 3 5 2 3 17 Other Scientific Output 2 1 5 3 -- 11 8 Self-evaluation Appendix I Scientific Output I-1 Overview of Dissertations and Master's Thesis (1997-2001) 157 I.1.1 Dissertations Year Name PhD-student I.1.2 Title of the Dissertation Supervisor Master's Thesis Here are reported the name of the Student, the title of the Thesis (in brackets the original title in Italian) and the names of supervisors. All the data are referred to Laurea degrees. 1997- Danilo FRULLI- Linearization of a poly functionalized heterotricyclic system. A new synthesis of aminopolyols. (Linearizzazione di un sistema triciclico polifunzionalizzato. Una nuova via di sintesi di composti azotati poliossidrilati). Rosini-Righi 1997- Floria ANTOLINI- Enantiopure chiral building blocks from sugars. A new approach to polyhydroxylated pyrrolidine and piperidine. ( “Building Blocks “ chirali da zuccheri. Approcci alla sintesi di pirrolidine e piperidine poliossidrilate). Paolucci-Rosini 1997- Lucio PANIZZA- Synthesis of tricyclic systems through a intramolecular [3+2] cycloaddition of 4hydroxyalkenyl derivatives of 2-isoxazoline N-oxides. (Sintesi di sistemi triciclici mediante cicloaddizione [3+2] intramolecolare di 4-O-alchenilderivati di sistemi 2-isossazolinici N-ossido). Rosini- Marotta 1997- Marco BARAVELLI- D-Mannitol as the chiral source for the EPC synthesis of precursors of aminopolyols. (DMannitolo quale sorgente chirale per la sintesi EPC di precursori di amminopolioli). Rosini-Marotta 1998- Laure Marie MICHELONI- EPC Synthesis of 4-hydroxy-2-isoxazoline N-oxides starting from enatiomerically pure ?,?-epoxyalcohols and their linearization to aminopolyols. (Sintesi EPC di 4-idrossi-2-isossazoline a partire da ?,?epossialcoli enantiomericamente puri e linearizzazione ad amminopolioli). Rosini-Righi. 1998- Antonella PEPE- The tandem reaction of activated primary nitrocompounds and substrates with multiple electrophilic centres: a systematic study. (La reazione tandem tra nitrocomposti attivati e substrati a più centri elettrofili: uno studio sistematico). Righi-Rosini 1998- Lucia MATTIOLI- EPC Synthesis of 1,2-dihydroxy-5-oxo-hexahydroindolizines. Versatile building blocks for the synthesis of poly hydroxylated indolizidines. Synthesis and reactivity of anomeric spirosugar dervatives from D-(-)fructose. (Sintesi EPC di 1,2-diidrossi-5-osso-esaidroindolizine. Versatili “Building Blocks” per la sintesi di indolizidine poliossidrilate.- Sintesi e reattività di spiro-zuccheri anomerici, derivati dal D-(-)-Fruttosio). PaolucciRosini. 1999- Antonio BRUNI- Enantioselective epoxidation of olefins: a study on the possible utilization of 1,4:3,6-dianidroD-Fructose and D-Sorbose as chiral auxiliary. (Epossidazione enantioselettiva di olefine: indagine sulla utilizzabilità dell’1,4:3,6-dianidro-D-Fruttosio e D-Sorbosio come ausiliari chirali). Paolucci-Rosini. 1999- Federico ASCARI- Synthesis of versatile precursors of substituted cyclopentanoids. Studies for a process optimization. (Sintesi di precursori versatili di ciclopentanoidi sostituiti. Studi per l’ottimizzazione di processo. RosiniMarotta. 1999- Noemi SCARDOVI- Stereoselective synthesis of 5-aminoalkyl-4-hydroxy-2-isoxazoline N-oxides in homogeneous phase and on a polymeric support. (Sintesi stereoselettiva di 5-amminoalchil-4-idrossi-2-isossazoline Nossidi in fase omogenea e su sopporto polimerico). Rosini-Marotta. 1999- Giovanna MORRI- Synthesis of stereoisomeric 5-oxa-esahydroindolizine: Building blocks towards the EPC synthesis of polyhydroxylated indolizidines having biological activity as inhibitors of glycosidases. (Sintesi di 5-oxaesaidroindolizine stereosisomeriche: “Building Blocks” verso la sintesi EPC di indolizidine poliossidrilate aventi attività biologica come inibitori di glicosidasi). Paolucci-Rosini. 1999- Roberto CASTALDI- Direct linearization of 4-hydroxy-2-isoxazoline N-oxides to enantiopure aminopolyols. (Linearizzazione diretta di amminopolioli di 4-idrossi-2-isossazoline 2-ossido enantiomericamente pure). RosiniMarotta. 2000- Luca BERNARDI- Synthesis of EP aminopolyols through direct linearization of 4-hydroxy-2-isoxazoline Noxides. (Sintesi di Amminopolioli EP mediante linearizzazione diretta di sistemi 4-idrossi-2-isossazolinici N-ossido). Righi-Rosini-Scardovi 2000- Andrea CASALINI- New results by using solid-phase reagents. An innovative synthesis of functionalized 4,5dihydroisoxazoles. (Nuovi sviluppi di reagenti in fase solida. Ana sintesi innovativa di 4,5-diidroisossazoli funzionalizzati). Righi-Rosini. 158 2001- Alessandro LORENZI- Optimization and automation of a scaled process for the synthesis of prostaglandine intermediates. (Ottimizzazione e automazione di un processo su scala per la sintesi di Prostaglandine. Dal laboratorio all’impianto pilota). Righi-Rosini. 2001- Antonio MANETTO- Selective transformations of bicyclo[3.2.0]hept-3-en-6-ones. (Trasformazioni selettive di biciclo[3.2.0]ept-3-en-6-oni). Rosini-Peri. 2001- Tommaso MARCELLI- Cerium (III) mediated cyclizations of ?-hydroxy-alkenoic acid esters. (Ciclizzazioni intramolecolari mediate da Cerio (III). Rosini-Marotta. I-2 Overview of Scientific Publications (1997-2001) per year 1997 See also 2 patents reported in Section I-4 Rosini, G; Confalonieri, G.; Marotta, E.; Rama, F.; Righi, P. Preparation of Bicyclo[3.2.0]hept-3-en-6-ones: 1,4Dimethylbicyclo[3.2.0]hept-3-en-6-one. Org. Synth. 1997, 74, 158-168. C. Paolucci, L. Musiani, F. Venturelli, A. Fava. Hydroxylated ?-Vinylpyrrolidines from Sugar-Derived 2,5Dihydrofurans. Synthesis of (1S,2S,8aR)-1,2-dihydroxyindolizidine by Ring Closing Olefin Methathesis. Synthesis 1997, 1415. 1998 Marotta, E.; Righi, P.; Rosini, G. -Consecutive and Domino Processes for the Synthesis of a Heavily Functionalised Tricyclic System. Tetrahedron Lett. 1998, 39, 1041. Rosini, G.; Laffi, F.; Marotta, E.; Pagani, I.; Righi, P.-Total Synthesis of the Marine esquiterpenoid Raikovenal through a Novel Utilization of the Bicyclo[3.2.0]heptenone Approach. J. Org. Chem. 1998, 63, 2389. Marotta, E.; Baravelli, M.; Maini, L.; Righi, P.; Rosini, G.- D- Mannitol as the Chiral Source for the EPC Synthesis of Both Enantiomers of 3-Ethoxycarbonyl-4-hydroxy-2-isoxazolines and Highly Functionalised Tricyclic Sistems. J. Org. Chem. 1998, 63, 8235. Righi, P.; Marotta, E.; Rosini, G.- Linear Aminopolyhydroxylated Structures Through Rapid Domino Assembly of a Highly Functionalized Heterotricyclic System and Its Selective Cleavage.- Chem. Eur. J. 1998, 4, 2501. 1999 Baldazzi, C.; Calderoni, F.; Marotta, E.; Piani, S.; Righi, P.; Rosini, G.; Saguatti, S.; Tiozzo, R.; Calandra, S.; Venturelli, F. “Medium Sized Lactones with Hypolipidaemic and Antioxidant Activity: Synthesis end Biological Evaluation of Promising Dual-action Anti-atherosclerosis Drugs” Bioorg. Med. Chem. 1999, 7, 411. Marotta, E.; Righi, P.; Rosini, G. “The Bicyclo[3.2.0]heptan-endo-2-ol and Bicyclo[3.2.0]hept-3-en-6-one Approaches in the Synthesis of Grandisol: The Evolution of an Idea and Efforts to Improve Versatility and Practicality” Org. Proc. Res. & Devel. 1999, 3, 206. Ballini, R.; Bosica, G.; Damiani, M.; Righi, P. “Nitroalkanes as a New Source of 2-Alkylidene-1,4-diols, in Two Steps” Tetrahedron 1999, 55, 13451. 2000 Marotta, E.; Righi, P.; Rosini, G. “A Bicyclo[3.2.0]hept-3-en-6-one Approach to Prostaglandin Intermediates” Org. Lett. 2000, 2, 4145. 2001 Paolucci, C.; Mattioli, L. Stereoisomeric Sugar-derived Indolizines as Versatile Building Blocks: Synthesis of Enantiopure Di- and Tetrahydrxyindolizidines. J. Org. Chem. 2001, 66, 4787-4794. Ballini, R.; Bosica, G.; Conforti, M. L.; Maggi, R.; Mazzacani, A.; Righi, P.; Sartori, G. “Three-component process for the synthesis of 2-amino-2-chromenes in aqueous media” Tetrahedron 2001, 57, 1395. Demicheli, G.; Maggi, R.; Mazzacani, A.; Righi, P.; Sartori, G.; Bigi, F. “Supported organic catalysts: synthesis of (E)nitrostyrenes from nitroalkanes and aromatic aldehydes over propylamine supported on MCM-41 silica as a reusable catalyst” Tetrahedron Letters 2001, 42, 2401. Marotta, E.; Micheloni, L. M.; Scardovi, N.; Righi, P. “One-pot direct conversion of 2,3-epoxy alcohols into enantiomerically pure 4-hydroxy-4,5-dihydroisoxazole 2-oxides.” Org. Lett. 2001, 3, 727. 159 Ballini, R.; Bosica, G.; Maggi, R.; Ricciutelli, M.; Righi, P.; Sartori, G.; Sartorio, R. “Clay-catalysed Solventless Synthesis of trans-Chalcones” Green Chem. 2001, 3, 178. (Royal Society of Chemistry; Cambridge, Regno Unito; ISSN 1463-9262) Ballini, R.; Bosica, G.; Maggi, R.; Mazzacani, A.; Righi, P.; Sartori, G. “Amberlyst® 15 as a Mild, Chemoselective and Reusable Heterogeneneous Catalyst for the Conversion of Carbonyl Compounds to 1,3-Oxathiolanes” Synthesis 2001, 1826. I-3 Overview of Professional Publications (1997 - 2001) per year 1997 Rosini, G. - Criteri per una sintesi organica moderna- Alle soglie del 2000 perseguendo l’efficienza. (Criteria for a modern organic synthesis- At the beginning of 2000 pursuing efficiency). La Chim.& l’Ind. (Milano) 1997, 79, 353359. 1999 Rosini, G.- L’autocatalisi in sintesi asimmetrica: una vicenda di chimica seguita e raccontata da uno spettatore.(Autocatalysis in asymmetric synthesis: a story through the eyes of an observer). La Chim. & l’Ind. (Milano) 1999, 81, 231. Righi, P. “Critical Surveys Covering the Year 1998: Total Syntheses of Natural Products” in Seminars in Organic Synthesis, Riccio, R. Ed., Società Chimica Italiana, 1999, p. 401-518. 2000 Rosini, G. - “Looking beyond Stereoselectivity. Some Contribution to Efficiency in Target-driven Synthesis through Explanatory Stories” in Seminars in Organic Synthesis, Sodano, G. Ed., Società Chimica Italiana, 2000, p. 239-270 2001 Rosini, G. – L’ acido (-)-cainico: da una vicenda emblematica alcune riflessioni sulla sintesi organica. [(-)-Kainic Acid: Some considerations on organic synthesis from an emblematical story) La Chim. & l’Ind. (Milano) 2001, 83, 75. Alessandro Lorenzi, Paolo Righi, Goffredo Rosini- Ottimizzazione ed automazione di un processo su scala per la sintesi di intermedi di prostaglandine. CLUEB-Bologna, 2001. I-4 Other Scientific Output 1997 Goffredo Rosini, Claudia Baldazzi, Eleonora Romagnoli, Stefano Saguatti, Silvano PianiLactones with antioxidising and hypolipidaemic activity useful in the therapy of the atherosclerosys. US Patent N. 5,608, 084 (1997). Goffredo Rosini, Claudia Baldazzi, Silvano Piani 3,4-Dihydro-2-iodomethyl-2,5,7,8-tetramethyl-2H-1-benzopyrans. US Patent N. 5,663,389 (1997). 1998 Goffredo Rosini (invited lecture)- A promising approach to the stereoselective synthesis of 2-aminopolyols and aaminoacids poly hydroxylated. The idea, the project and its development making and taking down cycles. XXV Congresso della Società Chimica Italiana- Divisione di Chimica Organica- Folgaria 8-12 Settembre 1998. 1999 Goffredo Rosini (invited lecture)- “The value of impurity”- Little stories of chemistry remembering Primo Levi. Università degli Studi della Calabria- Dipartimento di Chimica – Rende 14 Dicembre 1999. Goffredo Rosini (invited lecture)- Two approaches to the synthesis of grandisol and related compounds. The evolution of an Idea. Università degli Studi di Roma “La Sapienza” – Dipartimento di Chimica- Roma 30 Giugno 1999. Goffredo Rosini (invited lecture)- Criteria for a modern organic synthesis. FEDERCHIMICA Acfis- Scuola di Formazione Acfis- Corsi di Chimica Fine- Milano 15 Aprile 1999. Goffredo Rosini (invited lecture) - Chirality and Molecules. 160 IX Settimana della Cultura Scientifica e Tecnologica. Tema “Scienza ed Educatione”. Università di Bologna. Bologna 25 Marzo 1999. Paolo Righi (invited lecture)- “Critical Surveys Covering the Year 1998: Total Syntheses of Natural Products” Seminars in Organic Synthesis, Società Chimica Italiana , Summer School “A. Corbella”, Gargnano (BS)- 18 Giugno 1999. 2000 Emanuela Marotta, Paolo Righi, Goffredo Rosini. (invited lecture)- The Bicyclo[3.2.0]hept-3-en-6-one Approach. The Origin and Evolution of an Idea and Efforts to Achieve Versatility and Practicality. Second French Italian Symposium-Organic Chemistry, Stereocontrol and New Targets. Strasbourg (France)- 24-25 November 2000. Goffredo Rosini (invited lecture)- “Looking beyond Stereoselectivity. Some Contribution to Efficiency in Targetdriven Synthesis through Explanatory Stories”. Seminars in Organic Synthesis, Società Chimica Italiana , Summer School “A. Corbella”, Gargnano (BS)- 16 Giugno 2000. Emanuela Marotta, Paolo Righi, Noemi Scardovi (invited lecture)- Linear Aminopolyhydroxylated Compounds Through Multi-bond Forming Processes. 3rd Spanish-Italian Symposium on Organic Chemistry- September 3-5, 2000, BENALMADENA (Malaga), Spain. Appendix 3 Journal Portfolio Analysis Name of the Unit: Bologna 8 Research Director: Goffredo Rosini Years included 1997-2001 Name of Journal Chem-Eur J Green Chem J Org Chem Org Lett Tetrahedron Lett Tetrahedron Synthesis-Stuttgart Bioorg. Med. Chem Number Articles 1 1 3 3 1 2 2 1 Org Synth Org Process Res Dev 1 1 Comments on: a) the method: no comment of Journal Factor 4.614 2.477 3.280 3.670 2.280 2.276 1.985 1.798 1.293 0.848 Impact Field(s) Chemistry/Multidisc. Chemistry/Multidisc. Chemistry/Organic Chemistry/Organic Chemistry/Organic Chemistry/Organic Chemistry/Organic Chemistry/Medicinal Chemistry/Organic Chemistry/Organic Chemistry/Organic Chemistry/Medicinal Ranking 7/118 18/118 7/51 6/51 13/51 14/51 18/51 13/36 22/51 30/51 34/51 24/36 161 BOLOGNA 9 Name of the Research Unit BOLOGNA 9 Research Leader Prof. Giuseppe CHIAVARI University: University of Bologna, Italy Contact Person Faculty: Science MFN Department: Chemistry G.Ciamician Dr.Daniele FABBRI Laboratory of Chemistry c/o ITIS CIRSA-University of Bologna Via Marconi,2 I-48100 RAVENNA, Italy ++39-0544-270975 ++39-0544-275134 [email protected] Thematic area 1.Chemistry of ecosystems (chemistry of soil, water and air; environmental impact of chemicals). 2.New technologies for monitoring. Introduction and Context The Unit Bologna 9 conducts its research and teaching activity in the field of analytical chemistry for environment and cultural heritage at the Faculty of Science MFN of the University of Bologna. The research is principally carried out at the Laboratory of Chemistry of the Centro Interdipartimentale per le Ricerche in Scienze Ambientali (C.I.R.S.A., Researches in Environmental Sciences Interdept Centre), located in the city of Ravenna, where the curriculum in Environmental Sciences has been established. The laboratory is well equipped with modern instruments for environmental analyses of organic and inorganic constituents (GC/MS, HPLC/DAD-Flu, ion chromatography, atomic spectroscopy, polarography). Several theses related to environmental analytical chemistry are carried out in this laboratory mostly by undergraduate and PhD students from the curriculum in Environmental Sciences. The other structure of research and teaching activity is the Dept of Chemistry ‘G.Ciamician’ located in Bologna. Introduction to the Self-evaluation Report The research topics of the Unit deal with analytical chemistry for a better understanding and preservation of our environment. The term environment is used here in its widest sense which encompasses artistic patrimony and human activities. Indeed, integrated management of environment and resources might include ecosystems as well as works of arts (e.g. historical monuments) or the improvement of industrial processes (e.g. green chemistry). The Unit is interested in developing analytical procedures useful for characterising chemical constituents of environmental concern. The attention has been focussed on natural and synthetic macromolecules due to their important role in natural processes (e.g. chelators of heavy metals), human utilisation (e.g. combustion of coal, restoration). Synthetic polymers can be important contaminants of coastal and even oceanic areas. This topic is potentially well fitted for synergic collaborations with other INCA units of the University of Bologna, as macromolecules i) constitute a significant albeit almost unknown fraction of airborne matter (interaction with Unit Bologna 6), ii) affect the biodegradation of organic micropollutants (interaction with Unit Bologna 1), iii) are an important component of solid wastes to be recycled (interaction with Unit 3). Among inorganic constituents, the research has been mainly devoted on heavy metals, but in the last years, the attention has been driven to sulphur species considering their role in heavy metal bioavailability. The University, the Faculty and the Department The University of Bologna is the oldest in the western world: 1088 may be accepted as conventional date to indicate when teaching became free and independent of the ecclesiastic schools. Bologna University is one of the largest universities in Italy and in Europe. It is a state university and it is autonomous with its own "statuto" which indicates how the University governs itself through its various elected bodies. The University government and the main research and teaching activity are located in Bologna, but many new research and teaching activities have been recently dislocated in other Cities of the Emilia Romagna region, such as Cesena, Faenza, Forli’, Ravenna and Rimini. The whole University currently counts about 900 professors, 1,000 associated professors, 1,050 researchers and more than 100,000 students. It is divided in 19 Faculties, 65 Departments, 5 Federated Departments («Unità Complesse»), 3 162 Institutes and it currently offers about 65 «laurea» degree courses and 45 «diploma» degree courses in the following subject areas: a)Agriculture; b) Economics; c) Education and Humanities; d) Engineering; e) Industrial Chemistry, f)Law; g) Literature and Philosophy; h) Mathematical, Physical and Natural Sciences; i) Medicine; l) Pharmacy; m) Political Science; n) School of Modern Languages for Interprets and Translators; o) Statistical Sciences; p) Veterinary Medicine; q) Foreign Languages and Literatures. The Unit The Unit is composed of three permanent university members: Giuseppe CHIAVARI (full professor), Clinio LOCATELLI (associate professor), Daniele FABBRI (PhD, senior researcher). Each member is responsible of a reasearch sub-unit. The sub-units of GC and CL include both a PhD student in Environmental Sciences (Silvia Prati and Alberto Righetti, respectively), while the sub-unit of DF includes a Post-Doc in Environmental Sciences, presently research assistant (“assegnista”) within an European Project. Several students join the Unit each year to prepare their master thesis for the curricula of Environmental Sciences and Chemsity. GC and CL have been working in the field of analytical chemistry since the beginning of their research activity in academic institutions, DF has been active in academic and industrial research as well (R&D of ENI corporation) The docents of the Unit are responsible of the following courses : Analytical Chemistry (GC, curriculum in Environmental Sciences) Laboratory of Analytical Chemistry (CL, curriculum in Environmental Sciences) Chemical Oceanography (DF, curriculum in Environmental Sciences) Laboratory of Analytical Chemistry II (CL, curriculum in Chemistry) Laboratory of Analytical Chemistry III (CL, curriculum in Chemistry) Electrochemistry and corrosion (CL, GC, curriculum in Chemistry) Gas chromatography (GC, curriculum Chemistry). Chemisty for Cultural Heritage (GC, curriculum in Chemistry) Analytical Chemistry (GC, curriculum in Technology forPreservation and Restoration of Cutlural Heritage) The teaching load includes also the following activities within the Faculty of Science: GC and CL give lessons for the Specialisation School in Chemical Methodologies for Control and Analysis, CL also in the post-degree Course in Marine Pollution, DF is co-ordinator of the Chemistry section of the Master in Integrated Management of Coastal Zone. Programme Description and Evaluation 1 Title Development and Application of Analytical Procedures to Environmental Sciences and Preservation of Cultural Heritage 2 Research Leader Prof.Giuseppe Chiavari 2a Sub-programme titles and sub-programme leaders Development and Application of Analytical Procedures to study: 1.Interaction between environment and works of art (Giuseppe CHIAVARI). 2.Natural and synthetic macromolecules in the environment (Daniele FABBRI). 3.Distribution and speciation of heavy metals in fluvial and coastal ecosystems (Clinio LOCATELLI). 3 Composition of the scientific research staff of the unit per 1 January 2002 Names and Titles Year of Rank Birth Giuseppe Chiavari Clinio Locatelli Daniele Fabbri Ivano Vassura Silvia Prati Alberto Righetti Total research input 1937 1949 1958 1970 1975 1970 full prof Associated prof senior res Post-Doc PhD-student PhD student Research Input in fte in 2001 0.2 0.4 0.5 1.0 1.0 1.0 4.1 Remarks Sub-programme 1 Sub-programme 3 Sub-programme 2 Sub-programme 2 since 1999 Sub-programme 1 since 2000 Sub-programme 3 163 4 Input of Academic Staff in fte Category Full Professors Associated Professors Ricercatori Post-docs PhD-students Borsisti Total 1997 0.2 0.4 0.5 1.0 1998 0.2 0.4 0.5 1.0 1999 0.2 0.4 0.5 1.0 2.1 2.1 2.1 2000 0.2 0.4 0.5 1.0 1.0 1.0 4.1 2001 0.2 0.4 0.5 1.0 1.0 1.0 4.1 Total 1.0 2.0 2.5 5.0 2.0 2.0 14.5 2001 1.0 Total Comments Three members (namely GC, DF and IV) belonged to a former Unit of the INCA 5 Funding 5.1 Personnel (in fte) Source University CNR European Union Other Sponsors Total 5.2 1998 1999 2000 1.0 1.0 1.0 1.0 1.0 Materials and Equipment (in Million Lire) Source University – MURST CNR EU Other Sponsors Total 5.3 1997 1997 20 30 1998 25 30 1999 25 30 2000 25 30 50 55 55 55 2001 25 30 10 10 75 Total 120 150 10 10 290 Comments: * On the figures: in Table 5.1 permanent university members are not included, even when their hourly activity is part of the budget (for EU). In Table 5.2 the CNR budget includes payment of short-time activity of personnel not inserted in the Unit. * On the funding policy Please add a list of major sponsors and the character of the liaison with the major sponsors CNR and European Coal and Steel Community are the major sponsors. The liaison is the use of analytical pyrolysis for the molecular characterisation of complex organic materials. 6. Progress Report 6.1 Mission Statement The unit exerts its activity in the field of fundamental and applied analytical chemistry. As far as fundamental research is concerned, the contribution of the Unit in this field regards the development of new procedures in analytical pyrolysis, atomic spectroscopy and voltammetry. The applied research of the last five years has included the study of pristine and impacted marine and fluvial ecosystems, a protected coastal area (Ravenna Lagoon, Ramsar site) endangered by pollution, effects of human activity on works of art, emission of PAHs from coal utilisation. The activity is of interested for international academic institutions in oceanography and applied chemistry, institues of restoration, coal industry, municipal authority. 164 6.2 The Research Programme The research programme of the Unit is concerned with the development and application of methodologies in analytical chemistry related to the evaluation of pollution in contaminated areas, the chemistry of ecosystems, the preservation of cultural heritage, the improvement of industrial processes with environmental benefits. To this purpose several analytical techniques based on gas chromatography, liquid chromatography, mass spectrometry, atomic and molecular spectroscopy, electrochemistry and so forth are employed to study chemical components in a number of environmental matrices (water, airborne particles, sediments, biota), industrial feedstock (coals, oil) and materials used in the field of art and architecture (binders, protectives). Analytical methods developed within the programme pertain to the analysis of both organic and inorganic constituents, therefore two main sub-groups are identified in the Unit. One sub-group is mainly concerned with the composition of the organic fraction (sub-programme 1 and 2), the other with the analysis of inorganic species (sub-programme 3). The sub-group of organic analytical chemistry is interested to the analysis of macromolecules, and the principal technique utilised to this purpose is analytical pyrolysis. According to the field of application, this sub-group is further divided into two sub-units, one dealing with environmental topics (subprogramme 2) and the other with the preservation of cultural heritage (sub-programme 1). These sub-programmes exhibit close relationships. The principal overlapping between sub-programmes 1 and 2 resides in the utilised analytical technique (pyrolysis) and analysed materials (e.g. polysaccharides), but differ in the field of application. The principal connections between sub-programmes 2 and 3 are related to the study of polluted sites where the knowledge of both inorganic and organic contaminants is necessary. The research subjects of each sub-programme are outlined here below, with an indication of the most important results. Sub-programme 1: The sub-programme is concerned with the aging and degradation of art objects caused by the environmental parameters. To this purpose, standard materials (e.g. painting layers) are subjected to different environmental agents (e.g. UV radiation, NOx) and the chemical effects on the organic fraction are investigated by analytical pyrolysis. The aim is to individuate molecular markers (occurring in-situ or formed by pyrolysis) indicative of the changes in chemical composition caused by stress agents. Since the organic fraction is a complex network of high molecular weight components (resins, gums, proteinaceous materials), the preferred technique is analytical pyrolysis (Py-GC/MS), which is well fitted for the characterisation of macromolecules. To the end of increasing the field of application of the technique towards polar/unvolatile constituents, derivatisation procedures in pyrolysis are under investigation (reactive/pyrolysis). Pyrolysis/methylation with tetramethylammonium hydroxide (TMAH), the most utilised procedure in the literature, is routinely applied in our laboratory. The most important result in this field is the development of a new method in reactive pyrolysis based on silylating reagents, which overcomes some of the problems created by TMAH pyrolysis. As an example of the application of analytical pyrolysis to real samples, our Unit, presently involved in a multidisciplinary diagnostic campaign at the Scrovegni Chapel (Padua), has detected the nature of polymeric materials used in past restoration interventions on Giotto’s frescoes. In the topic interaction environment/work of art is worth mentioning the project “Conservation status and degradation mechanisms of the buildings “Fabbrica Vecchia – Marchesato” (Marina di Ravenna, Ravenna, Italy). Apart their historical value, the environmental interest of the two buildings resides in the fact that they are located in an area of intense anthropogenic influence and are also subjected to natural causes of degradation (e.g.marine aerosol). In this project the Unit is involved in chemical characterisation of the surface of the buildings, which are considered like in-situ sampling systems to monitor the environmental stress and source apportionment of degradation. Sub-programme 2: The main research topic is related to the structural characterisation of macromolecules of environmental concern, both natural and synthetic, using procedures based on analytical pyrolysis, in particular Py-GC/MS. Py-GC/MS is applied to study the chemical composition of organic matter in the water column and sediment of Black and Mediterranea Sea. Data arising from Py-GC/MS are correlated with the results obtained from traditional oceanographic measurements and provide complementary information at molecular levels. For a better interpretation of the pyrolytic data, Py-GC/MS is also applied to the analysis of zooplankton, cultured phytoplankton species, bacteria as well as standard biopolymers (e.g.polysaccharides). The identification of carbohydrate markers and their mechanism of formation in TMAH pyrolysis, is a remarkable result of this research since these markers are now widely used in the literature to recognise carbohydrates in complex environmental samples. Structural characterisation of geopolymers (humic substances, kerogens, sapropels, oil, coals) is an other important issue of the sub-programme. Apart as a descriptive technique of the molecular network of these complex materials, analytical pyrolysis is exploited as a rapid technique for screening the emission of organics during their thermal treatment. Within a Project supported by the European Coal and Steel Community, the sub-unit is investigating pyrolysis as a model system and a fast analytical procedure to predict the emission of PAHs during coal pyrolysis. The principal result in this field is the development of a simple off-line procedure for the quantitative estimate of PAH evolved from pyrolysis of coke precursor materials. The final aim of the project is that to produce coke of good quality with low environmental impact 165 The occurrence in the environment of PAHs formed by pyrolytic processes is an other subject we are interested in. A remarkable result in this area regards the source apportionment of PAHs occurring as major pollutants in a coastal lagoon. In collaboration with the University of Strathclyde and Scottish Universities Research Center, Glasgow (measurements of 13C/12C isotopic ratio of single PAHs) the source has been identified in the pyrolysis of biogenic natural gas, utilised by the local industry to produce acetylene. This latter study is part of a wider research programme aimed at investigating chemical pollution of a protected coastal lagoon located in the proximity of Ravenna and impacted by a multitude of potential sources of contamination (industry, municipal wastes, agricultural run-off, harbour activity, power plants). An important result of the sub-programme 2 has been the development of new methods in PyGC/MS and complementary analytical techniques for the analysis of synthetic polymers in sediments which enabled the detection of a strong contamination by artificial resins (PVC, polyvinylacetate) and rubbers. The procedures will be applied to other coastal ecosystems potentially contaminated by synthetic polymers. Sub-programme 3: This sub-programme is mainly concerned with the analysis of inorganic constituents in the environment. It consists of the following topics: 1) development of analytical methodologies based on atomic spectroscopy and voltammetry for the determination of trace elements in environmental matrices and food. This includes theoretical studies for the optimisation of analytical parameters related to accuracy, reproducibility limit of detection. Application to ecosystems, with particular attention to fluvial and coastal areas. 2) Study of adsorption processes of inorganic and organic constituents to suspended matter and their quantitative determination at ultratrace level. 3) Speciation of sulphur in connection with the distribution of heavy toxic metal in sediments. The last item is directly connected with the research programme aimed at evaluating the status of the Ravenna Lagoon, with particular attention to the fate of mercury. It is well known that sulphides are involved in trapping mercury in sediments reducing its bioavailability. However, recent studies have revealed that elemental sulphur is potentially capable to increase the mobility of mercury, especially in salt marsh systems. Development of procedures for the analysis of elemental sulphur and its ecotoxycological importance are emerging subjects of research activity of the Unit. 6.3 Position in Networks • Intra-university co-operation • • Regional co-operation National co-operation (including INCA) 1.CNR (National Research Council), Special Project Safeguard of Cultural Heritage. Progetto finalizzato per i Beni Culturali. The funds support the fundamental and applied research in collaboration with other research Institutes, in which our analytical techniques are compared to other methodologies for the appraisal of the state of degradation of standard painting layers and from the commission of analyses by external structures such as the Central Institute of Restoration. 2.CNR, Co-ordinated Project ‘Studies on industrial pollution’. Progetto Coordinato CNR ‘Studi su inquinamenti industriali’. 3.INCA Consortium. The collaboration has mainly involved members of the former Unit (presently Bologna 6) and has been concerned with the distribution and speciation of mercury in coastal areas. • International co-operation 1. The European Coal and Steel Community is financing a three years project co-ordinated by the Coal Products Industries Limited UK, other participants being the University of Nottingham UK and INCAR-CSIC Spain, titled “Improved Manufacture of Coke for Non-Ferrous Applications with Environmental, Operational and Market Benefits”. Analytical pyrolysis is used by our Unit as a rapid analytical method to evaluate PAH emissions during thermal treatment of coke precursors and to find structural relationships useful for the selection of starting materials. 2. Chinese-Italian Centre for the Conservation and Restoration of Cultural Relics, Xian, RP of China. 3. Conferenza dei Rettori delle Università Italiane-British Council: collaboration with the University of Strathclyde, Glasgow (UK) to study the organic pollution of coastal lagoon (Ravenna Lagoon). 4. A project in collaboration with the Middle East Technical University (METU), Turkey. entitled “The Source and the Composition of Particulate Organic Matter in the Black Sea” financially supported by Turkish Scientific and Technical Research Council (TUBITAK). In the framework of this Project a set of samples were collected 166 from the Black Sea during 1998-1999 cruises of R/V Bilim Research Vessel of METU and in May/June 2001 cruise of American Research Vessel R/V Knorr (Wood Hole Oceanographic Inst) and are analysed by GC/MS and Py-GC/MS in our Unit. within a wide project of remediation, with economical and touristic benefits, financed by muniipal and regional authoritie Further Indications of Quality and Reputation Prof.G.Chiavari : 1) President of the curriculum in Technology for the Preservation and Restoration of Cultural Heritage (University of Bologna). 2) Director of the Specialisation School in Chemical Methodologies for Control and Analysis (University of Bologna). Dr.D.Fabbri 1) Project leader of the European Project ECSC 2001-2003. 2) R.A.Glenn Award for the best work presented at the American Chemical Society, Fuel Chem.Division, 2001. Dr.I.Vassura 1) Ravenna Industry Association Award for the best master thesis in Environmental Sciences. 6.6 Key Publications Carole McRae, Colin E. Snape, Cheng-Gong Sun, Daniele Fabbri, Daniele Tartari, Claudio Trombini, Anthony E. Fallick, Use of compound specific stable isotope analysis to source anthropogenic natural gas-derived polycyclic aromatic hydrocarbons in a lagoon sediment Environmental Science and Tecnhology, 34, 4684-4686 (2000). Y.Coban-Yldiz, G.Chiavari, D.Fabbri, A.F.Gaines, G.Galletti, S.Tugrul, The chemical composition of Black Sea suspended particulate organic matter: pyrolysis-GC/MS as a complementary tool to traditional oceanographic analyses. Marine Chemistry, 69, 55-67 (2000). Fabbri Daniele: Use of pyrolysis-gas chromatography/mass spectrometry to study environmental pollution caused by synthetic polymers. A case study: the Ravenna Lagoon, Journal of Analytical and Applied Pyrolysis, 58-59, 361-370 (2001). G.Chiavari, D.Fabbri, S.Prati: In situ Pyrolysis and Silylation of Fatty Materials Used in Painting Layers, Chromatographia, 53 (5/6), 311-314, (2001). D. Fabbri, C.Locatelli, C.E.Snape, S.Tarabusi, ‘Sulphur Speciation in Mercury-Contaminated Sediments of a Coastal Lagoon. The Role of Elemental Sulphur.’, J.Environmental Monitoring, 3, 483-486 (2001). 7. Scientific Output 7.1 Publication Policy Our research works are published in international peer-reviewed journals of significant scientific relevance in the field of analytical chemistry and environmental sciences. Considering the multidisciplinary approach of environmental studies, journals in fields like oceanography and geochemistry are considered. Communications to important national journals, national and international conferences are part of the publication policy. Thesis are an important background of the scientific production. 7.2 Numerical data Category PhD-Dissertations 1997 1998 1999 2000 2001 Total Scientific Publications 10 11 14 16 15 66 Professional Publications Master’s Theses* 7 5 6 4 5 27 167 * only theses in Environmental Sciences have been considered. Appendix I Scientific Output I-1 Overview of Dissertations and Master's Thesis (1997-2001) I.1.1 Dissertations Year Name PhD-student Title of the Dissertation Supervisor I.1.2 Master's Thesis (only theses in Environmental Sciences have been considered.) Year Name Master’s student Title of the Dissertation Supervisor 1996-97 Lubrano Lavadera Caratterizzazione chimico-ambientale dei fondali al largo del delta Fabbri D. Debora del Po 1998-99 Tartari Daniele Studio sull'inquinamento da idrocarburi policiclici aromatici e Fabbri D. polimeri vinilici nella piallassa Baiona 1998-99 Mugnai Cristian Studio della bioturbazione in sedimenti della Laguna di Venezia 1999-00 Comandini Michela Caratterizzazione della componente organica in sedimenti Fabbri D. dell'Adriatico centro-settentrionale Studio della sedimentazione recente e della geochimica del lago Fabbri D. Cheko (Siberia centrale): eventuali correlazioni con l'evento di Tunguska Il bacino idrografico del fiume Marecchia: valutazione Locatelli C. dell'inquinamento organico, biologico ed inorganico delle acque superficiali Caratterizzazione ambientale della Pialassa Baiona mediante la Locatelli C. determinazione di specie metalliche nei sedimenti 2000-01 Sacchetti Fabio 1995-96 Ronchini Leonardo 1996-97 Astara Alberto 1997-98 Gabrielli Laura 1997-98 Castiglione Renato 1997-98 Cescuti Angelo Fabbri D. Il bacino idrografico del fiume Conca : valutazione Locatelli C. dell'inquinamento organico, biologico ed inorganico delle acque e dei sedimenti Variante di valico dell'autostrada Bologna-Firenze: fattori di impatto Locatelli C. ambientale sul territotio Setta Caratterizzazione chimica sia organica che inorganica del torrente Locatelli C. Marano 1998-99 Tarabusi Simone Speciazione dello zolfo in sedimenti inquinati di mercurio 1998-99 Benagli Marcello Studio di metalli pesanti atmosferici attraverso deposizioni secche ed Locatelli C. umide nell'area di Ravenna 1999-00 Siliquini Fabrizio Fiume Aso: valutazione del livello di inquinanti inorganici in acqua Locatelli C. e sedimento Distribuzione del carico inquinante relativamente ad un ecosistema Locatelli C. dell'Italia Centrale: il fiume Tronto Controllo dell'abbattimento dei metalli pesanti in un depuratore Locatelli C. industriale 1999-00 Angelini Ugo 1999-00 Lagosti Giorgia 1999-00 Castelli Silvia Locatelli C. Campionamento e determinazione della silice libera e dei metalli Locatelli C. pesanti nelle polveri aerodisperse in ambiente industriale 168 1999-00 Frassati Christian 2000-01 Asioli Andrea 2000-01 Romualdi Barbara 1997-98 Ravaioli Stefano 1997-98 Giuliani Silvia 1998-99 Olivi Alessandro 2000-01 Fiori Pietro Ozono in siti rurali e di altitudine della Valle d'Aosta. Dipendenza Locatelli C. dalle condizioni meteoclimatiche locali Distribuzione e valutazione di inquinanti inorganici in matrici di un Locatelli C. ecosistema fluviale: fiume Lamone Valutazione del carico inquinante nelle acque e nei sedimenti del Locatelli C. fiume Montone Metodologie cromatografiche per il controllo di effluenti industriali Chiavari G. con particolare riguardo ai composti fenolici Interazione e dinamica del particellato nell'Adriatico settentrionale: Chiavari G. studio dei processi a scala temporale breve attraverso i disequilibri 234Th/238U e 210Po/210Pb. Caratterizzazione chimica e merceologica dei prodotti di Chiavari G. demolizione pirolitica della paglia in funzione di un possibile riutilizzo Ambiente e degrado del materiale dei monumenti: il caso della Chiavari G. Fabbrica vecchia e del Marchesato in Marina di Ravenna 2000-01 Marianna Amaducci Inquinanti legati a traffico veicolare: loro determinazioni in matrice Locatelli C. ambientale 2000-01 Elena Tagliati Caratterizzazione chimica e biologica di un ecosistema all’interno Locatelli C. del Parco del Delta del Po 2000-01 Federico Foschini Analisi di idrocarburi policiclici aromatici pirogenici in ambienti Fabbri D. lagunari I-2 Overview of Scientific Publications (1997-2001) per year 1997: 1. S.Gagni, P.Goberti and G.Chiavari : " Determination of halogenated olefins by photoionization and Hall electrolytic conductivity detectors in series in matrices of hydrofluorocarbons and hydrochlorofluorocarbons" Chromatographia, 46, (1997),404-410. 2. P. Reschiglian, S. Valcher, C. Locatelli, F.N. Rossi, and G. Torsi A high current, battery-operated power supply with power control through an on-off fast switch. Rew. of Sci. Instr. 68, 1609 (1997). 3. C. Locatelli Metal analysis in real matrices. Simultaneous voltammetric determination of copper and antimony in alloys. Electroanalysis 9, 560 (1997). 4. G. Torsi, C. Locatelli, P. Reschiglian, F. Fagioli, D. Melucci, N. Rossi Nuova metodica per misure di metalli in ambiente urbano.Inquinamento 7, 46 (1997). 5. Standardless analysis in electrothermal atomic absorption spectroscopy with Pd as matrix modifier. C. Locatelli, P. Reschiglian, F. Fagioli, G. Torsi, D. Melucci, and N. Rossi Comparison of a new atomization system with a commercial system in the determination of Pb and Cd in fruit juice. Ann. Chim. (Rome) 87, 397 (1997). 6. C. Locatelli, F. Fagioli Determination at trace level of heavy metals in mussels and clams. Ann. Chim. (Rome) 87, 535 (1997). 7. C. Locatelli Anodic and cathodic stripping voltammetry in the simultaneous determination of toxic metals in environmental samples. Electroanalysis 9, 1014 (1997). 8. F.N. Rossi, P. Reschiglian, C. Locatelli, D. Melucci, and G. Torsi Level of cadmium associated with airborne particulate matter in the town of Bologna. Ann. Chim. (Rome) 87, 605 (1997). 9. G. Torsi, P. Reschiglian, C. Locatelli, and D. Melucci. A new fast and standardless method for direct determination of metals associated with particulate matter in air: avoiding error in the determination of Pb in an urban environment. J. Env. Pat. Tox. Onc. 16, 253 (1997). 10. G. Torsi, C. Locatelli, P. Reschiglian, D. Melucci, and F.N. Rossi Electrostatic Precipitation and Electrothermal Atomic absorption Spectrometry: a perfect combination for the analysis of metals associated with particulate matter. In «Advances in Atomic Spectroscopy», Vol. 4, J. Sneddon Ed., p. 1-25, JAI Press Inc., Greenwich, CT, 1998, USA. 169 1998 1. G.Chiavari, Gandini N., Russo P., D. Fabbri, ‘Characterisation of Standard Tempera Painting Layers Containing Proteinaceous Binders by Pyrolysis(/Methylation)-Gas Chromatography/Mass Spectrometry’, Chromatographia, 47, 420-426 (1998). 2. D.Fabbri, M.Mongardi, L.Montanari, G.C.Galletti, G.Chiavari, R.Scotti, ‘Comparison between CP/MAS 13CNMR and pyrolysis-GC/MS in the structural characterisation of humins and humic acids of soil and sediments’, Fresenius’ Journal of Analytical Chemistry 362, 299-306 (1998). 3. D.Fabbri, O.Felisatti, M.Lombardo, C.Trombini , I.Vassura,‘The Lagoon of Ravenna (Italy): characterisation of mercury-contaminated sediments’, The Science of the Total Environment, 213, 121-128 (1998). 4. D.Fabbri, C.Trombini, I.Vassura ‘Analysis of Polystyrene in Polluted Sediments by Pyrolysis-Gas Chromatography-Mass Spectrometry’, Journal of Chromatographic Science, 36, 600 (1998). 5. G.Chiavari, G.C.Galletti, P.Bocchini, P.Russo, N.Gandini, D.Fabbri, Thermally assisted hydrolysismethylation/gas chromatography/mass spectrometry of painting layers from the cupola of S.Maria del Fiore Cathedral in Florence, Science and Technology for Cultural Heritage 7(1), 19-25 (1998). 6. F.N. Rossi, D. Melucci, C. Locatelli, P. Reschiglian, G. Torsi, A. Millemaggi Influence of pressure and atomizer length on absorption curves in ETA-AAS measurements for standardless analysis. Fresenius J. Anal. Chem. 361, 504 (1998). 7. C. Locatelli, G. Torsi Simultaneous voltammetric determination of toxic metals in sediments. Talanta 46, 623 (1998). 8. G. Torsi, P. Reschiglian, C. Locatelli, F.N. Rossi, D. Melucci Standardless elemental analysis through electrothermal atomic absorption spectroscopy. Application to aqueous samples and particulate matter in air.Atomic Spectroscopy 10, 16 (1998). 9. C. Locatelli Simultaneous metal determination in Salerno Gulf. Proposal of a new analytical procedure.Fresenius Envir. Bull. 7, 406 (1998). 10. C. Locatelli, G. Torsi Peak area, peak current: critical comparison. Application to real samples. Electroanalysis 10, 904 (1998). 11. G. Torsi, F. Fagioli, G. Landi, P. Reschiglian, C. Locatelli, F.N. Rossi, D. Melucci, and T.Bernardi. Theoretical and experimental values of the spectroscopic constant relative to the Hg 253.7 line at different temperatures. Spectrochimica Acta 53B, 1847 (1998). 1999 1. D.Fabbri and R.Helleur, ‘Characterization of the tetramethylammonium hydroxide thermochemolysis products of carbohydrates’, Journal of Analytical and Applied Pyrolysis, 49, 277-293 (1999). 2. G.Chiavari, A.Colucci,R.Mazzeo, M.Ravanelli : "Organic Content Evaluation of Corrosion Patinas in Outdoor Bronze Monuments. Chromatographia, 49, (1999), 35-41 3. O.Cattani, D.Fabbri, M.Salvati, C.Trombini, I.Vassura, ‘Biomonitoring of mercury pollution in a wetland near Ravenna, Italy by translocated Bivalves (Mytilus galloprovincialis)’ Environmental Toxicology and Chemistry, 18, 1801-1805 (1999). 4. G.Chiavari. M.Ravanelli: " Characterisation methods for organic materials: the analytical pyrolysis, OPD Restauro 11, (1999), 130-136. 5. G.Chiavari and R.Mazzeo: "Characterisation of paint layers in chinese archaelogical relics by Pyrolysis-GCMS. Chromatographia,49,(1999), 268-272 6. G.Chiavari, D.Fabbri, S.Prati, R.Mazzeo, D.Bikiaris, Sister Daniila, Y.Chryssoulakis ‘Analytical Pyrolysis : Application to the Chemical Characterisation of Byzantine Painting Layers’ Atti del 6th International Conference on ‘Non-Destructive Testing and Microanalysis for the Diagnostics and Conservation of the Cultural and Environmental Heritage’Roma, Vol.2, 1147-1162 (1999). 7. C. Locatelli, G. Torsi, T. Garai. Determination of heavy metals in environmental bio-indicators by voltammetric and spectroscopic techniques.Fresenius J. Anal. Chem. 363, 662 (1999). 8. C. Locatelli, A. Astara, G. Torsi Major, minor and trace element distribution in sediments of Salerno gulf.Fresenius Environ. Bull. 8, 124 (1999). 9. C. Locatelli, A. Astara, E. Vasca, V. Campanella Voltammetric and spectroscopic determination of toxic metals in sediments and sea water of Salerno Gulf. Environmental Monitoring and Assessment 58, 23 (1999). 10. C. Locatelli, A. Astara, G. Torsi Inorganic species distribution in a lagoon ecosystem inside the delta of the Po River.Ann. Chim. (Rome) 89, 721 (1999). 11. G. Torsi, S. Valcher, P. Reschiglian, D. Melucci, C. Locatelli, A. Zattoni Pushing electrothermal atomic absorption spectroscopy to its physical limits.Recent Research Developments in Applied Spectroscopy 2, 19 (1999). 12. C. Locatelli Sea water quality criteria by bioindicators. Possible classification based on metal content in Ulva Rigida and Tapes Philippinarum.. Toxicological and Environmental. Chemistry 71, 435 (1999). 170 13. C. Locatelli, G.Torsi. Employment of peak area in the determination of metals having low reversibility degree of the electrodic process. Electroanalysis 11, 1203 (1999). 14. C. Locatelli, G. Torsi Cathodic and anodic stripping voltammetry: simultaneous determination of As-Se and Cu-Pb-Cd-Zn in the case of very high concentration ratios. Talanta 50, 1079 (1999). 2000 1. Y.Coban-Yldiz, G.Chiavari, D.Fabbri, A.F.Gaines, G.Galletti, S.Tugrul, The chemical composition of Black Sea suspended particulate organic matter: pyrolysis-GC/MS as a complementary tool to traditional oceanographic analyses. Marine Chemistry, 69, 55-67 (2000). 2. Fabbri D., Tartari D., Trombini C. Analysis of poly(vinyl chloride) and other polymers in sediments and suspended matter of a coastal lagoon by pyrolysis-gas chromatography / mass spectrometry , Analytica Chimica Acta, 413, 3-11 (2000). 3. S.Prati, G.Chiavari e D.Cam: "DSC application in the conservation field. J.ThermalAnal.Calorimetry, 66 315327 (2001). 4. Coban-Yildiz Y., Fabbri D., Tartari D., Tugrul S., Gaines A.F., Application of pyrolysis-GC/MS for the characterisation of particulate organic matter in the Mediterranean Sea: a comparison with the Black Sea, Organic Geochemistry, 31, 1627-1639 (2000). 5. Brown S.D., Chiavari G., Ediger V., Fabbri D., Gaines A.F., Galletti G., Karayigit A.I., C.E.Snape, Sirkecioglu O., Toprak S. Black Sea sapropels: relation to kerogen and fossil fuel precursors, Fuel, 79 1725-1742 (2000). 6. Fabbri D., Chiavari G. He Ling, Analysis of anthraquinoid and indigoid dyes used in ancient artistic works by thermally assisted hydrolysis and methylation in the presence of tetramethylammonium hydroxide, Journal of Analyitcal and Applied Pyrolysis, 56, 167-178 (2000). 7. Locatelli C., Fabbri D., Torsi G.: Accuracy, precision and limit of detection in the determination of inorganic species in environmental matrices. An application to the Marano river ecosystem., Annali di Chimica, 90, 613-620 (2000). 8. Carole McRae, Colin E. Snape, Cheng-Gong Sun, Daniele Fabbri, Daniele Tartari, Claudio Trombini, Anthony E. Fallick, Use of compound specific stable isotope analysis to source anthropogenic natural gas-derived polycyclic aromatic hydrocarbons in a lagoon sediment Environmental Science and Tecnhology, 34, 4684-4686 (2000). 9. G. Torsi, F.N. Rossi, D. Melucci, P. Reschiglian, C. Locatelli, D. Di Cintio Absorbance vs. time curves at high heating rate in electrothermal atomic absorption spectroscopy. Spectrochim. Acta part B 55, 65 (2000). 10. C. Locatelli, G. Torsi Inorganic characterization of Conca River Ecosystem. Ann. Chim. (Rome) 90, 73 (2000). 11. G. Torsi, S. Valcher, P. Reschiglian, C. Locatelli, A. Zattoni Extension of the standardless method of analysis in electrothermal atomic absorption spectroscopy to elements of medium volatility: experimental results for Co, Cr, Cu, Fe, Mn and Ni. Microchemical Journal 65, 23 (2000). 12. C. Locatelli Proposal of new analytical procedures for heavy metal determinations in mussels, clams and fishes. Food Additives and Contaminants 17, 769 (2000). 13. C. Locatelli, G. Torsi Determination of Se, As, Cu, Pb, Cd, Zn and Mn by anodic and cathodic stripping voltammetry in marine environmental matrices in the presence of reciprocal interference. Proposal of a new analytical procedure. Microchemical Journal 65, 293 (2000). 14. C. Locatelli, G. Torsi, F. Rossi A new analytical procedure for simultaneous voltammetric metal determinations in sea water, sediments, algae and fishes. Fresenius Environ. Bull. 9, 813 (2000). 15. C. Locatelli Measurement of voltammetric peak area and resolution of overlapping peaks in the simultaneous determination of copper, lead, cadmium and nickel in environmental matrices. Journal of AOAC International 83, 1321 (2000). 16. P. Reschiglian, A. Zattoni, D. Melucci, C. Locatelli, G. Torsi Standardless and absolute analysis through the Lambert-Beer law. Application to inhomogeneous dynamic samples with flow-assisted separation techniques, FIA and atomic absorption spectroscopy. Recent Res. Devel. Applied Spectroscopy 3, 61 (2000). 2001 1. Fabbri D., Locatelli C., Tarabusi S., A new procedure for the analysis of elemental sulphur in sediments based on combustion to sulphate and ion chromatography, Chromatographia, 53, 119-121, (2001). 2. G.Chiavari, D.Fabbri, S.Prati: In situ Pyrolysis and Silylation of Fatty Materials Used in Painting Layers, Chromatographia, 53 (5/6), 311-314, (2001). 3. Fabbri Daniele: Use of pyrolysis-gas chromatography/mass spectrometry to study environmental pollution caused by synthetic polymers. A case study: the Ravenna Lagoon, Journal of Analyitcal and Applied Pyrolysis, 5859, 361-370 (2001). 171 4. C.E. Snape, C-G. Sun, C. McRae, A.E. Fallick and D. Fabbri, Use of compound specific stable isotope measurements to probe anthropogenic PAH formation in environmental samples, Prepr. Am. Chem. Soc. Div. Fuel Chem., 46(1), 211-214 (2001). 5. D.Fabbri, M.Lombardo, C.Trombini, I.Vassura, E.Zavoli, M.Horvat, ‘Mercury contamination of a coastal lagoon (Pialassa Baiona, Ravenna, Italy) , RMZ – Materials and Geoenvironment, 48(1) (2001) 186-192. 6. Fabbri D., Gabbianelli G., Lubrano D., Locatelli C., Trombini C., Vassura I., Distribution of mercury and other heavy metals in core sediments of the northern adriatic sea, Water, Air and Soil Pollution, Water, Air and Soil Pollution, 129, 143-153, (2001). 7. G.Chiavari, D.Fabbri, S.Prati, Gas chromatographic-mass spectrometric analysis of products arising from pyrolysis of amino acids in the presence of hexamethyldisilazane, J.Chromatography A, 922, 235-241 (2001). 8. D. Fabbri, C.Locatelli, C.E.Snape, S.Tarabusi, ‘Sulphur Speciation in Mercury-Contaminated Sediments of a Coastal Lagoon. The Role of Elemental Sulphur.’, J.Environmental Monitoring, 3, 483-486 (2001). 9. C.Locatelli, D.Fabbri and G.Torsi, Heavy metal determinations in algae and clams and their possible employment for assessing the sea water quality criteria, Annali di Chimica, 91, 425-434, (2001). 10. D.Fabbri, G.Chiavari, ‘Analytical Pyrolysis of Carbohydrates in the Presence of Hexamethyldisilazane’, Analytica Chimica Acta, 449, 271-280 (2001). 11. D.Fabbri, S.Gemelli, L.Langone, S.Miserocchi, C.Trombini, I.Vassura. Anthropogenically Derived Mercury in Sediments of Pialassa Baiona, Ravenna, Italy.Annali di Chimica, 91, 563-575 (2001). 12. M.Marsili, M.Stracquadanio, C.Trombini and I.Vassura. The Epicuticular wax of Laurus nobilis Leaves as a Passive Sampler of Polycyclic Aromatic Hydrocarbons in Ambient Air Fresenius Environmental Bulletin, 10, 2630, (2001). 13. C. Locatelli, G. Torsi Heavy metal determination in aquatic species for food purposes.Ann.Chim. (Rome) 91, 65 (2001). 14. Locatelli, G. Torsi Voltammetric trace metal determinations by cathodic and anodic stripping voltammetry in environmental matrices in the presence of mutual interference. Journal of Electroanalytical Chemistry 509, 80 (2001). 15. C.Locatelli, G. Torsi Copper ore. Voltammetric and spectroscopic determination of metals: critical comparison. Recent Res. Devel. Pure & Appplied Anal. Chem. 3, 93 (2001). Appendix 3 Journal Portfolio Analysis Name of the Unit: BOLOGNA 9 Research Director: Prof.G.Chiavari Years includeed Name of Journal Number Articles Analytica Chimica Acta 2 Annali di Chimica 10 Atomic Spectroscopy 1 Chromatographia 6 Electroanalysis 4 Envir. Mon. Asses. 1 Envir. Tox. Chem. 1 Environ.Sci. Technol. 1 Food additives and 1 contaminants Fres. Envir. Bull. 4 Fres. J. Anal. Chem. 3 Fuel 1 J. Anal. Appl. Pyrol. 3 J. AOAC Inter. 1 J. Chromatography A 1 J. Electroanal. Chem. 1 J. Env. Mon. 1 J. Therm. Calor. 1 Journal of Chromatographic 1 of Journal Factor 2.073 0.394 1.730 1.317 1.702 0.388 1.964 2.707 1.050 0.297 1.649 0.905 1.787 1.330 2.793 1.960 1.055 0.545 0.987 1997-2001 Impact Field(s) Ranking Chemistry, Analytical Chemistry, Analytical Spectroscopy Chemistry, Analytical Chemistry, Analytical Environmental Science Environmental Science Environmental Science Chemistry applied 13/68 60/68 15/40 33/68 21/68 106/129 14/129 7/129 21/58 Environmental Science Chemistry, Analytical Energy and Fuel Chemistry, Analytical Chemistry, Analytical Chemistry, Analytical Chemistry, Analytical Environmental Science Chemistry, Analytical Chemistry, Analytical 113/129 22/68 16/66 20/68 32/68 6/68 16/68 53/129 52/68 41/68 172 Science Marine Chemistry 1 2.056 Microchemical Journal Organic Geochemistry 2 1 0.771 1.657 Rev. of Sci. Inst. Spectrochimica Acta Talanta The Science of the Total Environment Water, air and soil pollution 1 2 2 1 1 21/118 1.352 0.838 1.587 1.396 Multidisciplinary Chemistry Chemistry, Analytical Geochemistry and Geophysics Instrument Spectroscopy Chemistry, Analytical Environmental Science 0.772 Environmental Science 66/129 47/68 11/47 6/48 31/40 23/68 30/129 173 CAGLIARI 1 Name of the Research Unit CAGLIARI 1 Director of the Unit Prof. Giacomo Cao Faculty: Engineering Contact Person Giacomo Cao Dipartimento di Ingegneria Chimica e Materiali Piazza d’Armi - 09123 Cagliari, Italy Phone Fax 39-070-6755058 / 39-070-6755057 E-mail [email protected] University: Cagliari Thematic Area • Tecnologie di depurazione (membrane, sonochimica, fotocatalisi, elettrochimica e altre). The Unit The Unit is constituted by one full professor, two associate professors, two assistant professors (ricercatori), one postdoc, seven PhD students. The full professor is the research director of the Unit. PhD students and research associates are tipically supervised directly by the research director while the other associate and assistant professors are involved in the research work. The following courses are taught by professors belonging to the Unit: Principles of Environmental Chemical Engineering (University First Degree in three years, about 150 students), Principles of Environmental Chemical Engineering (University Degree, about 50 students), Applied Chemistry for Environmental Protection (University First Degree in three years, about 30 students), Applied Chemistry for Environmental Protection (University Degree, about 10 students), Metallurgy (University Degree, about 10 students), Metal Sciences (University Degree, about 5 students), chemistry (University First Degree in three year, about 200 students). Programme Description and Evaluation 1 2 2a 2 3 3 Title: Chemical Engineering and Applied Chemistry for the Environment Programme Director: Giacomo Cao Sub-programme titles and sub-programme leaders 1 Gas-liquid reaction and reactor engineering (G. Cao) Self-propagating High-temperature reactions for environmental protection (R. Orrù & G. Cao) Processes involving adsorbents and ion-exchangers (G. Cao) 4 Wastes sealing and vitrification (G. Usai & G. Cao) 5 Ball milling reactions for environmental protection (F. Delogu & G. Cao) 6 Soil remediation (G. Cao) Composition of the scientific research staff of the Unit per 1 January 1998 Name and Titles Year of Birth Rank Research Input in fte In 1997 Giacomo Cao Giorgio Usai Roberto Orru’ Giovanni Pilloni Francesco Delogu Roberta Licheri Antonio Mario Locci Alberto Cincotti Daniela Carta Alessandro Concas Anna Mameli Elena Medda Barbara Simoncini 1960 1941 1965 1945 1970 1974 1974 1969 1974 1973 1974 1971 1966 Professor Associate Prof Associate Prof Ricercatore Ricercatore Ph-D Student Ph-D Student Post doc Ph-D Student Ph-D Student Ph-D Student Ph-D Student Ph-D Student 0.5 0.5 0.5 0.9 0 0 0 0.9 0 0 0 0.9 Remarks After 2000 After 2000 After 2000 After 1999 After 2000 After 1999 After 2000 After 1999 PhD in 1998 174 Mariella Sannia 1968 Ph-D Student 0.9 Paola Serra Davide Zedda Guido Peronetti Nicola Lai Total research input 1969 1969 1969 Borsista Borsista Borsista Ph-D Student 0.9 0.9 0.9 0.9 9.5 PhD in 1999 PostDoc in 2000 Left in 1999 Left in 1999 Left in 2000 PhD in 2002 and Comments By taking into account the previous five years the research Unit should be more coordinated, although the performace anticipated by the Committee during the first Assessment has been confirmed. By taking into account the following five years it is expected one more associate professor professor and one more ricercatore positions to be achieved by Unit members. 4 Input of Academic Staff in fte Category Full Professors Associated Professors Ricercatori Post-docs PhD-students Borsisti Total 1997 0 1 0.8 0.9 2.7 2.7 8.1 1998 0 1 0.8 0.9 0.9 2.7 6.3 1999 0 1 0.8 0.9 3.6 0.9 7.2 2000 0 1 2.4 1.8 6.3 0.9 12.4 2001 0.5 1 1.6 1.8 6.3 0 11.5 Total 0.5 5 6.4 6.3 19.8 7.2 45.2 Comments Although the number of PhD students re-started to grow, it is becoming more and more difficult to attract excellent students since the title is not fully recognized in Italy. Moreover, the attached stipend is still on the low side. It is however relatively easy to find good students from abroad but the italian system of education is not ready to accept foreigners due to the spoken language as well as the time consuming burocracy which is more a cultural habit. The size of the group is anyway increasing being the policy to maintain a good balance between professors and PhD students/borsisti. 5 Funding 5.1 Personnel (in fte) Source University CNR European Union Other Sponsors Total 5.2 1998 2.3 1.0 1999 3.2 1.0 2000 5.5 0.4 2001 5.6 0.4 Total 17.8 7.7 2.5 8.6 3.5 6.8 3.5 6.8 7.0 12.0 6.0 11.1 22.5 45.3 1998 1999 2000 175 60 62 195 317 60 60 428 548 2001 275 50 318 493 265 590 Total 467.785 240 122 1241.7 2071.485 Materials and Equipment (in Million Lire) Source University - MURST CNR EU Other Sponsors Total 5.3 1997 1.2 4.9 1997 17.785 70 35.7 123.485 Comments: • On the figures It is seen that University/MURST is contributing to the research Unit funding for about 22% of the total budget. The relevant financial source falling in this category is given by the project MURST 488 submitted by the INCA Consortium where the Unit is involved in three sub-projects. CNR is contributing 175 for about 11% which clearly reflects the italian situation as far as the National Research Council is concerned. This is particularly true if one compares these figures with the corresponding ones related to one of our american collegue which regularly applies with success to the National Science Foundation. EU contribution is the less relevant one, i.e. about 6%. Although the situation is changed with respect to the previous assessment, EU funding is still lacking. The reason is probably due to the need of a more established research Unit, beside the capability of the Unit to establish strong european contacts. Other sponsors, with particular emphasis on the Italian Space Agency, are playing the leading role in funding the Unit, i.e. about 60% of the total budget. However the industrial support falling in this category should be increased. • On the funding policy As mentioned above, EU funding should be increased. This will require the involment of the INCA Consortium, beside the creation of strong european networks whose size could be really of impact per se and more important from the scientific point of view. The industrial support should be also increased. In this regard, the coordination capabilities of INCA will give more chances to be involved in important industrial relationships. Please add a list of major sponsors and the character of the liaison with the major sponsors Regione Aut. della Sardegna: Applied research contract on the combustion synthesis of materials CNR: Self-propagating reactions for environmental protection Dow Chemical: Applied research contract on the kinetics of terephthalic acid production Progemisa Srl: Applied research contract on the use of sardinian natural zeolites as adsorbents Italian Space Agency: Applied research contract on combustion synthesis of materials under microgravity Regione Aut. Della Sardegna: Advanced technologies for industrial wastes minimization and soil remedation planning Regione Aut. della Sardegna: Applied research contract on the use of sardinian natural zeolites as adsorbents MURST/ACNA CENGIO: Advanced soil remediation techniques MURST 488: Soil remedation techniques, adsorption activated carbon and separation using supported crown ethers 6 Progress Report 6.1 Mission Statement The Unit intends to strengthen its activity in the field of environmental science and technology, with particular emphasis on Tecnologie di depurazione (membrane, sonochimica, fotocatalisi, elettrochimica e altre) and to maintain the leadership at the National and European level on self-propagating reactions for environmental protection. While the character of the research will be more on the applied side, the ideal path to be followed is to catch real problems from consultancy activities, give the required answer if possible, start the relevant applied research activity when required and if necessary perform the fundamental one. This mission will be done either inside INCA and through the Interdepartimental Centre of Environmental Science and Technology (CINSA), which was established on April 18, 1996 at the University of Cagliari to conduct and coordinate research in the field of environmental protection. An agreement of cooperation between INCA and CINSA was signed in 1997 for collaboration in the field of environmental chemistry. The Unit intends to contribute to the solutions of environmental protection issues following a clear interdisciplinary strategy. PhDs/Borsisti will be considered even more as the driving force of the research as in most of the developed countries. The support of specialized technicians in the Unit will be also sought. There should also be a ratio PhDs/Borsisti to professors per year equal to about four. 6.2 The Research Programme The Unit intends to maintain its research activity in the following areas: a) reactions and reactors engineering, b) selfpropagating reactions for environmental protection, c) adsorption and ion-exchange, d) waste vitrification, e) mechanochemistry. In each area the research methods are similar, i.e. both experimental and theoretical activities are tipically performed. In area a), gas-liquid reactors with particular emphasis to terephthalic production through p-xylene are taken into account, mainly because of the presence of the corresponding production plants in the region where the Unit operates. In area b) studies related to the synthesis of advanced materials as well as the mechanism of products and structure formation during self-propagating reactions are addressed the use of self-propagating reactions for environmental protection is becoming a strategic field for the Unit. In area c) the following subjects are taken into account: trasport of heavy metals in porous media, where the scientific problem is to develop reliable models to describe the fate and migration of pollutants in soils; the simulation of multicomponent equilibria on natural zeolites and the corresponding characterization as marketable adsorbents for several pollutants. Area d) represents a major 176 concern of our society. The scientific/technological problem is to find new and easy-to-use techniques to inertize toxic wastes. Area e) represents a new research direction to be followed due to the input of new faculties within the Unit. In this area advanced soil remediation techniques can be developed. The most impressive results in the areas above over the past five years are as follows. In area a) a lumped kinetic model for liquid-phase oxidation of p-xylene to terephthalic acid catalyzed by cobalt naphtenate has been developed and tested by comparison with suitable experimental results. In area b) the synthesis of titanium aluminides using field assisted self propagating reactions has been achieved. In addition, the degradation of chloro-organics by selfpropagating rections seems to be a promising technology. In area c) a significant contribution towards the exploitation of sardinian natural zeolites for environmental applications has been given. In area d) for example a novel technique to inertize zinc hydrometallurgical wastes into products which incorporate heavy and toxic species is proposed. Its applicability has been extended to other toxic wastes. In area e) the mechanical alloying technique is applied to synthesize advanced materials. For the coming five years studies in the areas: a) reactions and reactors engineering, b) self-propagating reactions for environmental protection, c) adsorption and ion-exchange, d) waste vitrification and e) mechanochemistry applied to soil remediation will be strengthened. To this aim the financial support is guaranteed by Inca International, a subsidiary of Dow Chemical within area a), Italian Space Agency, European Space Agency and Regiona Autonoma della Sardegna for conducting research within area b), MURST PON project within areas c) and e), and CNR for projects pertaining to area d). No changes are expected due to the mobility of senior staff. 6.3 Position in Networks • Intra-university co-operation Τηε ιντρα−υνιϖερσιτψ χο−οπερατιον ηασ βεεν ωεακ ανδ σηουλδ βε στρενγτηενεδ. Α νυµβερ οφ ρεασονσ µα ψ εξπλαιν συχη σιτυατιον. Ηοωεϖερ, ιτ σηουλδ βε νοτεδ τηατ τηε ρεσεαρχη Υνιτσ οφ ουρ αµεριχαν χολλεγ υεσ δο νοτ νεχεσσαριλψ χοοπερατε ωιτηιν τηε σαµε υνιϖερσιτψ ασ χοµπαρεδ το τηε τψπιχαλ ΙΝΧΑ Υνιτσ. Ι ντρα−υνιϖερσιτψ χο−οπερατιον ισ προβαβλψ µορε εφφιχιεντ ιφ τηε ΙΝΧΑ Υνιτσ σηαρε α χοµµον αγρεεµεντ ον τηε στρατεγψ το βε φολλοωεδ ιν τερµσ οφ Πη∆/Νεω Φαχυλτιεσ ρεχρυιτινγ ατ τηε λοχαλ λεϖελ. • Regional co-operation At the regional level, the cooperation that needs to be strengthened, and in some cases started from scratch, is the one between the various institutions and the local universities. This cooperation should not be seen as a sporadic consultancy activity provided by single professors, personally, for specific issues, but instead, a continuous involvement of universities as a whole with the aim of achieving a “politically correct” decision-making process. In a few words, a new approach of cooperation among institutions. • National co-operation (including INCA) INCA is expected from the Unit to play a crucial role as institution that will be able to give a valuable contribution to the future environmental and industrial (i.e. chemical industry) policy of the italian governement. To this aim, one of the INCA’s objective should be to strengthen the participation from the whole italian chemical world (i.e. organic chemistry, analytical chemistry, inorganic chemistry, physical chemistry, industrial chemistry, chemical engineering, etc.). In addition a more intensive cooperation within the consortium and a more effective management of it should be achieved. The position of the Unit within INCA seems to be quite active not only in terms of financial support provided but also in terms of research activities which seem to be more oriented to solve enviromental problems with respect to the past. In addition the representative of the Cagliari University and Director of this Unit is presently serving as a member of the Board of Directors of the INCA Consortium. • International co-operation The cooperation structures that are seen most vital for the Unit are the intra-university Consortia as well as Consortia of public/private nature, where potential users of scientific knowledge and expertise are involved. This consideration is applicable not only at the national level but also internationally, with particular emphasis on the EC in order to have access to the regular international calls for proposal. In this regard, the Director of the Unit is responsible since 2001 of an International PhD Program on Environmental Science and Engineering which involved the University of Aveiro (Portugal) and the University of La Verne (Greece). The program which starts in 2002 will be strengthened through the involment of other EU Universities for which the presence of the INCA Consortium in the PhD framework will guarantee the success of the initiative. 6.4 Societal Relevance and Impact The Unit performs its research activities in the following areas: a) reactions and reactors engineering, b) selfpropagating reactions for environmental protection, c) adsorption and ion-exchange, d) waste vitrification and e) mechanochemistry. All of them are widely recognized as areas of extremely high relevance from the scientific point of view and, more generally, for an industrial country. The Unit contribution seems to be of national and international relevance as far as the gas-liquid reactor engineering is concerned. In fact, important contracts with Inca Inernational, a 177 subsidiary of Dow Chemical have been signed on this topic, i.e. the production of terephthalic acid through p-xylene oxidation. In area b), the Unit is considered to be the most important one in the EC and has been funded by the Italian Space Agency and the European Space Agency. Although the relevance of the Unit's contribution to the area of adsorption and ion-exchange has not reached the level of the other two areas mentioned above, the Unit has given a valuable contribution for the exploitation of sardinian natural zeolites for environmental applications. Finally, in the area of waste vitrification and mechanochemistry, new and easy-to-use techniques for soil remediation or to inertize toxic wastes are being currently investigated. These findings will represent new and successful developments which will be of major relevance in the field and consequently be used as a strategic projects for future funding. 6.5 Further Indications of Quality and Reputation C.N.R. NATO Fellowship (G. Cao) 2000 Nominee for 500 Leaders of Science (G. Cao) Dec. 2001 University of Cagliari Representative in the Interuniversity Consortium "Chemistry for the Environment" (G. Cao) 1994 – present Coordinator, Sardinian Branch of Italian Association of Chemical Engineering (G. Cao) 1995 - present Director, Interdepartmental Centre of Environmental Science and Engineering (G. Cao) 1996 - present Guest Editor for Chemical Engineering Communication (G. Cao) 1998 Prize “Mario Balbi” (R. Orrù) 1998 Member of the Founding Committee of International Combustion Synthesis Research Association (G. Cao) 1999 C.N.R. NATO Fellowship (R. Orrù) 1999 Chairman of the Session “Separation Technology” at the IV Italian Conference on Chemical and Process Engineering, Florence (G. Cao) May 1999 Member of the International Advisory Committee of the V Int. Symposium on SHS, Moscow (G. Cao) August 1999 Co-Chairman of the Session “Effect of Electric and Electromagnetic Field on Self-Propagating Reactions”at the V Int. Symposium on SHS, Moscow (G. Cao) August 1999 Member of the International Scientific Council of the International Journal of SHS (G. Cao) January 2000 – present Member of the International Advisory Committe of SHS-2001 (G. Cao) February 2000 Member of the International Advisory Committe of the Fourth International Workshop on Materials Processing at High Gravity (G. Cao) June 2000 Coordinator of the International PhD program in Environmental Science and Engineering (G. Cao) July 2001 President of the Scientific Forum of of Cleaner Production Centre (CPC) Italia (G. Cao) April 2001 – present Chairman of the Session “Separation” at The International Conference Icheap-5 (G. Cao) May 2001 Chairman of the Session “Effect of gravity on materials synthesis and processing" at EUROMAT 2001 (G. Cao) June 2001 President of of the Admission Committee for PhD in Environmental Science and Engineering (G. Cao) October 2001 6.6 Key Publications A. Cincotti, R. Orru', A. Broi and G. Cao, "Effect of catalyst concentration and simulation of precipitation processes on the liquid-phase catalytic oxidation of p-xylene to terephthalic acid", Chemical Engineering Science, 52, 4205-4213 (1997). G. Cao, S. Doppiu, M. Monagheddu, R. Orru', M. Sannia and G. Cocco, "The thermal and mechanochemical self-propogating degradation of chloro-organic compounds: the case of hexachlorobenzene over calcium hydride, Industrial Engineering Chemistry Research, 38, 3218-3224 (1999). G. Carta, A. Cincotti and G. Cao, "Linear driving force approximation for binary ion exchange", Separation Science and Technology, 34,1-16 (1999). M. Sannia, R. Orrù, A. Concas and G. Cao, “Self-propagating reactions for environmental protection: Remarks on treatment and recycling of zinc hydrometallurgical wastes”, Industrial Engineering Chemistry Research, 40, 801-807 (2001). A. Cincotti, R. Orrù, N. Lai, and G. Cao, “Sardinian Natural Clinoptilolites for Heavy 178 Metals and Ammonia Removal: Experimental and Modeling”, The Chemical Engineering Journal, 84, 275-282 (2001). 7. Scientific Output 7.1 Publication Policy In general the ratio scientific to professional publication should be increased. This result will be obtained by publishing one good paper in a qualified journal instead of publishing 3 or 4 good short papers in less important journals or conference proceedings. The publication policy is aimed to otain at least 3 good papers from each PhD student’s activity. It is then expected that the Unit will “produce” at least three good publication per year per professor, in addition to at least two professional publications, so that the trend in the quality and quantity of scientific output will be constantly increasing. 7.2 Numerical data Category PhD-Dissertations 1997 1 1998 1 1999 1 2000 0 2001 1 Total 4 Scientific Publications 2 3 8 10 13 36 Professional Publications Master’s Theses 6 4 5 6 4 1 5 4 3 4 23 19 8 Self-evaluation The Unit has the following strengths: • hard working capability (typical working hours per week are from 50 to 60 for each Unit member) • great enthusiasm and thorough knowledge of the state of the art of each field of interest • top Unit in Europe for studies on self-propagating reactions for environmental protection • strong academic international collaborations • strong contacts with industries and local administrations • presence of the Unit within INCA and INSTM The Unit has the following weaknesses: • lack of financial support for long periods projects • lack of financial support for the purchase of expensive equipments • small number of PhD students per year and difficulty of recruiting PhD internationally • small laboratories and offices and no dedicated technicians • long term delivery of consumables and high costs for transportation (no trains can be used !) Actions taken to further improve the quality of the Unit and to strengthen its viability • improve coordination among professors • accurate selection of PhD students • secretary personnel availability Actions to be taken to further improve the quality of the Unit and to strengthen its viability • write stronger research proposals for the EC • establish suitable networks in the EC to participate to EC calls for proposal • dedicate more time on research instead of writing insignificant abstracts and papers for conference proceedings decrease the teaching duties, at least to the level of other countries, and the time dedicated to meaningless meetings Appendix I Scientific Output I-1 Overview of Dissertations and Master's Thesis (1997-2001) I.1.1 Dissertations 179 Year Name PhD-student Title of the Dissertation Supervisor 1997 Barbara Simoncini Self-Propagating High-Temperature Synthesis Applications. G. Cao 1998 Alberto Cincotti Experimental Analysis and Modeling of Multiphase Reacting Systems. G. Cao 1999 Mariella Sannita Self-Propagating High-Temperature Synthesis of Advanced Materials G. Cao 2001 Nicola Lai Adsorption processes on natural zeolites: experimental and modeling G. Cao I.1.2 Master's Thesis Year 1997 Name Master’s student Title of the Dissertation Maria Vittoria Simeone Self-Propagating Reactions for Industrial Wastes Recycling. 1997 1997 Deborah Manca Adsorption Equilibria on Sardinian Natural Zeolites. Carlo Broi 1997 Marcello Murru 1998 Bruno Cau Supervisor G. Cao/R.Orrù G. Cao/R.Orrù On the Liquid Phase Oxidation of p-Xylene to Terephtalic Acid. Liquid-Liquid Equilibria for Hydrocarbons and Formil-Morpholine Self-propagating reactions for the treatment of hydrometallurgical wastes G. Cao/A. Cincotti G. Cao/A. Cincotti G. Cao/R. Orrù 1998 Alessio Marcus Self-propagating reactions for the treatment of hydrometallurgical wastes 1998 Andrea Floris Temperature measurements in laminar flames and modeling studies G. Cao Utilization of Sardinian Natural Zeolites for Environmental Applications. G. Cao/R.Orrù 1998 Cesare Dellacà 1998 Nicola Lai 1998 Gianluca Secci 1999 2000 2000 G. Cao/R.Orrù Simulation of the Ammono-oxidation Reactor Chemical microsensors for heavy metal detection in solution G. Cao/A. Cincotti G.Cao/P. Papet Alessandro Concas Environemntal applications of Self-propagating reactions Maurizio Ligas Effect of catalyst concentration and solvent medium on liquid-phase oxidation of p-xylene oxidation Antonio Mario Locci Field-assisted combustion synthesis: experimental and modeling G. Cao/R. Orrù G. Cao/A. Cincotti G. Cao/R. Orrù 2000 Stefano Perra Adsorption processes involving natural materials G. Cao/ R. Orrù 2000 Anna Rita Mameli Adsorption Equilibria on Sardinian Natural Zeolites G. Cao/ R. Orrù 2001 Carlo Patteri Advanced soil remediation techniques G. Cao 2001 Aristeo Marras Advanced soil remediation techniques G. Cao 180 2001 2001 Claudia Pizzalis Francesca Sini I-2 Adsorption processes involving Sardinian Natural Zeolites G. Cao Characterization and Exploitation of Sardinian Natural Zeolites G. Cao Overview of Scientific Publications (1997-2001) per year 1997 RELATED TO MAIN INCA TOPICS A.Cincotti, R. Orru', A. Broi and G. Cao, "Effect of catalyst concentration and simulation of precipitation processes on the liquid-phase catalytic oxidation of p-xylene to terephthalic acid", Chemical Engineering Science, 52, 4205-4213 (1997). NOT RELATED TO MAIN INCA TOPICS G. Cao, G. Concas, A. Corrias, R. Orru', G. Paschina, B. Simoncini, G. Spano, "Investigation of the Reaction between Ferric Oxide and Aluminum accomplished by Ball Milling and Self-propagating High-temperature Techniques", Zeitschrift fur Naturforschung-Part a, 539-549 (1997). 1998 RELATED TO MAIN INCA TOPICS A. Cincotti, R. Orru', G. Carta and G. Cao, "On the Liquid-Phase Catalytic Oxidation of p-Xylene: the Influence of Catalyst Concentration", Proceedings of the International Conference on Catalysis in Multipase Reactors, Toulose, France, 3-10 (1998). A. Gavriilidis, S. Melis and G. Cao, "Hydrodemetallation catalyst pellets with nonuniform radial pore size distribution", Chemical Engineering Communication, 163, 37-54 (1998). NOT RELATED TO MAIN INCA TOPICS R. Orru', B. Simoncini, P. F. Virdis and G. Cao, "Mechanism of Structure Formation in Self-Propagating Thermite Reactions: The Case of Alumina as Diluent", Chemical Engineering Communication, 163, 23-36 (1998). 1999 RELATED TO MAIN INCA TOPICS A.Cincotti, R. Orru' and G. Cao, "Kinetics and related engineering aspects of catalytic liquid-phase oxidation of p-xylene to terephthalic acid", Catalysis Today, 52, 331-347 (1999). R.Orru', M. Sannia, A. Cincotti and G. Cao, "Treatment and recycling of zinc hydrometallurgical wastes by self-propagating reactions", Chemical Engineering Science, 54, 3053-3061 (1999). G. Carta, A. Cincotti and G. Cao, "Linear driving force approximation for binary ion exchange", Separation Science and Technology, 34,1-16 (1999). G. Cao, S. Doppiu, M. Monagheddu, R. Orru', M. Sannia and G. Cocco, "The thermal and mechanochemical self-propogating degradation of chloro-organic compounds: the case of hexachlorobenzene over calcium hydride, Industrial Engineering Chemistry Research, 38, 3218-3224 (1999). G. Cocco, S. Doppiu, M. Monagheddu, G. Cao, R. Orru'and M. Sannia, “Self-propagating high-temperature reduction of toxic chlorinated aromatics”, Int. J. of SHS., 8, 521 - 526 (1999). NOT RELATED TO MAIN INCA TOPICS R.Orru', G.Cao and Z. A. Munir, "Mechanistic investigation in the field-activated combustion synthesis (FACS) of titanium aluminides, Chemical Engineering Science, 54, 3349-3355 (1999). 181 R.Orru', G.Cao and Z. A. Munir, "Field-assisted Combustion Synthesis of Titanium Aluminides", Metallurgical & Materials Transactions A-Physical Metallurgy & Materials Science, 30A, 1101-1108 (1999). A. Cincotti, M. Murru, G. Cao, B. Marongiu, F. Masia and M. Sannia, "Liquid-liquid e quilibria of hydrocarbons with n-formylmorpholine", Journal of Chemical Engineering Data, 44, 480-483 (1999). 2000 RELATED TO MAIN INCA TOPICS R. Orrù, N. Lai, A. Cincotti, G. Cao, P. Accardo, M. Boi, and R. Lonis, “Utilization of Sardinian Natural Clinoptilolites for Heavy Metals and Ammonia Removal”, IEX2000, J.A. Greig (ed.), The Royal Society of Chemistry, Imperial College Press, 158-165 (2000). Usai G., “Na-Borate as anti-corrosion admixture in reinforced concrete”, Materials Engineering, 2000, Vol. 11, n. 1, pp. 81/90. ΝΟΤ ΡΕΛΑΤΕ∆ ΤΟ ΜΑΙΝ ΙΝΧΑ ΤΟΠΙΧΣ G.Cao, M.L. Pilia and A. Viola, “Simulazione modellistica del reattore e del rigeneratore dell’unità FCC”, Pitagora Editrice Bologna, 1-96 (2000). V. Kostanyan, H. H. Nersisyan, S. L. Kharatian, D. Zedda, R. Orru’ and G. Cao, “Chemically Stimulated Combustion in Zr/SiO2/C System and Synthesis of ZrO2/SiC Composite Ceramic Powders Containing SiC Whiskers” Int. J. SHS, vol. 9, N. 4, 387-402 (2000) G. Cao, R. Orrù, A. Cincotti, and E. Medda, “Self-propagating high-temperature reactions: remarks and recent results”, Recent Research Developments in Chemical Engineering – Transworld Research Network, 4, 383-441 (2000). “A neutron diffraction study of mechanically alloyed and in-situ annealed Al75Mo25 powders”, S. Enzo, R. Frattini, P. Canton, M. Monagheddu, F. Delogu, J. Appl. Phys., 87 (6) (2000) 2753. “Relating single-impact events to macrokinetic features in mechanical alloying processes”, F. Delogu, G. Cocco, J. Mater. Synth. Proc., 8 (5-6) (2000) 271. “Toward a quantitative understanding of the mechanical alloying process”, G. Cocco, F. Delogu, L. Schiffini, J. Mater. Synth. Proc., 8 (3-4) (2000) 167. “A neutron diffraction study of the annealing behaviour of Al-Fe alloys prepared by Ball Milling”, S. Enzo, G. Mulas, F. Delogu, G. Principi, J. Mater. Synth. and Proc., 8 (5-6) (2000) 313. 2001 RELATED TO MAIN INCA TOPICS M. Sannia, R. Orrù, A. Concas and G. Cao, “Self-propagating reactions for environmental protection: Remarks on treatment and recycling of zinc hydrometallurgical wastes”, Industrial Engineering Chemistry Research, 40, 801-807 (2001). A.Cincotti, R. Orrù, M. Pisu and G. Cao, “Self-propagating reactions for environmental protection: reactor engineering aspects”, Industrial Engineering Chemistry Research, 40, 5291-5299 (2001). A.Cincotti, R. Orrù, N. Lai, and G. Cao, “Sardinian Natural Clinoptilolites for Heavy Metals and Ammonia Removal: Experimental and Modeling”, The Chemical Engineering Journal, 84, 275-282 (2001). R. Orrù, A. Cincotti, A. Concas and G.Cao, “Development of processes for environmental protection based on self-propagating reactions”, Environmental Science and Pollution Research, (2001). D. Carta, G. Cao and C. D’Angeli, “Chemical Recycling of Poly(ethylene tetephthalate) (PET) by Hydrolysis and Glycolysis”, Environmental Science and Pollution Research, (2001). 182 NOT RELATED TO MAIN INCA TOPICS R. Orrù, A. Cincotti, G. Cao and Z. A. Munir, “Mechanistic investigation of electric field-activated self-propagating reactions: experimental and modeling”, Chem. Eng. Sci., 56, 683-692 (2001). A.V. Abovyan, H. H. Nersisyan, S. L. Kharatian, R. Orrù, R. Saiu, G. Cao and D. Zedda, “Synthesis of alumina – silicon carbide composites by chemically activated self-propagating reactions, Ceramics International, 27, 163-169 (2001). R. Orrù, J. Woolman, G. Cao and Z.A. Munir, “The synthesis of dense nanometric MoSi2 through mechanical and field activation”, J. of Mater. Research, V16 N5:1439-1448 (2001). A. Cincotti, G. Murgia, R. Orru’ and G. Cao, “On the modeling of the copper block front quenching technique to investigate solid-solid self-propagating high-temperature reactions”, Ind. Eng. Chem. Res., 40, 3451-3458 (2001). A.S. Rogachev, V.N. Sanin, A.E. Sytschev, V.I. Yukhvid, E. Medda, R. Orrù and G. Cao, “Self-propagating High-temperature Centrifugal Processing: the case of Cu2O-Cu-Al and Cu2O-Al Systems”, Proceedings of the IVth International Workshop on Materials Processing at High Gravity: Processing by Centrifugation, Liya L. Regel and William R. Wilcox Editors, Kluwer Academic/Plenum Publishers, 201-212 (2001). M. Pisu, A. Cincotti, G. Cao and F. Pepe, “Simulation of the effect of mass transfer limitations in complex gas-liquid reactions”, Proceedings of the International Symposium Reaction Kinetics and Development of Catalytic Processes, Froment and Waugh Editors, Elsevier, 471-476 (2001). “A quantitative description of the amorphisation behaviour by mechanical alloying”, F. Delogu, L. Schiffini, G. Cocco, Mater. Sci. Forum, 360-362 (2001) 337. “The invariant laws of the amorphisation processes by Mechanical Alloying. Part I: experimental findings”, F. Delogu, L. Schiffini, G. Cocco, Phil. Mag. A, 81 (8) (2001) 1917. I-3 Overview of Professional Publications (1997 - 2001) per year 1997 RELATED TO MAIN INCA TOPICS B. Simoncini, R. Orru' and G. Cao, "Self-propagating Reactions for Treating and Recycling Zinc Hydrometallurgical Wastes", Proceedings of the 5th Conference and Exibition of the European Ceramic Society - Key Engineering Materials Vols. 132-136, 2276-2279 (1997). NOT RELATED TO MAIN INCA TOPICS R. Orru', B. Simoncini, D. Carta, and G. Cao, "On the Mechanism of Structure and Product Formation in Self-propagating Thermite Reactions", Proceedimgs of the International Conference on Advances in Chemical Engineering ICAChE 96, Allied Publishers, Bombay, 21-26, (1996) and Inter. J. Self-Prop. High-Temp. Synth., 6, 15-27 (1997). R. Orru', B. Simoncini, P. F. Virdis and G. Cao, "Self-propagating Thermite Reactions: Effect of Alumina and Silica in the Starting Mixture on the Structure of the Final Products", Metallurgical Science & Technology, 15 (1), 31-38 (1997). R. Orru', B. Simoncini, M. Sannia, A. Cincotti and G. Cao, "Combustion synthesis of intermetallics", FRANTIC '97, Chia Laguna, I/1.1-I/1.4, (1997). R. Orru', B. Simoncini, M. Sannia, A. Cincotti and G. Cao (speaker), "Materiali innovativi per sintesi autopropagante ad alta temperatura", Atti del Convegno-Esposizione Materiali Ricerca e Prospettive Tecnologiche alle soglie del 2000, Milano, 889-896 (1997). “Resistenza all’attacco solfatico di calcestruzzi contenenti Na-silicati” G. Usai. L’EDILIZIA, 11-12, 183 1997 PP 72-75 1998 RELATED TO MAIN INCA TOPICS B. Simoncini, R. Orru' and G. Cao, "An Innovative Approach for Treating and Recycling Zinc Hydrometallurgical Wastes", Proceedings of the I National Congress - Valorization and Recycling of Industrial Wastes, Mucchi Editore, 307-314 (1998). M. Sannia, B. Simoncini, R. Orru', A. Cincotti and G. Cao, "Sviluppo di una tecnica innovativa per il trattamento e il riciclo di residui della idrometallurgia dello zinco", Atti del IV Congresso Nazionale AIMAT, PTM editrice, 594-601 (1998). NOT RELATED TO INCA MAIN TOPICS R.Orru', Z. A. Munir and G.Cao, "Sintesi per combustione di alluminuri di titanio", Atti del IV Congresso Nazionale AIMAT, PTM editrice, 185-192 (1998) and Atti del XXVII Convegno Nazionale AIM, AIM (ed.), 29-35 (1998). A.Cincotti, R. Orru', M. Sannia, G. Storti and G. Cao, "Indagine sperimentale e modellistica della tecnica di estinzione del fronte in reazioni di combustione autopropagante per la sintesi di materiali avanzati", Atti del IV Congresso Nazionale AIMAT, PTM editrice, 209-216 (1998). 1999 NOT RELATED TO INCA MAIN TOPICS A. Cincotti, R. Orru', M. Sannia, D. Zedda and G. Cao, "Combustion front quenching techniques for SHS macrokinetics studies", Advances in Science and Technology - Ceramics: Getting into the 2000's - Part C, P. Vincenzini Ed., Techna Srl, Vol. 15, 231-238 (1999). T. Faravelli, A. Goldaniga, E. Ranzi, M. Pisu and G. Cao, “Ignition Delay Times and Knocking Tendency of Kerosene”, Proceedings of The Fourth Italian Conference on Chemical and Process Engineering, AIDIC Conference Series, Vol. IV, ERIS C.T., Milano, 9-16 (1999). G. Usai, G. Cao, “Spezialbeton fur transport und lagerung radioaktiver abfalle”, Proceedings KONTEC-99 / Hamburg, pagg. 773/783. G. Usai, R. Porcu, “Il Tufo di Cagliari: Indagine preliminare sul degrado”, Proceedings del congresso ART-99 (ConserV. Of the cultural and Environ. Heritage), Roma maggio ’99, vol. I, pp. 661/670. 2000 NOT RELATED TO INCA MAIN TOPICS M. Pisu, A. Cincotti, R. Orrù, G. Cao and Z. A. Munir, “Modeling of electric field-activated self-propagating reactions”, Proceedings of the International Conference “Mass and Charge Transport in Inorganic Materials”, P. Vincenzini, V. Buscaglia Eds., 905-912 (2000). A.S. Rogachev, V.N. Sanin, A.E. Sytschev, V.I. Yukhvid, E. Medda, R. Orrù and G. Cao, “Studio dell’influenza della gravità nei processi di sintesi autopropagante ad alta temperatura: il caso dei sistemi Cu2O-Cu-Al e Cu2O-Al”, Atti del XXVIII Convegno Nazionale AIM, AIM (ed.), 729-737 (2000). Υσαι Γ., Γλι εφφεττι δελλ αγγιυντα δι σαλι φοσφατι α παστε δι χεµεντο , Λ Ε∆ΙΛΙΖΙΑ, ν. 3/4 απριλε 2000, ππ. 42/48. Υσαι Γ., Ρεµοϖαλ οφ πηοσπηατεσ φροµ Ωαστε ωατερσ , Προχεεδινγσ δελ χονγρεσσο ΣΙ∆ΙΣΑ 2000, Τρεντο σεττ. 2000, ςολ. 2, ππ. 147/150. Υσαι Γ., Χ. Χαυ, Σιντεσι ιδροτερµαλε δι µατεριαλι νεολιτιχι , ΙΧΠ, ριϖιστα δελλ Ινδυστρια Χηιµιχα, Μιλανο, γιυγνο 2000. 2001 NOT RELATED TO INCA MAIN TOPICS 184 E.Medda, R. Orrù, G. Cao, J. Fry, J. Y. Guignè and M. Zell, “Effects of microgravity on high-temperature self-propagating reactions”, Proceedings of the First International Symposium on Microgravity Research in Physical Sciences and Biotechnology, ESA SP-454, January 2001, 299-306 (2001). R. Orrù, F. Delogu, A. Uda, A. Cincotti, A. Locci, R. Licheri, G. Cao, “Tecnologie innovative di sintesi di materiali per applicazioni aerospaziali”, Atti del Workshop "Materiali per lo spazio: sintesi, metodologie, tecnologie - BONASSOLA (SP)", Passerone A. and Muolo M. L. Eds., 79-109 (2001). Usai G., “High Density Concretes for radioactive wastes storage”, (part. I). Proceedings of ICEM-01; Int. 1 Conf. On Envir. Management (CD Rom) Brugge (Belgium) october 2001. I-4 Other Scientific Output Appendix 2 Ranking Scientific Journals It is well known how difficult is to rank scientific journals. For example, absolute values of impact factors outside the context of other journals within the same subject area is virtually meaningless. On the other hand, impact factors, may be useful to establish the influence journals have within the literature of a discipline. Anyway, the selected citation measures seem to be efficient tools for a necessarily quick evaluation of the research units. Appendix 3 Journal Portfolio Analysis Name of the Unit: Research Director: Years included Name of Journal CHEM ENG SCI IND ENG CHEM RES Z NATURFORSH A INT J SHS CHEM ENG COMM CATALYSIS TODAY SEP SCI TECH METALL MAT TRANS J CHEM ENG DATA J APPL PHYS J MAT SYNTH PROC CHEM ENG J ENV SCI POLL RES CERAMICS INTERN J MAT RES MAT SCI FORUM PHIL MAGAZINE METALL SCI TECH CAGLIARI 1 Giacomo Cao 1997-2001 Number Articles 4 4 1 2 2 1 1 1 1 1 3 1 2 1 1 1 1 1 of Journal Factor 1.218 1.29 0.744 ? 0.36 1.860 0.911 1.06 1.081 2.275 0.49 0.637 1.46 0.4 202 0.981 1.915 ? Impact Field(s) Chemical Engineering Chemical Engineering Chemistry Phys Mater Sci Tech Chemical Engineering Applied Chemistry Chemical Engineering Mater Sci Tech Chemical Engineering Applied Physics Mater Sci Tech Chemical Engineering Environmental Sciences Mater Sci Tech Mater Sci Tech Mater Sci Tech Physics Mater Sci Tech Ranking 9/90 10/107 60/76 ? 61/107 3/46 29/107 0.92 17/107 9/63 0.51 38/107 0.75 0.68 0.91 0.74 11/47 ? Comments on: a) the method: Although the selected citation measures seem to be efficient tools for a necessarily quick evaluation of the research units, a good balance between quality and quantity of papers is probably one of the best techniques to evaluate the scientific relevance of a unit. Peer review from a qualified panel of five key publications selected by the unit is probably a very effective route for a thorough evaluation of the unit. b) the results: The unit has published totally 36 scientific and 23 professional publications, respectively in the last five years. 29 of the 36 scientific publications are published in scientific journals, i.e. about 5 papers per year. 12 of them, i.e. about 3 per year are published in top chemical engineering (8), applied chemistry (1), physics (2) and material 185 science (1) journals, respectively. Only 3 scientific publications are published in journals which are not reported in the ISI Journal Impact Factor Index. 186 CAGLIARI 2 Name of the Research Unit CAGLIARI 2 Research Leader Lallai Antonio University: Università di Cagliari University of Cagliari Faculty: Ingegneria Engineering Contact Person Name: Lallai Antonio Mailing Address: Dipartimento di Ingegneria Chimica e Materiali - Piazza d'Armi – 09123 Cagliari Phone: +39-0706755060 Fax: +390706755067 E-mail: [email protected] E-mail: lallai@ dicm.unica.it Department: Dipartimento di Ingegneria Chimica e Materiali ∆επαρτµεντ οφ Χηεµιχαλ Ενγινεερινγ ανδ µατεριαλσ Thematic area • Tecnologie biologiche enzimatiche e biomimetiche per le sintesi ecosostenibili e la decontaminazione ambientale. Introduction and Context Introduction to the Self-evaluation Report The research unit begins its activity at the earlier 90s to connect the experience previously acquired by the two components in the field of environmental biotechnology (Lallai) and chemical reaction engineering (Mura). The aim of the unit is to study the environmental problems, with a particular reference to those of the region where they work. The research carried out has always a fundamental character, but a particular attention is devoted to the application to problems having a local importance. Unfortunately, the lack of a lower level staff to work together, always slowed the activity of the unit. The University, the Faculty and the Department The State University of Cagliari, that was founded in 1607 following the pattern of the old Spanish Universities, has 9 faculties, 26 Departments and 49 Institutes. The University is at present made up of the following faculties: Law; Political Science; Economics and Commerce; Arts and Philosophy; Education; Medicine and Surgery; Mathematics; Physics and Natural Sciences; Pharmacy; Engineering. The University has about 38,000 regular enrolled students, a teaching staff of over 1,200 and an technical administrative staff of about 1,300 people. There are 27 degree courses, 42 specialization courses, 47 research doctorates (13 of which with administrative seat within the University), 6 special purpose schools and various postgraduate courses. The University awards the following educational qualifications: University Degree, Specialistic Degree, Master, PhD. The University of Cagliari is a well established part of the national and international scientific community due to the qualified and deep research activity in in many different and most advanced technology fields. The University is directed by the Provost who is the President of both the Administration Council and the Academic Senate. Only two Universities are present in Sardinia, while the University of Cagliari is the largest one in terms of student population and faculty members. The Faculty of Engineering where the Professors of the research unit perform their work has an annual student population over 7000 with about 250 faculty members. The unit that will conduct the work relevant to this project is constituted by 2 associated professors. The Unit . organisational structure From 1997 to 2001 the Unit has two permanent members (Profs. Lallai e Mura) plus the temporary presence of three "borsisti" (Leu in 1998, Caddeo in 1999 and Squilloni in 2001). The two professors carry out full time work in the university with teaching duties as outlined below. 187 The Unit has a very large teaching load in different curricula: Chemical Engineering (Impianti di trattamento degli effluenti inquinanti, Elementi introduttivi di Ingegneria Chimica, Teoria dello sviluppo dei processi chimici), Environmental Engineering (Impianti di trattamento degli effluenti inquinanti), Biotechnology (Laboratorio di bioingegneria, Bioingegneria Industriale) The University has participated and still participates in several EU programmes (Erasmus/Socrates, etc.). Within these programmes the Unit hosted several students coming from both UE and non-UE countries. Apart from their load, the two professors are involved with research activity as well as the management of the Department and Faculty. They are directly concerned with relations with public bodies, private companies and other socially committed groups or organisations. The aim of some of these contacts is to generate funds to help finance research projects. The two permanent members of the Unit handle all bureaucratic matters concerning the above activities. Apart from supplying essential services (telephone, electricity, photocopies, etc.), their Department also makes available the laboratories in which the research is carried out as well as providing library and accounting services. . teaching load =>Lallai - 100-hour course for full degree in Chemical Engineering and Environmental Engineering - 50-hour course for first degree (diploma, up to 1999) and degree (laurea from 1999 to 2001) in Environmental Engineering 2000-01 - 70-hour course for first degree in Agro-Industrial biotechnology - Faculty of MFN Sciences - from 2001 - 8-hour postgraduate course - member of board for Doctoral Degree in Chemical Engineering (up to 2000) - member of board for full degree in Chemical Engineering - member of board for first degree in Environmental Engineering . supervisor of 20 first and full degree theses. =>Mura - 150-hour course for full degree in Chemical Engineering - 60-hour course for first degree in Agro-Industrial biotechnology - Faculty of MFN Sciences - from 2001 - 8-hour postgraduate course - member of board for Doctoral Degree in Chemical Engineering - president of board for full degree in Chemical Engineering . supervisor of 10 full degree theses. Programme Description and Evaluation 1.Title: Chemical Engineering Technologies applied to the treatment of pollutant effluents 2.Programme Director Lallai Antonio 2a Sub-programme titles and sub-programme leaders Among the research fields developed by the team, particular emphasis has been placed on the two themes (i) environmental biotechnology, (ii) chemical reaction engineering applied to the environmental field. The first research theme is co-ordinated by Lallai and the second by Mura. 3.Composition of the scientific research staff of the unit at 1 January 2002 188 Name and Titles Year of Birth Rank Research Input in fte in 2001 Lallai Antonio, Prof. Mura Giampaolo, Prof. Squilloni Emanuela, Ing. Total research input 1947 1948 1974 Assoc. Prof. Assoc. Prof. Borsista 0,5 0,5 0,2 1,6 1.Input of Academic Staff in fte Category 1997 Full Professors Associated Professors 1 Ricercatori Post-docs PhD-students Borsisti Total 1 Remarks 6 months only 1998 1999 2000 2001 Total 1 1 1 1 5 0,5 1.5 0,5 1.5 1 0,2 1.2 1,2 6.2 Comments Engineer Leu, A. joined this unit (sub unit Chemical Reaction Engineering) during the year 1998 as Borsista for a period of two years, but abandoned the unit after one year Engineer Caddeo, C. joined this unit (sub-unit Biothec Engng) during the year 1999 as Borsista for a period of two years, but abounded the unit after one year. Engineer Squilloni, E. joined this unit (sub-unit Chemical Reaction Engineering) during the year 2001 as Borsista for a period of two years, but abounded the unit after six months. At this time no modification of the unit may be forecast. However, we are seriously considering to merge our unit with another “small” unit to constitute a new greater one. 1.Funding 5.1 Personnel (in fte) Source University CNR European Union Other Sponsors Total 1997 1 1998 1.5 1999 1.5 2000 1 2001 1.2 Total 6.2 1,4 1,9 1,9 1,4 1,6 8,2 2001 79 Total 223.5 79 16 54 293.5 1.3Materials and Equipment (in Million Lire) Source University – MURST CNR EU Other Sponsor Total 1997 10 1998 12.5 1999 28 2000 94 16 25 51 12 24.5 8 36 9 103 1.3Comments: The amounts reported above, represent the whole financial support given by MURST-University. However, this amount can be used only in part by the unit since about 10%of the total used by the Department and INCA for overheads. 189 Moreover, we should point out the progressive decrease of the financial support deriving by public subjects. This unit can provide for this decrease using funds deriving by other sponsors. This fact has a positive side as regards the ability achieved by the unit in facing problems regarding plants at a scale larger than those (at lab-scale) generally used during research work. Besides, funding problems induces the unit to contact local producers and authorities with the final result of an outside fall-out of the research activity that is essentially fundamental research. The negative side is due to the need to face external work, so reducing the strictly scientific productivity, computed in terms of publications in journals. Major sponsors and the character of the liaison 6. The University: L. 488 and ex-40% and 60% Ministry funding. Sotacarbo: a contract for feasibility study of an incineration system EMSA: a contract regarding the treatment of red mud produced by the Bayer process Progress Report 1.3Mission Statement This Unit's area of research is that of pollutants removal. Our aim has been to make a contribution in both basic and applied research. In particular, attention, has been focused on some of the serious problems related to air pollution, water pollution and soil contamination. For the former, the emphasis has been posed on the emerging technologies for the elimination of acid gases from combustion effluent with dry processes. As regards the second theme, work is being carried out on the application of soft, inexpensive technologies biological processes - both for the treatment of high-organic-load wastewater (using aerobic reactors) and for the decomposition of toxic compounds too (e.g. phenolics present in olive oil mill effluent using bacterial cultures). Regarding the contaminated soil two lines have been developed: (a) the bioremediation of soil polluted with recalcitrant compounds and (b) the forecast of organic pollutants dispersion in unsaturated soil by means of mathematical models. This basic research is devoted to a kinetic study of the processes and to identify the principal parameters that affect the performance of various processes (e.g.s. efficiency of gaseous acid elimination, degree of phenol removal, etc.). Along with this research, efforts have been made to establish closer contact with local producers and authorities in order to apply the processes under study to the resolution of the environmental problems created by working plants in our region. For example, contacts have been made with companies dealing with plants for burning coal together with refuse, our contribution has regarded both the problems related to the pre-treatment of the refuse to be burnt and the removal of particulate and acid gases from combustion effluent. In addition, contact with olive oil mills managers has been concerned with treating polluted wastewater with microbial cultures. 1.4The Research Programme Sub-programme Chem.Engng Reaction This line of research tackles the problems relating to the removal of gaseous acids present in the flue gas produced by the combustion of both traditional fuels (coal, oils) and of municipal and industrial waste. The work, which began in the previous years, on the dry removal of HCl produced during the incineration of municipal solid waste, was continued also in the last five years. Two distinct lines were followed. The first line involved the simulation of an existing dry removal plant. In collaboration with a company, we studied the semi-dry type process that uses a suspension of slaked lime as a sorbent. The most important equipment (the chemical reactor and the filter bag) were simulated. The results obtained emphasized the essential function of the filter bag in HCl removal. Some simplified and not usual kinetics were used in designing the mathematical model. The second line of research is of a more fundamental kind. The influence on reactivity of the presence of both water vapour and other pollutants (SO2 and HF) in addition to HCl was studied. In the last years we were interested also in sulphur dioxide wet removal. The kinetics of SO2 removal by means of both seawater and various suspensions of Bayer red mud were studied in a wetted wall column. The same study is now carried out in a laboratory scale packed bed column. Another study was carried out on the dispersion of organic pollutants in unsaturated soil. A very sophisticated model was produced, taking into account the adsorption and the biological degradation in addition to the dispersion phenomena. We are now designing some experimental test to verify the goodness of the theoretical results obtained. 190 The essential equipment to conduct this research is already available. There remains, however, as in the past, a shortage of research staff. At the time of writing no changes in the staff levels are forecast. Sub-programme Biotechnology The Biotechnology sub-project is developing along three lines of research: (a) the biological degradation of organic substances normally considered resistant to decomposition with mixed bacterial cultures;(b) the treatment of highorganic-load wastewaters using fixed bed biological reactors and (c) the remediation of soil polluted with organic phenolic compounds As regards (a), in the last five years our research investigated the degradation of phenolic compounds (chlorophenols and some of phenols and polyphenols present in olive oil mill effluent) with aerobic mixed bacterial cultures. But a research have been done to study dephenolisation of catechol solution by olive husk. Both the kinetics of bacterial growth and the degradation of the particular phenol used were studied, as well as the role of the other organic substrates present. The aim was to identify the best kinetic model and the optimal conditions (from the point of view of the presence of other organic substances). to favour the decomposition of the phenolic compounds mentioned. Experiments were carried out using batch reactors (both mechanically agitated and shaken flasks). The main part of these experiments are within the research, sponsored by University Ministry (law n. 488) in progress with another unit of INCA (Cagliari 3). We are studying together the possibility to realise an integrated treatment of olive oil mill effluent using two different kinds of process (electrochemical and biological) in series. Some of the results obtained have been examined and published, while others are still being worked on. As for the next five years, we expect to continue to study the degradation of phenolic compounds mentioned above using aerobic cultures and to begin studying the degradation of phenolic compounds with anaerobic cultures as well. In one way, we expect to continue the collaboration with the other INCA unit cited. In particular, our intention is to adopt batch systems to study the role of the preventive acclimatisation of mixed cultures to these substances, the growth and kinetics of the recalcitrant substances and to verify the convenience to treat in the anaerobic reactor the waste previously treat in a electrochemical reactor. As for (b), work over the last five years examined the application of up-flow anaerobic biofilters for the treatment of pig waste effluent. The performance of such reactors was studied as regards both the removal of COD and the production of biogas. The aim was to find a correlation between the running and the performance parameters of the process with a view to the future application of this kind of reactor in plants of a larger scale compared to the lab-scale reactors used so far. As for (c), work over the last few years has been done to study the decontamination of 2-monochlorophenolcontaining forest soil. The main aim was to find the kinetics of disappearance of monochlorophenol (adsorption by soil and degradation by organisms present in soil), but also to evaluate the role of organisms previously acclimatised and inoculated in the soil containing monochlorophenol. The next five years should see the continuation of the experimental research in studying the degradation of different phenolic compounds in soil polluted by heavy metals. The essential equipment to conduct this research is already available. There remains, however, as in the past, a shortage of research staff. At the time of writing no changes in the staff levels are forecast. 1.5Position in Networks • Intra-university co-operation Since 1997, the unit is working to a project study (Preliminary investigation and feasible optimisation actions for the production processes in the Sardinian food industry) involving various different cultures inside Cagliari Engineering Faculty. • Regional co-operation Sotacarbo In collaboration with a research group of the Mechanical Engineering Department of our University together with a regional research centre on coal applications (Sotacarbo), we studied the feasibility of a full-scale plant for MSW pre-treatment and its co-combustion with coal in a fluid bed to produce electric energy. In this project, our unit particularly attended to the study of the MSW pre-treatment section as well as gaseous contaminant section. Bayer Red Mud During last years, the Unit was involved in a project together with various research teams from different Universities (Cagliari, Sassari, Trento) that studied the re-use of Red Mud remaining as a by-product in the Bayer 191 process for Alumina production. A very large such plant is present in Sardinia (Eurallumina). Regione Sarda founded the contract with EMSA (the Sardinian Authority for Mines) in 1997. In this project, the Unit was particularly concerned with the following topics: (a) mud thickening and (b) use of suspensions of red mud in seawater as a sorbent to be used in a wet scrubber where the acid gas pollutants could be removed from flue gas effluent. • National co-operation (including INCA) Within the research projects having high national importance (MURST 40%, year 1998), the unit was included in a project regarding the study of biological reactors, co-ordinated by Prof. Guido Greco Jr. (Naples University). The research unit attended to study the treatment of high organic load wastewaters produced by the pig breeding industry. Beginning from November 2001, for about one year, the unit has been involved in the project on Biodegradation of recalcitrant compounds present in agriculture and food industry wastewaters, co-ordinated by Prof. Lucio Previtera (Naples University). This project is carried out by INCA. 1.6Societal Relevance and Impact Most of the research topics studied by this unity deal with environmental problems present in the Sardinian land. The presence of a land that is largely uncontaminated induces to adopt soft technologies such as renewable energy and processes having a low environmental impact. On the other hand, the agriculture and food industries play an important role in the regional economic texture. This fact convinced the unit to apply the competence acquired in the field of depuration to problems dealing with the treatment of wastewater produced by the food industry, sometimes with energy production. As an example, the biological treatment with biogas production and depuration of wastewater containing recalcitrant compounds were studied. As the previous research, the study on dry removal of HCl is strictly correlated with the presence in our region of several incineration plants that are able to treat up to 42% of the municipal waste here produced, a rate that is the higher among those of other Italian regions. Also the interest in soil bioremediation partially derives from the presence in the Sardinian land of several industrial areas, strongly polluted and not yet used. 1.7Further Indications of Quality and Reputation As regards the work with the local community, the following contracts awarded by public authorities, may be cited. • Examination of the environmental impact study of the plant IGCC plant by Italian Environmental Ministry delegated by Regione Sardegna (1999) • Committee for Regional Energy policy (2000-2001) • Preliminary study on remediation of a dismissed steel plant - by Judicial authority (1997) • Study on remediation of a soil polluted by heavy metals - by Judicial authority (1999 - 2001) • Prof. Lallai is a member (from September 2000) of the Porto Conte Ricerche scientific committee for the evaluation of research and development project 1.8Key Publication - A.M.Polcaro, S.Palmas, A.Lallai – “Sequential electrochemical/biological treatment for the removal of 2,6diclorophenol from synthetic wastewater” – Annali di chimica, 91, 303-310 (2001) - G.Mura, A.Lallai – “Dry removal of hydrochloric acid from flue gas with sodium carbonates” 3rd European Meeting on Chemical and Environment – Krakow, September 1999, vol. I, 99-104 - A.Lallai, G.Mura, M.Piredda – “Enzymatic detoxification of polyphenols from wastewaters” – 3rd European Meeting on Chemical and Environment – Krakòw, September 1999, vol. I,. 571-576 - G.Cau, D.Cocco, A.Lallai, G.Mura, M.T.Pilloni – “Power generation from fluidized bed MSW and coal cofiring. A preliminary design for a 10 MWe demonstration plant” – Proc. of 2nd National Congr. on valorization and recycling of industrial wastes, L’Aquila, 5-8 luglio 1999 - G.Mura, M.Tabarelli, A.Lallai – “A mathematical model of the semi-dry process for HCl removal from flue gas using Calcium Hydroxide suspensions” – PRES01 Conf., 20-23 May 2001, Florence. Proceedings p. 279-283 1.Scientific Output 1.3Publication Policy 192 The topics developed by the unit deal with both applied and fundamental research in the field of Chemical and Environmental Engineering. Taking this into account, the results obtained were submitted for publication in specialised journals of these cited fields or presented to specific scientific congresses. Several results reported in the very large number degree theses that had been recently discussed are not yet published. In recent times, the unit had to privilege professional publications rather than scientific communications, to reach the requirements of industrial subjects. However this particular condition may be considered only incidental, so in the next future a balance between the two publication forms can be attained. 1.4Numerical data Category PhD-Dissertation 1997 ScientificPublications Professional Publications 2 Master’s Theses 7 1998 1999 2000 2001 Total 5 4 7 5 21 2 6 7 6 4 30 Self-evaluation The positive side of the activity of the unit can be summarised as follows. The topics developed by the unit in the research work are situated in the field of chemical and environmental engineering. They appear to be innovative and are susceptible of further investigations. The aggregation with other research units is also promoted by the up-to-dateness of the research. This makes it possible to participate both to national and local co-operation for their funding and also to acquire consulting works. All the research work carried out up to now always has a fall out in our region. In spite of these positive subjects we register a productivity which appears low as for scientific publications and congress communications. However, this fact is justified in part by an almost total absence of other members of the team in addition to the high teaching load of both the members of the unit. As a matter of fact the low number of the unit members, represents its main weakness factor. As regards the trend of the quantity of scientific output, it is noted that there has been a sensible reduction of the number of papers published in Journals. This is the most evident weakness of the Unit. A reduction of the number of publications was registered in the last years. To understand this figure we have to consider the following factors: i) The teaching load. – This is dramatically increased in the 1998-2001 period because new degree courses have been activated and, consequently, both the professors of the Unit have produced extra-efforts on them. Presently, the teaching load of the Unit is 8 courses covered by 2 teachers ii) In addition, one professor of the Unit is the co-ordinator of the board for the degree in Chemical Engineering from 1997 up to now. This office involved a very high work and care, since our Chemical Engineering degree was transformed in 1998 (the first in Italy together with the Salerno University) according to the new teaching system. Appendix 1 Scientific Output I.1 Overview of Dissertation and Master’s Thesis (1997-2001) 193 I.1.1 Dissertation I.1.2 Master’s Thesis Year 1997 Name Master’s student Corrado Pangrani 1997 Angelo Schiavino Penco 1997 Barbara Loi 1997 Giovanni Basilio Angioni 1997 Francesco Primavera 1997 Fabio Orru' 1997 Manuela Melis 1998 Enrico Giovanni Maffeis 1998 Salvatore Palmas 1998 Massimo Piredda 1998 Massimo Deidda 1998 Manuela Foddis 1998 Michelangelo Porta 1999 Grazia Maria Contini 1999 Michele Tore Title of the Dissertation Studi di fluidodinamica e di avviamento di un filtro anaerobico Fluodynamics and starting-up of an experimental anaerobic filter Depurazione di un refluo acquoso di origine industriale Treatment of industrial wastewater Gestione dei rifiuti solidi urbani: smaltimento in discarica controllata, recupero e riciclaggio Management of municipal solid waste: disposal in landifill and recycling Combustione di rifiuti ospedalieri: gestione di un impianto di incenerimento Combustion of hospital wastes: management in a inceneretion plant Problemi tecnici nell’impianto di trattamento acque di Cagliari Techical problems of the domestic wastewater plant of Cagliari Gestione dell’impianto di trattamento acque urbane di Cagliari Management of the domestic wastewater plant of Cagliari Rimozione a secco di HCl e SO2 dai fumi di combustione mediante Carbonati di Sodio Dry removal of HCl and SO2 from flue gas by means Sodium Carbonates Rimozione di HCl gassoso con bicarbonato di sodio a bassi tempi di contatto Kinetics of gas HCl removal with Sodium Bicarbonate at low residence times Rimozione di HCl gassoso con carbonati di sodio e di potassio Kinetics of gas HCl removal with Sodium and Potassium Carbonates Supervisor Lallai Degradazione biologica di composti fenolici mediante colture miste in condizioni anaerobiche. Biological degradation of phenolic compounds by anaerobic micro-organisms Modello matematico del processo di ossidazione e sedimentazione negli impianti di depurazione Mathematical model of the oxidation and sedimentation equipment in wastewater treatment Bonifica da materiali in amianto Reclamation from asbestos contaminated materials Modelli di dispersione di inquinanti idrofobici in terreno saturo e insaturo NAPL dispersion in saturated and unsaturated soil Desolforazione a umido con fanghi rossi Bayer Kinetics of wet desulfurization with Bayer Red Mud suspensions Degradazione di composti fenolici nel terreno Lallai Lallai Lallai Lallai Lallai Lallai Mura Mura Mura Mura Lallai Mura Mura Lallai 194 1999 Sergio Pozzo 1999 Marcella Desogus 1999 Alessandro Battiata 1999 Federica Carta 1999 Nicola Onnis 2000 Adriano Cocco 2000 Andrea Agus 2000 Raimondo Vinci 2000 Manuela Tabarelli De Fatis 2000 Daniele Mulas 2000 Luca Baraccani 2001 Silvia Montisci 2001 Lara Erby 2001 Alessandro Orsini 2001 Riccardo Zonza I.2 Degradation of phenolic substances in soil Depuratore delle acque reflue di Cagliari: problematiche tecniche e gestionali Management and technical problems in the wastewater treatment plant of Cagliari La certificazione ambientale di uno stabilimento industriale Environmental certification of an industrial plant Organizzazione e strategie di sviluppo della raccolta differenziata dei rifiuti solidi urbani in Sardegna Smaltimento dei reflui da allevamenti suini: trattamento anaerobico e produzione di energia Anaerobic treatment of pig slurry and energy production Trattamento di reflui di allevamento di suini mediante filtro anaerobico. Treatment of pig slurry by anaerobic filter Desolforazione di fumi con sospensioni di fango rosso Bayer. SO2 removal from flue gas by red mud from Bayer process Dimensionamento di massima di un impianto compatto per il trattamento delle acque di scarico urbane Design of compact plant for treating urban wastewaters Azione della Polifenolossidasi nella depurazione delle acque di vegetazione. Polyphenoloxidase in treating olive oil mill effluent Rimozione di HCl da fumi mediante Idrossido di Calcio Kinetics of HCl removal from flue gas with Calcium Hydroxide Problemi ambientali connessi all’imbottigliamento di di una cantina sociale Environmental problems in wine bottling Degradazione di acido p-idrossibenzoico mediante microrganismi aerobici. Degradation of p-idroxibenzoic acid by means of aerobic microorganisms Modelli cinetici per reazioni gas-solido non catalitiche Analysis of the kinetic models for non-catalytic gas-solid reactions Dispersione di inquinanti organici in terreno insaturo Dispersion of organic pollutants in unsaturated soil Crescita microbica su soluzioni di glucosio e 2,6diclorofenolo dopo trattamento elettrochimico. Microbial mixed cultures growing on glucose and 2,6dichlorophenol after electrochemical treatment Crescita di colture batteriche miste in presenza di composti fenolici. Microbial mixed cultures growing on glucose and 2,6dichlorophenol Lallai Lallai Lallai Lallai Lallai Mura Lallai Lallai Mura Lallai Lallai Mura Mura Lallai Lallai Overview of Scientific Publications (1997-2001) per year 1998 Proceedings of Congress - A.LALLAI, G.Mura, M.Piredda – “Degradazione di clorofenoli mediante colture anaerobiche miste” Congresso GRICU, Ferrara, 23-25 settembre 1998.- Atti: pp. 19-22 - G.Mura, A.Lallai – “Rimozione a secco di HCl da gas di combustione mediante carbonati di sodio” – Congresso GRICU, Ferrara, 23-25 settembre 1998 - Atti: pp. 265-268 195 - A.P.Leu, A.Lallai, G.Mura – “Modello matematico di un reattore per la rimozione a semisecco di HCl da fumi con idrossido di calcio” –Air Quality 98, Ravenna, 25-28 ottobre 1998, Atti: pp. 205-210 Abstract book - L.Massidda, A.Polcaro, S.Palmas, G.Mura, A.Lallai – “Riutilizzo di fanghi rossi da produzione di allumina Bayer” - Congresso GRICU, Ferrara, 23-25 settembre 1998 - Abstracts - A.Lallai, G.Mura, Monitoring system for a batch microbial culture – Water in the Mediterranean area – Conference on Quality and Quantity of Mediterranean Water Recources – October 11-18, 1998 Conference Proceedings – WTM-P13 - Abstracts 1999 Proceedings of Congress - G.Cau, D.Cocco, A.Lallai, G.Mura, M.T.Pilloni – “Power generation from fluidized bed MSW and coal cofiring. A preliminary design for a 10 MWe demonstration plant” – Proc. of 2nd National Congr. on valorization and recycling of industrial wastes, L’Aquila, 5-8 luglio 1999 rd - G.Mura, A.Lallai – “Dry removal of hydrochloric acid from flue gas with sodium carbonates” 3 European Meeting on Chemical and Environment – Krakow, September 1999, vol. I, pp. 99-104 rd A.Lallai, G.Mura, M.Piredda – “Enzymatic detoxification of polyphenols from wastewaters” – 3 European Meeting on Chemical and Environment – Krakòw, September 1999, vol. I, pag. 571-576 Other - G.Mura - "Considerazioni sull'uso del metano in Sardegna", Working papers Assessorato Programmazione Regione Sardegna, Luglio 1995 2000 Journal - G.Mura, A.LALLAI, M.Porta – “Trasporto di contaminanti organici idrofobici in acquiferi superficiali. Un modello monodimensionale per terreno insaturo e saturo”, Atti della Facoltà, vol. 43 n. 27 Ottobre 2000 pp. 101114 Proceedings of Congress - A.Lallai, G.Mura - "Fluid flow patters in up-flow filter" - Proceedings of European Meeting on Chemical and Environment - Alghero, September 1996, Vol. I, p.185 - G.Mura, A.Lallai, A.Cocco – “Assorbimento di anidride solforosa con sospensioni di fango rosso Bayer in acqua di mare” – S.C.I. 2000 – Rimini, 4-9 giugno 2000 - A.Lallai, G. Mura, “Degradazione del 2-clorofenolo nel terreno” – Atti 18° Congresso Nazionale AIDII– Trento 2124 giugno 2000, a cura di D. Cottica, GB Bartolucci A. Peretti, E.Grignani, G.Nano, M.Imbriani, Maugeri Foundation Book, Pavia –pp. 81 - 83 - A.M.Polcaro, S.Palmas, A.LALLAI – “Trattamenti elettrochimici di acque reflue industriali” – S.C.I. 2000 – Rimini, 4-9 giugno 2000 - A.M.Polcaro, S.Palmas, A.LALLAI, C.Caddeo – “Integration of biological and electrochemical treatments of wastewaters: optimization of the electrochemical detoxification process” 51th ISE Meeting, Varsawia, September 2000 Abstract book - G.Mura, A.Lallai – “Assorbimento di anidride solforosa con sospensioni di fango rosso Bayer in acqua di mare” – Convegno “La Chimica per l’Ambiente” – Roma, 28/2/2000 – Abs. n. 11 Abstracts 2001 Journal A.M.Polcaro, S.Palmas, A.Lallai, – “Sequential electrochemical/biological treatment for the removal of 2,6diclorophenol from synthetic wastewater” – Annali di chimica, 91, 303-310 (2001) Proceedings of Congress - G.Mura, M.Tabarelli, A.Lallai – “A mathematical model of the semi-dry process for HCl removal from flue gas using Calcium Hydroxide suspensions” – PRES01 Conf., 20-23 May 2001, Florence. Proceedings p. 279-283 196 - G. Mura, A.LALLAI – “Sulla cinetica di rimozione a secco di HCl con Ca(OH)2” – VI congresso nazionale di chimica ambientale – Rosignano Solvay (LI), 5- giugno 2001 (2 pagine) Abstract book - A. Lallai, G. Mura, N. Onnis, “ The effects of certain antibiotics on biogas production in the anaerobic digestion of pig waste slurry” – 4° Convegno INCA – 25-28 febbraio 2001 S.M. Ligure - Abstracts - A. Lallai, G.Mura, S. Palmas, A. M. Polcaro, L. Baraccani, “ Degradation of para-hydroxybenzoic acid by means of mixed microbial cultures” - 4° Convegno INCA – 25-28 febbraio 2001 S.M. Ligure - Abstracts I.3 Overview of Professional Publications (1997-2001) per year 1997 A.Lallai, G.Mura - "Impianto dimostrativo di pre-trattamento rifiuti e co-combustione con carbone in letto fluido per produzione di energia elettrica" - Contratto con Sotacarbo, 1997 A.Lallai, G.Mura - "Progetto riutilizzo fanghi rossi da produzione di allumina Bayer (Eurallumina) - Contratto con EMSA - Regione Sardegna, 1997 Appendix II Journal Portfolio Analysis Name of the Unit: Research Director: Prof. Antonio Lallai Year included 1997-2001 Name of Journal Number of Articles Atti Facoltà Ingegneria Annali di Chimica 1 1 Journal Impact Field(S) factor not available Engineering 0.5 Chemistry Ranking 197 CAGLIARI 3 Name of the Research Unit CAGLIARI 3 Research Leader Prof. Anna Maria Poicaro University: Facuity: Enginecring University of Cagliari Disinquinamento Contact Person Name Anna Maria Poicaro Mailing Address Dip. Ingegneria Chimica e Materiali (Fac. Ingegneria) p.zza d’armi 09123 Cagliari Faculty: (In Italian and English) Ingegneria Enginnering Department: (In Italian and English) Dip. Ingegneria Chimica e Materiali Thematic area Phone 070-6755059 Fax 070-6755067 E-mail [email protected] • Tecnologie di depurazione (membrane, sonochimica, fotocatalisi, elettrochimica e altre). • Chimica degli ecosistemi (chimica del suolo, delle acque e dell’aria; impatto dei prootti di sintesi sull’ambiente). Introduction and Context The Unit At the present time the unit is structured in the following way: Anna Maria Polcaro Simonetta Palmas Annalisa Vacca Michele Mascia Full Professor Researcher PhD student PhD student leader assistant leader collaborator collaborator Professor Polcaro and Palmas are involved in didatics as follows: Polcaro: Hours/year credits average student’s number Chemistry 60 6 300 Chemistry Lab 30 3 30 Industrial Electrochemistry 30 3 15 Palmas: Industrial Chemistry 50 6 15 Petroleum processing 50 6 10 Furthermore Professor Polcaro and Palmas are involved as supervisors of degree thesis (average number of thesis/year 5) Programme Description and Evaluation 1 Title New technologies for the treatment of effluents 2 Research Leader: Anna Maria Polcaro 198 3 Composition of the scientific research staff of the unit per 1 January 2002 Names and Titles Year of Rank Birth Prof. Anna Maria Polcaro 1941 Eng. Simonetta Palmas 1961 Associate professor Researcher Eng. Michele Mascia 1971 PhD student 1 Eng. Annalisa Vacca 1973 PhD student 1 Total research input Research Input in fte in 2001 0.5 Remarks She became full professor in march 2002 In gen 2001 she became teacher so that part of its activity was devoted to didatics We expected he becomes researcher next year We expected she becomes researcher at the end of the PhD course 0.7 3.2 Comments 4 Input of Academic Staff in fte Category Full Professors Associated Professors Ricercatori Post-docs PhD-students Borsisti Total 1997 0.6 1 - 1998 0.6 1 - 1999 0.6 1 - 2000 0.5 0.8 - 0.6 2.2 2 3.6 1 2.6 1 2.3 2001 0.5 0.8 2 3.3 Total 2.8 4.6 2 4.6 14 Comments The composition of the unit had some variations: the programme director became full professor, and two PhD students joined to the Unit. 5 Funding 5.1 Personnel (in fte) Source University CNR European Union Other Sponsors Total 5.2 1998 1.6 1999 1.6 2000 1.3 2001 3.3 Total 9.4 0.6 2.2 2 3.6 1 2.6 1 2.3 3.3 4.6 14 2000 40 2001 40 Total 80 40 40 132 212 Materials and Equipment (in Million Lire) Source University - MURST CNR EU Other Sponsors Total 5.3 1997 1.6 Comments: 1997 - 1998 1999 45 45 40 40 47 47 199 The major sponsors were: Regione Sardega in 1997-1999 6. Progress Report 6.1 Progress analysis The research on electrochemical removal of organic polllutants from waste waters has been continued. In particular, the studies on electrochemical oxidation of chlorofenols on bi-dimensional dioxide electrodes have been completed. Furthermore, the indirect oxidation mediated by oxidant agents electrogenerated “in situ” has been investigated and a mathematical model has been formulated in order to interprete the experimental results. At the present time the study is focused on a new electrode material, boron doped diamond, which, due to its properties is being of interest to scientific and industrial community. A new research field has been recently opened on soil pollution and remediation. To this aim, the interaction of heavy metal ions and organic pollutants with soils has been investigated. The results will be the starting point to extend the study to electrokinetic technique for the remediation of polluted soils. 6.2 Position within INCA The Unit is involved in a research project “Recupero e smaltimento ecocompatibile dei reflui dell’industria agroalimentare ad alto contenuto fenolico mediante processi chimici e biologici “ in collaboration with Cagliari Unit 2. The project is still in progress. We hope that the heavy burocratic procedures with INCA will be reduced in a future. 6.3 Key Publications 1. R. COSSU, A.M. POLCARO, M.C.LAVAGNOLO, M. MASCIA, S. PALMAS, F. RENOLDI "Electrochemical treatment of landfill leachate" Environ. Sci Technol. 1998, 32, 3570. 2. A.M. POLCARO, S. PALMAS, F. RENOLDI and M. MASCIA, "On the performance of Ti/SnO2 andTi/PbO2 anodes in electrochemical degradation of 2-chlorophenol for waste water treatment", J. Appl. Electrochem, 29, 147-151, 1999. 3. A.M. POLCARO, S. PALMAS, F. RENOLDI e M. MASCIA, "Three-dimensional electrodes for the electrochemical combustion of organic pollutants", Electrochim. Acta, 46, p.389-394, (2000). 4. A.M. POLCARO, S. PALMAS, LALLAI A. "Sequential electrochemical/biological treatment for the removal of 2,6 dichlorophenol from synthetic wastewater", Annali di Chimica, vol.91, 203 (2001). 5. A.M. POLCARO *, M. MASCIA, S.PALMAS, A. VACCA “Kinetic study on the removal of organic pollutants by electrochemical oxidation process”, Ind.Eng.Chem., 41, 2874 (2002) 7. Scientific Output 7.1 Publication Policy The pubblication policy of the Unit is aimed at pubblication in journals of significant scientific relevance in the fields of Electrochemistry, Environmental Science and Chemical Enginnering. Comunications at some important national and international congresses and symposia on these fields with preference for restricted symposia devoted to specific thematics. 7.2 Numerical data Category PhD-Dissertations 1997 1998 1999 2000 2001 Total Scientific Publications 3 2 3 4 3 16 200 Professional Publications Master’s Theses 8 2 5 2 4 6 19 Self-evaluation Special attention has been paid in the selection of national and international meetings and congreeses, specifically devoted to fields of interest, which gave some interesting results 1.The Unit is effectively involved in a National research programm (PRIN) financed by MIUR in 1999-2000; at the present time, a new research programme has been presented. Moreover, the Unit is involved in a national research programme (PON) on soil remediation which has been submitted to be financed. 2. Recently, the Unit has been invited to partecipate as expert in the field of treating of drinking and industrial waters, to a Network of Excellence/Integrated Project on “Sustainable Water Supply for Mankind” suggested as a topic in the VI European Programme We hope that these may be useful contacts to attract greater funding, and improuve our productivity. Appendix I Scientific Output I-1 Overview of Dissertations and Master's Thesis (1997-2001) I.1.1 Dissertations I.1.2 Master's Thesis Accademic Year 2000-2001 2000-2001 2000-2001 2000-2001 2000-2001 2000-2001 1999-2000 1999-2000 1999-2000 1999-2000 1998-99 Name master’s Title of the Dissertation student Giampaolo Serra Effetto del Trasferimento di Materia sull’ossidazione Elettrochimica di Fenolo su Anodi di Diamante Drogato al Boro Pamela Ruffino Cinetica di Ossidazione Elettrochimica di Composti Fenolici su Anodi di Diamante Drogato al Boro Antonio Scalas Reattori Elettrochimici per il Trattamento di Acque di Scarico: Prestazioni ed Opportunità Valentina Cappai Degradazione Elettrochimica della Frazione Fenolica delle Acque di Vegetazione delle Olive Giorgio Marongiu “Caratterizzazione e Pretrattamenti delle Acque di Vegetazione delle Olive”, Patrizia Chessa Recupero per via elettrochimica dello zinco da acque contaminate da metalli pesanti Bernadetta Piseddu Analisi dell’effetto dei parametri operativi nella rimozione elettrochimica di composti biorefrattari da acque di rifiuto Annalisa Vacca Pretrattamento elettrolitico di reflui contenenti composti fenolici Roberto Coghe Rimozione di acido p-toluen solfonico da soluzioni acquose Valeria Serri Pretrattamento di reflui industriali mediante agenti ossidanti elettrogenerati in situ Claudia Porru Integrazione del trattamento biologico ed elettrochimico per la depurazione di scarichi: Supervisor Polcaro Polcaro Polcaro Polcaro Polcaro Polcaro Polcaro Polcaro Polcaro Polcaro Polcaro 201 199899 Alessia Meloni 199798 Gianni Deidda 1997-98 Alessandro Valli 1997-98 Anna Arca 1997-98 Carlo Lodovici 1997-98 Alessandro Murgia I-2 influenza dei parametri operativi sullo stadio elettrochimico Ritenzione di metalli pesanti con adsornbenti non convenzionali: adsorbimento di Cd, Pb, Zn su fango rosso residuo del processo Bayer Rimozione di cromo da soluzioni acquose per trattamento con elettrodi di carbone poroso. Inertizzazione di residui solidi da processo bayer mediante acidi forti e sali di calcio Depurazione elettrochimica di soluzioni acquose inquinate da cadmio: effetto dei parametri operativi sul rendimento Produzione di materiale inerte per interventi di ripristino ambientale da residui del processo Bayer Rimozione di metalli pesanti tramite un adsorbente non convenzionale: fango rosso da processo Bayer Polcaro Polcaro Polcaro Polcaro Polcaro Polcaro Overview of Scientific Publications (1997-2001) per year 1997 A.M.POLCARO, S.PALMAS, "Electrochemical Oxidation of Chlorophenols at Porous Electrodes", Ind.Eng.Chem . Res, 36, 1791-1798, 1997 A.M.POLCARO, S.PALMAS, and S. Dernini “Electrochemical removal of organic pollutants from waste waters” in "Current Topics in Electrochemistry" Pubblisher: Research Trends, Trivandrum, India - vol.4 p138-146, 1997 R. COSSU, A.M.POLCARO, M.C. LAVAGNOLO, S.PALMAS “Treatment of MSW landfill leachate by electrochemical oxidation”, in Leachate and landfill gas menagement, Vol.II p.463 editors T.H. Christensen, R. Cossu, R. Stegman, Cagliari 1997 1998 A.M. POLCARO, S. PALMAS, F. RENOLDI E M. MASCIA, “Trattamento elettrochimico di acque di scarico: rimozione di Cu(II) e Cd (II) da soluzioni acquose.” ICP Rivista dell'Industria Chimica p.149-153 marzo 1998 R. COSSU, A.M. POLCARO, M.C.LAVAGNOLO, M. MASCIA, S. PALMAS, F. RENOLDI "Electrochemical treatment of landfill leachate" Environ. Sci Technol. 1998, 32, 3570. 1999 A.M. POLCARO, S. PALMAS, F. RENOLDI and M. MASCIA, "On the performance of Ti/SnO2 andTi/PbO2 anodes in electrochemical degradation of 2-chlorophenol for waste water treatment", J. Appl. Electrochem, 29, 147-151, 1999. A.M. POLCARO, S. PALMAS, M. MASCIA, F. RENOLDI, and R. L. CORREA DOS SANTOS, "Reticulated vitreous carbon electrode for copper removal from dilute acidic solutions: effect of dissolved oxygen", Ind. Eng. Chem. Res, 38, N4, p. 1400-1405, (1999). A.M. POLCARO, S. PALMAS, F. RENOLDI and M. MASCIA, "Performance of different electrode materials for electro-oxidation of organic pollutants in waste waters", IChemE Symp. Series No.145 pag.171-180 (1999). 2000 A.M. POLCARO, S. PALMAS, M. MASCIA, F. RENOLDI "Co-disposal of industrial wastes to obtain an inert material for environmental reclamation", Annali di Chimica, N90, pag.103, (2000) 202 A.M. POLCARO, S. PALMAS, F. RENOLDI e M. MASCIA, "Three-dimensional electrodes for the electrochemical combustion of organic pollutants", Electrochim. Acta, 46, p.389-394, (2000). L.SZPYRKOWICZ, F. GRANDI, S. N.KAUL, & A.M. POLCARO, Copper electrodeposition and oxidation of complex cyanide from wastewater in an electrochemical reactor with a Ti/Pt anode", Ind.Eng.Chem . Res, vol 39, N.7, p.2132, 2000 A.M. POLCARO, S. PALMAS “Electrochemical oxidation as a stage of combined treatment to reduce the environmental impact of industrial wastewaters, "Current Topics in Electrochemistry" Pubblisher: Research Trends, Trivandrum, India - vol.7 p147-151, 2000 2001 A.M. POLCARO, S. PALMAS, LALLAI A. "Sequential electrochemical/biological treatment for the removal of 2,6 dichlorophenol from synthetic wastewater", Annali di Chimica, vol.91, 203 (2001). A.M. POLCARO *, M. MASCIA, S.PALMAS, A. VACCA, “ Electrochemical Removal of the Phenolic Fraction from Olive Oil Mill Wastewater” Annali di chimica, vol. 92, (2002) A.M. POLCARO *, M. MASCIA, S.PALMAS, A. VACCA “Kinetic study on the removal of organic pollutants by electrochemical oxidation process”, Ind.Eng.Chem . Res, 41, 2874 (2002) All the pubblications fully meet the thematic area: depollution technologies Appendix 3 Journal Portfolio Analysis Name of the Unit: Research Director: Years included Name of Journal Cagliari 3 Anna Maria Polcaro 1997-2001 Number Articles Ind.Eng.Chem . Res 3 Annali di Chimica 3 Env. Sci.&Technol 1 J.Appl.Electrochem. 1 IchemE Symp. Series 1 Electrochim. Acta 1 Others (congress 18 proceedings) of Journal Factor 1.181 0.5 3.623 1 1.518 Impact Field(s) Chemical Eng. Environm. Sci. Environm. Sci. Eectrochemistry Electrochemistry Ranking 203 CAMERINO 1 Name of the Research Unit Camerino 1 Research Leader Prof. ROBERTO BALLINI (The name of the person in charge of the research programme of the unit) University: CAMERINO (In Italian and English) Faculty: SCIENZE E TECNOLOGIE (Sciences and Technologies) Department: SCIENZE CHIMICHE (CHEMICAL SCIENCES)) (In Italian and English) Contact Person Prof. Roberto Ballini Mailing address: Dipartimento di Scienze Chimiche dell’Università, via S. Agostino 1, 62032 Camerino (MC) Phone: +390737402270 Fax: e-mail: [email protected] Thematic area Please indicate to which thematic area of INCA the unit belong (in priority order): • • • • Processi chimici e tecnologie pulite Trasformazioni nell’ambiente Metodologie analitiche avanzate Disinquinamento Introduction and Context Introduction to the Self-evaluation Report The University, the Faculty and the Department City: Camerino, a city of about 6.000= inabitants and the University has about 10.000= students, is located on the Marche Region where there are three other Universities, anyway, the University of Camerino is distinguished by the presence of the istorical Faculty of Science. Univerity: The University is a small University in the Italian context, but it is well characterised by an good level of scientific production, expecially in the field of Chemistry, Fisic and Biology, and by a good teacching level. The following Faculty are present at the University of Camerino: (i) Science; (ii) Pharmacy, (iii) Jurisprudence; (iv) Architecture, and (v) Veterinary. The unit belong to the Faculty of Science and Pharmacy. The Department: The unit belongs to the Dipartimento di Scienze Chimiche, which is composed of 14 full professors, 24 associated professors, 19 researchers, 10 administrative employees, 15 technicians. In 2001 the Department income was around 2.700 million lire. The value of the equipments available in the Department is 6800 million lire and the available space is 6150 sqm. Table 1: Università di Camerino (2000/2001) Facoltà ARCHITETTURA FARMACIA GIURISPRUDENZA MEDICINA VETERINARIA Scienze MM.FF.NN BIOCHIMICA CLINICA (AD INDIRIZZO ANALITICO-TECNOLOGICO) BIOCHIMICA E CHIMICA CLINICA CHIMICA CHIMICA (N.O.) D.U. GEOLOGO D.U.TECNICO DELLO SVILUPPO ECOCOMPATIBILE DIPLOMA UNIVERSITARIO IN Professori 19 34 37 17 81 Ricercatori 7 18 12 13 55 laureati iscritti 62 83 416 40 228 818 1082 5511 516 1916 68 19 8 23 2 7 19 18 106 9 39 1 86 204 MATEMATICA FISICA FISICA (N.O.) GESTIONE DELL'AMBIENTE NATURALE E DELLE AREE PROTETTE INFORMATICA INFORMATICA (N.O.) MATEMATICA MATEMATICA (N.O.) SCIENZE BIOLOGICHE (V ANNI) SCIENZE BIOLOGICHE IV SCIENZE E TECNICHE CARTARIE SCIENZE GEOLOGICHE SCIENZE GEOLOGICHE (N.O.) SCIENZE NATURALI SCIENZE NATURALI (N.O.) SCIENZE TECNICHE CARTARIE (SDFS) Totale complessivo 18 105 3 10 25 12 82 65 3 18 25 27 8 5 9 14 9 11 276 3 57 165 351 40 56 30 172 42 214 829 9843 The Unit The unit is composed by a Full Professor of Organic Chemistry, two Researchers, two Ph-D Students. The unit possess a good experience in Organic Synthesis, and the main fields of research are in the following projects: -Chemistry of nitroalkanes; -Synthesis of natural products; -Studies and application of heterogeneous catalysis in organic synthesis; -Synthesis of important targets, through nitroalkanes, in aqueous medium. Teachind load: Prof Roberto Ballini Organic Chemistry (for Biological Sciences) Prof Roberto Ballini Laboratory of Org. Chem. 2° (for Chemistry) Dr. Luciano Barboni Organic Chemistry for druggists Dr. Giovanna Bosica Organic Chemistry (for Biotechnology) Numbers of PhD-students: At ptresent two PhD students are included in the unit, one (Dr Denni Fiorini) involved in the application of heterogeneous catalysis in organic synthesis, and the other one (Dr Guido Giarlo) involved both in the reaction in aqueous medium and in the use of heterogeneous catalysis. Programme Description and Evaluation 1 Title Application of hetrogeneous catalysis and/or aqueous medium in organic synthesis 2 Research Leader: Prof. Roberto Ballini 2a Sub-programme titles and sub-programme leaders 3 Composition of the scientific research staff of the unit per 1 January 2002 Names and Titles Year of Rank Birth Roberto Ballini – Prof. Luciano Barboni – Dott. Giovanna Bosica – Dott. Dennis Fiorini – Dott. Guido Giarlo – Dott. 1946 1965 1967 1975 1972 Full Professor Researcher Researcher PhD-student PhD-student Research Input in fte in 2001 0.4 0.8 0.8 0.9 0.9 Remarks Full Professor since 2000 Reseracher since 1991 Researcher since 1999 PhD-student 2002-2005 PhD-student 2002-2005 205 Total research input 3.8 Comments During the next 5 years we expected that Dr Giovanna Bosica and Dr Luciano Barboni will get a position of Associate Professors and a new researcher position will increase our Unit. 4 Input of Academic Staff in fte Category Full Professors Associated Professors Ricercatori Post-docs PhD-students Borsisti Total 1997 1998 1999 2000 0.4 2001 0.4 0.8 1.6 1.6 1.6 Total 0.8 2.4 6.4 0.8 0.8 0.8 0.8 1.6 1.6 2.4 2.0 2.0 9.6 Comments The number of structured people is constant during the period under scrutiny and different young graduated and students are involved in the research activity. 5 Funding 5.1 Personnel (in fte) Source University CNR European Union Other Sponsors Total 5.2 1997 1.6 1998 1.6 1.0 1.0 1999 2.4 2000 2.0 2001 2.0 Total 9.6 1.0 2.0 5.0 Materials and Equipment (in Million Lire) Source University - MURST CNR EU Other Sponsors Total 5.3 Comments: 6. Progress Report 1997 41096205 8910000 1998 58655659 1999 55714624 2000 61028611 2001 60449292 Total 276944391 8910000 9250000 3000000 12000000 20000000 35000000 79250000 1.3Mission Statement The main unit’s mission is devoted to the organic synthesis, and in particular, to some “Green” aspects of the organic synthesis: -Use of the hetrogeneous catalysis in organic synthesis and transformations (formation of C,C bond through nitroalkanes, Nitroaldol reaction, Michael reaction, indroduction of protecting groups, deprotection of protecting groups, dehydration, synthesis of thioureas, etc.); -Use of water as medium in organic synthesis (nitroaldol reaction, Michael reaction, cleavage of C,C bond); -One-pot reactions (one pot synthesis of cyclopentenones, 1,4-dicarbonyl derivatives, 1,3-diols, ?-nitro ketones, cyclohexanol derivatives, and polyfunctionalized molecules) ; -Solventless reactions (Formation of C,C bond through nitroalkanes). -Multicomponent reactions (synthesis of dihydropirimidines, chromenes, tetrahydroquinolines, amino chromenes). 6.2 The Research Programme 206 A short summary of the design of the programme (scientific problem formulation, objectives, subject matter, research methods and anticipated results: Our goal will be the study of new heterogeneous, or/and aqueous medium conditions for the nitroaldol (Henry) reaction (synthesis of ?-nitroalkanols), the nitroaldol condensation (synthesis of conjugated nitrolefins) and the Michael addition of nitroalkanes to electron poor alkenes. The Henry and the Michael reactions are two of the most useful processes for the formation of C,C bond in organic synthesis. These reactions are normally carried out under homogeneous processes using organic solvents and soluble bases. Under these conditions, however, the yields are not satisfactory and other functionalities on the molecule are often not tolerate. In addition the nitroalkanols are usually obtained in diastereomeric mixtures and during the acidic work up the dehydration to nitroalkenes or the conversion of the nitrogroup to carbonyl (nef reaction) can occur. We will search new basic heterogeneous or/and aqueous medium conditions that can allow to get best results in terms of chemo- and diastereoselectivity and therefore in terms of yields. In fact, if the use of appropriate chiral-supported solid bases can favour the diastereoselectivity of the reaction, their immediate removal by filtration without acidic work up will avoid the formation of the above mentioned by-products that often limit the applicability of the Henry reaction. In addition the project will focus on the realization of the synthesis of special nitroalkanols, particularly those deriving from aromatic aldehydes that show important fungicide properties. Concerning the conjugated nitroolefins formation, it usually requires multistep processes: the first step is represented by the Henry reaction that affords the nitroalkanols, the second one needs the activation of the OH function through the use of mesylates, acetates, carbodiimides, and therefore a base-promoted elimination reaction that occurs in organic solvents under homogeneous conditions. This strategy requires different work-up, different purification techniques noticeably increasing the “E factor” of the overall synthetic process. On the basis of preliminary results from our laboratory a new solid catalyst and/or cqueous medium conditions are able to promote the one-pot nitroalkenes synthesis though the reaction of nitroalkanes with carbonyl compounds. It is our intention to apply these methodologies to the synthesis of particular nitroalkenes that find a widespread use as fungicides and insecticides. An other project is the formation of C,C double bond by the reaction of nitroalkanes with alkenes showing two electron-withdrawing groups in ?- and ?-positions. By this reaction it is possible to obtain polyfunctionalized ???unsaturated carbonyl derivatives that are the ideal precursors of a variety of heterocyclic compounds. • A substantive overview of the most impressive results over the past five years: In the last years we developed different methods for the formation of both C,C single and double bond through nitroalkanes and the application of the obtained molecules to the synthesis of important targets such as natural products, heterocyclic compounds (furans, pyrroles, pyrrolidines, lactones, furoxans, etc). A short overview of the programme development in the future (the coming 5 years) including the means needed for realising the programme's mission. Please comment on any change due to expected mobility of senior staff: We will search new basic heterogeneous or/and aqueous medium conditions that can allow to get best results in terms of chemo- and diastereoselectivity and therefore in terms of yields. In fact, if the use of appropriate chiral-supported solid bases can favour the diastereoselectivity of the reaction, their immediate removal by filtration without acidic work up will avoid the formation of the above mentioned by-products that often limit the applicability of the Henry reaction. In addition the project will focus on the realization of the synthesis of special nitroalkanols, particularly those deriving from aromatic aldehydes that show important fungicide properties. Concerning the conjugated nitroolefins formation, it usually requires multistep processes: the first step is represented by the Henry reaction that affords the nitroalkanols, the second one needs the activation of the OH function through the use of mesylates, acetates, carbodiimides, and therefore a base-promoted elimination reaction that occurs in organic solvents under homogeneous conditions. This strategy requires different work-up, different purification techniques noticeably increasing the “E factor” of the overall synthetic process. On the basis of preliminary results from our laboratory a new solid catalyst and/or cqueous medium conditions are able to promote the one-pot nitroalkenes synthesis though the reaction of nitroalkanes with carbonyl compounds. It is our intention to apply these methodologies to the synthesis of particular nitroalkenes that find a widespread use as fungicides and insecticides. An other project is the formation of C,C double bond by the reaction of nitroalkanes with alkenes showing two electron-withdrawing groups in ?- and ?-positions. By this reaction it is possible to obtain polyfunctionalized ???unsaturated carbonyl derivatives that are the ideal precursors of a variety of heterocyclic compounds. 6.3 Position in Networks • Intra-university co-operation: We have a cooperation with other organic chemists such as Prof Marino Petrini and Prof Enrico Marcantoni. • Regional co-operation 207 • National co-operation (including INCA): We have a cooperation with the groups of Prof Giovanni Sartori (Univ. of Parma, INCA), and Prof Paolo Righi (Univ. of Bologna, INCA) • International co-operation: We have a cooperation with the group of Prof Emilio Roman Galan (Univ. de Badajoz, Spain) The collaboration with the group of Prof Sartori (Parma) is of great importance for us since we interact in the preparation of new catalyst(Univ. of Parma) for their application (Univ. of Camerino) in the formation of new C,C single and double bond. 6.4 Societal Relevance and Impact Our research could be of great interest in the field of the development of new eco-friendly synthetic processes. 6.5 Further Indications of Quality and Reputation The research leader Prof. ROBERTO BALLINI has been inserted in the ISI’s 10858 Most cited Chemists (position n. 4782). 6.6 Key Publications 1.R. Ballini, P. Marziali, A. Mozzicafreddo J. Org. Chem. 1996, 61, 3209. 2.R. Ballini, G. Bosica J. Org. Chem. 1997, 62, 425. 3.R. Ballini, L. Barboni, G. Bosica J. Org. Chem. 2000, 65, 6261. 4.R. Ballini, F. Bigi, E. Gogni, R. Maggi, G. Sartori J. Catal. 2000, 191, 348. 5.R. Ballini, G. Bosica Tetrahedron Lett. 1996, 37, 8027. 7. Scientific Output 7.1 Publication Policy The Unit research interest has been devoted, for about 20 years, to the chemistry of aliphatic nitrocompounds and their application in the synthesis of several targets such as natural feromones, perfumes, antibiotics, heterocyclic systems etc. However, during these studies a lot of the research has been devoted to the use of eco-friendly methodologies such as the use of heterogeneous catalysis, aqueous medium, solventless conditions, tandem reactions, one-pot reactions and so on. Then, different publications of the Unit was devoted to the use of eco-friendly conditions in the chemistry of aliphatic nitroalkanes. Moreover, since the Unit has an intensive collaboration with the Unit directed by Prof Sartori (Parma) different our publications report both the Unit’s members (Parma and Camerino) in the application of heterogeneous catalysts for many synthestic transformations. Some of our manuscript appeared in the Journals specialised in the green chemistry. 7.2 Numerical data Category PhD-Dissertations 1997 - 1998 - 1999 - 2000 - 2001 - Total - Scientific Publications 14 11 10 9 11 55 Professional Publications Master’s Theses 1 10 2 3 1 17 Appendix I Scientific Output I-1 Overview of Dissertations and Master's Thesis (1997-2001) 208 I.1.1 Dissertations Year Name PhD-student I.1.2 Master's Thesis Year 1997 1998 Name Master’s student Elvira Marchei Fabiola Gigli 1998 Corrado Abate 1998 Marco Damiani 1998 Lorenzo Pintucci 1998 Lara Ciaralli 1998 Marco Bordoni 1998 Silvia Perella 1998 Mauro Perrini 1998 Annarella Rubino 1998 Lara Petrelli 1999 Patrizia Vita 1999 Desy De Santis 2000 Sabina Peretti 2000 Guido Giarlo 2000 Aldo Masè 2001 Damiana Livi Title of the Dissertation Supervisor Title of the Dissertation Addizioni coniugate di nitroalcani in acqua ?-Nitrochetoni come precursori di 1,4dichetoni, ?-chetoaldeidi, ?-chetoesteri e metil ω-aldoesteri Una nuova sintesi di acidi ω-nitrocarbossilici in ambiente acquoso partendo da ?nitrocicloalcanoni Un nuovo approccio sintetico alla preparazione di sistemi 1,4-diolici Una nuova reazione di apertura dei 2nitrocicloalcanoni: sintesi di 1,3-dioli polifunzionalizzati Gruppi protettivi e catalisi eterogenea: acetati ed acetali Sintesi e deprotezione dei di acetati geminali mediante zeoliti Sintesi di ?-lattoni-?-alchiliden-?-monoalchilati e di ?-lattoni-?-alchiliden-??? -dialchilati Sintesi one-pot di ?-nitrochetoni lineari senza solvente Nuova sintesi di ossame in catalisi eterogenea Supervisor Prof. R. Ballini Prof. R. Ballini Prof. R. Ballini Prof. R. Ballini Prof. R. Ballini Dott. L. Barboni Prof. R. Ballini Prof. R. Ballini Prof. R. Ballini Prof. R. Ballini Prof. R. Ballini Dott. L. Barboni Un nuovo approccio sintetico alla preparazione Prof. R. Ballini di 1,4-dichetoni-2-alchilati e ?-chetoesteri-?alchilati Riduzione di ?-nitrochetoni: sintesi Prof. R. Ballini diastereoselettiva di ?-nitroalcoli “Three components reaction”: sintesi one-pot Prof. R. Ballini di cromeni Nitroalcani come precursori di sistemi ciclici a Prof. R. Ballini sei termini: cicloesanoli e benzeni polisostituiti I nitroalcani come equivalenti sintetici di Prof. R. Ballini carbocationi: sintesi di 3-alchil-2,5- Dott. G. Bosica dimetilfurani da 2,5-dimetilfurano Nuovo approccio alla sintesi di sistemi Prof. R. Ballini eterociclici azotati: pirroli e pirrolidine Sintesi di ?-metilene butirrolattoni a partire da Prof. R. Ballini nitroalcani Dott. G. Bosica I-2 Overview of Scientific Publications (1997-2001) per year I-3 Overview of Professional Publications (1997-2001) per year 1997 1.R. Ballini, G. Bosica Nitraoldol Reaction in Aqueous Media: An Important Improvement of the Henry Reaction. J. Org. Chem. 1997, 62, 425. 2.S. Fioravanti, L. Pellacani, S. Stabile, P. A. Tardella, R. Ballini Aziridination of Conjugated Nitroalkenes. Tetrahedron Lett. 1997, 38, 3309. 209 3.R. Ballini, G. Bosica, T. Mecozzi C-C Bond Fission via Sulphones: A New Ring Cleavage of Cyclic ?-Keto Penylsulphones. Tetrahedron 1997, 53, 7341. 4.R. Ballini, L. Barboni, P. Filippone Amberlyst A-21 an Excellent Heterogeneous Catalyst for the Conversion of Carbonyl Compounds to Oximes. Chem. Lett. 1997, 475. 5.R. Ballini, F. Bigi, S. Carloni, R. Maggi, G. Sartori Solvent Free Tetrahydropyranylation of Phenols and Alcohols over Zeolite HSZ as Reusable Catalyst. Tetrahedron Lett. 1997, 38, 4169. 6.R. Ballini, G. Bosica Formation of Carbon-Carbon Bond via Nitroalkanes Under Heterogeneous Catalyst. Recent Res. Devel. in Organic Chem., Transworld Research Network Ed., Trivandrum, 1997, Vol. 1, Pag. 11 (REVIEW). 7.R. Ballini, G. Bosica, R. Maggi, G. Sartori Envirocat EPZG as a New Heterogeneous Catalyst for the Regeneration of Ketones from Their Tosylhydrazones. Synlett 1997, 795. 8.R. Ballini, E. Marcantoni, E. Torregiani Synthesis of (Z)-9,10-Epoxynonacosane, a Long-Chain Epoxide Isolated from Stem Wax of Rubus thibetanus. J. Nat. Products 1997, 60, 505. 9.R. Ballini Synthesis of Natural Products via Aliphatic Nitroderivatives. Studies in Natural Products Chemistry, (Atta-ur-Rahman Ed.), Elsevier: Amsterdam, 1997, Vol. 19, Pag. 117 (REVIEW). 10.R. Ballini, G. Bosica ?-Nitrocycloalkanones as a Source of ???-Dicarboxylic Acid Dimethyl Esters. Tetrahedron 1997, 53, 16131. 11.R. Ballini, L. Barboni, L. Pintucci Synthesis of Polyfunctionalized 1,3-Diols Through a One-Pot “Double Nitroaldol Reaction-Ring Cleavage” of 2-Nitrocycloalkanones. Synlett 1997, 1389. 12.L. Barboni and E. Torregiani, “Styrylamine based cyclopeptide alkaloids” in “Virtual activity, real pharmacology” Ed. L. Verotta, Research Signpost, Trivandrum, India, 1997, 33-48. ISBN 81-8641-17-6. 13.L. Barboni, C. Lambertucci, G. Appendino and B. Gabetta, “A taxane epoxide from taxus wallichiana”, Phytochemistry, 1997, 46 (1), 179-80. (Impact Factor 2000: 1.112) 14.G. Appendino, E. Belloro and L. Barboni, “Unusual reactivity of taxine A in an oxidation-reduction protocol”, Gazz. Chim. It., 1997, 127, 373. 1998 1.R. Ballini, G. Bosica Conjugated Addition Reactions of Nitroalkanes with Electrophilic Alkenes in Aqueous Media. Eur. J. Org. Chem. 1998, 355. 2.R. Ballini, G. Bosica, B. Frullanti, R. Maggi, G. Sartori, F. Schroer 1,3-Dioxolanes from Carbonyl Compounds over Zeolite HSZ-360 as a Reusable, Heterogeneous Catalyst. Tetrahedron Lett. 1998, 39, 1615. 3.S. Fioravanti, L. Pellacani, S. Stabile, P. A. Tardella, R. Ballini Solvent-Free Aziridination of ?Nitroalkenes. Tetrahedron 1998, 54, 6169. 4.R. Ballini, G. Bosica, F. Gigli ?-Nitrocycloalkanones as a New Source of the One-Pot Synthesis of Functionalized 1,4-Diketones, ?-Oxoaldehydes, ?-Ketoesters, and Methyl ?-Oxoalkanoates. Tetrahedron 1998, 54, 7573. 5.R. Ballini, G. Bosica Synthesis of (E)-4-Oxonon-2-enoic Acid, a Natural Antibiotic Produced by Streptomyces olivaceus. J. Nat. Products 1998, 61, 673. 6.R. Ballini, G. Bosica, S. Carloni, L. Ciaralli, R. Maggi, G. Sartori Zeolite HSZ-360 as a New Reusable Catalyst for the Direct Acetylation of Alcohols and Phenols Under Solventless Contitions. Tetrahedron Lett. 1998, 39, 6049. 210 7.L. Barboni, C. Lambertucci, R. Ballini, G. Appendino, E. Bombardelli Synthesis of a Conformationally Restricted Analogue of Palixatel. Tetrahedron Lett. 1998, 39, 7177. 8.R. Ballini, M. Bordoni, G. Bosica, R. Maggi, G. Sartori Solvent Free Synthesis and Deprotection of 1,1Diacetates Over a Commercially Available Zeolite Y as a Reusable Catalyst. Tetrahedron Lett. 1998, 39, 7587. 9.R. Ballini, G. Bosica, M. Parrini A One Pot, Solvent-Free Synthesis od Acyclic ?-Nitro Ketones Through the Nitroaldol Reaction. Tetrahedron Lett. 1998, 39, 7963. 10.R. Ballini, M. Curini, F. Epifano, M. C. Marcotullio, O. Rosati A New, Modulated, Oxidative Ring Cleavage of ?-Nitrocycloalkanones by Oxone: Synthesis of ???-Dicarboxylic Acids and ???-Dicarboxylic Acid Monomethyl Esters. Synlett 1998, 1149. 11.R. Volpini, E. Camaioni, S. Vittori, L. Barboni, C. Lambertucci and G. Cristalli, “Synthesis of New Nucleosides by Coupling of Chloropurines with 2- and 3-Deoxy Derivatives of N-Methyl-Dribofuranuronamide”, Helv. Chim. Acta, 1998, 81, 145. (Impact Factor 2000: 2.209) 1999 1.R. Ballini, F. Papa, C. Abate Synthesis of ?-Nitro Acids and ?-Amino Acids by Ring Cleavage of ?Nitrocycloalkanones. Eur. J. Org. Chem. 1999, 87. 2.R. Ballini, L. Barboni, R. Maggi, G. Sartori Thioacetalization of Carbonyl Compounds by Zeolite HSZ-360 as a New, Heterogeneous Catalyst. Synthetic Commun. 1999, 29, 767. 3.M. Ballabeni, R. Ballini, F. Bigi, R. Maggi, M. Parrini, G. Predieri, G. Sartori Synthesis of Symmetrical N,N’-Disubstituted Thioureas and Heterocyclic Thiones from Amines and CS2 over a Zn/Al2O3 Composite as Heterogeneous and Reusable Catalyst. J. Org. Chem. 1999, 64, 1029. 4.R. Ballini, E. Marcantoni, S. Perella A Two Steps Synthesis of ?-Substituted and ???-Disubstituted ?(Alkyl)methylene-?-butyrolactones. J. Org. Chem. 1999, 64, 2954. 5.R. Ballini, G. Bosica, L. Petrelli A New, Two Steps Synthesis of 2-Alkylated 1,4-Diketones and ?-Alkylated ?-Ketoesters. Synthesis 1999, 1236. 6.R. Ballini Recent Progress on the Ring Cleavage of Cyclic 2-Nitro Ketones by External Nucleophiles. Synlett 1999, 1009 (REVIEW). 7.R. Ballini, M. Petrini Base Assisted Substitution of ?-Amidoalkyl Sulfones by Nitromethane Anion. A New Entry to Functionalized ?-Amino Acids. Tetrahedron Lett. 1999, 40, 4449. 8.R. Ballini, G. Bosica, M. Parrini Fast Nitroaldol Reaction Using KOH in Dry Media. Chem. Lett. 1999, 1105. 9.R. Ballini, G. Bosica, M. Damiani, P. Righi Nitraolkanes as a New Source of Alkylidene-1,4-diols, in Two Steps. Tetrahedron 1999, 55, 13451. 10.O. Attanasi, R. Ballini, L. De Crescentini, P. Filippone, F. Mantellini Easy Access to (E,Z)-?-Nitro-???olefinated Hydrazones, 6-Oxo-1,6-dihydropyrazines, and 4-Chloro-1-aminopyrroles by Domino Reactions of 1,2-Diaza-1,3-butadienes with Halogen-Coactivated Methylene or Methine Compounds. J. Org. Chem. 1999, 64, 9653. 2000 1.R. Ballini, L. Barboni, G. Bosica, M. Petrini 2,5-Dialkylfurans and Nitroalkanes as Source of 2,3.5Trialkylpyrroles. Synlett 2000, 391. 2.Fontana, P. De Maria, G. Siani, M. Pierini, S. Cerritelli, R. Ballini Equilibrium Constants for Ionisation and Enolisation of 3-Nitrobutan-2-one. Eur. J. Org. Chem. 2000, 1641. 211 3.R. Ballini, F. Bigi, E. Giorgi, R. Maggi, G. Sartori Zeolite as Base Catalyst: Nitroaldolic Condensation. J. of Catalysis 2000, 191, 348. 4.R. Ballini, L. Barboni, G. Bosica, P. Filippone, S. Peretti One-Pot Diastereoselective Synthesis of 2-Acyl-4nitrocyclohexanol Derivatives in Aqueous Medium. Tretrahedron 2000, 56, 4095. 5.R. Ballini, G. Bosica, A. Masè, M. Petrini Synthesis of (E)-3-Alkylidenepyrrolidines by Nucleophilic Ring Closure of (E)-2-Alkylidene-1,4-diol Derivatives. Eur. J. Org. Chem. 2000, 2927. 6.R. Ballini, F. Bigi, M. L. Conforti, D. De Santis, R. Maggi, G. Oppici, G. Sartori Multicomponent Reaction Under Clay Catalysis. Catal. Today 2000, 305. 7.R. Ballini, G. Bosica, E. Marcantoni, P. Vita, G. Bartoli First TiCl4-Mediated Diastereoselective Reduction of ?-Nitro Ketones to Anti-?-Nitro Alcohols by BH3.SMe2. J. Org. Chem. 2000, 65, 5854. 8.R. Ballini, L. Barboni, G.Bosica Nitroakanes as a New, Convenient Source of 1-Acyl-2,5-dialkylbenzene Derivatives, in Two Steps. J. Org. Chem. 2000, 65, 6261. 9.M. Curini, F. Epifano, M. C. Marcotullio, O. Rosati, R. Ballini, G. Bosica Alumina Promoted Cyclization of ?-Nitro-Oximes: a New Entry to the Synthesis of 1,2,5-Oxadiazoles N-Oxides (Furoxans). Tetrahedron Lett. 2000, 41, 8817. 2001 1.Ballini, G. Bosica, M. L. Conforti, R. Maggi, A. Mazzacani, P. Righi, G. Sartori Three-Component Process for the Synthesis of 2-Amino-2-chromenes in Aqueous Media. Tetrahedron 2001, 57, 1395. 2.R. Ballini, G. Bosica, D. Fiorini, M. V. Gil, M. Petrini Stereoselective Synthesis of (E)-4Alkyllidenecyclopent-2-en-1-ones by a Tandem Ring Closure-Michael Addition-Elimination. Org. Lett. 2001, 3, 1265. 3.R. Ballini, G. Bosica, S. Cossu, O. De Lucchi, P. Peluso Observation on the Alkylation of ?-Acetalic Carbanions: Monoalkylation versus Dialkylation and Elimination. Tetrahedron 2001, 57, 4461. 4.R. Ballini, L. Barboni, G. Bosica, D. Fiorini, M. V. Gil, M. Petrini Synthesis of Functionalized Nitrocyclohexene Derivatives from 2-Nitrocycloalkanones, via Anionic Domino Reactions. Tetrahedron 2001, 57, 6079. 5.R. Ballini, G. Bosica, D. Livi A New Synthesis of exo-Methylene Butyrolactones from Nitroalkanes. Synthesis 2001, 1519. 6.R. Ballini, G. Bosica, R. Maggi, M. Ricciutelli, P. Righi, G. Sartori, R. Sartorio Clay-Catalysed Solventless Synthesis of trans-Chalcones. Green Chemistry 2001, 3, 178. 7.R. Ballini, G. Bosica, R. Maggi, A. Mazzacani, P. Righi, G. Sartori Amberlyst 15 as a Mild, Chemoselective and Reusable Heterogeneous Catalyst for the Conversion of Carbonyl Compounds to 1,3-Oxathiolanes. Synthesis 2001, 1826. 8.R. Ballini, G. Bosica, D. Fiorini, G. Giarlo Synthesis of 3-Alkyl-2,5-dimethylfuran Derivatives by In Direct Alkylation of 2,5-Dimethylfuran with Aliphatic Nitrocompounds. Synthesis 2001, 2003. 9.R. Ballini, G. Bosica, D. Fiorini Stereoselective Preparation of (E)-?-Nitro-???-unsaturated Methyl Esters: Amberlyst A 27, Using Microwave, as Superior Catalyst for the 1,6-Conjugate Addition of Nitroalkanes to Methyl 1,3-Butadiene-1-carboxylate. Tetrahedron Lett. 2001, 42, 8471. 10.Luciano Barboni, Catia Lambertucci, Giovanni Appendino, David G. Vander Velde, Richard H. Himes, Ezio Bombardelli, Minmin Wang and James P. Snyder “Synthesis and NMR-Driven Conformational Analysis 212 of Taxol Analogues Conformationally Constrained on the C13 Side Chain”, J. Med. Chem., 2001, 44 (10), 1576-1587. (Impact Factor 2000: 4.134) 11.Luciano Barboni, Apurba Datta, Dinah Dutta, Gunda I. Georg, David G. Vander Velde, Richard H. Himes, Minmin Wang and James P. Snyder, “Novel D-seco Paclitaxel Analogs: Synthesis, Biological Evaluation, and Model Testing”, J. Org. Chem., 2001, 66 (10), 3321-3329. (Impact Factor 2000: 3.689) Appendix 3 Journal Portfolio Analysis Years included 1997-2001 Name of Journal Number Articles Tetrahedron Letters 10 Tetrahedron 9 The Journal of Organic 8 Chemistry Synlett 5 Synthesis 4 European Journal of Organic 3 Chemistry Chemistry Letters 2 of Journal Impact Factor (2001) 2.280 2.276 3.280 Field(s) Ranking Organic Chemistry Organic Chemistry Organic Chemistry 13/51 14/51 7/51 2.465 1.985 2.193 Organic Chemistry Organic Chemistry Organic Chemistry 12/51 18/51 17/51 1.557 Chemistry, Multidisciplinary Applied Chemistry Plant Sciences Chemistry, Multidisciplinary Organic Chemistry Physical Chemistry Applied Chemistry Organic Chemistry Chemistry, Multidisciplinary Medicinal Chemistry 29/118 Journal of Natural Products Phytochemistry Helvetica Chimica Acta 2 1 1 1.737 1.296 2.027 Synthetic Communications Journal of Catalysis Catalysis Today Organic Letters Green Chemistry 1 1 1 1 1 0.912 3.293 2.333 3.670 2.477 Medicinal 1 4.139 Journal of Chemistry 7/58 42/134 23/118 35/51 17/93 4/58 6/51 18/118 6/36 213 CASERTA 1 Name of the Research Unit Caserta 1 Research Leader Prof. Benedetto Di Blasio University: Seconda Università di Napoli Contact Person Dr. Messere Anna Faculty: Scienze Ambientali/ Environmental Science Department: Scienze Ambientali/ Environmental Science Address:Dipartimento di Scienze Ambientali Via Vivaldi 43, 81100 Caserta (Italy) Phone :0823-274415 Fax : 0823-274605 E-mail : [email protected] Thematic area Please indicate to which thematic area of INCA the unit belong (in priority order): • Tecnologie biologiche enzimatiche e biomimetiche per le sintesi ecosostenibili e la decontaminazione ambientale. • Catalisi eterogenea per le sintesi ecosostenibili e la decontaminazione ambientale. • Sintesi ecosostenibili (solventi, fotochimica, catalisi, riciclo e altre). Introduction and Context Introduction to the Self-evaluation Report The Faculty of Environmental Sciences was founded in 1993, while the Department started its activities in 1997. The University campus is located in Via Vivaldi, Caserta. In the last three years, the number of professors, researchers and technicians and administration personnel has rapidly grown to the current 40 units, plus post-doctoral and visiting research fellows. The Self-evaluation Report of this unit has been produced by following the CHEPS Guidelines and by using further information given by INCA Secretariat. The University, the Faculty and the Department The Seconda Università di Napoli was founded in 1989 with Prime Minister's degree of the Ministers in order to come encounter to the requirement to decongest the Neapolitan Athenaeum "Federico II”. It has begun its independent activity from 1 November 1992. The Univarsity has 9 Faculties: Architecture, Economy, Engineering, Letters and Philosophy, Medicine to Surgery, Psycology, Environmental Sciences, Mathematical Physical and Natural Sciences, which are present with one or more course than Bachelor. Only characteristic of the Second University of Naples is the breakup in an immense very comprising territory five common ones of the Campania Region: Aversa, Capua, Caserta, Naples, Saint Maria Capua Vetere, in which are combined in homogenous poles. The University awards the following educational qualifications: University Diploma, University Degree, Specialization Diploma, PhD. The Faculty of Environmental Science, where the professors of the research unit perform their work, have a student population over 300 with 27 faculty members. The main goal of the two institutions, Faculty and Department, of Environmental Sciences, is to form a new professional that is able to: interact with specialists from other disciplines to define a new approach in the management of environmental resources; support companies in defining new ecomanagement criteria that are economically sustainable and technologically reliable. The main cultural and scientific goals, of the staff of this unit research are characterized by a multidisciplinary approach to research and student formation in the environmental field. The Unit Our Unit working inside the Department of Envorimental Science. The organizational structure consist of : 1 full prof., 3 associate prof., 1 researcher, fellowship and PhD-students. 214 Programme Description and Evaluation 1 Environmental Technology 2 Research Leader: Prof. B. Di Blasio 2a Sub-programme titles and sub-programme leaders 1. Molecular systems of biological interest: structural studies of peptides and proteins and their interaction with metal ions 2. Molecular systems of biological interest: conformational features of macrocycles and their interactions with metal ions. 3.Oxidation of selected phenolic compounds present in water waste of olive with heterogeneous phase 4. Development of new natural bioherbicides (phytotoxins). 3 Composition of the scientific research staff of the unit per 1 January 2002 Names and Titles Year of Rank Birth Prof. Benedetto Di Blasio Prof. Paolo V. Pedone Prof. Roberto Fattorusso Prof. Carla Isernia Dr.ssa Anna Messere Dr.ssa Rosa Iacovino Dr.ssa Sabrina Esposito Dr. Isidoro Garella Dr.ssa Rosa Maria Vitale Dr.ssa Paola Di Lello Dr.ssa Alessia Minichino Dr. Nicola Sorrentino Dr.ssa Baglivo Ilaria Total research input 1945 1968 1969 1961 1965 1964 1970 1966 1971 1971 1975 1977 1977 Full Professor Associated Prof. Associated Prof. Associated Prof. Researcher Fellowship Fellowship Fellowship PhD-student PhD-student PhD-student PhD-student PhD-student Research Input in fte in 2001 0.4 0.5 0.5 0.5 0.7 0.5 0.5 0.7 0.6 0.6 0.5 0.5 0.5 6.8 Remarks Joined the unit in 2000 Joined the unit in 2001 Joined the unit in 2001 Comments Dr.ssa Anna Messere become researcher at university of Caserta in 2000. 4 Input of Academic Staff in fte Category Full Professors Associated Professors Ricercatori Post-docs PhD-students Borsisti Total 5 Funding 5.1 Personnel (in fte) Source University CNR 1997 0.4 1998 0.4 1999 0.4 2000 0.4 0.5 0.6 2001 0.4 1.5 0.7 Total 2.0 2.0 1.3 0.4 0.7 1.2 2.3 1.2 1.2 2.8 1.7 1.2 4.4 2.7 1.2 6.5 6.3 4.8 16.4 1997 0.4 1998 1.6 1999 1.6 2000 3.0 2001 4.5 Total 11.1 215 European Union Other Sponsors Total 5.2 1.2 1.4 4.4 1.8 0.7 7.0 5.1 0.7 16.9 2.3 2.8 1999 150 2000 80 2001 30 Total 260 100 100 360 Materials and Equipment (in Million Lire) Source University - MURST CNR EU Other Sponsors Total 5.3 0.4 0.7 1997 1998 Comments: • On the figures The staff is paid by the University, the PhD-students worked for the unit as a grantee, paid by the University and EU. No administrative or technician personel works specifically for the group. For this reason the academic staff has to take care also of administrative and technician duties. • On the funding policy Most of the funds came from the Minister of University and Scientific and Technological Research (MURST) for research Projects of Relevant National Interest. The PhD-student program was funded by EU. Other grants came from Regione Campania. 6. Progress Report 6.1 Mission Statement The location of the Unit in a multidisciplinary Department and the perspective of the organization of a new technologyoriented public University leads to the decision to have a proper balance between basic and applied science. The mission is obviously connected to the mission of INCA. Clients are the international scientific community and educational and training programmes. So far, the Unit has dedicated much attention to the development of new molecules with biological activity as well as model molecules for environmental research and application. The aim of the overall research lines of the group is to bring together different scientific experiences and disciplinary curricula with the ambition to carry out the knowledge of the basic mechanism of transport and the molecular interaction with target biological structure of environmental pollulants (metal) in to living organism. The other research line is the oxidation of selected phenolic compounds present in water waste of olive with heterogeneous phase. Our research objective is not only the reduction of the polluting load of the wastes, but particularly, its utilization/valorization. Furthemore, an other program of this unit is the development of new natural bioherbicides (phytotoxins). 6.2 The Research Programme Systems of Biological Interest Molecular systems of biological interest: structural studies of peptides and proteins and their interaction with metal ions The research activity is based on the conformational study of compound with peculiar biological features. The activity of those compounds is determined by the conformation adopted during the interaction with the receptor. Selectivity and specificity can, in fact, be explained on the basis of the structures of the interacting species. The study of the structural features of biomolecules of different sizes can contribute, therefore, to the understanding of the mechanism regulating the molecular recognition, so being very helpful in the scientific, industrial and environmental fields. The research , performed in collaboration with other italian and foreign groups, has been mainly focused on: • analysis of the conformational properties of model peptides; • determination of the structural features needed for the interaction between metal ions and synthetic peptides; • structural studies in solution of proteins able to interact with metal ions and/or DNA. These studies have been carried out using spectroscopic techniques in solution (CD, NMR, FT-IR, UV), single crystal X-ray diffraction and computational methods. Recently, we have characterised the structure and function of a single 216 zinc finger domain present in the SUPERMAN protein and also well conserved in other proteins from Arabidopsis thaliana. We acquired NMR spectra on a 37 amino acids fragment complexing the zinc and containing the entire zinc finger motif. After the analysis of the spectra we obtained a structure well defined in solution in the presence of the zinc ion: the three-dimensional structure consists of the classical motif ?strand-?strand-?helix. Recently we have also solved the structure of the SUPERMAN zinc finger domain complexed with the cadmium ion, an important toxic metal which could interfere with normal biological processes by displacing zinc from zinc binding protein. We have also performed the complete structural characterisation in solution of the thioredoxin double mutant K18G/R82E expressed by the Bacillus acidocaldarius. The features of the genic expression of this mutant make the protein more stable at high temperatures than the wild-type. Molecular systems of biological interest: conformational features of macrocycles and their interactions with metal ions. The research activity is focused on the study of the interaction of molecules of biological interest with metal ions and on the definition of the parameters influencing the stability and the structure by the use of spectroscopic techniques (Xray, NMR, IR). The research program has regarded supramolecular systems of different types and in particular has consisted of: • the study of macrocycles able to form inclusion compounds such as the cyclodextrins, with the aim to use them as model systems of natural enzymes, receptor and carriers; • the study of mechanism regulating the molecular recognition and the capture of ions in modified calix[4]resorcinarenes; In particular, several efforts were directed to the comprehension of cyclodextrin inclusion complex formation mechanism: essential requisite appear to be the three-dimensional compatibility between the host and the guest. It is still unclear which is the driving force for the complex formation and not much is known on the interactions able to stabilize the inclusion compound. Moreover, it is of considerable interest in this field to find applications in the environmental field; our aim, actually, is the study of this “host-guest interaction” focused to obtain inclusion compounds with pesticides. Calixarenes represent a class of molecules exhibiting characteristic cavity-shaped architecture; they have been extensively studied for their ionophoric and enzyme mimic properties. They are characterized by large flexibility and, as a consequence, their ion selectivity is somehow impaired. We have recently prepared new derivatives, in which a porphyrin has been capped with several differently functionalized C-alkyl calix[4]resorcinerenes. These systems could be used as selective sensors and as extractants for heavy metal ions. Oxidation of selected phenolic compounds present in water waste of olive with heterogeneous phase Olive oil mill waste (OMW) waters show significant polluting properties due to their content of organic substances, and have been shown to present high toxicity towards several biological systems. Waste waters toxicity has been attributed to their phenolic constituents. A chemical study of waste waters from a ligurian oil mill led to the identification of phenolic by-products such as 1,2-dihydroxybenzene, hydroxylated by-products of benzoic acid, phenylacetic acid, phenylethanols, and cinnamic acids. We have tested a chemical treatment to destroy polluting power of the hardly biodegradable organic substances present in OMW. Oxidative methods have been shown to be extremely useful to determine aromatic rings breaking or their modification in compounds potentially useful in industry or in pharmaceutical field. We have also used solid-supported oxidants, which could give several benefits considering their remarkable easyness of handling and use. Oxidation products have been obtained and will be tested on the same organisms to evaluate the residual toxicity. Development of new natural bioherbicides (phytotoxins). The main goals of this research project are part of a general strategy to find alternatives to the use of chemical herbicides (biocontrol). They can be summarized as follows: production of the natural toxin; determination of the absolute configuration of the chyral centres of the molecule; steroselective total synthesis of the toxin. 6.3 Position in Networks • Intra-university co-operation • Dipartimento di Scienze della Vita, Seconda Università di Napoli • Regional co-operation Regione Campania • National co-operation (including INCA) Dipartimento di Chimica, Università Federico II di Napoli 217 Centro di Biocristallografia, CNR, Napoli Centro Interuniversitario di Ricerca sui Peptidi Bioattivi (CIRPEB), Napoli Centro di Ricerca Interdipartimentale di Scienze Computazionali e Biotecnologiche (CRISCEB), Napoli Dipartimento di Studi di Chimica e Tecnologia Facolta di Farmacia, Università “La Sapienza” Roma Dipartimento di Scienze Chimiche, Università di Catania Dipartimento di Chimica IFM, Università di Torino. • International co-operation • Institute of Molecular Biotechnology, Jena, Germany • Department of Biochemistry and Molecular Biology, University of Georgia, Athens, USA • Department of Biological Chemistry, Brown University, Rhode Island, USA 6.4 Societal Relevance and Impact The importance of the area of research in which this Unit in involved has been already underlined in the mission statement above. The research activity is mainly focused on the study of the interactions of biological molecules with metal ions; with the purpose to understand the mecanism of toxicity of some metal ions and to design new strategy for decontamination. Furthemore we are also interested in developing new pesticides, more enviromentally friendly, and improving the techniques of pollutants removal. All these activity can be considered to have a high relevance for a better quality of the enviroment. The contribution of the Unit clearly appears in the scientific publications and the PhD thesis of the last years. The international scientific reputation of the Unit was recognized also through the contributed to the organization of the 6th Naples Workshop on Bioactive Peptides held in Capri in 1998; 7th Naples Workshop on Bioactive Peptides held in Capri in 2000 and, 27th Symposium of the European Peptide Society will be held in Sorrento in September 2002. 6.5 Further Indications of Quality and Reputation Professor Di Blasio, since June 1996 he has been appointed Dean of the Environmental Science Faculty of the Second University of Naples. Since November 1996, he has been coordinator of the PhD course “Design and use of molecules with biotechnological interest” organized by the Second University of Naples and by the University of Tuscia. Most of his studies have dealt with the various aspects of structure-activity relationships in various inorganic and organic materials, which have been investigated by a variety of experimental and theoretical techniques, with the aim to understand their properties and behaviour. He is a member of the International Scientific Advisory Board for the Jounal of the Chemical Society , Dalton Transaction. 6.6 Key Publications 1.M. Pellecchia, R. Fattorusso and G. Wider, “Determination of the Dihedral Angle Based on J Coupling Measurements in 15N/13C-Labeled Proteins”, J. Am. Che. Soc., (1998), 120, 6824-25. 2.Pedone, P. V., Omichinski, J. G., Nony, P., Trainor, C., Gronenborn, A. M., Clore, G. M. and Felsenfeld, G.. “The N-terminal fingers of cGATA-2 and cGATA-3 are independent sequence-specific DNA binding domains”. EMBO J. (1997) 16, 2874-2882. 3.Omichinski, J. G., Pedone, P. V., Felsenfeld, G., Gronenborn, A. M. and Clore, G. M.. “The solution structure of a specific GAGA factor/DNA complex reveals a new twist in classical zinc finger/DNA recognition”. Nature Struct. Biol., (1997)4, 122-30. 4.M. Saviano, E. Benedetti, B. Di Blasio, E. Gavuzzo, O. Fierro, C. Pedone, R. Iacovino, E. Rizzarelli, G. Vecchio: “Difunctionalized ?-cyclodextrins:synthesis and X-ray diffraction structure of 6I,6II-dideoxy-6I,6IIbis[2-(2-pyridyl)ethylamoni]-?-cyclomaltoheptaose ” J. Chem. Soc. Perkin Trans 2., (2001) 6, 946-952. 5.F. Rossi, M. Saviano, P. Di Talia, B. Di Blasio, C. Pedone, G. Zanotti, M. Mosca, G. Saviano, T. Tancredi, K. Ziegler, E. Benedetti: “Solution and Solid State Structure of an Aib-containing Cyclodecapeptide Inhibiting the Cholate Uptake in Hepatocytes”Biopolymers, (1997) 40,465-478. 7. Scientific Output 218 7.1 Publication Policy The scientific papers, all based on experimental researches, are published on relevant international journals specialized in the fields of chemistry, organic chemistry, biochemistry, molecular design and structural biology (NMR and x-ray diffraction). 7.2 Numerical data Category PhD-Dissertations 1997 1998 1999 2001 1 Total 1 Scientific Publications 16 14 10 12 52 1 1 4 Professional Publications Master’s Theses 8 Self-evaluation The Unit is constituted by scientist belonging to different cultural areas (biochemistry, organic chemistry, crystallography, bioinorganic-, coordination-, and physical chemistry). The use of a multidisciplinary approach gives an important opportunity to the research. Moreover, the Unit have the possibility to utilise, for the research activity, a modern and rather complete set of scientific apparatus. Appendix I Scientific Output I-1 Overview of Dissertations and Master's Thesis (1997-2001) I.1.1 Dissertations Year Name PhD-student 2000 Iacovino Rosa 1998-2002 Di Lello Paola 1999-2003 Vitale Rosa Maria 2000-2004 Minichino Alessia 2001-2005 Sorrentino Nicola Title of the Dissertation Caratterizzazione Conformazionale di Biomolecole Conformational characterization of biomolecules Struttura ed attività di sistemi proteici di interesse biotecnologico mediane tecniche di NMR NMR structural and functional chatacterization of proteins of biotechnological interest Progettazione e caratterizzazione conformazionale di ligandi peptidici di GPCRs con potenziali applicazioni diagnostiche e terapeutiche Design and characterization of GPCRs peptidic ligands with potential diagnostic and terapeutics applications Caratterizzazione conformazionale di sistemi metallo proteici Conformational characterization of metallo-protein systems Studi cristallografici di proteine che presentano interazioni con il DNA. Crystallographic studies of DNA binding proteins Supervisor B. Di Blasio B. Di Blasio B. Di Blasio B. Di Blasio B. Di Blasio 219 I.1.2 Master's Thesis Year Name Master’s student 1999 2001 2002 2002 I-2 Canzano Anna D’ Andrea Assunta Malgieri Gaetano Riccio Salvatore Title of the Dissertation Valutazione dell'inquinamento atmosferico da traffico veicolare nell'area urbana della città di Caserta Evaluation of the air pollution by vehicular traffic in the urban area of Caserta. Progettazione e caratterizzazione di complessi di inclusione di ciclodestrine con fitofarmaci. Design and characterization of inclusion complexes of β-Cyclodextrin with pesticides Influenza della sostitutuzione dello ione Zn2+ con lo ione Cd2+ sulla struttura di un dominio zinc finger di pianta; studi strutturali NMR Influence of the Zinc ion sostitution with Cadmium on a plant zinc finger domain strusture: NMR structural characterization Trattamento chimico ossidativo di componenti fenolici delle acque reflue di vegetazione provenienti dai frantoi oleari Chemical treatment of phenolic constituents from Olive oil mill waste waters Supervisor Benedetto Di Blasio Carla Isernia Roberto Fattorusso Anna Messere Overview of Scientific Publications (1997-2001) per year 1997 E.Benedetti, R.Iacovino, C.Pedone, F.Rossi, M.Saviano, C.Isernia, D.Montesarchio, L.De Napoli & G.Piccialli “?Amino Acid Residues: Synthesis and Conformational Characterization of N- and C-protected homo-?-(S)-leucine” LIPS (1997), 4, 129-134. L.D.D’Andrea, M.Mazzeo, C.Isernia, F.Rossi, M.Saviano, L.Paolillo & C.Pedone “Solution Conformational Preferences of a Peptidomimetic Analogue of FK506” Biopolymers (1997), 42, 349-361. F. Rossi, M. Saviano, P. Di Talia, B. Di Blasio, C. Pedone, G. Zanotti, M. Mosca, G. Saviano, T. Tancredi, K. Ziegler, E. Benedetti: “Solution and Solid State Structure of an Aib-containing Cyclodecapeptide Inhibiting the Cholate Uptake in Hepatocytes”Biopolymers, (1997)40,465-478. B. Botta, G. Delle Monache, M.C. De Rosa, C. Seri, E. Benedetti, R. Iacovino, M. Botta, F. Corelli, V. Masignani, A Tafi, E. Gacs-Baitz, A. Santini, D. Misiti: “Synthesis of C-Alkylcalix[4]arenes. 5. Design, Synthesis, Computational Studies and Homodimerization of Polymethylene-Bridged Resorc[4]arenes” J. Org.Chem., (1997) 62, 1788-1794. M.Gatos, F. Formaggio, M. Crisma, G.M. Bonora, E. Benedetti, B. Di Blasio, R. Iacovino, , A. Santini, M. Saviano, J. Kamphuis:"Conformational characterization of the 1-Aminocyclobutane-1-carboxylic Acid Residue in Model Peptides" J. Pept. Sci, (1997) 3, 110-122. M.Crisma, F. Formaggio, G.Valle, C.Toniolo, M. Saviano, R. Iacovino, L. Zaccaro, E. Benedetti: “Experimental evidence at atomic resolution for intramolecular NH… π (Phenyl) interactions in a family of amino acid derivatives” Biopolymers, (1997) 42, 1-6. L .De Napoli, A. Messere, D. Montesarchio, G. Piccialli, M. Varra:” 6-Chloroxanthosine as useful intermediate for efficient syntheses of [6-15N] Isoguanosine, Isoinosine and other purine nucleoside analogues” Nucleosides and Nucleotides, 16 (1&2: 183 (1997). L. De Napoli, A. Messere, D. Montesarchio, G. Piccialli and M. Varra:”1-Substituted 2’-deoxyinosine analogues” J. Chem.Soc.Perkin Trans. I , (1997). 2079 220 L. De Napoli, A. Messere, D. Montesarchio, A. Pepe, G. Piccialli, and M. Varra” Synthesis and triple helix formation by alternate strand recognition of oligonucleotides containing 3’-3’ phosphodiester bonds” J. Org: Chem., (1997).62, n.26: 9024. M. Goodman, Q. Zhu, D. Kent, Y. Amino, R. Iacovino, E. Benedetti, A. Santini: “Conformational Analysis of a Dipeptide Taste Ligand L-Aspartyl-D-2 aminobutyric acid-(S)-???ethylbenzylamide and its Analogs by NMR Spectroscopy, Computer Simulations and X-ray Diffraction Studies”.J.Pept.Sci., (1997) 3, 231-241 E. Benedetti, B. Di Blasio, R. Iacovino, V. Menchise, M. Saviano, C. Pedone, G.M. Bonora, A. Ettorre, L. α α Graci, F. Formaggio, M. Crisma, G. Valle, C. Toniolo: "Conformational restriction through C i ↔ C i cyclization: 1-aminocycloheptane-1-carboxylic acid (Ac7c)"J. Chem. Soc., Perkin Trans. 2, (1997) 2023-2032. M. Gatos, F. Formaggio, M. Crisma, G. Valle, C. Toniolo, G.M. Bonora, M. Saviano, R. Iacovino, V. Menchise, S. Galdiero, C. Pedone and E. Benedetti: "Conformational characterization of peptides rich in the α,α cycloaliphatic C -disubstituted glycine 1-amino-cyclononane-1-carboxylic acid". J. Pept. Sci., (1997)3, 367382. Casola, S., Pedone, P. V., Cavazzana, A. O., Basso, G., Luksch, R., d’Amore, E. S. G., Carli, M., Bruni, C. B. and Riccio, A.. “Expression and parental imprinting of the H19 gene in human rhabdomyosarcoma”. Oncogene, (1997) 14, 1503-10. Omichinski, J. G., Pedone, P. V., Felsenfeld, G., Gronenborn, A. M. and Clore, G. M.. “The solution structure of a specific GAGA factor/DNA complex reveals a new twist in classical zinc finger/DNA recognition”. Nature Struct. Biol., (1997) 4, 122-30. Pedone, P. V., Omichinski, J. G., Nony, P., Trainor, C., Gronenborn, A. M., Clore, G. M. and Felsenfeld, G.. “The Nterminal fingers of cGATA-2 and cGATA-3 are independent sequence-specific DNA binding domains”. EMBO J. (1997) 16, 2874-2882. Ungaro, P., Casola, S., Vernucci, M., Pedone, P.V., Bruni, C.B. and Riccio, A.. "Relaxation of Insulin-like Growth Factor-2 imprinting in rat cultured cells" Mol. Cell. Endocrinol., (1997) 135, 153-163. 1998 S. De Luca, G. Bruno, R. Fattorusso, C. Isernia, C. Pedone and G. Morelli, " New synthetic tools for peptidetetraphenylporphyrin derivatives", Letters in Peptide Science (1998), 5, 269-276. E. Benedetti, C. Isernia, F. Nastri, C. Pedone, M. Saviano, D. F. Mierke, P. Melchiorri, L. Negri, R. L. Potenza, C. Severini and V. Erspamer, " Conformational Analysis by NMR and Distance-Geometry Techniques of Deltorphin Analogs", Eur. J. Org. Chem. (1998), 2279-2287. M. Pellecchia, R. Fattorusso and G. Wider, “Determination of the Dihedral Angle Based on J Coupling Measurements in 15N/13C-Labeled Proteins”, J. Am. Che. Soc., (1998), 120, 6824-25. M. Martino, A. Bavoso, M.Saviano, B.Di Blasio, A. M. Tamburro; ” Structure and dynamics of elastin building blocks Boc-LG-OEt, Boc-VGG-OH” J. Biomol. Struct. Dyn. (1998) 14, 861-75. G. Bruno, S. De Luca, C. Isernia, R. Fattorusso, F. Rossi, C. Pedone and G. Morelli, "New substituted tetraphenylporphyrins": Synthesis, NMR Characterization and Mn(III) and Fe (III) complexes", J. Chem. Res. (S) (1998), 18-19, (M) 214-230. R. Fattorusso, C. De Pasquale, G. Morelli, C. Pedone, “ Hemoprotein Models based on a Covalent Helix-Heme-Helix Sandwich 4. Discrimination of Paramagnetic Fe (III)-Mimochrome I ? and ? Isomers by NMR Spectroscopy” Inorganica Chimica Acta, (1998), 278, 76-82. E. Benedetti, R. Iacovino, M. Saviano: “The use of uncoded α-amino acids residues in drug design”. P.W. Codding (ed.), Structure-Based Drug Design. 103-112. 1998 Kluwer Academic Publishers. Printed in the Netherlands. 221 M. Goodman, R-H. Mattern, A. Santini, R. Iacovino, M. Saviano, E. Benedetti,:“X-ray Structures of New Dipeptide Taste Ligands” J.Pept.Sci., (1998).4, 229-238 S. Benedetti, R. Iacovino, F. Rossi, M. Saviano: “Crystall structure of benzyloxycarbonyl-1-aminocyclopropan-1carboxylic acid N-(2,2,5,5,-tetramethylcylopentanyl) amide, C21H30N2O3” Zeitschrift fur Kristallographie- New Crystal Structures, (1998).2131-2 B. Pengo, F. Formaggio, M. Crisma, C. Toniolo, G.M. Bonora, Q. B. Broxterman, J. Kamphuis, M. Saviano, R. Iacovino, F. Rossi, E. Benedetti: “Linear oligopeptides. Part 406. 1 Helical screw sense of peptide molecules. the pentapeptide system (Aib)4\L-Val[L-(αMe)Val] in solution”J. Chem. Soc. Perkin Trans. 2 (1998), 1651-1657. E. Benedetti, M. Saviano, R. Iacovino, C. Pedone, A. Santini, M. Crisma, F.Formaggio, C. Toniolo, Q. B. Broxterman, J. Kamphuis: “Helical screw sense of peptide molecules: the pentapeptide system (Aib)4\L-Val [L-(αMe)Val] in the crystal state” Biopolymers (1998) 46, 433-443. L. De Napoli, G. Di Fabio, A. Messere, D. Montesarchio, G. Piccialli, M. Varra “A facile solid phase synthesis of oligonucleotides containing a 3’-3’ phosphodiester bond for alternate strand triple helix formation” Europ. J. Org. Chem (1998). 2119 I.F.2.300 L De Napoli, G. Di Fabio, A. Messere, D. Montesarchio, G .Piccialli, M. Varra ” A new synthesis of Oxanosine and 2’-Deoxyoxanosine” Tetrahedron Letters, 39: 7397 (1998). I.F.2.400 L. De Napoli, A. Galeone, L. Mayol, A. Messere, D. Montesarchio, A. Pepe, G. Piccialli “ Studies on alternate strand triple helix formation by oligodeoxyribonucleotides containing a 3’-3’ phosphodiester bond” Nucleosides and Nucleotides, (1998). 17, (9-11): 1709 1999 M. Saviano, R. Iacovino, E. Benedetti, V. Cucinotta, G. Grasso and D. Sciotto: “Crystal structure of 6,6’-ditosyl-α-α’trehalose-methanol-water (1/2/2), C52H68O30S4.2CH3OH.2H2O” Kristallogr. NCS, , (1999) 214, 297-299. L. De Napoli, R. Iacovino, A. Messere, D. Montesarchio, G. Piccialli, A. Romanelli, F. Ruffo and M. Saviano: “Synthesis of platinum (II) complex of thymidine and 1-methyl-thymine (1-MeThy); crystal structure of cis-[PtCl(1MeThy)-(PPh3)2]” J. Chem. Soc., Dalton Trans., (1999).1945-1949. C. Isernia, E. Bucci, L. De Napoli, P. Di Lello, R. Iacovino, D. Montesarchio, G. Piccialli, F. Rossi, M. Saviano and E. Benedetti, "Homo-??amino Acid Residues: Synthesis And Conformation Of New Dipeptides Taste Ligands", J. Phys. Org. Chem. (1999) 12, 1-11. R. Fattorusso, M. Pellecchia, F. Viti, P. Neri, D. Neri and K. Wüthrich, “NMR structure of the human oncofoetal fibronectin ED-B domain, a specific marker for angiogenesis”, Structure (1999), 7, 381-390. Pedone, P. V., Pikaart, M. J., Cerrato, F., Vernucci, M., Ungaro, P., Bruni, C. B. and Riccio, A.. “Role of histone acetylation and DNA methylation in the maintenance of the imprinted expression of the H19 and Igf2 genes”. FEBS Letters, (1999) 458, 45-50. L. De Napoli, G. Di Fabio, A. Messere, D. Montesarchio, G. Piccialli, M. Varra “Synthetic studies on the glycosylationof the base residues of inosine and uridine “ J. Chem.Soc.Perkin Trans. I (1999)., 3489-3493. E. Bucci, L. De Napoli, G. Di Fabio, A. Messere, D. Montesarchio, A. Romanelli, G. Piccialli, M. Varra “A new ferrocenemethyl-thymidine: synthesis, incorporation into oligonucleotides and optical spectroscopic studies on the resulting single strand, duplex and triplex structures” Tetrahedron., (1999).55: 14435-14450. L De Napoli, A. Messere, D. Montesarchio, G. Piccialli, E. Benedetti, E. Bucci, F. Rossi “A new solid-phase synthesis of oligonucleotides 3’-conjugated with peptides “Bioorg. & Med. Chem., (1999) 7: 395. L. De Napoli, G .Di Fabio, A. Messere, D .Montesarchio, D. Musumeci, G. Piccialli “New 3’-3’ linkers for alternate strand triplex forming oligonucleotides” Nucleosides and Nucleotides, (1999) 18, (6 & 7): 1639. 222 L. De Napoli, G. Di Fabio, A. Messere, D. Montesarchio, D. Musumeci, G. Piccialli” Synthesis and characterization of new 3’-3’ linked oligodeoxyribonucleotides for alternate strand triple helix formation” Tetrahedron, (1999) 55: 9899. 2000 Sperandeo, M.P., Ungaro, P., Vernucci, M., Pedone, P. V., Cerrato, F., Perone, L., Casola, S., Cubellis, M. V., Bruni, C. B., Andria, G., Sebastio, G. and Riccio, A. “Relaxation of Insulin-like Growth Factor 2 imprinting and discordant methylation at KvDMR1 in two first-cousins affected by Beckwith-Wiedmann and Klippel-Trenaunay-Weber syndromes” Am. J. Hum. Genet. (2000) 66 (3):841-7. Vernucci, M., Cerrato, F., Besnard, N., Casola, S., Pedone, P.V., C.B. and Riccio, A.. "The H19 endodermal enhancer is required for Igf2 activation and tumor formation in experimental liver carcinogenesis" Oncogene (2000) 19,. 63766385. F. Rossi, E. Bucci, C. Isernia, M. Saviano, R. Iacovino, A. Romanelli, P. Di Lello, M. Grimaldi, D. Montesarchio, L. De Napoli, G. Piccialli, and E. Benedetti, "Effect Of Lengthening Of peptide backbone By Insertion Of Chiral Homo-?Amino Acid Residue. Conformational Behaviour Of Linear Peptides Containing Alternating L-Leucine And -homo-?L-Leucine Residues", Biopolymers (2000) 53, 140-149 M. Saviano, C. Isernia, F. Rossi , B. Di Blasio, R. Iacovino, M. Mazzeo, C. Pedone & E. Benedetti "Solid state structural analysis of the cyclooctapeptide cyclo(Pro1-Pro-Phe-Phe-Ac6c-Ile-D-Ala-Val8)", Biopolymers (2000). 53, 189-199 G. Aliotta, G. Cafiero, V. De Feo, B. Di Blasio, R. Iacovino, A. Oliva. “Allelochemicals from Rue (Ruta graveolens L.) and Olive (Olea europea L.) oil mill waste waters as potential natural pesticide” Current Topics in Phytochemistry, (2000) 3, 167-177. G. Impellizzeri, G. Pappalardo, F. D’Alessandro, E. Rizzarelli, M. Saviano, R. Iacovino, E. Benedetti, and C. Pedone: “Solid state and solution conformation od 6-{4-[N-tert-Butoxycarbonyl-N-(N’-ethylpropanamide]imidazolyl}-6deoxycyclomaltoheptaose: evidence of self-inclusion of the boc group within the β-Cyclodextrin cavity” Eur. J. Org. Chem. (2000) 1065-1076. M. Saviano, R. Iacovino, V. Menchise, E. Benedetti, G.M. Bonora, M. Gatos, L. Graci, F. Formaggio, M. Crisma & C. ? ? Toniolo "Conformational Restriction through Ci ↔Ci Cyclization: Ac12c, the Largest Cycloaliphatic ???? C ???Disubstituted Glycine Known", Biopolymers (2000), 53, 200-212. E. Benedetti, M. Saviano, V. Menchise, R. Iacovino, M. Crisma, F. Formaggio, A. Moretto and C. Toniolo: "Peptide folding as a result of the incorporation of large-ring, cycloaliphatic C??? disubstituted glycines" In Pept. New Millennium, Proc. Am. Pept. Symp., 16th (2000), Meeting Date 1999, 275-276 M. Saviano, R. Iacovino, E. Benedetti, V. Moretto, A. Banzato, F. Formaggio, M. Crisma, C. Toniolo “Preferred conformation of peptides based on cycloaliphatic C?,?-disubstituted glycines: 1-amino-cycloundecane-1-carboxylic acid (Ac11c).“ J. Pept. Sci. (2000), 6(11), 571-583. L. De Napoli, S. De Luca, G. Di Fabio, A. Messere, D. Montesarchio, G. Morelli, G. Piccialli, D. Tesauro “A facile solid phase strategy for the synthesis of oligonucleotide–tetraphenylprphyrin conjugate” Eur. J. Org. Chem, (2000) 1013-1018. L. De Napoli, A. Messere, D. Palomba, G. Piccialli, G. Piccialli, A. Evidente ”Studies Toward the Synthesis of Pinolidoxin, a Phitotoxic Nonelolide from the Fungus Ascocyta pinodes. Determination of the Configuration at the C-7, C-8 and C-9 chiral Centres and stereoselective Synthesis of C6-C18 Fragment.” J. Org. Chem, (2000) 65: 3432-3442. A. De Capua, L. De Napoli, G. Di Fabio, A. Messere, D. Montesarchio, G. Piccialli “Glycosylation of Inosine and Uridine Nucleoside Bases and Synthesis oh the new 1-(β-D- Glucopyranosyl)-Inosine-5’,6’-Diphosphate” Nucleosides and Nucleotides, (2000) 19 (8): 1289-1299. 2001 223 A. Romanelli, I. Garella, V. Menchise, R. Iacovino, M. Saviano, D. Montesarchio, C. Didierjean, P. Di Lello, F. Rossi, E. Benedetti. “Crystal-state conformation of C???-dialkylated peptides containing chiral ?-homo-residues”. J. Pept. Sci. (2001), 7(1), 15-26. C. Peggion, F. Formaggio, M. Crisma, C. Toniolo, J. Kamphuis, B. Kaptein, Q. N. Broxterman, R.M. Vitale, R. Iacovino, M. Saviano, E. Benedetti. “C?-Methyl,C?-allylglycine (Mag) Homooligomers”. Macromolecules (2001), 34, 4263-4269. A. Moretto, F. Formaggio, M. Crisma, C. Toniolo, M. Saviano, R. Iacovino, R.M.Vitale, E. Benedetti “ Ac10c: a medium-ring, cycloaliphatic C??? disubstituted glycine. Incorporation into model peptides and preferred conformation” J. Pept. Res.,(2001) 57, , 307-315. S. De Luca, D. Tesauro, P. Di Lello, R. Fattorusso, M. Saviano, C. Pedone, G. Morelli. “Synthesis and solution characterization of a porphyrin-CCK8 conjugate”. J Pept Sci (2001) 7, 386-94. M. Saviano, E. Benedetti, B. Di Blasio, E. Gavuzzo, O. Fierro, C. Pedone, R. Iacovino, E. Rizzarelli, G. Vecchio: “Difunctionalized ?-cyclodextrins:synthesis and X-ray diffraction structure of 6I,6II-dideoxy-6I,6II-bis[2-(2pyridyl)ethylamoni]-?-cyclomaltoheptaose ” J. Chem. Soc. Perkin Trans.2, 6, 946-952 (2001). C. Toniolo , M. Crisma, F. Formaggio, C. Peggion, Q. B. Broxterman, B. Kaptein, H. E. Schoemaker, F. P.J.T. Rutjes, J. J.N. Veerman, R. M. Vitale, E. Benedetti and M.e Saviano “Allyl-based, C-Methylated –Amino acids in the sidechain to side chain ring g-closing metathesis reaction of-turn/310-helical peptides. Abstract American Peptide Society (2001) Appendix 3 Journal Portfolio Analysis Name of the Unit: Research Director: Years included Caserta 1 Benedetto Di Blasio 1993-1997 Name of Journal JACS Number Articles 1 Mol. Cell. Endocrinol J. Chem. Soc. Perkin Trans. 1 1 2 Biopolymers Macromolecules J. Pept. Sci LIPS J. Org. Chem. Nucleosides and Nucleotides Oncogene EMBO J. Tetrahedron Letters Tetrahedron J. Chem. Soc. Dalton Trans. Bioorg. & Med. Chem. J. Chem. Soc. Perkin Trans. 2 Other 7 1 7 2 3 4 2 1 1 2 1 1 2 14 of Journal Factor 5.948 Impact Field(s) Ranking Chemistry 5/110 1.874 1.799 Chemistry, Analytical Chem Org. 13/54 14/37 2.331 3.534 1.311 0.700 3.722 0.798 6.517 13.973 2.497 2.232 2.310 1.791 1.929 Chem Org Chem Org Chem Org Chem Org Chem Org Chem Org Chem Org Chem Org Org. Chem. Org. Chem. Chem Org Bioorg. Chem. Applird 5/37 8/37 11/37 4/32 224 CATANIA CATANIA 2 Name of the Research Unit Gruppo di Fotochimica Group of Photochemistry University: Universita’ degli Studi di Catania University of Catania Faculty: Facolta’ di Scienze Matematiche Fisiche e Naturali e Facoltà di Farmacia Faculty of Mathematical, Physical and Natural Sciences and Faculty of Pharmacy Department: Dipartimento di Scienze Chimiche Department of Chemical Sciences Thematic area Research Leader Prof. Giuseppe Condorelli Contact Person Giuseppe Condorelli Dipartimento di Scienze Chimiche, Università di Catania V.le A.Doria, 6 95125 Catania, Italy Phone: +39 95 334674 Fax: 39 95 580138 E-mail: [email protected] Please indicate to which thematic area of INCA the unit belong (in priority order): 1.Chimica degli ecosistemi (chimica del suolo, delle acque e dell’aria; impatto dei prodotti di sintesi sull’ambiente). 2.Sintesi ecosostenibili (solventi, fotochimica, catalisi, riciclo e altre). 3.Tecnologie di depurazione (membrane, sonochimica, fotocatalisi, elettrochimica e altre). Introduction and Context Introduction to the Self-evaluation Report The Unit, that is actually coincident with the research team Photochemistry of the Department of Chemical Sciences of the University of Catania, is located in an area that is defined by the EU a depressed area; in fact, the once flourishing industrial basin is steadily declining. The team, put together more then ten years ago, is constituted by members belonging to the area of General and Inorganic Chemistry of the Faculties of Pharmacy and of Sciences. In the past the team focused his attention on the photoreactivity of organometallic compounds but, since the beginning of 1990, the research has been shifted towards the photoreactivity of drugs. The Department provides all the experimental equipment. The research group does not have any administrative personnel; consequently, the vast majority of administrative matters (e.g. the compilation of the present forms) is dealt with by the people listed in Section 4. The University, the Faculty and the Department The University of Catania (www.unict.it) was founded in 1434 as a Studium Generale, Catania. It is today the 9th University in Italy, as far as student population is concerned. The University serves mainly five districts (Catania, Enna, Caltanissetta, Siracusa and Ragusa). The high percentage of students coming from districts other than Catania’s prompted the opening of new Laurea and Diploma courses in towns located in the vicinity of Catania (Siracusa, Ragusa, Enna, Caltagirone, Giarre). The University of Catania is the 2nd University in Italy that filed a report for the Quality Audit Programme of the Conference of European Rectors. The University of Catania was also one of the first Universities that joined INCA. The University of Catania is also well connected with other Italian Universities; in fact, a School of Excellence has recently been promoted as a part of a national network. 225 The University has some 29 departments and 3 research centres which are arranged in twelve faculties (namely Agricultural Sciences, Architecture, Arts and Philosophy, Economics, Engineering, Foreign Languages and Literature, Law, Mathematical, Physical and Natural Sciences, Medicine and Surgery, Pedagogical Sciences, Pharmacy, and Political Sciences). Students: The total number of the students (Academic Year 2000-2001) is 53030; out of these 5652 are enrolled in Courses offered by the Faculty of Mathematical, Physical and Natural Sciences and 2000 are enrolled in Courses offered by the Faculty of Pharmacy. Faculty and Staff members: The University of Catania comprises a total of 1506 faculty staff members. 316 of them belong to the Faculty of Mathematical, Physical and Natural Sciences and 68 belong to the Faculty of Pharmacy. Department: The Department of Chemical Sciences (www.unict.it/dipchi/) is the largest Department of the University of Catania in terms of both faculty and staff members with a total of 87 Professors and Researchers; the Department has a total of 27 technicians and administrative personnel. The research activities of the Department cover all the most important areas of chemistry. The Department is involved in several EU projects, in cooperative projects with national and international institutions and is strictly linked to the main local industries. The Department supports the research groups through its technical and administrative services, providing sophisticated equipment and an updated library. A detailed Activity Report of the Department for the period 2000-2001 may be found in (http://www.unict.it/psmfn/Department_of_Chemical_Sciences.htm). The Unit The Unit of INCA directed by Professor Giuseppe Condorelli is actually composed by 3 Full Professors: Prof. Giuseppe Condorelli, Prof. Lucia Laura Costanzo, Prof. Salvatore Giuffrida 1 Associated Profesor: Prof. Guido De Guidi 1 Researcher: Dr. Salvatore Sortino 3 Ph.D Students: Mrs Alessandra Belvedere, Mr. Salvatore Petralia, Mr. Stefano Torrisi A variable number of undergraduate students. Teaching load: The members of the unit teach several courses. Professor Condorelli: Environmental Chemistry for Pharmacy Degree Environmental Chemistry for Pharmacy Short Degree Bioinorganic Chemistry for Pharmacy Degree; Photochemistry (Advanced Course) for PhD Course. Professor Costanzo: General and Inorganic Chemistry for Biology Degree. Photochemistry (Advanced Course) for PhD Course. Professor Giuffrida: General and Inorganic Chemistry for Geology Degree; Chemistry Short Degree Advanced Inorganic Chemistry for Chemistry Degree. Prof. De Guidi: General and Inorganic Chemistry for Biology Degree. General and Inorganic Chemistry for Agricultural Sciences Photochemistry (Advanced Course) for PhD Course Dr. Sortino: Principle of General and Inorganic Chemistry for Pharmacy Short Degree 1 Principle of General and Inorganic Chemistry for Pharmacy Short Degree 2 Radiochemistry for Pharmacy Degree Photochemistry (Advanced Course) for PhD Course 226 Programme Description and Evaluation 1 Title Molecular mechanisms of photosensitization induced by drugs on biological systems and design of photoprotective systems. 2 Research Leader Professor Giuseppe Condorelli 2a Sub-programme titles and sub-programme leaders 3 Composition of the scientific research staff of the unit per 1 January 2002 Names and Titles Year of Rank Birth Prof. Giuseppe Condorelli Prof. Lucia Laura Costanzo Prof. Salvatore Giuffrida 1930 1935 1946 Prof. Guido De Guidi 1956 Dr. Salvatore Sortino Mrs Alessandra Belvedere Dr. Salvatore Petralia Dr. Stefano Torrisi 1966 1973 1973 1975 Full Prof. Full Prof. Associated Prof. Associated Prof. Researcher Ph. D Ph. D Ph. D Research Input in fte in 2001 0.4 0.4 0.4 Remarks 0.4 0.8 1 1 1 Comments Major changes in the previous five years: Dr. De Guidi has become Associated Professor; his previous position was Researcher In the following five years the major changes in the Unit should be: Dr. Sortino has applied for an Associate Professor position 4 Input of Academic Staff in fte Category Full Professors Associated Professors Ricercatori Post-docs PhD-students Borsisti Total 1997 0.8 0.4 1.5 2.7 1998 0.8 0.8 0.8 1999 0.8 0.8 0.8 2000 0.8 0.8 0.8 2001 0.8 0.8 0.8 Total 4.0 3.6 4.7 2 3 3 3 11 4.4 5.4 5.4 5.4 23.3 Comments The trend in size of the Photochemistry team of the Department of Chemistry of the University of Catania is constant since 1999 due to the simultaneous presence of three Ph.D students. 5 Funding 5.1 Personnel (in fte) Source University 1997 2.7 1998 4.4 1999 4.4 2000 3.4 2001 3.4 Total 18.3 227 CNR European Union Other Sponsors Total 5.2 2.7 2 2 5 5.4 5.4 5.4 23.3 1999 143.3 2000 46.0 5.0 2001 160.0 Total 404.1 12.0 90.9 38.0 56.0 (Ist. Sup. (Ist. Sup. (Ist. Sup. Sanità) Sanità) Sanità) 400.0 (INCA 488/96) 12.5 (INCA) 105.9 181.3 519.5 160.0 597.4 4.4 Materials and Equipment (in Million Lire) Source University - MURST CNR EU Other Sponsors 1997 39.8 7.0 Total 46.8 5.3 1 1998 15.0 1013.5 Comments: • On the figures The majority of the staff is paid by the University and is permanent; the University and the EU support Ph.D. students. No administrative personnel works specifically for the group; this forces the academic staff to take care of administrative matters, since the department administrative personnel is not enough to take care of research groups. * On the funding policy In the last year, a remarkable financial support by the Istituto Superiore di Sanità on the subject of “drugs photostability” was an input for a further shift of the research a more practical aspect. This financial support was renewed for 1998 and 2000. 6. Progress Report 6.1 Progress analysis The research unit has focused the attention on the sunlight impact on xenobiotic substances such as drugs, cosmetics, industrial products and so on can create serious environmental problems with consequent dangerous effects on living matter. The attention of the unit has been mainly focused to the light action on the drugs after therapeutic administration. The photophysical, photochemical and photosensitization properties of drugs belonging to different pharmacological classes such as non-steroidal antiinflammatory, antibacterial fluoroquinolones, anticancers and vasoregulators have been extensively studied in details. These studies have been addressed to the clarification of the molecular mechanisms involved in the processes induced upon sunlight absorption by these compounds and to the development of suitable photoprotective systems able to improve the drug photostability and to reduce the drugphotoinduced toxic effects. Particular attention has been devoted to the study of the drug photobehavior in real biological systems such as proteins and DNA and biological mimicking systems such as cyclodextrins, micellar aggregates and vescicual systems. These investigation have been motivated by the fact that the drug phototoxicity is often not correlated to the photophysical and photochemical properties of the drug in homogeneous solution. Actually, shape, charge, size, hydrophobicity and geometry of the photosensitizer are some of the parameters that can lead to the formation of supramolecular aggregates with the biological substrates. The photochemical behavior of these supramolecules has been observed to be frequently fairly different if compared to that of the free molecule. Therefore, a stepwise or sequential approach consisting in investigating the drug photobehavior in increasing complexity media has represented an ideal strategy for a better correlation between drug photochemistry and phototoxicity. Moreover, the investigation on the drug photoreactivity in micromedia with particular polarity features and in the presence of steric constraints or specific interactions, apart contributing to the understanding of the photoreactivity in a native biological system has provided useful knowledge for the development of photoprotective devices addressed to improve the drug photostability and to reduce the amount of the light-induced toxic effects. Thus, these studies, performed by combining 228 steady state and time resolved spectroscopic techniques, have allowed to delucidate of the factors influencing the molecular reactivity of almost all the drugs investigated in order to get control of it. 6.2 Position within INCA The Unit has collaborated with the Pavia Unit and, at the present, a new collaboration with the Unit of Lecce directed by Prof. Ludovico Valli has been created. The goal of this new collaboration is the development of new optical sensors for gas molecule. 6.3 Key Publications S. Monti, S. Sortino, E. Fasani and A. Albini, Multifaceted photoreactivity of 6-fluoro-7-aminoquinolones from the lowest excited states in aqueous media: a study by nanosecond and picosecond spectroscopic techniques Chem. Eur. J. 7, 2001, 2185-2196. S. Sortino, G. Marconi and G. Condorelli, New insight on the photoreactivity of the phototoxic anti-cancer flutamide: photochemical pathways selectively locked and unlocked by structural changes upon drug compartmentalization in phospholipid bilayer vesicles, Chem. Comm. 2001, 1226-1227 S. Sortino, J. C. Scaiano, G. De Guidi and L.L. Costanzo, Copper (II) in the part per million range, modulates photochemical and photosensitizing properties of tolmetin via electron transfer with a triplet carbanion Chem. Comm. 19 (1999) 2003-2004 S. Sortino, J.C. Scaiano and G. Condorelli, Transient photochemistry of diflunisal: photoejection and trapping of hydrated electrons leading to the formation of phenoxy radicals, photostimulated defluorination and cross combination reaction. J. Phys. Chem. B 103 (1999) 9279-9284. S. Sortino, S. Giuffrida and J.C. Scaiano, Phototoxicity of naphazoline. Evidence that hydrated electrons, nitrogen centered radicals and OH radicals trigger DNA damage: a combined photocleavage and laser flash photolysis study. Chem Res. Toxicol. 12 (1999) 971-978. 7. Scientific Output 7.1 Publication Policy The research carried out by the team, has offered the possibility to publish on both fundamental research and specialist scientific journals. 7.2 Numerical data Category PhD-Dissertations 1997 1 1998 1999 2000 2 2001 Total 3 Scientific Publications 4 6 12 5 8 35 Professional Publications Master’s Theses 2 2 6 2 4 16 Please give a quantitative summary of the publication list, presented under Sections 7.3 -7.5 and elaborate on the selection criteria used for the overviews 229 8 Self-evaluation The Unity of Catania, has acquired a considerable experience in several fields of photochemistry and in particular on the molecular mechanisms of drug photodegradation and photosensitization and in the design of photoprotective systems. On the basis of its expertize the Unit has participated fruitfully to three projects financed by the National Institute for Pubblic Health (Istituto Superiore di Sanità) on "Chemical-physical properties of drugs and their safety use" with an item regarding "drug photostability and photoreactivity" and two projects financed by MURST on Drug photochemistry in Organized media. Some of the components of the team have spent time to work in other scientific institutions and this has been the occasion to initiate fruitful scientific collaborations. The main national and international institution to which the unit collaborate with are listed below: Istituto per la Sintesi Organica e la Fotoreattività CNR of Bologna (Dr. S. Monti, G. Marconi) Dipartimento di Tecnologie Farmaceutiche dell'Università di Palermo (Prof. G. Giammona) Dipartimento di Chimica Organica dell'Università di Pavia (Prof. A. Albini) Dipartimento di Chimica Organica dell'Università di Genova (Prof. A. Bargagna) Departamento de Quimica/Instituto de Tecnologia Quimica UPV-CSIC, Universidad Politecnica Valencia (Spain) (Prof. M.A. Miranda) Department of Chemistry University of Ottawa (Canada) (Prof. J.C. Scaiano) - Deparment of Chemistry at Union College Schenectady, New York (USA)(Dr. L.J. Martinez) Max-Plank Institute fur Stralenkemie, Muhlheim (Dr. S. Braslawsky) The clearness of the research goals, which can contribute to solve some problems of the community, the good agreement between goals and acquired experience, the concentration of the whole skills directed to obtain the maximum result along with the presence of young people in the group represent the main positive aspects of the team. On the other hand, the main weakening are represented by the small dimension of the group, the inadequate technicaladministrative support provided from the Department structure, the lack of adequate financial support, the excess of didactic charge, the hard bureaucratic and institutional charges in which some group members are involved. Appendix I Scientific Output I-1 Overview of Dissertations and Master's Thesis (1997-2001) I.1.1 Dissertations Year Name PhD-student I.1.2 Master's Thesis Year 1997 PhD-student Paolo Miano 2000 Alberto Velardita 2000 Gabriella Salemi I.1.2 Master’s Thesis Title of the Dissertation Supervisor Title of the Dissertation Molecular mechanisms of photosensitization induced by xenobiotic agents DNA. Molecular mechanisms of photosensitization induced by drugs on membranes and DNA Photoprotective effects of particellar systems towards photodegradation and photosensitization effects induced by drugs Supervisor Prof. S.Giuffrida Prof. G. Condorelli Prof. G. Condorelli 230 Year 1997 Student Maria Concetta Curcuruto 1997 Tiziana Tramontana 1998 Francesco Rametta 1998 1999 Valeria Scalora Stefania Romeo 1999 Costanza Bellecci 1999 Alessandra Belvedere 1999 Chiara Messina 1999 Mario Mancini 1999 Sandro Fazio 2000 Salvatore Petralia 2000 Stefano Torrisi 2001 Marcello Riolo 2001 Salvatore Beffumo 2001 Elena Solfato 2001 Alfio Catalfo I-2 Title of the Dissertation Study on the interaction non steroidal antiinflammatory drugs-DNA by differential scan calorimetry and photoinduced cleavage. Molecular mechanisms induced by Enoxacin on DNA. Photodegradation of Rufloxacin in aqueous medium The photochemistry of Flutamide Molecular mechanisms of photodegradation and photosensitization of Naphazoline Photosensitization processes induced by Rufloxacin The photochemistry of Diflunisan in aqueous solution and in micellare systems Effects of Copper(II) on the photochemical anc photosensitization processes of tolmetin Machanisms of photochemical reactions in Copper-DNA complexes Influence of the cyclodextrin microenvironment on the photophysical and photochemical processes of non.steroidal anti-inflammatory drugs The photochemistry of Flutamide in cyclodextrin cavities and micellare systems Effects of phosphate ions on the deactivation of the lowest excited states of enoxacin Photoprotective effects of anionic micelles on the photodegradation of lomefloxacin Fluorescence polarization, quenching, energy transfer and photodegradation of the complex albumin-diflunisal Mechanisms of guanine selective oxidation photosensitised by rufloxacin Photosensitized generation of 8-idroxy2’-deoxiguanosine in the oxidative damage of DNA induced by rufloxacin Supervisor Prof. G.De Guidi Prof. G.De Guidi Prof. S. Giuffrida Prof. S. Giuffrida Prof. S. Giuffrida Prof. S. Giuffrida Prof. S. Giuffrida Dr. S. Sortino Prof. L.L. Costanzo Dr. S. Sortino Prof. G. De Guidi Prof. S. Giuffrida Dr. S. Sortino Prof. S. Giuffrida Dr. S. Sortino Prof. S. Giuffrida Dr. S. Sortino Prof. S. Giuffrida Dr. S. Sortino Prof. S. Giuffrida Dr. S. Sortino Prof. G. De Guidi Prof. G. De Guidi Overview of Scientific Publications (1997-2001) per year 1997 1.S.Monti, S.Sortino, G.De Guidi and G.Marconi, Photochemistry of 2-(3-benzoylphenyl)propionic acid (ketoprofen).Part 1. A picosecond and nanosecond time resolved study in aqueous solution, , J.Chem.Soc., Faraday Trans., 93 (1997) 2269-2275. 2.G.Giammona, G.Pitarresi, V.Tomarchio, G.De Guidi and S.Giuffrida, Swellable microparticles containing Suprofen: evaluation of in vitro release and photochemical behaviour, J.Contr.Release (1997) 231 3.G.Condorelli, G.De Guidi, S.Giuffrida, S.Monti, S.Sortino and A.Velardita, A comparative study of photosensitizing activity of four fluoroquinolones: Clinafloxacin, Enoxacin, Ofloxacin and Orbifloxacin, . Photochem. Photobiol. 65S (1997) 75-76 4.L.L.Costanzo, G.De Guidi, S.Giuffrida, S.Monti, S.Sortino and A.Velardita, Photochemical and photophysical study of Enoxacin in aqueous solution, . Photochem. Photobiol. 65S (1997) 22. 1998 1.S.Monti, S.Sortino, G.De Guidi and G.Marconi, Supramolecular photochemistry of 2-(3benzoylphenyl)propionic acid (Ketoprofen). A study in the β-cyclodextrin cavity New J. Chem. (1998) 599604. 2.S.Sortino, G.De Guidi, S.Giuffrida, S.Monti and A.Velardita, pH effect on the spectroscopic and photochemical behavior of enoxacin: a steady state and time resolved study Photochem. Photobiol. 67 (1998) 167-173 3.S.Sortino, G.De Guidi, G.Marconi and S.Monti, Triplet photochemistry of suprofen in aqueous environment and in the ??cyclodextrin inclusion complex., Photochem. Photobiol. 67 (1998) 603-611. 4.S.Sortino, G. Condorelli, G. De Guidi and S. Giuffrida, Molecular mechanism of photosensitization XI. Membrane damage and DNA cleavage photoinduced by enoxacin Photochem. Photobiol. 68 (1998) 652-659. 5.G. De Guidi, G. Condorelli, L.L. Costanzo, S. Giuffrida, S. Monti, and S. Sortino, Molecular mechanisms of photosensitization induced by drugs on biological systems and design of photoprotective systems, in Drugs Photochemistry and Photostability, Ed. by A. Albini and E. Fasani, The Royal Society of Chemistry (1998) 194-210. 6.S. Monti, S.Sortino, S. Encinas, G. Marconi, G. De Guidi and M.A. Miranda, Photoprocesses in photosensitizing drugs containing a benzophenone-like chromophore, in Drugs Photochemistry and Photostability, Ed. by A. Albini and E. Fasani, The Royal Society of Chemistry (1998) 150-161. 1999 1.S. Sortino and J.C. Scaiano, Laser flash photolysis of tolmetin: a photoadiabatic decarboxylation with a triplet carbanion as a key intermediate in the photodecomposition Photochem. Photobiol. 69 (1999) 167-172. 2.S. Sortino, J. C. Scaiano, G. De Guidi and L.L. Costanzo, Copper (II) in the part per million range, modulates photochemical and photosensitizing properties of tolmetin via electron transfer with a triplet carbanion Chem. Comm. 19 (1999) 2003-2004 3.S.Sortino, J.C. Scaiano and G. Condorelli, Transient photochemistry of diflunisal: photoejection and trapping of hydrated electrons leading to the formation of phenoxy radicals, photostimulated defluorination and cross combination reaction. J. Phys. Chem. B 103 (1999) 9279-9284. 4.S.Sortino and J.C. Scaiano, Photogeneration of hydrated electrons, nitrogen centered radicals and singlet oxygen from naphazoline: a laser flash photolysis study Photochem. Photobiol. 70 (1999) 590-595. 5.S. Sortino, S. Giuffrida and J.C. Scaiano, Phototoxicity of naphazoline. Evidence that hydrated electrons, nitrogen centered radicals and OH radicals trigger DNA damage: a combined photocleavage and laser flash photolysis study. Chem Res. Toxicol. 12 (1999) 971-978. 6.S. Sortino, J.C. Scaiano, G. De Guidi and S. Monti, Effect of ??cyclodextrin complexation on the photochemical and photosensitizing properties of tolmetin: a steady state and time resolved study. Photochem. Photobiol. 70 (1999) 549-556. 7.S. Sortino, G.Marconi, G.De Guidi, S. Giuffrida and S. Monti, Photophysical properties of rufloxacin neutral aqueous solution. Photochem. Photobiol. 70 (1999) 731-736. 8.S. Sortino, G. De Guidi, S. Giuffrida, S. Fazio, G. Salemi and S. Monti, On the Absorption and Emitting Properties of Three New Non Steroidal Antiinflammatory Drugs-β-Cyclodextrin Host-Guest Inclusion Complexes: Differentiated Sensitivity to the Microenvironment upon Light Excitation, Int.J.Photoenergy. 1 (1999) 19-23. 9.S. Sortino, J.C. Scaiano, and S. Giuffrida, Transient photochemistry of naphazoline in a protein environment, New J. Chem. 23 (1999) 1159-1162. 10.F.Castelli, G.De Guidi, S.Giuffrida, P.Miano and S.Sortino, Molecular mechanism of photosensitization XIII. A combined differential scan calorimetry and DNA photosensitization study in non-steroidal antiinflammatory drug-DNA interaction Intern. J. Pharm. 184 (1999) 21-33 11.G. Condorelli, G. De Guidi, S. Giuffrida, S.Sortino, R. Chillemi and S. Sciuto, Molecular mechanism of photosensitization induced by drugs. XII. Photochemistry and photosensitization of rufloxacin: an unusual photodegradation path for the antibacterials containing a fluoroquinolones like chromophore. Photochem. Photobiol. 70 (1999) 280-286. 232 12.G. De Guidi, S. Giuffrida, S. Monti, P.S. Pisu, S. Sortino and L.L. Costanzo, Molecular mechanisms of photosensitization induced by drugs XIV: two different behaviours in the photochemistry and photosensitization of antibacterials containing a fluoroquinolone-like chromophore, Int. J. Photoenergy. 1 (1999) 13-18. 2000 1.S. Sortino, G. Cosa and J.C. Scaiano, pH Effect on the efficiency of the photodeactivation pathways of naphazoline: a combined steady-state and time-resolved study, New J. Chem. 24 (2000) 159-163. 2.S. Conoci and S. Sortino, 2-anthrylmethyl pyrrole as a new fluorescent indicator for fluoride, Proceedings of the 5th italian conference on sensor and microsystems. Ed. by World Scientific Publ. of Singapore 2000. 3.C. Borsarelli, S. Braslawsky, S. Sortino, G. Marconi and S. Monti, Photodecarboxylation of ketoprofen in aqueous solution. A time-resolved laser-induced optoacoustic study. Photochem. Photobiol.72, 2000, 163-171. 4.S. Sortino and S. Conoci, Selective binding of 2-anthrylmethylpyrrole with fluoride: fluorescence and theoretical studies. Chem. Phys. Lett. 323, 2000, 389-392. 5.S. Sortino, G. De Guidi, S. Giuffrida, A. Belvedere and G. Condorelli, The photochemistry of Diflunisal in non-ionic (Brij-35) micelles: influence of the microenvironment on photoionization, electron trapping and persistent radical effect. J. Phys. Chem. A 104 (51), 2000, 11918-11925 2001 1.S. Sortino, S. Giuffrida, G. De Guidi, R. Chillemi, S. Petralia, G. Marconi, G. Condorelli and S. Sciuto, The photochemistry of flutamide and its inclusion complex with β-cyclodextrin. Dramatic effect of the microenvironment on the nature and on the efficiency of the photodegradation pathways. Photochem. Photobiol. 73, 2001, 6-13. 2.S. Monti, S. Sortino, E. Fasani and A. Albini, Multifaceted photoreactivity of 6-fluoro-7-aminoquinolones from the lowest excited states in aqueous media: a study by nanosecond and picosecond spectroscopic techniques Chem. Eur. J. 7, 2001, 2185-2196. 3.S. Sortino, G. De Guidi and S. Giuffrida, Drastic photochemical stabilization of lomefloxacin through selective and efficient self-incorporation of its cationic form in anionic sodium dodecyl sulfate (SDS) micelles New J. Chem. 25, 2001, 197-199. 4.S. Sortino, S. Giuffrida, S. Fazio and S. Monti, Spectroscopic characterization and photochemical behavior of host-guest complexes between β-cyclodextrin and drugs containing a biphenyl-like chromophore, New J. Chem. 25, 2001, 707-713. 5.S. Sortino, L. J. Martinez and G. Marconi, On the photophysical and photochemical behavior of fenbufen: a study in homogeneous media and micellar environments, New J. Chem. 25, 2001, 975-980. 6.S. Sortino, G. Marconi and G. Condorelli, New insight on the photoreactivity of the phototoxic anti-cancer flutamide: photochemical pathways selectively locked and unlocked by structural changes upon drug compartmentalization in phospholipid bilayer vesicles, Chem. Comm. 2001, 1226-1227. 7.G. Pitarresi, G. Cavallaro, G. Giammona, G. De Guidi, M. G. Salemi and S. Sortino, New hydrogel matrices containing an anti-inflammatory agent. Evaluation of in vitro release and photoprotective activity, Biomaterials, 2001, 1-14. 8.S. Monti, S. Encinas, A. Lahoz, G. Marconi, S. Sortino, J. Perez-Prieto, M. A. Miranda Structure and photochemical behavior of the cyclodextrin inclusion complexes of the benzoylthiophene-derived drugs tiaprofenic acid and suprofen, Helvetica Chimica Acta, 84, 2001, 2452-2466. I-3 Overview of Professional Publications (1997 - 2001) per year 233 I-4 Other Scientific Output Appendix 2 Ranking Scientific Journals Name of Journal Number Articles Chemistry an European Journal 1 Chemical Communications 2 New Journal of Chemistry 6 Chemical Research in Toxicology 1 Helvetica Chimica Acta 1 Journal Control Release 1 Journal of Physical Chemistry A 1 Journal of Physical Chemistry B 1 J. Chem Soc. Faraday Trans. 1 Chem. Phys. Letters 1 Photochem. Photobiol. 12 International Journal Pharmaceutics 1 Biomaterials 1 International Journal Photoenergy 2 Drugs Photochemistry and Photostability 2 Sensors and Microsystems of Journal factor 4.614 3.902 2.445 3.180 2.027 2.626 2.630 3.379 1.787 2.364 2.146 1.419 2.489 Impact Field(S) Chemistry Chemistry Chemistry Chemistry Chemistry Chemistry Physical Chemistry Physical Chemistry Physical Chemistry Chemical Physics Biophysics Chemistry Pharmceutics Material Chemistry Ranking 7/118 11/118 19/118 12/118 23/118 17/118 22/93 16/93 35/93 6/30 29/63 89/186 3/11 Book Ed. by Royal Society of Chemistry 1 Appendix 3 Journal Portfolio Analysis Name of the Unit: Research Director: Years included Name of Journal Group of Photochemistry Prof. Giuseppe Condorelli 1997-2001 Number of Journal Articles factor Chemistry an European Journal 1 4.614 Chemical Communications 2 3.902 New Journal of Chemistry 6 2.445 Chemical Research in Toxicology 1 3.180 Helvetica Chimica Acta 1 2.027 Journal Control Release 1 2.626 Journal of Physical Chemistry A 1 2.630 Journal of Physical Chemistry B 1 3.379 J. Chem Soc. Faraday Trans. 1 1.787 Chem. Phys. Letters 1 2.364 Photochem. Photobiol. 12 2.146 International Journal Pharmaceutics 1 1.419 Biomaterials 1 2.489 International Journal Photoenergy 2 Drugs Photochemistry and Photostability 2 Sensors and Microsystems 1 Impact Field(S) Chemistry Chemistry Chemistry Chemistry Chemistry Chemistry Physical Chemistry Physical Chemistry Physical Chemistry Chemical Physics Biophysics Chemistry Pharmceutics Material Chemistry Book Ed. by Royal Society of Chemistry Ranking 7/118 11/118 19/118 12/118 23/118 17/118 22/93 16/93 35/93 6/30 29/63 89/186 3/11 234 CATANIA 3 Name of the Research Unit (In Italian and English) Laboratorio per il riciclo dei materiali polimerici Research Leader (The name of the person in charge of the research programme of the unit) Prof. Giorgio Montaudo Laboratory for the polymer materials recycling Contact Person (The name and address of the person who will act as liaison between the unit and the INCA-Secretariat) University: (In Italian and English) Università degli Studi di Catania University of Catania Faculty: (In Italian and English) Scienze Matematiche, Fisiche e Naturali Mathematical, Physical and Natural Sciences Please specify: Name: Prof. Giorgio Montaudo Mailing Address: Dipartimento di Scienze Chimiche Università di Catania V.le A. Doria, 6 95125 Catania Phone: +39 95 7585002 Fax +39 95 221541 E-mail: [email protected] Department: (In Italian and English) Dipartimento di Scienze Chimiche Department of Chemical Sciences Thematic area • Sintesi ecosostenibili (solventi, fotochimica, catalisi, riciclo e altre). • Tecnologie biologiche enzimatiche e biomimetiche per le sintesi ecosostenibili e la decontaminazione ambientale. • Chimica degli ecosistemi (chimica del suolo, delle acque e dell’aria; impatto dei prootti di sintesi sull’ambiente). Introduction and Context Introduction to the Self-evaluation Report The Unit is a research team of the Department of Chemical Science of the University of Catania. This is located in an area that is defined by the EU as a “depressed area”; in fact, the once flourishing industrial basin is steading declining. The Polymer and Industrial Chemistry area compares well with other areas such as Inorganic, Physical and Organic Chemistry. Recently, a new industrial reality is being consolidated in the sector of the Microelectronics (Etnavalley). The University, the Faculty and the Department University of Catania Faculties Arts Economics Law Pedagogical Science Engineering Science Departments Medicine Architectur e Pharmac y Agricultura Polit Scien l Science 235 Botan y Animal Chemica Mathematic Biolog l Science s y Physic s Physiologic Science Geologic Science Microbiologi c Science Students (Accademic Year 2000-2001) : Students: Total number of students, 52030; 5652 are in coursed by Faculty of Mathematical, Physical and Natural Sciences. Members:The total teaching staff of the University is composed of 1506 members. 316 are members of the Faculty of Mathematical, Physical and Natural Sciences: of these 86 are members of the Chemistry Department. Position of the University:The University of Catania is the 9th university in Italy, as far as student population is concerned. It is the 2nd university in Italy to have filed a report for the Quality Audit Programme of the Conference of European Rectors and is among the first 32 European Universities that are participated to the Evaluate programme. The University serves mainly five provinces (Catania, Enna, Caltanissetta, Sirucusa and Ragusa). The high percentage of students coming from districts other than Catania’s (43% induced the opening of new courses in other cities like Siracusa, Ragusa, Modica, Scicli, Caltagirone and Giarre. The University of Catania is also well connected with other Italian Universities; in fact, a School of Excellence has recently been promoted as a part of a national network. The University was also one of the first Universities to participate to the INCA consortium. The Unit The Unit of INCA direct by Prof. Giorgio Montaudo is actally composed by 2 full professors: G. Montaudo, Emilio Scamporrino 1 associated professor: Alberto Ballistreri 3Ph.D. students: Paola Malvagna, Rossana Alicata, Sebastiano Bazzano a variable number of graduating students. Teaching load: The members of the Unit are involved in the teaching of these courses. Prof. G. Montaudo: Industrial Chemistry IIc. for industrial chemistry degree Prof. E. Scamporrino: Macromolecular Chemistry for chemistry and industrial chemistry degree; Polymeric Chemistry and Technology for chemistry and industrial chemistry degree; Industrial Chemistry and Polymeric Material Chemistry for Material Science degree. Prof. A. Ballistreri: Physical Methods in Organic Chemistry for Pharmaceutical Chemistry and Technology degree. Programme Description and Evaluation 1.Title: Recycling Biomass, Agricultural Waste and Polymeric Materials by Pyrolysis to Obtain Active Carbons. 2 Research Leader: Prof. Giorgio Montaudo 2a Sub-progamme titles: Analysis and Characterization of polymeric wastes Study of Polymeric Material Pyrolysis in a Batch Reactor 3 Composition of the scientific research staff of the unit per 1 January 2002 Names and Titles Year of Rank Birth Giorgio Montaudo Emilio Scamporrino Alberto Ballistreri Paola Malvagna Rossana Alicata Sebastiano Bazzano 1934 1951 1948 full professor full professor associated prof. Ph.D student Ph.D student Ph.D student Research Remarks Input in fte in 2001 0.4 0.4 0.5 1 1 1 236 Total research input 4.8 Comments Major changes in the previous five years: Prof. P. Maravigna has gone retired; his previous position was associated professor. Prof. E. Scamporrino has become full professor; his previous position was associated professor. In the following five years the major changes in the Unit should be: The Ph. D. students (Malvagna, Alicata and Bazzano) will finish their Ph. D. Courses. 4 Input of Academic Staff in fte Category Full Professors Associated Professors Ricercatori Post-docs PhD-students Borsisti 1997 0.4 1.5 1998 0.4 1.5 1999 0.4 1.5 2000 0.4 1.5 2001 0.4 1.5 Total 2.0 7.5 2 2 2 3 3 12 Total 3.9 3.9 3.9 4.9 4.9 21.5 Comments: The trend in the size of the Polymer Chemistry team of the Department of Science of the University of Catania is quite stable. 5 Funding 5.1 Personnel (in fte) Source University CNR European Union Other Sponsors Total 5.2 1998 1.9 1999 1.9 2000 1.9 2001 1.9 Total 9.5 Materials and Equipment (in Million Lire) Source University - MURST CNR EU Other Sponsors Total 5.3 1997 1.9 1997 39.5 1998 230 1999 140 2000 40 2001 45 Total 495.5 200 239.5 230 140 40 170 215 370 865.5 Comments: 1.On the figures The component of the staff is paid by the University and is permanent; PhD students are supported by the University. 2.On the funding policy Funds are from MURST, industrial sponsor (Novamont Company: research on some biodegradable polymeric materials) and INCA (a national research project called “Recycling Biomass, Agricultural Waste and Polymeric Materials by Pyrolisis to Obtain Active Carbons”, ministerial law 488/92). 6. Progress Report 237 6.1 Mission Statement The Unit missions directed towards the development of useful technologies in the field of synthetic and biological polymeric materials. Members of the Unit are actively involved in research projects, both industrial and academic, to develop industrial applications useful for small and medium industries. 6.2 The Research Programme The study of the chemical exchange reactions occurring among the reactive groups of polymers during melt-mixing processes is necessary to predict their occurrence and to control their extent to preparation materials at controlled composition. Recently our group has proposed a first classification and some unifying criteria for melt-mixing processes of most common condensation polymers as polyesters, polyamides and polycarbonates. Mixtures of polycarbonate/polyester (PC/PET and PC/PBT), polycarbonate/Nylon6 (PC/Ny6) and polyethylenterephthalate/polyethyleneadipate (PET/PEA) have been heated in a glass reactor or in a Brabender at temperatures between 240 and 300 °C, under stirring and air or N2 flow. In these conditions, different mechanisms of exchange reactions could happen according to the presence of catalysts and to the polymer composition [i.e. the direct reaction between functional groups located inside the polymer chains ( inner-inner reactions) or the end groups, originally present in the polymers or generated inside by thermal or hydrolytic degradation reactions, attack on the inside functional linkages ( outer-inner reactions). These exchange reactions, of scarce significance in the case of homopolymers, become most important when mixtures of different polymers are processed because variable amounts of block, graft or random copolymers (that often change the chemical and physical properties of the blends) may be form. On the basis of the structural and molecular characterization of the materials produced in the reactive mixing, a detailed study of the mechanisms and of the kinetics of the exchange reactions have been made determining also experimental conditions to obtain materials with a known structure and properties. As an example, it has been found that for the PC/PET and PC/PBT blends the outer-inner reactions occurs at low temperature (about 240°C) by attack of the OH and/or COOH polyester end groups to the inside PC carbonate linkages. In particular, it has been ascertained that the formed phenol end groups do not react. Contrary the exchange inner-inner reactions become operative at higher temperature then 290°C or at 270°C in presence of catalysts. As a consequence variable amounts of block copolymers which gradually change to random are formed. Recently there is increasing technological interest in the directly insertion of active units (special groups) in pre-formed polymers through reactive mixing processes to form guest-host systems. Good results have been obtained, as an example, in the case of some porphyrin, fullerene and diimine groups inserted in a commercial polycarbonate. The remarkable properties of poly(3-hydroxyalkanoate)s have resulted in a growing interest in these bacterically produced biodegradable polyesters. Blends with synthetic polymers such as polycaprolactone, poly(lactic acid) or nylons and natural polymers from renewable sources are under observation. One of the problems associated with these materials is their compatibility restriction that frequently limit their use. For this reason procedures directed to increase the compatibility, modulating the chemical and physical properties of these mixtures are investigated. The growing use of plastics in the most varied industrial, agricultural and urban sectors, is leading to the accumulation of notable quantities of polymer based waste and solid refuse.The disposal of this refuse has become a great problem without any easy solution, and must take account of respecting and protecting the environment. European legislature concerning pollution favours the choice of tertiary recycling over disposal in rubbish tips or incineration when it is not possible the reuse of waste for a primary or secondary recycling of polymers. The technologies employed must of course take account of the economic aspect of the process and the new products, as well as the method of obtaining them, which must no longer prove damaging to the environment. Recently, a national research project called “Recycling Biomass, Agricultural Waste and Polymeric Materials by Pyrolisis to Obtain Active Carbons”, ministerial law 488/92, has been launched in which our group also participates in the role of Research Unit of the INCA consortium. The project concerns the recycling of biomass and agricultural waste (lignocellulose residues from herbaceous, wood and forest crops, almond husks, hazelnut husks, olive residues etc.) and polymeric refuse from agricultural uses (containers, greenhouse covers, wrapping film and mulching, etc.). Thermochemical recycling has been proposed for the production of active carbons, a highly valuable product, which in addition is imported into Europe. With regard to biomass, research has already reached an advanced stage of development and now aims toward further improvements to make recycling economically competitive. In the case of polymer refuse recycling, although a number of studies have been carried out on the thermal decomposition mechanisms of polymers, the problem has been confronted in a marginal fashion and very few data regarding carbonisation have been reported in literature. The preliminary study of the thermic behaviour of the more widely consumed polymers (PE, PP, PS, EVA, PVC, PET, Ny6 and their mixtures and mixtures with suitably additives) was carried out by thermogravimetric analysis simulating different degradation conditions, working under air or nitrogen flows and varying both the final temperature as well as the heating velocity. The carbonisation tests were thus performed on the basis of the best results obtained, using, under controlled conditions, a Brabender and a Batch reactor designed and built by us. Batch reactor allows working with broader temperature limits using small sample quantities and different atmosphere compositions. The lower part of the 238 reactor, where the thermal decomposition of the polymeric sample occurs, may in addition be removed thus facilitating the quantitative recovery of the decomposition residue after each test. For the carbonisation of the various polymers, it is necessary to find the optimal conditions leading to a partial decomposition of the chains with the formation of a highly reticulated and thermostable system. It is usually necessary to heat the polymeric material to a temperature close to its thermal decomposition temperature (at an excessively low temperature the polymer chains would be too stable to trigger the decomposition reactions, while a higher temperature would provoke the total decomposition of the material). Other variables to consider are the presence or not of oxygen and the opportune addition of suitable additives to catalyse the carbonisation reactions of the polymeric chains. First carbonisation experiments in the Batch reactor were performed under air flow at 350°C. Because the obtained carbon residues are not thermostable but destined for a further and often marked drop in weight in the successive activation treatments (T>500°C) to form active carbon, to evaluate the real yield of the thermostable residues, the carbons of the Batch reactor were submitted to heating at 800°C under nitrogen flow (TGA tests). It results that some of the polymers such as PE, PP, PS and EVA (tests 1-4), despite having the greatest percentage content of carbon in the molecules and leaving high quantities of residue after treatment at 350°C, are not able to form thermostable residue; Ny6 and PET form small amounts while PVC leaves about 17.9% residue, an amount corresponding to 46% of the total carbon content in the polymer. Considering the tendency of PVC to decompose leaving a fairly abundant carbon residue, mixtures of PVC with other polymers to determine if the reticulation processes of the PVC chains, which take place after the dehydrochlorination phase, may also involve the other molecular chains in the formation, were prepared In the case of PVC, as expected, the presence of zinc determines a consistent increase in the carbon residue which well exceeds 50% of the theoretical carbon content in the polymer. Also in the case of the mixtures with other polymers, an increase in the carbon residue with respect to the mixtures without zinc was observed; the catalytic effect proves particularly efficacious in the case of the PVC/PET/ZnO mixture, for which a carbon yield of 28.5% was calculated (corresponding to 76% of the theoretical carbon content in the starting mixture), well above that of the mixture without zinc with an increase of about 50%. 6.3 Position in Networks • Intra-university co-operation The Unit is connected with other research groups of the same Department as confirmed by the publication of several papers with researches of these groups. • Regional co-operation The Unit actively collaborates with: - Istituto per la Chimica e la Tecnologia dei Materiali Polimerici, CNR of Catania - prof. La Mantia, University of Palermo. - University of Messina - Istituto CNR di Messina • National co-operation (including INCA) The Unit collaborates with national companies and research centers: University of Genova University of Pisa “Consorzio INCA”. The active collaboration with the researches of INCA is essential for the future growing of the Unit. • International co-operation In the last years some of the more active collaborations have been maintained with Exxon International (Belgium), Essilor International, (France), NIOZ Institute (The Netherlands), Indian Institute of Science (India). 6.4 Societal Relevance and Impact The growing use of plastics in the most varied industrial, agricultural and urban applications is leading to the accumulation of remarkable amounts of polymer based waste. The problem concerning the recycling of polymeric materials is particularly relevant in a region as Sicily where large amounts of these materials are produced and used every years. The disposal of this refuse has become a great problem and must take account of respecting the environment. The recycling of polymeric materials is generally performed by chemical, thermo-meccanical and combustion processes. Recent researches are directed toward the pyrolysis of polymeric to prepare useful products. Another relevant problem concerning the ambient pollution by plastics is the development and use of biodegradable materials for the packaging. Researches are directed toward the synthesis of biodegradable polymeric materials both by chemical and microbial processes. 239 6.5 Further Indications of Quality and Reputation Prof. G. Montaudo: Postdoctoral Fellow, 1966-68; Brooklyn Polytechnic and University of Michigan, USA Research Associate, 1971 University of Michigan Humboldt Foundation Fellow, 1973 Mainz University Visiting Professor May-July 1980 Mainz University Visiting Professor March-September 1988 Cincinnati University Visiting Professor September-November 1995 Universitù de Paris, France Award of the Italian Chemistry Industry, Milan 1990 6.6 Key Publications 1.Montaudo G., Puglisi C., Montaudo G. (1999). Copolymer Composition: a key to the mechanisms of Exchange in Reactive Polymer Blending. In FAKIROV S. Transreactions in Condensation Polymers. (pp. 159-191). ISBN: 3-527-29790-1 NEW YORK: Wiley-VCH (UNITED STATES). 2.Montaudo G., Rizzareli P. (2000). Synthesis and Enzymatic Degradation of Aliphatic Copolyesters. POLYMER DEGRADATION AND STABILITY. vol. 70, pp. 305. 3. Vitalini D., Mineo P., Iudicelli V., Scamporrino E., Troina G.: Preparation of Functionalized Copolymers by Thermal Processes: Porphyrination of a CommercialPolycarbonate; MACROMOLECULES, 2000, 33, p.7300. 4.A. Ballistreri, M. Giuffrida, S.P.P. Guglielmino, S. Carnazza, A. Ferreri, G. Impallomeni: Biosynthesis and structural characterization of medium-chain-length poly(3-hydroxyalkanoate)s produced by Pseudomonas aeruginosa from fatty acids;. J. BIOLOG. MACROMOLECULES, 2001,29, 107. 5.Montaudo G., Puglisi C., Samperi F., Chionne D., Turturro A. (2001). Species Produced in the Thermal Oxidation of Nylon 6 Determined by MALDI-TOF Mass Spectrometry. MACROMOLECULAR RAPID COMMUNICATIONS. vol. 22, pp. 524-528. 7. Scientific Output 7.1 Publication Policy The Unit is mainly involved in fundamental research and, accordingly, the produced scientific papers are published in fundamental research journals of international diffusion. Applied research is made too, but frequently scientific results cannot be published because date reserved to the clients. 7.2 Numerical data Category PhD-Dissertations 1997 1998 1999 1 2000 2 2001 Total 3 Scientific Publications 2 9 12 2 7 32 Professional Publications Master’s Theses 3 2 2 2 9 8 Self-evaluation The polymer chemistry team entered in the field of the thermal degradation of polymeric materials since 1980, producing more of one hundred high quality papers on the subject. The group was also active on studying the 240 mechanisms of smoke suppression and flame retardation of polymeric materials, producing some patent and high quality papers. Research contracts with some national industries were also activated. The knowledge obtained in polymer combustion and in particular on the char forming processes is resulted important in the study of the production of active carbon from the pyrolysis of post-consume plastics. The team is also involved in research programs about the synthesis and characterization of polymers with particular attention to biodegradable polymers. In the last year several works concerning the mass spectrometric analysis of polymeric materials have been also produced. Appendix I Scientific Output I-1 Year 1997 1997 1997 1999 1999 1999 2000 2000 Overview of Dissertations and Master's Thesis (1997-2001) Name Master’s student Sabrina Carrocccio Giovanna Schilirò Giovanni Troina Paola Rizzarelli Paola Maria Malvagna Rossana Alicata Sabrina Carroccio Nicolai Tasca 2000 Gaetano Guzzetta 2000 Rosaria Cozzolino Daniele Di Mauro Sebastiano Bazzano 2001 2001 I-2 Title of the Dissertation Supervisor Sintesi e Caratterizzazione di Copolimeri a Blocchi e Statistici G. Montaudo Sintesi e Caratterizzazione di Polieteri a base bisfenolica contenenti unità E. Scamporrino porfiriniche e lunghe catene alifatiche in catena Determinazione del peso molecolare di polimeri polidispersi mediante E. Scamporrino analisi MALDI-TOF Biodegradabilità di Copoliesteri Sintetici G. Montaudo Degradazione termica del Policarbonato Miscelazione reattiva di Nylon6 G. Montaudo e Polibutilenetereftalato G. Montaudo Studio dela Degradazione termica e termo-ossidativa di materiali polimerici Sintesi, Caratterizzazione e Degradazione Enzimatica di Copoliesteri Alifatici Caratterizzazione di Copoliesteri Alifatici Biodegradabili Mediante Spettrometria di Massa Matrix-Assisted laser Desorption/Ionization Time of Flight Metodi di analisi di biopolimeri mediante spettrometria di massa MALDITOF Prodotti di Ossidazione del Policarbonato G. Montaudo G. Montaudo G. Montaudo G. Montaudo Sintesi, mediante processi termici, e caratterizzazione di copolicarbonati E. Scamporrino contenenti unità diimminiche aventi proprietà ottiche non lineari Overview of Scientific Publications (1997-2001) per year 1997 Molecular Weight Determination and Structural Analysis in Polydisperse Polymers by Hyphenated Gel Permeation Chromatography/Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry; G.Montaudo, M.S.Montaudo, C.Puglisi, F.Samperi Int. J.Polymer Analysis & Charact. 3, 177. Further Application of a Procedure for Molecular Weight and Molecular Weight Distribution Measurements of Polydisperse Polymers from Their Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectra; D. Vitalini, P. Mineo, E. Scamporrino. Macromolecules, 30, 5285. 1998 241 Structural Characterization of Multicomponent Copolyesters by Mass Spectrometry; M.S.Montaudo, C.Puglisi, F.Samperi, G.Montaudo Macromolecules. 31, 8666 (1998) Pyrolysis Pathways of Polyethers and a Method for the Interpretation of their Pyrolysis Mass Spectra of Polyethers; C.G.Georgakopoulos, M.Statheropoulos, G.Montaudo Polymer Degradation and Stability, 61, 481 An expert system for the interpretation of Pyrolysis mass spectra of condensation polymers; C.G.Georgakopoulos, M.Statheropoulos, G.Montaudo Analytica Chimica Acta 359, 213. Partially Selective Methanolysis of Sebacic Units in Biodegradable Multicomponent Copolyesters; M.S.Montaudo, G.Montaudo, C.Puglisi, F.Samperi Macromol.Rapid Commun.19, 445. Application of Size Exclusion Chromatography Matrix - assisted Laser Desorption/Ionization Time-of-flight to the Determination of Molecular Masses in Polydisperse Polymers; M.S.Montaudo, G.Montaudo, C.Puglisi, F.Samperi Rapid Commun.Mass Spectrom. 12, 519. Chemical Reactions Occurring in the Thermal Treatment of PC/PMMA Blends; G.Montaudo, C.Puglisi, F.Samperi J.Polymer Science: Part A. 36, 1873. Molar Mass Distributions and Hydrodynamic Interactions in Random Copolyesters investigated by Size Exclusion Chromatography / Matrix Assisted Laser Desorption Ionization; M.S.Montaudo, C.Puglisi, F.Samperi G.Montaudo Macromolecules. 31, 3839. Mechanism of Exchange in BPT/PC and PET/PC Blends.Composition of the Copolymer Formed in the Melt Mixing Process; G.Montaudo, C.Puglisi, F.Samperi Macromolecules. 31, 650. A New Procedure for Quantitative Correction of MALDI-TOF Mass Spectrometric Response; E. Scamporrino, P. Maravigna, D. Vitalini, P. Mineo. Rapid Communication in Mass Spectrometry, 12, 646 1999 Analysis of Poly(Bispheno A Carbonate) by Size Exclusion Chromatography/Matrix-assisted Laser Desorption/Ionization.2.Self-association Due to Phenol End Groups; C.Puglisi, F.Samperi, S.Carroccio, G.Montaudo Rapid Commun.In Mass Spectrom. 13, 2268 (1999) Analysis of Poly(Bispheno A Carbonate) by Size Exclusion Chromatography/Matrix-assisted Laser Desorption/Ionization.1.End Group and Molar Mass Determination; C.Puglisi, F.Samperi, S.Carroccio, G.Montaudo Rapid Commun.In Mass Spectrom. 13, 2260 (1999) Maldi-Tof Investigation of Polymer Degradation. Pyrolysis of Poly(Bisphenol A Carbonate); C.Puglisi, F.Samperi, S.Carroccio, G.Montaudo Macromolecules. 32, 8821 (1999) Bivariate Distribution of PMMA/PBA Copolymers by Combined SEC/NMR and SEC/MALDI; M.S.Montaudo, G.Montaudo Macromolecules. 32, 7015(1999) Thermal Degradation mechanisms of Polyetherimide investigated by direct pyrolysis mass spectrometry; S.Carroccio, C.Puglisi, G.Montaudo Macromol.Chem.Phys. 200, 2345. Thermal Decomposition Processes in Aromatic Polycarbonates Investigated by Mass Spectrometry; Puglisi, L.Sturiale, G.Montaudo Macromolecules. 32, 2194. 242 Copolymer Composition: a Key to the Mechanisms of Exchange in Reactive Polymer Blending; G.Montaudo, C.Puglisi, F.Samperi S.Fakirov(Ed)WILEY-VCH Chapter 4, 159. Recent Advances in Mass Spectrometry of Polymers”;E. Scamporrino, D. Vitalini; in Modern Techniques for Polymer Characterisation, Edited by R.A. Pethrick and J.V. Dawkins, Chapter 8, p. 233, John Wiley & Sons Ltd, 1999 Effect of Combined Changes of Delayed Extraction Time and Potential Gradient on the Mass Resolution and Ion Discrimination in DE-MALDI-TOF Mass Spectrometric Analysis of Polydisperse Polymers and Polymer Blends”; D. Vitalini, P. Mineo, E. Scamporrino; Rapid Communication in Mass Spectrometry, 13, 2511. Synthesis and Characterization of Some Copolyformals Containing, in the Main Chain, Different Amounts of Fullerene Units; E. Scamporrino, D. Vitalini, P. Mineo. Macromolecules, 32, 4247. Synthesis and Characterization of Some Main Chain Porphyrin Copolyformals, Based on Bisphenol-A and Long Linear Aliphatic Units, Having a Low Glass Transition Temperature”; D. Vitalini, P. Mineo, E. Scamporrino; Macromolecules, 32, 60. Characterization by mass spectrometry of poly(3-hydroxyalkanoate)s produced by Rhodospirillum rubrum from 3hydroxyacids; A. Ballistreri, M. Giuffrida, G. Impallomeni, R.W. Lenz, R.C. Fuller Inter. J. Biolog. Macromolecules, 26, p. 201 2000 Synthesis and enzymatic degradation of aliphatic copolyesters; G.Montaudo, P.Rizzarelli Polymer Degradation and Stability, 70, 305. Preparation of Functionalized Copolymers by Thermal Processes: Porphyrination and Fullerenation of a Commercial Polycarbonate; D. Vitalini, P. Mineo, V. Iudicelli, E. Scamporrino, G Troina; Macromolecules, 33, 7300. 2001 Thermal Oxidation Products of Nylon 6 Determined by MALDI-TOF Mass Spectrometry; Donatella Chionna, Concetto Puglisi, Filippo Samperi, Giorgio Montaudo, Antonio Turturro Macromol.Rapid.Commun. 22, 524. Mass Spectrometry of Polymers; G.Montaudo, R.P.Lattimer (EDS) CRC Press Polymer Characterization Methods; Giorgio Montaudo and M.S.Montaudo G.Montaudo, R.P.Lattimer (EDS) CRC Press Chapter 2, 41. Direct Pyrolysis of Polymers into the Ion Source of a Mass Spectrometer (DP-MS); Giorgio Montaudo and Concetto Puglisi G.Montaudo, R.P.Lattimer (EDS) CRC Press, Chapter 5, 181. Fast Atom Bombardment of Polymers; Giorgio Montaudo and Filippo Samperi G.Montaudo, R.P.Lattimer (EDS) CRC Press, Chapter 7, 269. Matrix-Assisted Laser Deserption Ionization Mass Spectrometry of Polymers (MALDI-MS); G.Montaudo, M.S.Montaudo, and F.Samperi G.Montaudo, R.P.Lattimer (EDS) CRC Press, Chapter 10, 419. 243 Biosynthesis and structural characterization of medium-chain-length poly(3-hydroxyalkanoate)s produced by Pseudomonas aeruginosa from fatty acids; A. Ballistreri, M. Giuffrida, S.P.P. Guglielmino, S. Carnazza, A. Ferreri, G. Impallomeni. Int. J. Biolog. Macromolecules, 29, 107 Appendix 3 Journal Portfolio Analysis Name of the Unit: Research Director: years included Name of Journal Laboratory for the polymer materials recycling Giorgio Montaudo 1997-2001 Number Articles Macromolecules 10 Rapid Commun.Mass 5 Spectrom Macromol.Rapid Commun 2 Analytica Chimica Acta 1 J.Polymer Science, Polym. 1 Chem. Macromol.Chem.Phys 1 2 Polym. Degr.&Stability Int. J.Polymer Analysis & 1 Charact Inter. J. Biolog. 2 Macromolecules of Journal Factor 3.738 2.478 Impact Field(s) Ranking Polymer chemistry Chemistry,Analytical 3/73 9/68 2.372 2.073 1.975 Polymer chemistry Chemistry,Analytical Polymer chemistry 5/73 13/68 6/73 1.629 0.905 0.490 Polymer chemistry Polymer chemistry Polymer chemistry 10/73 22/73 45/73 1.978 Biochemistry & Molecular 147/308 Biology Comments on: a) the method: The data are according to ISI Journal Citation Reports 2001 Edition b) the results: The Unit publications appear in the major journals regarding the polymeric materials which have higher impact factor and ranking values. 244 CATANIA 4 Name of the Research Unit Analytical Chemistry Group Research Leader Giuseppe Arena University: Universita’ degli Studi di Catania University of Catania Contact Person Please specify: Name: Giuseppe Arena Mailing Address: Dipartimento di Scienze Chimiche, Universita’ degli Studi di Catania Viale Andrea Doria 6, 95125, Catania Phone : 39 095 7385071 Fax : 39 095 580138 E-mail : [email protected] Faculty: Facolta’ di Scienze Matematiche Fisiche e Naturali Faculty of Mathematical, Physical and Natural Sciences Department: Dipartimento di Scienze Chimiche Department of Chemical Sciences Thematic area •Tecnologie innovative di monitoraggio •Tecnologie di depurazione (membrane, sonochimica, fotocatalisi, elettrochimica e altre). • Chimica degli ecosistemi (chimica del suolo, delle acque e dell’aria; impatto dei prootti di sintesi sull’ambiente). Introduction and Context Introduction to the Self-evaluation Report The Unit, that is actually coincident with a research team of the Department of Chemical Sciences of the University of Catania, is located in an area that is defined by the EU a depressed area;in fact, the once flourishing industrial basin is steadily declining. The research team was put together in the early nineties when Professor Arena moved to Catania and took the chair of Analytical Chemistry. The Analytical Chemistry area is a small one compared to other areas such as Inorganic, Physical, Organic and Industrial Chemistry. The research group does not have any secretariat or administrative personnel; consequently, the vast majority of administrative matters (e.g. the compilation of the present forms) is dealt with by the people listed in Section 3. The University, the Faculty and the Department The University of Catania: The University of Catania (www.unict.it) was founded in 1444 as a Studium Generale, Catania. It is today the 9th University in Italy, as far as student population is concerned. The University serves mainly five districts (Catania, Enna, Caltanissetta, Siracusa and Ragusa). The high percentage of students coming from districts other than Catania’s prompted the opening of new Laurea and Diploma courses in towns located in the vicinity of Catania (Siracusa, Ragusa, Enna, Caltagirone, Giarre). The University of Catania is the 2nd University in Italy that filed a report for the Quality Audit Programme of the Conference of European Rectors. The University of Catania was also one of the first Universities that joined INCA. The University of Catania is also well connected with other Italian Universities; in fact, a School of Excellence has recently been promoted as a part of a national network. The University has some 29 departments and 3 research centres which are arranged in twelve faculties (namely Agricultural Sciences, Architecture, Arts and Philosophy, Economics, Engineering, Foreign Languages and Literature, Law, Mathematical, Physical and Natural Sciences, Medicine and Surgery, Pedagogical Sciences, Pharmacy, and Political Sciences). Students: The total number of the students (Academic Year 2000-2001) is 53030; out of these 5652 are enrolled in Courses offered by the Faculty of Mathematical, Physical and Natural Sciences. Faculty and Staff members: The University of Catania comprises a total of 1506 faculty and staff members. 316 of them belong to the Faculty of Mathematical, Physical and Natural Sciences. 245 Department: The Department of Chemical Sciences (www.unict.it/dipchi/) is the largest Department of the University of Catania in terms of both faculty and staff members with a total of 87 Professors and Researchers; the Department has a total of 27 technicians and administrative personnel. The research activities of the Department cover all the most important areas of chemistry. The Department is involved in several EU projects, in cooperative projects with national and international institutions and is strictly linked to the main local industries. The Department supports the research groups through its technical and administrative services, providing sophisticated equipment and an updated library. A detailed Activity Report of the Department for the period 2000-2001 may be found in (http://www.unict.it/psmfn/Department_of_Chemical_Sciences.htm). The Unit Organization structure: The Unit of INCA directed by Professor Giuseppe Arena is actually composed by 2 full professors: Prof. Giuseppe Arena, Prof. Vincenzo Cucinotta 3 associated professors: Prof. Annalinda Contino, Prof. Alberto Torrisi; Prof. Giuseppe Maccarrone 1 researcher: Dr. Giuseppe Spoto 1 Post-doc: Dr. Elisa longo 3 Ph. D student: Mr. Carmelo Sgarlata, Mr. Alessandro Giuffrida, Miss. Marianna Messina a variable number of undergraduate students. Teaching load: The members of the unit teach several courses. Professor Arena teaches : 1.Analytical Chemistry for the Chemistry (New Course); 2.Analytical Chemistry for the Industrial Chemistry (New Course); 3.Analytical Chemistry for the Chemistry Course (Old Course) 4. Analytical Chemistry for the Material Sciences Course; 5.Thermodynamics of Solution Equilibria (Advanced Course) for the PhD Course. Professor Cucinotta teaches: 1.Instrumental Analytical Chemistry the Chemistry (New Course) 2.Instrumental Analytical Chemistry for the Industrial Chemistry Course, 3.Analytical Chemistry of Pollutants for the Chemistry Course (Old Course) 4.Analytical Chemistry of Pollutants for the Industrial Chemistry Course (Old Course) 5.Analytical Chemistry of Pollutants for Environmental and Cultural Heritage Chemistry Course (Siracusa). 6.Techniques of Chemical Analysis and Structural Determination for “SISSIS” 7.The Chemical Analysis for “SISSIS” Professor Maccarrone teaches: 1.Laboratory of Instrumental Analytical Chemistry for the Chemistry (New Course) 2.Laboratory of Instrumental Analytical Chemistry for the Industrial Chemistry (New Course) Professor Contino teaches: 1.Analytical Chemistry Laboratory for the Chemistry Course (New Course); 2.Analytical Chemistry Laboratory for the Industrial Chemistry Course (Old Course) Professor Torrisi teaches: 1.Analytical Chemistry for the faculty of Agricultural Sciences 2.Instrumental Analytical Chemistry for the faculty of Agricultural Sciences. • The average teaching load is 3.6 Courses/person Programme Description and Evaluation 1 Title Advanced Chemical Methodologies: Molecular recognition and innovative monitoring technology 2 Research Leader 246 Professor Giuseppe Arena 2a Sub-programme titles and sub-programme leaders 3 Composition of the scientific research staff of the unit per 1 January 2002 Name and Titles Year of Birth Rank Research Remarks Input in fte in 2001 Prof. Arena Giuseppe Prof. Cucinotta Vincenzo Prof. Contino Annalinda Prof. Maccarrone Giuseppe Prof. Torrisi Alberto Dr. Giuseppe Spoto Dr. Elisa Longo Mr. Carmelo Sgarlata Mrs Marianna Messina Mr Alessandro Giuffrida Dr Fabio Gulino Total research input 1949 1949 1962 1958 1956 1963 1974 1972 1976 1973 1964 Full Professor Full Professor Associate Professor Associate Professor Associate Professor Researcher Post-Doc Ph.D Student Ph.D Student Ph.D Student Grantee 0.2 0.1 0.1 0.1 0.2 0.2 0.2 0.4 0.1 0.1 1.0 . Part time (3 months only) Part time (1 year only) Comments Major changes in the previous five years: Contino and Maccarrone have become associate professor in 2001 and 1997 respectively; their previous position was researcher . Professor Cucinotta and Dr Spoto joined the research group in 1999. Dr. Elisa Longo has been a Ph.D student in the Academic Years 1998-2000 In the next five years the following major changes are expected: Miss Messina, Mr Giuffrida and Mr. Sgarlata will finish his Ph.D. Thesis and will be looking for a job. 4 Input of Academic Staff in fte Category Full Professors Associated Professors Ricercatori Post-docs PhD-students Borsisti Total 1997 0.4 1.2 0.9 2 1998 0.4 1.2 0.9 0.6 1999 0.4 1.2 0.9 0.5 0.6 2000 0.3 1.2 0.7 0.5 0.6 2001 0.3 0.4 0.2 0.2 0.6 Total 1.8 5.2 3.6 1.2 3.4 4.5 3.1 3.6 3.3 1.7 15.2 Comments The trend in the size of the Analytical Chemistry Unit of the Depatment of Chemical Sciences of the University of Catania has not changed significantly from the previous Review, if one takes into account that four components are (or have been) PhD students and will shortly be leaving and Dr Gulino (grantee) has left already. The ratio between permanent staff and temporary personnel (post-docs, Ph.D. students, grantees) ftes is fairly stable at the moment; this is much more so if one takes into account also the work done by undergraduate (Laurea) students. 5 Funding 247 5.1 Personnel (in fte) Source University CNR European Union Other Sponsors Total 5.2 1998 3.1 1999 3.6 2000 3.3 2001 1.7 1.4 Total 15.2 1.4 Materials and Equipment (in Million Lire) Source University - MURST CNR EU Other Sponsors Total 5.3 1997 4.5 1997 41.7 7.0 1998 12.0 30.0 1999 35.9 8.0 2000 47.5 8.0 48.7 42 43.9 854.0 909.5 2001 180.0 180.0 Total 317.1 53 854.0 1224.1 Comments: • On the figures The majority of the staff is paid by the University and is permanent; Ph.D. students are supported by the University. No component of the permanent staff is paid by INCA. No administrative personnel works specifically for the group; this forces the academic staff to take care of administrative matters, since the department does not allow its administrative personnel to take care of research groups “Other Sponsors” refers to funding obtained through Act 488/92. These funds come both from projects presented jointly with other INCA research Units (304 Million Liras) and from projects presented from within the Department (550 Million Liras). Of these, whilst the latter funds have been entirely obtained and spent already, roughly one third of the money obtained for materials/personnel has not been received from INCA. • On the funding policy So far all funds have come from State Agencies or from EU, with the exception of the stationary phase that was sent to Le Commissariat a l’Energie Atomique Française (Please see Section 6.1). In 1995 the Government cut CNR funding by 20%; in turn CNR did the same, and this was readily reflected in the decrease of funding coming from CNR.. The Unit is expected to obtain funds from contracts obtained from both the Departments and local Institutions ( Act 297, PON). 6. Progress Report 6.1 Progress analysis - Main results As planned in the 1998 Review (Please see point 6.2) , the Unit has synthesised, characterised and anchored onto silica gel a suitable calixcrown. The new stationary phase has been used in ion chromatography, and has proved to be particularly efficient for the selective separation of Cs+. This new stationary phase has been sold to CEA-Cadarache (Commissariat a l’Energie Atomique). Parallelly, ad hoc designed calixcrowns have been embedded into polymeric inclusion membranes, that turned out to be very efficient for the separation of Sr2+ from nuclear plant acidic “synthetic” waste waters even in the presence of very large amounts of Na+. Calixcrowns have also been employed to detect minute amounts of some cations in water. To this end, suitable ligands have been immobilized onto a gold surface of a quartz crystal sensing element. This device has been tested in a dual quartz crystal microbalance prototype that has been built in collaboration with the Chemistry Department of the University of Leicester, UK. These findings together with similar literature reports show that calixarenes can be exploited for the removal/monitoring of target species; calixarene based systems are being currently studied/employed in Oak Ridge National Laboratory. 248 Main changes As indicated in Table 3, new researchers have joined the group over the last five years. They have brought in expertises the Unit was lacking. The Unit has thus extended its activity to the study of spatially resolved techniques for the study of the interaction between environment and materials of interest in art and archaeology. The results are clearly testified by a book (Co-edited by G. Spoto) and a series of publications. Efforts have also been devoted to the study of herbicide racemates. These were separated in capillary electrophoresis by dissolving in the BGE cyclodextrin derivatives, particularly a new class of compounds, that were synthesized in our laboratory and called “hemispherodextrins” for their characteristic hemispherical shape. Mission of the Unit The mission of the Unit, that has remained practically unchanged, is the synthesis, characterization and use of expert systems to be employed for the separation/monitoring of environmentally relevant species and/or processes. 6.2 Position within INCA The Unit has been desperately trying to start new collaborations with other INCA members/Units. However, a part from the collaboration with the Parma Unit, that incidentally had already started long before the Units were created and the Consortium expanded to its actual dimensions, no new collaborations have been actually established. One exception, in this context, is the collaboration just started with the Cagliari Unit, within the framework of the 488 Act. However, neither the stationary phase ad hoc synthesised for the Cagliari unit nor the raw extraction data passed to the same unit have as of now resulted in a scientific paper. The Unit does hope to be heavily involved in the SISIFO project, especially as far as the inorganic aspects of the analysis are concerned. This would also allow the ICP-MS and the ion chromatograph to be extensively used for purposes other than purely scientific ones, in conjunction with other INCA Units. In fact, the Unit has its own contacts with Industries/Agencies , as indicated in Section 8. 6.3 Key Publications G. Arena, A. Contino, A. Magri', D. Sciotto, J. D. Lamb, "Selective Transport of Cesium and Strontium Ions Through Polymer Inclusion Membranes Containing Calixarenes As Carriers" , Supramolecular Chemistry , 10, 1998, 5-15 G. Arena, A. Casnati, A. Contino, G. G. Lombardo, D. Sciotto, R. Ungaro, "Specific Inclusion of The Aliphatic Moiety or The Aromatic Moiety of Ammonium Cations Ion By Water Soluble Calixarene Receptors: A Combined 1H- NMR and Calorimetric Investigation", Chemistry an European Journal , 5, 1999, 738. G. Spoto, A. Torrisi, A. Contino Probing Archaelogical and Artistic Solid Materials by Spatially Resolved Analytical Techniques Chem. Soc. Rev., 29, 2000, 429 E. Ciliberto e G. Spoto, Eds., Modern Analytical Methods in Art and Archaeology, John Wiley & Sons, Inc., New York, 2000. A. Casnati, D. Sciotto and G.Arena, Water Soluble Calixarenes in Molecular Recognition. Calixarenes 2001, Z. Asfari, V. Böhmer, J.M. Harrowfield and J. Vicens (Eds)., Kluwer Academic Publishers, Dordrecht, Chapter 24, p.440 (2001). 7. Scientific Output 7.1 Publication Policy The Unit is mainly involved in fundamental research; only recently, attention has been devoted to bench scale applications. Accordingly, the majority of scientific papers produced are published in fundamental research Journals. Over the last five years, 43 scientific papers have been published; in addition to these, 10 Master’s theses and 3 Ph.D. dissertations have been deposited. These figures show that clients, other than the scientific community, are scarce. As indicated by the reference list, some of the papers (paper n. 4 1997, paper n. 1 1998, paper n. 3 1998, paper n. 4 2000) testify that some of the work done by the Unit has or may find immediate practical application. However, the actual situation is sgnificantly changed. In fact, as indicated in Section 5.3, two projects submitted in conjunction with important local Industries, have passed the first screen getting a good score and are very likely to be funded. 249 7.2 Numerical data Category PhD-Dissertations 1997 2 1998 1999 2000 2001 1 Total 3 Scientific Publications 10 8 5 12 8 43 Professional Publications Master’s Theses 2 5 1 1 1 10 8 Self-evaluation The analytical chemistry Unit represents a minority within the Department of Chemistry of the University of Catania (6/87) and, consequently , has to bear the burden of a heavy teaching load (please see Teaching Load). Some of the courses are taught in towns other than Catania, which further reduces the time that can be spent for research activities. This reduces the apparent critical mass of the research unit. The unit often has to rely on work done by undergraduates (termed Master students, in the present report). Department facilities (equipment and labs) go from excellent to good. This does not apply to funding directed to people hiring; unfortunately, according to Italian regulations, very seldom funds can be employed to hire people. This creates serious problems as concerns the adequacy of staff needed to fulfil the mission. People trained during their Master thesis period (e.g. Paolo Bruno, who was awarded a national prize for his master thesis), very often quit because they are hired by other agencies/institutions (C.N.R., Istituto per l’essenze Agrumarie etc.). Perhaps, the centralized handling of the 488 funding, that represented the main funding source efforts were devoted to in this specific field (Please see end of Section 8 of 1998 review), together with the stop-and-go procedure adopted by the Ministry to allocate funds has contributed to accentuate the problems concerning the management of the Unit. Despite the above problems, the Unit has succeeded in reaching the goals set in the 1998 review. As specified in Section 6.1 . In line with the 1998 Review suggestions, thanks to fruitful collaboration with the Parma Unit, the Unit has designed and produced a chromatographic column that has been employed for the separation of Cs+. The Unit has also obtained results in the separation field that have attracted the attention of researchers active in the MRT field. This is testified by the invited lectures given over the past five years on this specific subject. The Unit leader has given the invited lectures listed below: Invited Speaker “Thermodynamics of Supramolecular Complexes”, Symposium on “New Materials and Reaction Design”, Saarbrücken, Germany, May 16, 1997. Invited Speaker “Supramolecular complexes of Water soluble Calix[4]arenes: A Combined H NMR and Calorimetric Investigation”, Department of Chemistry, University of Nagoya, Japan, March 3, 1998. 1 Invited Speaker “The use of Supramolecular complexes in Separation Science”, Department of Bioinorganic Chemistry, Kyoto Pharmaceutical University, Japan, March 4, 1998. Invited Speaker “Supramolecular complexes of Water soluble Calix[4]arenes: The Calorimetric Perspective”, Department of Inorganic and Bioinorganic Chemistry, Kanazawa University, Japan, March 5, 1998. Invited Speaker “Forces driving host-guest complexation: A thermodynamic perspective”, XIth International Symposium on Supramolecular Chemistry, Kyushu University, Fukuoka, Japan, August 3rd, 2000. Invited Speaker “Host-guest complexation: A thermodynamic perspective”, XXVIIth International Symposium on Macrocyclic Chemistry, Park City, Utah, U.S.A., June 26th , 2002. Invited Speaker “Host–guest interaction: Thermodynamics and Applications” , Chemistry and Biochemistry Department, Brigham Young University, Provo, Utah, U.S.A., June 21st , 2002 250 Invited Speaker “Molecular Design and Synthesis of Supramolecular Architectures” 2-nd International Symposium, Institute of Organic Chemistry, Kazan State University, Russia, August 26th 2002. The activity carried out in the field of the use and the optimization of spatially resolved methods in the study of the interaction between environment and materials of interest in art and archaeology has also attracted the attention of the researchers operating in the field as it is testified by a series of invitations obtained by one of the components of the Unit: Invited speaker: G. Spoto “Study of solid artistic and archaeological material by using spatially resolved analytical techniques”, 5th National Seminal of Analytical Spectroscopy, Aprile 2001, Gargnano (BS). Invited speaker: G. Spoto, The use of some surface analytical techniques in the study of ceramic and glass materials of relevance to art and archaeology, IV National School of Chemistry for Cultural Heritage, June, 2002, Altare (SV) Invited contribution: Chemistry in Britain, The Royal Society of Chemistry (G. Spoto, A restorer on trial, Chemistry in Britain, The Royal Society of Chemistry, 37(8), 2001, 2223.) Invited contribution: Accounts of Chemical Research, American Chemical Society (G. Spoto, Detecting past attempts to restore two important works-of-art, Accounts of Chemical Research, 35(8), 2002, 652-659.) Invited contribution: Kirk-Othmer Encyclopedia of Analytical Chemistry, John Wiley & Sons (G. Spoto, Chemical Methods in Archaeology, Kirk-Othmer Encyclopedia of Analytical Chemistry, John Wiley & Sons, submitted) The Analytical Chemistry group has also extended its research activity to herbicides and soil by using capillary electrophoresis and ESI mass spectrometry as testified by the papers listed in Section I-2. However, despite the goals reached on the scientific side, the Unit has still a lot to do as far as the interaction with nonacademic world is concerned. Only recently, some of the Unit components have submitted two projects (Act. 297 and PON) with well known Industries (Meridionale Impianti, ATS, Elen). These projects, (for a total amount of 500.000 and 15 million €, respectively) have already passed the first screening and, if funded, should significantly involve at least part of the Unit, provided a mutual agreement between the Department and INCA is duly signed. These projects should allow a more rationale use of the INCA equipment allocated in the Department. Appendix I Scientific Output I-1 Overview of Dissertations and Master's Thesis (1997-2001) I.1.1 Dissertations Year 1997 Ph.D. -student Antonio Magri 1997 Leonardo Mirone 2001 Elisa Longo Title of the Dissertation Supervisor Synthesi of calixarene derivatives and their Prof. G. Arena use as selective carriers in polimeric inclusion membranes for the separation of alkaline and alkaline-earth cations. Use of new calixcrowns in molecular Prof. D. Sciotto recognition technology for the detection and the separation of alkaline cations Synthesis and characterization of macrocyclic ligands to be employed in separation Co-Tutor Prof. D. Sciotto Prof. G. Arena 251 processes I.1.2 Master’s Thesis Supervisor Co-Tutor Name Master’s Title of the Dissertation Student 1997 Paolo Bruno* Thermal removal processes and Prof. G. Arena Dr. A. Febo determination of the UV absorption cross section of the nitrous oxide in relation to its role in the chemistry of the athmosphere 1997 Carmelo Sgarlata Prof. G. Arena Inclusion of natural L-α-aminoacids in water Prof. D. Sciotto soluble calix[4]arenic receptors 1998 Elisa Longo Inclusion of methylammonium cations in Prof. G. Arena Prof. R. Bonomo water soluble calixresorcinarenes 1998 Sonia Rita Capitanini Inclusion of neutral organic molecules in Prof. G. Arena Prof. R. Bonomo calix[4]arenes in non-aqueous solvents in water 1998 Giuffrida Alessandro α, α’-D-trehalose and β-cyiclodextrin Prof. Cucinotta V. bonded through β-alanine bridges: a new example of hemispherodextrin 1998 Corrado Maria Synthesis, NMR and potentiometric study of Prof. Cucinotta V. Concetta new trehalose derivatives 1998 Cultrera Massimiliano Synthesis, NMR characterisation and Prof. Cucinotta V. antitumoral activity of platinum(II) complexes with diamine derivative of βcyclodextrin 1999 PietroGemmellaro Flow isotherm calorimetry: optimization and Prof. G. Arena Prof. V. Cucinotta test of a new prototype 2000 Messina Marianna A new hemispherodextrin: synthesis, Prof. V. Cucinotta characterisation and its applications in capillary eelctrophoresis 2001 Costanza Ruggero Species formed by Hg(II) with a 1,3-alternate Prof. G. Arena Prof. A. Contino calix[4]arene derivatized with thioamidic groups *This thesis was recognized as one of the best theses in the environment field and awarded a national prize Year I-2 Overview of Scientific Publications (1997-2001) per year 1997 1. Arena G., A. Casnati, A. Contino, D. Sciotto, R. Ungaro, "Charge assisted hydrophobic binding of ethanol into the cavity of calix[4]arene receptors in aqueous solution." , Tetrahedron Letters , 38, 1997, 4685. 2. M. Cantiano, A. Scandurra, A. Licciardello, A. Torrisi, “SNMS Quantification of III-V Compounds Heterostructures”, in Secondary Ion Mass Spectrometry SIMS X, A. Benninghoven, H. Werner, editors, Wiley, Chichester, 1997. 3. E. Ciliberto, S. Scuto, G. Spoto, “Osservazioni Preliminari sulla Forma e sulla Composizione Chimica e Strutturale di Pentole Tripodate nella Poliochni Rossa”, in Poliochni e l’Antica Età del Bronzo nelle’Egeo Settentrionale, Scuola Archeologica Italiana di Atene, (1997), 134-144. 4. E. Ciliberto, G. Spoto, "Fluorapatite Coatings by Metal Organic Chemical Vapor Deposition", Chemical Communications, 16, 1997, 1483-1484. 5. R.Rizza, D. Fitzmaurice, S. Hearne, G. Hughes, E.Ciliberto, G. Spoto, "Self-Assembly of Monolayers of Semiconductor Nanocrystallites", Chemistry of Materiarls, 18, 1997, 2969-2982. 252 6. G. Arena, R. P. Bonomo, A. Contino, F. Gulino, A. Magrì, D. Sciotto “New water soluble calixarenes: 5,11,17,23tetrasulphonated-25,27-bis(hydroxycarbonylmethoxy)-26,28-dihydroxy calix[4]arene. a thermodynamic and spectroscopic investigation of its proton and copper(II) complexes”, J. Inclusion Phenom., 29, 1997, 3-4. 7. G. Arena, A. Casnati, L. Mirone, D. Sciotto, R. Ungaro, “A New Water-Soluble Calix[4]Arene Ditopic Receptor Rigidified By Microsolvation:Acid Base And Inclusion Properties”, Tetrahedron Lett., 38, 1997, 1999. 8. V.Cucinotta, G.Grasso, S.Pedotti, E.Rizzarelli, G.Vecchio Three-Dimensional Cyclodextrin: A New Class Of Hosts By Trehalose Capping Of β-Cyclodextrin., J.Incl.Phenom., 25 (1997) 81. 9. V.Cucinotta, F.D'Alessandro, G.Impellizzeri, G.Maccarrone, E.Rizzarelli, G.Vecchio, L.Carima, R:Corradini, G.Sartor and R.Marchelli Chiral Recognition By The Copper(Ii) Complex Of 6-Deoxy-6-N-(2-Methylaminopyridine)-βCyclodextrin, Chirality, 9, 341, 1997. 10. V.Cucinotta, D.Grasso, G.Grasso and D.Milardi Calorimetric Evidences For Copper(II)-Regulated Chiral Recognition Between Decanucleotide 5'd(CTGGATCCAG)2 And Ala-Trp Dipeptides., Nucleosides Nucleotides, 16 (1997) 1847. 1998 1. E. Ciliberto, G. Spoto, M. Matteini" A Scientific Approach for Cultural Heritage Preservation: Case Study of Vandalic Acts on Important Roman Mosaics", Journal of Chemical Education, 75, 1998, 1302-1306. 2. G. Arena, C. Conato, A. Contino, F. Pulidori, R. Purrello, M. Remelli and G. Tabbì “Cu(II)-L-Glutamine and LAsparagine Binary Complexes. A Thermodynamic and Spectroscopic Study” Annali di Chimica, 88, 1998, 1. 3. Arena G., A. Contino, A. Magri', D. Sciotto, J. D. Lamb, "Selective Transport of Cesium and Strontium Ions Through Polymer Inclusion Membranes Containing Calixarenes As Carriers" , Supramolecular Chemistry , 10, 1998, 5-15 . 4. R.Bonomo, V.Cucinotta, G.Grasso, G.Maccarrone and L.Mastruzzo Stereoselectivity in the interactions between an oligo-deoxynucleotide and dipeptides in the presence of the copper(II) ion.. J. Inorg. Biochem., 70, 1 1998. 5. From Capped To Three-Dimensional Cyclodextrins: The First Example Of A New Class Of Receptors By Trehalose Capping Of β-Cyclodextrin. V.Cucinotta, G.Grasso, G.Vecchio, J.Incl.Phenomena. 31 (1998) 43. 6. Three-dimensional cyclodextrins. Diaminotrehalose capped β-cyclodextrin: a thermodinamic and spectroscopic study, V.Cucinotta, G.Grasso, G.Maccarrone, A.Mazzaglia, G.Vecchio, Proceedings of the "Xth International Symposium on Molecular Recognition and Inclusion" Warsaw (Polonia) 20-25 Giugno 1998 p-1. 7. Three Dimensional Cyclodextrins: A New Class Of Receptors, V.Cucinotta, G.Grasso, G.Maccarrone, A.Mazzaglia, G.Vecchio, Proceedings of the "1st International Conference on Supramolecular Science & Technology", Zakopane 27-3 ottobre 1998, p. 78 8. Hemispherodextrins: A New Class Of Hosts By Trehalose Capping Of Cyclodextrins, V.Cucinotta, G.Grasso, G.Maccarrone, A.Mazzaglia, G.Vecchio, Proceedings of the "First COST D11 Workshop on Supramolecular Chemistry" Perugia 1-4 Ottobre 1998, p-37. 1999 1. Arena G., A. Casnati, A. Contino, G. G. Lombardo, D. Sciotto, R. Ungaro, "Specific Inclusion of The Aliphatic Moiety or The Aromatic Moiety of Ammonium Cations Ion By Water Soluble Calixarene Receptors: A Combined 1H- NMR and Calorimetric Investigation", Chemistry an European Journal , 5, 1999, 738. 2. Arena G., A. Contino, F.G. Gulino, A. Magri', F. Sansone, D. Sciotto, R. Ungaro, "Complexation of Native L-αAminoacids By Water Soluble Calixarenes" , Tetrahedron Letters , 40 , 1999, 1597-1600. 3. Giuseppe Arena, Annalinda Contino, Takako Fujimoto, Domenico Sciotto and Yasuhiro Aoyama. “1H NMR and calorimetric studies of the inclusion of trimethyl-ammonium cations into water soluble calixresorcinarenes” Supramolecular Chem., 11, 1999, 279. 4 V.Cucinotta, G.Grasso, G.Maccarrone, A.Mazzaglia, G.Vecchio. Inclusion Properties, Metal Ion Coordination Ability And Analytical Applications Of Trehalose Capped Cyclodextrins. Proceedings of the Ninth International on Cyclodextrins, 501, 1999. Kluwer Academic Publishers. 5. M.Saviano, R.Iacovino, E.Benedetti, V.Cucinotta, G.Grasso and D.ScioCrystal Structure Of 6,6’-Ditosyl-α,α’-Trehalose – Methanol – Water (1/2/2), C52H68O30S4 2CH3OH 2H2O. tto, Z.Kristallogr. NCS, 214 (1999) 297. 2000 253 1. Arena G., A. Casnati, A. Contino, F.G. Gulino, D. Sciotto, R. Ungaro, "Entropic origin of the sulfonate groups electrostatic assistance in the complexation of quaternary ammoniun cations by water soluble calix[4]arenes." , J. Chem. Soc., Perk. Trans. II , 3, 2000, 419-423 ,. 2. Chiara Conato, Annalinda Contino, Giuseppe Maccarrone, Antonio Magrì, Maurizio Remelli and Giovanni Tabbì, “.Copper (II) complexes with L-lysine and L-ornithine: is the side-chain involved in the coordination? A thermodynamic and spectroscopic study”, Thermochim. Acta, 362, 2000, 13. 3. Probing Archaelogical and Artistic Solid Materials by Spatially Resolved Analytical Techniques Giuseppe Spoto, Alberto Torrisi and Annalinda Contino Chem. Soc. Rev., 29, 2000, 429. 4. Giuseppe Arena, Annalinda Contino, Antonio Magrì, Domenico Sciotto, Giuseppe Spoto, Alberto Torrisi “Strategies Based On Calixcrowns For The Detection And Removal Of Cesium Ions From Alkali Containing Solutions” Ind. Eng. Chem. Res., 39, 2000, 3605. 5. Giuseppe Arena, Annalinda Contino, Fabio Giuseppe Gulino, Antonio Magrì, Domenico Sciotto, Rocco Ungano “Complexation of Small Neutral Organic Molecules By Water Soluble Calix[4]Arenes” Tetrahedron Lett., 41, 2000, 9327. 6. G. Spoto , E. Ciliberto, G.C. Allen, C.M. Younes, P. Piccardo, M.R. Pinasco, E. Stagno, M.G. Ienco, R. Maggi, “Chemical and Structural Properties of Ancient Metallic Artefacts: A Multitechnical Approach for the Study of Early Bronzes”, British Corrosion Journal, 35(1), 2000, 43-47. 7. F. Iacona, G. Casella, F. La Via, S. Lombardo, V. Raineri, G. Spoto, “Structural Properties of Fluorinated SiO2 Thin Films”, Microelectronic Engineering, 50 (1-4), 2000, 67-74. 8. G. Spoto, P. Rizzarelli, A. Torrisi, “Fluorinated Phosphoric Ester-based Protective Material for Limestone-made Ancient Monuments, Buildings and Artifacts: an X-ray Photoelectron Spectroscopy Study”, Applied Spectroscopy, December, 54(12), 2000, 172-179. 9. Giuseppe Spoto, “Secondary Ion Mass Spectrometry in Art and Archaeology”, Thermochimica Acta, December, 365(12), 2000, 157-166 10. E. Ciliberto e G. Spoto, Eds., Modern Analytical Methods in Art and Archaeology, John Wiley & Sons, Inc., New York, 2000. 11. E. Ciliberto, G. Spoto, in “Donatello restaurato : i marmi del pulpito di Prato”, Anna Maria Giusti, Ed. Artout : Maschietto & Musolino, Pistoia, 2000, pp. 79-86. 12. R. Lauceri, S. Gurrieri, E. Bellacchio, A. Contino, L. Monsù Scolaro, A. Romeo, A. Toscano, R. Purrello, J-Type Aggregates of the Anionic Meso-Tetrakis(4-Sulfonatophenyl)Porphine Induced by ''hindered'' Cationic Porphyrins, Supramolecular Chem., 12, 193 (2000). 2001 1.1. G. Spoto, A restorer on trial, Chemistry in Britain, 37, 22 (2001). 2. G. Arena, A. Contino, E. Longo, D. Sciotto, G. Spoto, Selective Complexation of Soft Pb2+ and Hg2+ by a Novel Allyl Functionalized Thioamide Calix[4]arene in 1,3-Alternate Conformation: a UV-Visible and 1H NMR Spectroscopic Investigation, J. Chem. Soc. Perkin 2, 2287 (2001). 3. G. Arena, A. Contino, A. Magrì, D. Sciotto, A. Arduini, A. Pochini, A. Secchi, Energetics of the Inclusion of Organic Molecules by Rigidified Cone Calix[4]arenes in Carbon Tetrachloride, Supramolecular Chem., 13, 379 (2001). 4. A. Casnati, D. Sciotto and G.Arena, Water Soluble Calixarenes in Molecular Recognition. Calixarenes 2001, Z. Asfari, V. Böhmer, J.M. Harrowfield and J. Vicens (Eds)., Kluwer Academic Publishers, Dordrecht, Chapter 24, p.440 (2001). 254 5. F. Iacona, G. Ceriola, G. Spoto, “Infrared Spectroscopy Study of the Thermal Stability of Fluorinated SiO2 Thin Films”, Journal of Electrochemical Society, The Electrochemical Society, Pennington, (USA), Aprile, 148(4), F47-F50 (2001). 6. V. Cucinotta, A.Giuffrida, G.Grasso, G.Maccarrone, A.Mazzaglia, G.Vecchio New Cyclodextrin Derivatives As Chiral Selectors In Capillary Electrophoresis, , Fresenius .J.Anal.Chem., 370 (2001) 363. 7. Vincenzo Cucinotta, Alessandro Giuffrida, Giulia Grasso, Giuseppe Maccarrone, Graziella Vecchio Hemispherodextrins, A New Class Of Cyclodextrin Derivatives, In Capillary Electrophoresis, , J.Chromatogr. A, 916 (2001) 61. 8. R.P.Bonomo, V.Cucinotta, G.Maccarrone, E.Rizzarelli, G.Vecchio Thermodynamic stereoselectivity assisted by weak interactions in metal complexes. Chiral recognition of L/D-aminoacids by the copper(II) complex of 6-deoxy-6-[4-(2aminoethyl)imidazolyl]-cyclomaltoheptaose, , J.Chem.Soc., Dalton Trans., 2001, 1366 Appendix 2 Ranking Scientific Journals Name of Journal Number of Journal Impact Field(s) Articles factor Chemical Society Reviews 1 9.137 Chemistry Chemistry an European 1 4.614 Chemistry Journal Chem. Comm. 1 3.902 Chemistry Chemistry of Materials 1 3.690 Chemistry, Physical J. Chem. Soc., Dalton Trans 1 2.820 Chemistry, Inorganic and Nuclear Journal of Chromatography 1 2.793 Chemistry Analytical A Tetrahedron Letters 4 2.280 Chemistry, Organic J. Electrochem Soc. 1 2.033 Electrochemistry J. Chem. Soc., Perkin Trans 2 2 1.837 Chemistry, Organic Applied Spectroscopy 1 1.752 Spectroscopy J. Inorg. Biochem. 1 1.729 Chemistry, Inorganic and Nuclear Fresenius Journal of 1 1.649 Chemistry Analytical Analytical science Chirality 1 1.554 Chemistry, Analytical Supramolecuar Chemistry 3 1.543 Chemistry Industrial and Engineering 1 1.351 Engineering Chemical Chemical Research J. Inclusion Phenom. 3 1.150 Chemistry Termochim. Acta 2 1.010 Chemistry, Analytical Microelectronic Engineering 1 0.705 Engineering Electrical & Electronic Journal of Chemical 1 0.596 Chemistry Education Chemistry in Britain 1 0.586 Chemistry Nucleosides and nucleotides 1 0.508 Biochemistry & Mol. Bio. Annali di Chimica 1 0.394 Chemistry, Analytical Zeitschrift Fur 1 0.283 Cristallography Kristallographie-New Crystal Structures British Corrosion Journal 1 0.211 Metallurgy Appendix 3 Journal Portfolio Analysis Ranking 3/118 7/118 11/118 12/93 10/42 6/68 13/51 3/15 20/51 14/40 16/42 22/68 25/68 30/118 13/123 36/118 39/68 81/200 70/118 71/118 281/308 60/68 18/19 41/67 255 Name of the Unit: Catania Research Director: Years included Name of Journal Analytical Chemistry Laboratory, Department of Chemical Science, University of Professor Giuseppe Arena 1997-2001 Number of Journal Impact Field(s) Articles factor Chemical Society Reviews 1 9.137 Chemistry Chemistry an European 1 4.614 Chemistry Journal Chem. Comm. 1 3.902 Chemistry Chemistry of Materials 1 3.690 Chemistry, Physical J. Chem. Soc., Dalton Trans 1 2.820 Chemistry, Inorganic and Nuclear Journal of Chromatography 1 2.793 Chemistry Analytical A Tetrahedron Letters 4 2.280 Chemistry, Organic J. Electrochem Soc. 1 2.033 Electrochemistry J. Chem. Soc., Perkin Trans 2 2 1.837 Chemistry, Organic Applied Spectroscopy 1 1.752 Spectroscopy J. Inorg. Biochem. 1 1.729 Chemistry, Inorganic and Nuclear Fresenius Journal of 1 1.649 Chemistry Analytical Analytical science Chirality 1 1.554 Chemistry, Analytical Supramolecuar Chemistry 3 1.543 Chemistry Industrial and Engineering 1 1.351 Engineering Chemical Chemical Research J. Inclusion Phenom. 3 1.150 Chemistry Termochim. Acta 2 1.010 Chemistry, Analytical Microelectronic Engineering 1 0.705 Engineering Electrical & Electronic Journal of Chemical 1 0.596 Chemistry Education Chemistry in Britain 1 0.586 Chemistry Nucleosides and nucleotides 1 0.508 Biochemistry & Mol. Bio. Annali di Chimica 1 0.394 Chemistry, Analytical Zeitschrift Fur 1 0.283 Cristallography Kristallographie-New Crystal Structures British Corrosion Journal 1 0.211 Metallurgy Ranking 3/118 7/118 11/118 12/93 10/42 6/68 13/51 3/15 20/51 14/40 16/42 22/68 25/68 30/118 13/123 36/118 39/68 81/200 70/118 71/118 281/308 60/68 18/19 41/67 256 CATANIA 5 Name of the Research Unit Processi e trasformazioni ambientali Environmental Processes and Transformations University: Università degli studi di Catania University of Catania Faculty: Scienze Sciences Department: Scienze Chimiche Chemical Sciences Thematic area Research Leader Prof. Vito Librando Contact Person (The name and address of the person who will act as liaison between the unit and the INCA-Secretariat) Prof. Vito Librando Dipartimento di Scienze Chimiche Viale A. Doria, 6 95126 Catania 095 7385201 095 330424 [email protected] Please indicate to which thematic area of INCA the unit belong (in priority order): • Chimica degli ecosistemi (chimica del suolo, delle acque e dell’aria; impatto dei prootti di sintesi sull’ambiente). •Tecnologie innovative di monitoraggio •Tecnologie di depurazione (membrane, sonochimica, fotocatalisi, elettrochimica e altre). Introduction and Context Introduction to the Self-evaluation Report The University, the Faculty and the Department The University of Catania is the 9th University in Italy, as far as student population is concerned. The total number of the students (Academic Year 2000-2001) is 53030; outs of these 5652 are enrolled in Courses offered by the Faculty of Mathematical, Physical and Natural Sciences. The University serves mainly five provinces (Catania, Enna, Caltanissetta, Siracusa and Ragusa). The high percentage of students coming from districts other than Catania’s induced the opening of courses in other cities in the nearby (Siracusa, Ragusa, Enna, Caltagirone). The University of Catania is the 2nd University of Italy to have filed a report for the Quality Audit Programme of the Conference of European Rectors. The University of Catania was also one of the first Universities to participate to the INCA consortium. The total teaching staff of the University is composed of 1506 members. 316 are members of the Faculty of Sciences. The Department of Chemical Sciences is the largest Department of the University of Catania in terms of staff, with 86 professors and researchers and 37 technicians and administratives. The research activities of the Department cover all the most important chemical areas (environmental, organic, inorganic, analytic, industrial, physical and biological). The Department is involved in several EU projects, in cooperative projects with national and international institutions and is strictly linked to the main local industries. The Department supports the research groups through its technical and administrative services, providing sophisticated equipment and a well-furnished library. The Unit The unit is the only Southern unit that include «Environmental Chemistry» as teaching course serving different student of the Faculty. In this way the group is involved hardly also in teaching other than carry out research in «Environmental Chemistry». The research team, at the moment, is constitute by four researchers: Prof. Vito Librando, Prof. Gaetano Tomaselli, Prof. Giuseppe Scarlata, Prof. Stefania Stefani, Prof. Guido Romano, Prof. Francesco Castelli and Dott. Giancarlo Perrini. The unit is well equipped and in June 2002 moved in a larger lab where find place hall scientific 257 instrument (Several PC, Capillary GC Perkin - Elmer 800 provided with three different detectors ( FID, ECD, NPD), GC - MS Fison MD 800, HPLC Perkin - Elmer series 200, UV detector for HPLC Perkin – Elmer, Fluorescence detector with programmable wavelength for HPLC Perkin – Elmer). The research topics concern exclusively environmental chemistry and particularly the Biogenic and athropogenic pollutants that interests atmosphere and waters. Our more recent topics are the reactivity of DMS and terpenes in OH initiated reactions, the degradation of PAH and N-PAH by ozone, the PAH extraction procedure by SFE from soil and the use of passive biological samplers (leaves of plants) to measure air pollution. The components of our group have the following teaching load: Prof. V. Librando: Environmental Chemistry, near the followings: Biological Sciences degree, Industrial Chemistry degree, Environmental Chemistry Diploma (Siracuse site), Environmental Economics degree; Fundamentals of Evironmental Impact Assessment Natural Sciences degree; Atmospheric Chemistry near the Master in Environmental Impact Assessment held at the Superior School of Catania (Excellence School). Prof. Gaetano Tomaselli, Organic Chemistry, Chemistry Degree, Prof. Giuseppe Scarlata: Dyes Chemistry, Industrial Chemistry Degrees; Prof. Francesco Castelli, Applied Farmaceutical Chemistry, Chemical and Farmaceutical Technologies Degree; Environmental Chemistry Laboratory, Environmental Toxicology Degree. Prof. Stefania Stefani, Environmental Microbiology, Biological Sciences Degree. Prof. Guido Romano: Forensic Toxicology and Chemistry followed by students from Medical School; Dott. Giancarlo Perrini: Laboratory of Chemistry for Biological sciences students and Environmental Chemistry, Natural Sciences degree. In the laboratory are at this moment present four graduate students (one Industrial Chemistry and tree Biological Sciences) that work on their theses on themes concerning environmental organic chemistry. At the moment there are not PhD-students. It is due to the fact that the unit leader holds his institutional course in the Biological Sciences Degree where there isn't a PhD-course in Environmental Chemistry; as opposed to Chemistry Department degree courses where there is a PhD in Chemistry but aren't Environmental Chemistry curricula.. Programme Description and Evaluation 1 Title Environmental Processes and Transformations 2 Research Leader Prof. Vito Librando 2a Sub-programme titles and sub-programme leaders 3 Composition of the scientific research staff of the unit per 1 January 2002 Names and Titles Vito Librando, Dr Year Birth 1946 Giuseppe Scarlata, Dr. Castelli Francesco Guido Romano, Dr. 1936 1954 1948 Corsato A. Dr. 1944 Giancarlo Perrini, Dr. 1953 Sarpietro M. Grazia Dr. Tomasello Massimo Dr. Tringali Giuseppe Dr. 1966 1971 1974 Manigrassi Damiano Dr. 1974 Pozzoli Luca Dr. 1978 Total Comments of Rank Associated Professor Full Professor Full Professor Associated Professor Associated Professor Senior Researcher Borsista Borsista Prestazione d’opera INCA Prestazione d’opera INCA Prestazione d’opera CNR Research Input in fte Remarks in “2001 0.5 0.2 0.5 0.2 Starting 1999 0.0 Until 2000 0.8 0.3 0.3 0.5 0.2 0.1 4 258 At the first January 2001 the unit grown respect to 1997 increasing the fte from 3.7 to 4.0. Starting from 1999 Prof. Francesco Castelli, Full Professor of Farmaceutical Chemistry, joined the group. Starting from 2002 Prof. Gaetano Tomaselli, Full Professor of Organic Chemistry joined the group with the aim of strengthen the ability of the unit to work also on the thematic area of his expertise (synthesis environmental friendly). The participation to the unit had a first result documented by a paper submitted to Env. Sci. & Technology. Starting from 2002 Prof. Stefania Stefani, Full Professor of Environmental Microbiology joined the group with the aim of strengthen the ability of the unit to work on soil bio-remediation topic. At the moment it isn't possible to plan a researcher assumption, since Chemistry Department policy is to support scientific-disciplinary areas with a greater number of voting people, and Environmental chemistry is not among those areas. For that reason we continue in the immediate future (2-3 years) to recruit researchers whit annual turnover and contract paid with team fund. 4 Input of Academic Staff in fte Category Full Professors Associated Professors Ricercatori Post-docs PhD-students Borsisti Total 1997 0.5 1 0.9 0 0 1 3.4 1998 0.4 1 0.9 0 0 1 3.3 1999 .5 1 0.9 0 0 1.2 3.6 2000 .5 1 0.8 0 0 1.4 3.7 2001 .5 1.0 0.8 0 0 1.4 3.7 Total 2.9 2.5 4.3 0 0 6 15.7 Comments Comparing the Professor Academic Staff input of the year 2001 to the one of 1997 it is clear that aren't been major changes despite we observe a greater input from full professors rather than associated professors. The reasons are explained on the comments to point 3. The researcher contribution is diminished because of a greater teaching load. The number of people joined the unit is grown anyway. The greater contribution is supplied by grantees, who, as said before, are financed by the staff funds. Comparing the totals it is clear how the Academic Staff input is constantly grown up in the years 1993-2001, from 0.4 (1993) to 4.0 (2001) instead the total input of the years 93-97 grew from 8.5 (93-97) to 19.3 (97-01). Last note: The mean input/year of the Academic Staff was 3.86 fte during 1997-2001 period. 5 Funding 5.1 Personnel (in fte) Source University CNR European Union Other Sponsors Total 5.2 1997 2.4 0 0 0 3.7 1998 2.3 0 0 0 3.1 1999 2.4 0 0 1.2 4.3 2000 2.3 0 0 1.4 4.2 2001 2.3 0.1 0 1.3 4 Total 10.7 0.1 0 3.9 19.3 1999 19,0 4 0 10 33 2000 81,5 5 0 0 91 2001 102,7 50 0 5 164 Total 252 79 1,5 70 398 Materials and Equipment (in Million Lire) Source University - MURST CNR EU Other Sponsors Total 1997 19,5 15 1,5 35 71 1998 14,0 5 0 20 39 5.3 Comments: The annual trend of the Total Personnel increase slowly due the strong contribute of non permanent staff. The reduction of the permanent staff is physiological and we foresee in the next future an inversion of trend due the aggregation of other colleagues that want co-operate with our unit. The annual trend of material and equipment expenses need no comments. 259 The strategy of our unit has been to relay the funding mostly participating to local (University, Sicily Region), national (MIUR, CNR) and European (EU) competition. In this respect the applications were successfully supported by the grants given regularly by University, MIUR and CNR during the period considered. Particularly relevant were the funding obtained in 2001 by CNR under the scheme AGENZIA 2000 which were not available in the previous time. The success in obtaining funding from CNR testifies the good quality of the applied research of the Unit carried out within an effective national collaboration. Further the Unit was one of only five Units selected for financial support under AGENZIA 2000 CNR call. The EU support has been looked for and obtained in the framework of an INTAS call. Further funds come from the Project Terrestrial Environment Cluster, directed by Prof. P. Tundo within the 488 law. In the future, besides the effort to enhance the support from grant Agencies, the unit believe that the co-operation with local firms and Authorities should guarantee increasing funding for researches linked to the Unit mission. The grants will be used to cover personal expenses on the basis of mean term contracts. The most part of the funds is and will be used for the formation grants, consumer and durable materials. Among these funds the research contracts costs counterbalances the lack of steady personnel in the staff. It is and it will be necessary to support maintenance and repair costs of the staff equipment, which are not far from obsolescence. Further the unit is examining the possibility to establish a Consortium between INCA and local Authorities of the highly polluted area of Siracuse Province, to study remediation techniques of contaminated soils. In this case the grants will be used to acquire an Extractor in Supercritical Phase. Please add a list of major sponsors and the character of the liaison with the major sponsors Regione Sicilia, Programma Operativo Plurifondo cofinanced by EU, Monitoring of Chemical Pollution of Superficial Waters in Highly Polluted Area. INCA, Piano Ricerca Interesse Nazionale, Progetto Chimica dell’atmosfera urbana, Coordinator Prof. S. Coluccia, Director of the Unit Torino 5, INCA. 6. Progress Report 6.1 Mission Statement Taking account of the previous assessment results, formulated by the International Review Committee, the Unit has reexamined its research focus, based principally on analytical aspects of Polycyclic Aromatic Compounds (PACs), decreasing the attention given to PACs and extending the interest to others environmental topics with respect to the thematic area of the INCA. The research focus of our group is within environmental chemistry and during the last five years concerned the followings four themes: a) Advanced monitoring techniques of environmental pollutants; b)Degradation studies Biogenic and of Anthropogenic pollutants; c)Mechanism of transport of micropollutants in biological system models; d)Reactivity of environmentally interesting compounds toward dipoles. Part of the theme (b) is going to finish, the theme (c) is a new theme active from 1999 and topic (d) is not more active from 2000 due the increasing “environmental” interest of the other topics. From last year the unit is also involved in an innovative research topic: e) Biochemical and Chemical Remediation. At the moment, continuing the focusing on the most impressive topics that have relevance for the science but firstly for society, we are addressing our interest towards the only following three: Degradation studies and impact of environmentally important chemicals, Mechanism of transport of micropollutants in biological system models, Biochemical and Chemical remediation. However in the 6.2 point we describe all researches program. Our interests concern both aspects of Pure and Applied research. The firsts themes are finalised to optimise the methods used in the environmental control and remediation. Particularly degradation studies are also finalised to knowledge of atmospheric reactivity and, consequently, to climate change, but also to treatment wastewater’s and soil remediation. The methods that use passive samplers, systems of great interest, have an immediate applicability and made possible the routine control of the air quality in industrial, urban and rural area. The local Authorities and Industrial Firms could be strongly interested to our researches which results can help to solve the problems ranging from pollution to environmental impact of industrial emissions. We are also involved on the formation of young graduate in the above Sciences with a strong basis in Environmental Chemistry and young post-graduate people in Environmental Chemistry topics. All the above research topic are within the following thematic INCA area: Chimica degli ecosistemi; tecnologie innovative di monitoraggio; tecnologie di depurazione. 6.2 The Research Programme Theme a. Advanced monitoring techniques of environmental pollutants a1) Environmental chemometrics. This theme, following the previous assessment results, has been cut on 1998 due the fact that statistical methods, which are put forward as a sub-programme, were seen by the Committee more as research 260 tools than as a major area of innovative research. However the last research results has been published (see paper 5, 6 and 19). a2) Biological passive samplers A short summary of the design of the programme Polycyclic aromatic hydrocarbons (PAH) are a major group of environmental pollutants, carcinogens and mutagens, they are the products of incomplete combustion of organic substances and are released from both natural and anthropogenic sources such as motor vehicles, power plants, industrial sites, incinerators and others. During combustion PAH are at first emitted as gases, heavier PAH (with more than three rings) are rapidly attached to existing particles, usually soot particles, by adsorption or condensation. The more volatile PAH will exist in the gas phase. PAH are mostly sorbed on small inhalable particles which can be deposited in the respiratory tract causing potential risks on human health. For this reason, monitoring the PAHs atmospheric concentration has become a problem of great relevance. The aim of the research work is to develop an atmospheric analytic method through biological passive samplers as opposed to time-wasting particulate matter sampling. Biological passive samplers are vegetable organisms (leaves and fruits of plants) whose surface accumulates atmospheric or aquatic organic pollutants. At this moment the compounds of interest are PACs but we are extending the research to other environmental important molecules. Superior plants produce lipids which are distributed on the surface of leaves, providing a protective function. When they come into contact with organic substances they establish an equilibrium between the adsorbed compounds and those in vapour phase. PAHs present in vapour phase are dissolved by lipids making it possible to evaluate the quantity present in the atmosphere on the basis of concentrations found in the lipophile surface layer. The adsorption level of pollutants under examination on various types of leaves can vary considerably due to the difference in the lipid content and the surface available for the accumulation. Samplings take place in different seasons and in different sites of the urban area of Catania, by collecting three different plant species in each site in order to evaluate atmospheric PAHs spatial distribution. On the other hand, chosen a site it is possible to sample many different species, since there are quali-quantitative differences between PAHs accumulated by different species. Only evergreen plants with long life leaves are sampled, in the same time particulate matter is sampled too through a high volume electric pump. Samples are solvent extracted and purified by SPE cartridges before GC/MS analysis. 15 PAHs (Mw 152 to 278) concentration are measured and each PAH is identified through its mass spectra and retention time; then PAHs leaves concentrations are correlated to particulate matter's. Among sampled plants, Olea europaea and Quercus ilex show high values of linear correlation coefficient in all the seasons and their profiles are similar to particulate matter's, it is so possible to extrapolate atmospheric PAHs concentration values by measuring those found on the leaves. Washing the leaves with distilled water has no influence on PAHs leaves content since these pollutants are strongly adsorbed on the leaves waxy layer and are not simply deposited on their surface. This method reduces the problems which influence the usual methods ofsampling: it is independent from meteorological factors, is not influenced by accidental peaks of pollution and doesn't requires particular sampling devices that are subject to errors caused by PAHs degradation during sampling. A substantive overview of the most impressive results over the past five years In order to find the best passive samplers among the widespread evergreen plants of the urban area of Catania, a one year screening was made among eleven different plant species. The results were impressive, since it was possible to discard some plant such as pines whose particulate matter correlation was bad in all the seasons and to focus on other plants such as Olea europea (olive tree) and Quercus ilex (holm-oak) whose R2 (referred to particulate matter) were greater than 8,5 all the year through. A brand new purification method based on SPE has been developed in order to make the whole process faster and more reproducible than previous silica gel column purification. A short overview of the programme development in the future New samplings has been scheduled both in urban and rural areas of oriental Sicily in order to strengthen the previous results. Other plant species will be investigated to find suitable passive samplers. Results has been presented also at some symposium. Theme b. B1) Degradation studies of Biogenic compounds A short summary of the design of the programme (scientific problem formulation, objectives, subject matter, research methods and anticipated results) The research activity was based on the study of two important kinds of biogenic compounds of environmental interest: monoterpenes, by taking into consideration the atmospheric behaviour of α - pinene, β-pinene, limonene, sabinene and 3-carene; compounds containing sulphur such as dimethylsulphide(DMS). Monoterpenes represent about 11% (500 ± 825 Tg/y) of the total amount of Volatile Organic Compounds (VOCs) of biogenic origin emitted to the atmosphere and they are highly reactive with oxidising species in troposphere, like OH radical and nitrate radical, NO3. Among compounds containing sulphur of biogenic origin, DMS has an important role as a determining factor of a feedback loop regarding phytoplankton, atmospheric sulphur, the Clouds Condensation Nuclei (CCN) and clouds 261 albedo. DMS, in fact, constitutes the greatest natural source of atmospheric sulphur and represents about 40% of the total of compounds containing sulphur emitted to the atmosphere. The emission of DMS from biogenic sources plays an important role in the atmospheric chemistry and physics, since the tropospheric degradation of these species contributes to the total amount of acids and to aerosols formation and growth. The oxidation processes involving monoterpenes are expected to have a great importance, both considering formation and release in the atmosphere of CO and acetone, and formation of tropospheric ozone and OH radicals. As a consequence, the investigation of the reaction products obtained both in gas phase and in liquid/aerosol phase from their photo-oxidation could help us to evaluate the contribution to atmospheric levels of acetone and acids and to estimate the total amount of sulphur species available for the formation of aerosol sulphates. The degradation processes of the two kind of chemical compounds were performed into an atmospheric reactor (Smog chamber) at Joint Research Centre, Institute for environment and sustainability, using OH radical as oxidizing species and investigating decrease of the reagents and increase of the reaction products by FT-IR spectroscopy. Ion chromatography and HPLC-MS were used to investigate products in liquid phase collected on Teflon filters from the smog chamber. A substantive overview of the most impressive results over the past The data obtained from monoterpenes oxidation were shown at scientific meetings and congresses and submitted to various journals. Our laboratory results allow us to propose a reaction mechanism for α - pinene with OH radicals. Acetone was obtained from all monoterpenes considered in this laboratory work. The importance of acetone lies in the possibility of further reactions with UV light, O2 and NO2, from which peroxyacetylnitrate (PAN) is obtained, an organic compound with a significant environmental toxicity. The formation of pinic and pinonic acid confirmed the remarkable role of these species to the total amount of secondary aerosols in the atmosphere, obtained from condensation processes of such a species with low vapour pressure. These results constitute the base of the article “OH-INITIATED OXIDATION OF MONOTERPENES: REACTION MECHANISM OF α-PINENE”, submitted to “Annali di Chimica” (2002). From DMS degradation experiments carried out at increasing levels of NOx (<20 ppb, 1 ppm, 10 ppm), we found as main products containing sulphur: dimethylsulphoxide (DMSO), dimethylsulphone (DMSO2), SO2, methanesulphonic acid (MSA), methanesulphinic acid (MSIA) and methylsulphonylperoxynitrate (MSPN). We used NOx almost exclusively constituted by NO2: initial concentration of NO varied from 24 ppbV (NOx = 1ppmV) and 953 ppbV (NOx = 10 ppmV). Any substantial variation in the molar yields (%) of reaction products have been recorded in the experiments performed at a NOx (NO+NO2) level of 1 ppm; at higher NOx levels a decrease in the molar yield of SO2 is obtained, with the contemporary increase of MSPN formation. Products obtained in aerosol phase were deeply discussed in the article “AEROSOL FORMATION AND REACTION PATHWAYS OF ATMOSPHERIC OXIDATION OF DIMETHYLSULFIDE” Published by the scientific journal “Annali di Chimica” (2001). A more detailed explanation of the other conclusions obtained from this laboratory work can be find in the article "OH-INITIATED OXIDATION OF DMS/DMSO: REACTION PRODUCTS AT HIGH NOx LEVELS" submitted to the scientific review "Physical Chemistry Chemical Physics". A short overview of the programme development in the future (the coming 5 years) including the means needed for realising the programme's mission. Please comment on any change due to expected mobility of senior staff. The Environmental Chemistry Group of the University of Catania is involved in a scientific network on Atmospheric Chemistry that contemplates an important partnership with the Chemistry Department of the University of Torino in which, the availability of a new Smog chamber coupled with an FT-IR spectrometer for on-line analysis would allow us to consider further deepening of the degradation mechanism of the different compounds, taking into consideration the micro-climatic conditions of particular regions as the possible formation of new degradation products in the presence of co-pollutants, like CFC, pesticides and so on. Furthermore, other oxidizing species can be used, such as ozone, chlorine, bromine, and the cooling/heating system, the vacuum system and the mixing device can be tuned in order to obtain results which best fit not only real pollution conditions but also specific conditions of temperature and lightening. B2) High oxidisation capacity of Ozone makes this molecule important both in environmental ambit, because of a lot of molecules can be oxidisation into Stratosphere or aquatic environments. At begin of this century, Ozone was used like disinfectant in treatment plants of waste water and drinking-water; today is used also like oxidisation agent of a lot of water impurities. In respect of the majority of conventional oxidisation/disinfectant molecules Ozone is very reactive molecule and no gives chlorinated derivatives which are very noxious for human life. The use of this molecule for the predict aims is limited for low solubility in water (1), high cost and easy decomposition in water. In this research we show the degradation capability of Ozone on substrata like hetero-polycyclic aromatic hydrocarbons (N-PACs). Widespread interest in the analytical chemistry of N-PACs is a result of the extraordinary mutagenicity 262 displayed by some members of this compounds class. They appear to be widespread in the environmental and are emitted from a variety of sources. Compounds studied are: 1,10 Phenanthrolin, 4,7 Phenanthrolin, Acridine, Phenazine, Quinoline, Isoquinoline. The samples of 1,10 and 4,7 Phenanthroline, Quinoline and Isoquinoline, are prepared by ozonization of 50 mL of an aqueous solution at pH= 3 ( for sulfuric acid) containing the substratum. Phenazine and acridine samples due their low solubility in water are prepared by ozonization in organic phase (CHCl3 ). The ozonisation conditions are: Flow of O2/O3 = 20 L/h, electrical current= 200 mA (ozonizator used is: Fisher 501and implant n. 18 TP Monotube). All products are analyzed by GC-MS (Hewlett Packard model 5890 with detector HP-MSD 5972 -II). The reactions of 1,10 , 4,7 Phenanthroline, Quinoline and Isoquinoline are stopped after 60 minutes by nitrogen bubbling. Full kinetics and mechanicistic data were derived. Paper describing results of that research are 1 and 43 . Our research group is focusing the attention also on the sequential treatment of PAHs, involving chemical followed by biological oxidation to (i) obtain mechanistic reactivity aspects of the ozone-initiated degradation of B[a]P and B[e]P in the aqueous phase, (ii) test the biodegradability of resultant intermediates and (iii) test the feasibility of the integrated chemical-biological treatment of the five-ring PAHs. For this reason ozonation batch reactors are used, and after different times, samples containing reaction intermediates and byproducts are collected. The samples are identified for organic contents, then biologically inoculated to determine their biodegradability. The O3-pretreated samples are incubated from five to twentyfive days; afterward biochemical oxygen demand (BOD), chemical oxygen demand (COD), and toxicity tests are conducted. Further qualitative and quantitative determinations of B[a]P and B[e]P, intermediates, and reaction products by HPLC and GC/MS techniques are conducted. Major intermediates identified at different stages are ring-opened aldehydes, phthalic derivatives, and hydrocarbons. The degradation of B[a]P and B[e]P is primarily initiated viaO3-mediated ring-opening, followed by O3 and hydrohyl radical fragmentation. The last step is the complete mineralization via OH° radicals. The proposed approach seems suitable for treating recalcitrant compounds, while pretreatment by chemical oxidation appears useful to generate soluble intermediates from otherwise highly insoluble, biologically unavailable B[a]P and B[e]P. The results are reported in a paper (34). Theme c Mechanism of transport of micropollutants in biological system models A short summary of the design of the programme (scientific problem formulation, objectives, subject matter, research methods and anticipated results) Several cancinogenic compounds are present in the environment then it is important to consider the methodology which could be used to evaluate the amount of such compounds, their capacity to be absorbed by the human organism and the preferential absorption ways. This problem is also important to understand mechanisms that permit the use of bilogical passive samplers (see theme a2). It is, in fact, well known that the cell better absorbs highly lipophilic substances when dispersed in a lipophilic medium instead of a hydrophilic one. The objectives of our research is a better understanding of the transport and absorption processes of some polycyclic aromatic hydrocarbons in the human body and of the factors that modulate these processes. Differential scanning calorimetry (DSC) is a technique usually employed to study the interaction of such kind of compounds with biomembranes. By using DSC it has been possible to develop a theoretical-experimental method to study the interaction and absorption kinetics of environmental impact compounds with cellular membrane model and to consider the experimental and structural factors which affect the action mechanisms. A substantive overview of the most impressive results over the past In order to better understand the transport and absorption processes of some polycyclic aromatic hydrocarbons in the human body and the factors that modulate these processes, the effect exerted by pyrene, N-pyrene, benzo[a]pyrene, anthracene, fluorene, fluoranthene, indeno(1,2,3-cd)pyrene on the thermotropic behavior of membrane model, constituted of dimyristoylphosphatidylcholine vesicles, has been studied by using DSC. Some of the polycyclic aromatic hydrocarbons shift the transition temperature towards lower values, while, other of them do not significantly effect the thermotropic behaviour of liposomial vesicles. The ability of these compounds (in a solid form or absorbed on silica gel) to migrate through an aqueous or a lipophilic medium has been studied. The results demonstrate that almost all the examined compounds are not able to go through the aqueous medium whereas are able, even if in a different extent, to migrate through the lipophilic medium and that the absorption of polycyclic aromatic hydrocarbons by a biomembrane depends on their structure and is facilitate by the presence of a lipophilic environment. The technique could be exported to look for membranes to utilise in specific chemical sensors. Scientific results were presented in several scientific journals (18, 24, 30-35, 40) the last of which is the third most cited journals in the Environmental Sciences Category “Journal of Environmental Sciences and Technology”. A short overview of the programme development in the future (the coming 5 years) including the means needed for realising the programme's mission. Please comment on any change due to expected mobility of senior staff. The transport kinetics and the uptake process of other PAHs through and by cell membrane are under study. We will be also involved in searching the factors that can affect these processes. Studies on the effect exerted by PAH compound on the surface tension of monolayer; for this purpose the Langmuir Blodget technique will also be used. The technique permits to better understand the interactions between such kind of compounds and human cells by considering the 263 effects exerted on the variations on the properties of an unilamellar lipid layer and on the variation of surface tension as well as on the surface potential. Theme d For over 8 years we are interested in the study of the reactivity of polycyclic aromatic hydrocarbons (PACs) towards 1,3-dipolar systems in order to find their new derivatives for their potential use in the environmental chemistry. The thema is linked also to pure research activity carried out in co-operation with the organic chemistry group of Prof. Chiacchio. However to extend our interest to other environmental topics we decided to reduce from 2001 the attention to the current research theme. While the reactivity of PACs as 4?-components in the Diels-Alder reactions has been extensively studied,1 their dipolarofilicity has attracted scant attention. To our best knowledge, the only known cycloadditions are their reactions with ozone,2 the Diels-Alder reactions with hexachlorocyclopentadiene3 and 1,3-dipolar reactions with the azomethine ylid derived from 1-(4-methoxyphenyl)aziridine-2,3-(trans)-dicarboxylate.4 Our interest focused in reactions of some PACs [phenanthrene (1a), pyrene (1b), anthracene (1c), perylene (1d), triphenylene (1e) and naphthalene(1f)] with nitrile oxides [mesitonitrile oxide (2a) and 3,5-dichloro-2,4,6trimethylbenzonitrile oxide (2b)] under classical heating and we found that, in contrast with an predictable chemical inertia towards the 1,3-dipolar cycloaddition reaction owing to the loss of aromaticity, PACs add nitrile oxides to give mono- and bis-cycloadducts with moderate yields. When the same reactions were performed under microwave irradiation in the absence of solvent, yields of cycloadducts increased of a 2-7.5 factor. More recently, our researches have been extended to aza- and diaza-analogues of PACs towards nitrile oxides with the aim to compare their reactivity with that of PACs and to examine the regiochemistry of the cycloaddition in relation to the position of nitrogen atom(s) in the ring. Actual results concern reactions of phenanthridine (1g), benzo[h]quinoline (1h), acridine (1i) and 1,10- (1l), 4,7- (1m) and 1,7-phenanthroline (1n) with portion-wise added mesitonitrile oxide (2a) and benzonitrile oxide (2c) under refluxing benzene. In all cases cycloadducts to the N5=C6 and C5=C6 double bond were obtained with modest yields, but the nitrogen atom of pyridine rings was inactive with the exception of 1m, which also afforded a biscycloadduct to the C=N and C=C of a pyridine ring with the expected regiochemistry. Finally we are in progress a study regarding the reduction of the isoxazolinic ring of monocycloadducts previously isolated. In the case of linear PACs, the reduction moreover would afford ketones with the carbonyl moiety in the 1 position and then in a different position with respect to the 9 position, in which the normal acylation takes place. Actual results regard the reduction by treatment with LiAlH4 of cycloadducts of phenanthrene, pyrene, anthracene and acridine which all give the corresponding oximes deriving from the cleavage of the C-O bond. This is a special case in which LiAlH4 reacts as a base instead as a reducent. In confirmation of this result, the treatment of cycloadducts with metoxide ions, but not with triethylamine, give same oximes which were confirmed by their conversion into the corresponding ketones. The research theme given several results extensively published in several scientific journals. Theme e Remediation studies E 1) Supercritical phase extraction and degradation of pollutants from contaminated soil A short summary of the design of the programme (scientific problem formulation, objectives, subject matter, research methods and anticipated results) Supercritical fluid extraction, SFE, is drawing much attention as emerging technique for soil remediation due to the following attractive features: (a) Cleanness. A supercritical fluid process employs environmentally benign solvents (CO2 and water) to extract/destroy pollutants in contaminated soils/sediments without destroying the structure and altering the major properties of the treated soils/sediments. (b) Quickness. The cleanup can be achieved in a relatively short processing time (10 - 60 min). (c) Wide range of application. In supercritical extraction, CO2 is largely use as a solvent because of its low critical properties (Tc=304 K and Pc=73 bar), low cost and toxicity and the capacity to solvate a wide range of organic compounds. SFE technique was used in order to quantitatively extract from a certified marine sediment (NIST SRM® 1944), by using CO2 as solvent, a large number of organic pollutants. This sample is characterized by a great variety of organic and inorganic pollutants, present in small quantities (under 10 ppm). The preliminary research was performed in cooperation with the Chemistry Department of University of Bari (INCA Unit Bari 1). The products related to the two different analytical extraction have been quantified and characterized by GC -MS of the reaction mixture. Results have been compared to those obtained by a conventional Soxhlet extraction. A substantive overview of the most impressive results over the past Both polar and non-polar liquid modifiers have been used to increased yields of extracted compounds, to evaluate the differences in the recovery of pollutants. A thorough evaluation of the amount of recovery of organic pollutants and the following analysis of the solid sample allow us to optimize the analytical technique, characterizing the crucial steps of the process. Results of this laboratory work, under the above mentioned experimental conditions (P = 230 bar, T = 323 K), demonstrate that extraction of polycyclic aromatic hydrocarbons by CO2 – SC from contaminated sediment increases by using an organic modifier, both polar co-solvent and non-polar co-solvent. 264 The recovery of naftalene (m.w. = 128.17), for example, goes from 3.64 %, using only SC-CO2, to around 20 %, using SC-CO2 + 5% methanol, SC-CO2 + n-hexane and SC-CO2 + 5% toluene. For benzo[a]pyrene (m.w. = 252.31), the amount of recovery goes from 0.47 % to 12-16% as a function of the organic modifier used. Then, we don’t see any significant change in the amount of the recovered species, probably because we have analyzed a sample of marine sediment with a so low concentration of organic species that constitute the “non-mobile” fraction, the so called “extraction limit”, of pollutants on the sediment matrix. The results obtained in this experimental work were deeply discussed in the article “EXTRACTION OF POLYCYCLIC AROMATIC HYDROCARBON FROM POLLUTED MATRIX BY CO2 IN SUPERCRITICAL PHASE” which will be submitted to important scientific reviews. A short overview of the programme development in the future (the coming 5 years) including the means needed for realising the programme's mission. Please comment on any change due to expected mobility of senior staff. The Environmental Chemistry Group of the University of Catania will carry on the important collaboration with the Chemistry department of the University of Bari in order to evaluate analytical methods that taking into consideration the different condition influencing the final results, to perform in-situ oxidization of the extracted organic compounds for a total degradation of soil pollutants. Besides, from data obtained in the experimental work, new mathematical models can be created to define, on the basis of the analytical conditions, the density of supercritical fluid which influences the total amount of the recovery of environmental pollutants. Further deepening are required to evaluate the behaviour of other supercritical fluids such as supercritical water (SCH2O), considering a comprehensive degradation process which couples the extraction technique with a parallel oxidation process. E2) 1. Summary of the design of the programme (scientific problem formulation, objectives, subject matter, research methods and anticipated results) Further studies concern the bio-degradability of recalcitrant compounds. This compounds, due to their low hydrosolubility and strong ability to be absorbed in soil and sediments, are scarcely biodegradable compounds. The decontamination of PAH-polluted sites is of major importance because many PAH compounds are either known or suspected carcinogens and mutagens. One way to enhance their solubility is to apply mobilising agents such as surfactants. Being anphiphilic compounds, surfactant molecules can be incorporated with other surfactant molecules as part of a micelle. The micelle formation permits to polycyclic aromatic hydrocarbons to partition in the micelle hydrophobic inner and then to apparently increase their solubility in the liquid phase. The aim of this research is to monitor the bacteria degradation of these compounds in the presence and in the absence of surfactants. 2. Results We report an evaluation of Triton X-100 for its utility in improving the biodegradation of two polycyclic aromatic hydrocarbons, fluorene and pyrene, by Stenotrophomonas maltophilia. For this research we have used the following method: a) the effects of surfactants on bacteria growth have been determinate; b) bacteria have been allowed to grew on a medium containing a polycyclic aromatic hydrocarbon in the presence and absence of Triton X-100; c) the degradation products and the not degraded polycyclic aromatic hydrocarbon have been extracted twice with dichloromethane; d) the extracted products have been analysed by gaschromatography. The obtained results show that in the presence of Triton X-100, 40% of fluorene is degraded instead when Triton X100 is not used the percentage of degraded fluorene is very low. The results obtained by the degradation experiments of pyrene show that 35% of pyrene is degraded when Triton X100 is used while no degradation occurs when Triton X-100 is not added to the culture medium. The obtained results give indication on the ability of Triton X-100 to enhance the degradation both of fluorene and pyrene by Stenotrophomonas maltophilia. 3. Programme development in the future As the first experiments have given promising results, in the future we will extent our research to the degradation of other polycyclic aromatic hydrocarbons using Triton X-100. Surfactants with different chemical-structural properties will also be used in order to evaluate differences in the bacteria degradation of polycyclic aromatic hydrocarbons.. 6.3 Position in Networks • Intra-university co-operation Two main co-operation are relevant for the research unit: a) Prof. G. Tomaselli, leader of the research group active in the chemical reactivity research 265 b) Prof. U. Chiacchio, leader of the research group active in the chemical synthesis research • Regional co-operation • Multi-fund Operative Program. From 1995 to 1999 our group establishing co-operation connections between the others two Sicilian Universities. Our research theme was «Management of waters: Pollution monitoring of the superficial waters crossing highly industrialised area. • National co-operation (including INCA) • University of Turin, Department of Chemistry IFM, prof. S. Coluccia, leader of TORINO 1 Unit INCA, Piano di Interesse Nazionale INCA, Chemistry of the urban atmosphere, to which our unit participate. • University of Bari, Chemistry Department; Prof. Michele Aresta, leader of BARI 1 Unit INCA and responsible of research project «Soil remediation» in the framework of the INCA Project, cluster terrestrial environment. • University of Lecce, Material Sciences Department, Prof. Giuseppe Vasapollo, leader of LECCE 1 Unit INCA • University of Milan, Department of Environmental Sciences, with which our group exchange also thesis students visits. • CNR-ISAO, Atmospheric chemistry group, M.G. Facchini, Project “ Modelling micropollutants formation processes and aerosols in mixt rural-urban environment”, Program CNR AGENZIA 2000. • University of Turin, Prof. Arnaldo Longhetto, Project “ Modelling micropollutants formation processes and aerosols in mixt rural-urban environment”, Program CNR AGENZIA 2000. • University of Modena, Prof. Renato Santangelo, Project “ Modelling micropollutants formation processes and aerosols in mixt rural-urban environment”, Program CNR AGENZIA 2000. • LaMMA, Firenze, Ing. Giovanni Gualtiero, Project “ Modelling micropollutants formation processes and aerosols in mixt rural-urban environment”, Program CNR AGENZIA 2000. • International co-operation • Network on PACs, leader Dr. Philippe Garrigues, (CNRS, Environmental and Toxicological Chemistry Department, Bordeaux, France) in the field of the chemistry of Polycyclic Aromatic Compounds strengthening the co-operation between European and US scientists. • Network on Heterocyclic Chemistry, leader Prof. Norbert de Kimpe, Gent University. Set-up during 1993 permitted to valorise some expertise’s acquired previously aimed to strengthening the co-operation with some European researchers and from ex Soviet Union. • Co-operation between France and Italy, Program GALILEO. Set-up during 1996 permitted to valorise some expertise’s acquired previously in the field of the automatic monitoring of Polycyclic Aromatic Compounds strengthening the cooperation with the Universitè de Paris-Sud and particularly with the prof. Taieb of the Department of Photophisique Moleculaire. The opportunity arisen from the call for tender CNRS/CRUI relatively the GALILEO program. A program of research and researchers exchange was set-up concerning «Advanced methods of automatic monitoring of Mediterranean sea». The project was selected for supporting during 1996 and for the subsequent year. • Plurifund Operative Program. From 1995 to 1999 our group establish a co-operation with the Joint Research Centre of Ispra. Our research theme was «Management of waters: Pollution monitoring of the superficial waters crossing highly industrialised area. • Persistent Organic Pollutants Network. A network sponsorized by European Environmental Research Organisation, set-up on 1996; the executive manager is Prof. Ivan Holoubek, Environmental Studies Department, Masarik University, Czek Republic. • Atmospheric Chemistry Network. Informal network centred on Prof. Beker, Bergische Universität Wuppertal, DE and Prof. Bruno Rindone, Milan University, IT; our project title is «Degradation of biogenic compounds in air». The role of INCA: our unit has benefit of the organisation structure of INCA because trough it various co-operations are started. 6.4 Societal Relevance and Impact It’s necessary to state before hand our research results are of importance in environmental and human health analysis produced by sources of energy emissions ( main causes of PAC presence in environment) in soil and air, and are of importance as well in young graduates formation to propose solution and operate for minimising energy production processes impact. The environmental behaviour of biogenic compounds plays a remarkable role in the formation of ozone, other secondary pollutants and aerosols, so influencing not only the tropospheric chemistry of Mediterranean region, where they have been observed to dominate to other natural emitted hydrocarbons, but also producing climatic changes that lead to desertification phenomena which are affecting Southern regions of Italy. 266 The SFE technique contribute to set up an “environmental friendly” extraction technique for remediation of soil matrix polluted by a large number of organic and inorganic compounds, avoiding great amount of organic solvents, avoiding further chemical contamination and variation in the chemical structure and in the physical characteristics of the processed soil samples. Most of polyclyclic aromatic hydrocarbons are proven to be mutagenic and carcinogenic. Since they are found massively in polluted urban and industrial areas, to semplify PAHs monitoring has become a very important problem in order to safeguard human health. Some geographical areas subjected to industrial risk were identified in Italy, three of which are in Sicily, where the high probable Persistent Organic Pollutants concentration in environment puts control problems with regard to their carcinogenic activities too. Several advantage can get therefore the community: Territorial advantages: Availability of a reference centre, in the regional territory to study and to propose interventions in regional areas at industrial risk. Work-force strengthening by new-graduates and doctorate students formative activities, as well as professional figure formation to put in appropriate productive contexts. Advantages for all the community: Greater knowledge and control of environment quality in risk areas, with consequence possibility foreseeing actions to undertake for quality of life improvement. Availability of research results utilizable at once to promote innovation in energy production processes as incentive for long-term and short-term employment development. 6.5 Further Indications of Quality and Reputation Prof. Vito Librando has been: -Chairman of the Organising Committee of the International Symposium “Environmental thresholds and pollutant stress” of the Europe Annual 1996 Meeting, SETAC -Chairman of the Environmental Chemistry Division Symposium “Degradation of Chemicals with Environmental impact”, American Chemical Society, San Francisco CA, 1996. He is or has been member of Committee and or Editorial Board of: -Annali di Chimica Editorial Board, 2000-today -Journal of Environmental Chemistry and Toxicology Editorial Board, 1995-1997 -ACQUA ARIA Editorial Board,1995-today -Environmental Chemistry Division of the Italian Chemical Society, Council Board, 2000-today Also he is referee of: -MIUR research projects; -Czek Republik Grant Agency; -Third World Network of Scientific Organisation, Intenational Center (Trieste). He is member of: -American Chemical Society, Environmental Chemistry Division -Society of Environmental and Toxicology Chemistry -International Association of Environmental Chemistry Further Prof. Librando served as Member: -Regione Sicilia, Pluri-fund Operative Program, Committee for the Evaluation of Environmental Impact of Projects for Energy Initiative 1998-1999. -Regione Sicilia, Regional Operative Program 2000-2006, Environmental Chemist Member of the Advisory Committee for the Regional Innovation Strategy. 6.6 Key Publications Because the interests of our group span over various field, at our opinion, at least 8 papers should be representative of the unit work: 1. V. Librando, U. Chiacchio and G. Magazzù, Monitoring Studies of Augusta Bay Marine Waters, Environmental Monitoring and Assessment, 44, 383-390 (1997). 2. A. Corsaro, V. Librando, U. Chiacchio, V. Pistarà and A. Rescifina, Cycloaddition of Nitrile Oxides to Azaanalogues of Phenanthrene, Tetrahedron, 54, 9187-9194 (1998). 3. A.M. Zvonok, V. Librando, E.B. Okaev, and S.A. Mikhalyonok, Synthesis of Epoxycarbonyl Pyrroline by Cycloaddition of benzonitrile-4-nitrobenzylide to a,b-unsaturated epoxy ketones, Khimiya Geterotsykl. Soed., 5, 630-633, (1998). 4. Librando, V., Corsaro, A., and Perrini, G. Comparison among active and passive samplers for monitoring polycyclic aromatic hydrocarbons. Polycyclic Aromatic Compounds 17[1-4], 241-254. 1999. 267 5. A. Corsaro, U. Chiachio, V. Librando, V. Pistarà and A. Rescifina, An unusual route for the regioselective acylation of Polycyclic Aromatic Hydrocarbons: Nitrile oxide addition followed by isoxazoline degradation, Synthesis, 10, 1469-1473 (2000). 6. Castelli, F., Librando, V., and Sarpietro, M. G. A calorimetric evidence of the interaction and transport of environmentally carcinogenic compounds through biomembranes. Thermochimica Acta 373[2], 133-140. 2001. 7. Vito Librando, Giuseppe Tringali, Jens Hjorth, Niels R. Jensen, Aerosol formation and reaction pathways of atmospheric oxidation of Dimethylsulfide, Annali di Chimica, 91, 415-424 (2001). 1. F Castelli, V. Librando, M.G. Sarpietro, Calorimetric approach of the interaction and absorption of Polycyclic Aromatic Hydrocarbons with model membranes. Environmental Science and Technology, 36 (2002) 2717-2723. 7. Scientific Output 7.1 Publication Policy Our unit initially published researches results in very specialised reviews that nevertheless, do not had high impact factors because directed to a narrow readers number. Now some of this journals (JPAC) have a better Impact Factor than in the past and this demonstrate that also the minimal contribution of our unit contributed to it. Recently our unit has published scientific articles on journals of large diffusion at international level, taking account, during the journals selection, not only of the topic and the target readers. The publications in fact appeared, during the 1997-2001 period, in 20 different journals (books excluded) with an average impact factor of 1.55 and an average ranking of 46 top percent. Master theses contributed to the overall publication policy but the number of PhDs now is zero because based on the places (6-8) given by the MIUR in the field of the Chemistry (in which over 100 professor and researchers are involved) of which neither is assigned to Environmental Chemistry Curricula. Further in the Chemistry Degree do not exists any “Environmental Chemistry” course and in Industrial Chemistry that course is an optional course. So chemistry students prefers as PhD tutors that teaches traditional disciplines (Organic Chemistry, General Chemistry, etc.). Our strategy permit us to publish, until 2001, 36 papers in international journals; other 7 papers, already accepted but, due the editing delays, will published on 2002; other 4 papers has been submitted to the appropriate editor during the 2002 year. 7.2 Numerical data Category PhD-Dissertations 1997 1 1998 1 1999 4 2000 3 2001 2 Total 11 Scientific Publications 6 10 5 7 8 36 Professional Publications Master’s Theses 8 Self-evaluation The actual composition of the unit is not appropriate taking account of the number and the age of the members: in fact the unit needs one or two young researches to reach a permanent stable critical mass. The overall trend, within the period 1997-2001, of the scientific output reported in table 7.2 and commented in appendix II is to be considered positively as concerns the quality and quantity. The important choice to extend our scientific interests towards new frontier topics permitted however to publish in the top level journal ES&T during 2002. The percentage of papers published in the 1/3 top journals appears satisfactory even in consideration of the low number of permanent staff members of our unit and of the teaching load which is very heavy. In the current year this load will increase due the fact that Environmental Chemistry has been included as fundamental courses in about 12 new degree courses, activated at Catania University, where there are only two Professor of Environmental Chemistry. Further an important action has been undertaken in order to increase the interests towards innovative sectors of the environmental chemistry and to increase the interests of PhD students towards our research topics: to encourage the 268 students mobility towards stages in international labs to acquire experience and partially prepare their theses. To this purpose appropriate searching for financial support will be pursued. Appendix I Scientific Output I-1 Overview of Dissertations and Master's Thesis (1997-2001) I.1.1 Dissertations Year 1997 Name PhD-student Rita Franzò 1998 Dario Di Bella 1999 Claudia Mattina 1999 Corrado Sgandurra 1999 Concettina Morabito 1999 Giuseppe Tringali 2000 Massimo Tomasello 2000 Irene Mangiameli 2000 Rosaria Addamo 2001 Rosario Gallucci 2001 Alessandra Trigilia Title of the Dissertation Supervisor Valutazione di differenti metodologie di V. Librando campionamento di Idrocarburi policiclici aromatici nell’inquinamento atmosferico dell’area urbana catanese Simulazione di ossidazione in troposfera V.Librando di monoterpeni da parte del radicale OH: aspetti cinetici e caratterizzazione dei prodotti di reazione Modelli di reattività e rilevamento V.Librando di microinquinanti organici atmosferici con particolare riferimento ai BTX Studio di alcuni campionatori V.Librando biologici passivi nella valutazione dello inquinamento atmosferico di aree urbane* Determinazione di derivati del V.Librando fenolo nell'atmosfera urbana con particolare riferimentoe al 2- e 4-nitrofenolo.* Chimica troposferica del Dimetil solfuro: V.Librando modelli di reattività ed aspetti cinetici* Valutazione chimica delle capacità di V.Librando accumulo di campionatori biologici nei confronti degli idrocarburi policiclici aromatici* Studio dell’effetto genotossico del G. Perrini particolato atmosferico dell’area urbana di Catania con riferimento agli idrocarburi policiclici Aromatici adsorbiti* Gli Idrocarburi policiclici aromatici e loro G. Perrini ruolo nell’induzione di danni genotossici* Valutazione della biodisponibilità del Cadmio nei sedimenti e nelle acque del Fiume Jarama (Spagna) G. Perrini I campionatori biologici passivi: applicazioni alle misure di inquinamento atmosferico causato da Idrocarburi Policiclici aromatici V. Librando -Degradation studies with ozone of aza-areni of environmental interest -Feasibility study of a network for the monitoring of Polycyclic Aromatic Compounds in the industrial area of Augusta, Priolo, Melilli. -Evaluation of different sampling methologies of Polycyclic Aromatic Hydrocarbons with reference to the urban area of Catania City -Simulation of the tropospheric oxidation of monoterpens with OH radical:kinetic aspects and characterization of the reaction products -Reactivity models and monitoring of atmospheric organic micropollutants with reference to BTXs. -Studies of some passive biological samplers in the evaluation of air pollution of urban areas. -Determination of phenolic compounds derivatives in urban air with particular reference to 2- and 4-nitrophenol. -Thropospheric chemistry of the DMS: reactivity models and kinetics -Chemical evaluation of the ability of biological samplers to accunulate Polycyclic Aromatic Hydrocarbons. -Geno-toxic effect of urban particulate matter regarding the Polycyclic Aromatic Hydrocarbons 269 -Polycyclic Aromatic Hydrocarbons and their role in the geno-toxic hazard. -Bioavalability of Cadmium in the sediment of jarama river. -Biological passive samplers: application to the atmospheric PAH monitoring. I-2 Overview of Scientific Publications (1997-2001) per year 1997 1. Librando, V., Rindone, B., Scarlata, G., Perrini, G., Bolzacchini, E., and Scicali, C. Advanced techniques of polycyclic aromatic compounds degradation studies. Book of Abstracts, 213th ACS National Meeting, San Francisco, April 13-17 , ENVR-083. 1997. 2. Chiacchio, Ugo, Corsaro, Antonino, Gumina, Giuseppe, Pistara, Venerando, Rescifina, Antonio, Alessi, Manlio, Piperno, Anna, Romeo, Giovanni, and Romeo, Roberto. Stereoselective synthesis of isoxazole and pyrazole annulated sultams via intramolecular 1,3-dipolar cycloaddition reactions. Tetrahedron 53[40], 1385513866. 1997. 3. Corsaro, Antonino, Chiacchio, Ugo, Librando, Vito, Fisichella, Salvatore, and Pistara, Venerando. 1,3-Dipolar cycloadditions of polycyclic aromatic hydrocarbons with nitrile oxides under microwave irradiation in the absence of solvent. Heterocycles 45[8], 1567-1572. 1997. 4. U. Chiacchio, A. Corsaro, V. Librando, A. Rescifina, R. Romeo and G. Romeo, Intramolecular Nitrile Oxide Cycloaddition (INOC) of Substituted Amido-Oximes, Tetrahedron 52(45), 14323-14334 (1996). 5. V. Librando, N. Cardellicchio, C. Garozzo, A. Dell’atti, G. Strisciullo, Chemometric Study of the Groundwaters in two Areas of Puglia Region, Annali di Chimica, (87) 685-697 (1997). 6. V. Librando, U. Chiacchio and G. Magazzù, Monitoring Studies of Augusta Bay Marine Waters, Environmental Monitoring and Assessment, 44, 383-390 (1997). 1998 1. A. Corsaro, V. Librando, U. Chiacchio, V. Pistarà and A. Rescifina, Cycloaddition of Nitrile Oxides to Azaanalogues of Phenanthrene, Tetrahedron, 54, 9187-9194 (1998). 2. A.M. Zvonok, V. Librando, E.B. Okaev, and S.A. Mikhalyonok, Synthesis of Epoxycarbonyl Pyrroline by Cycloaddition of benzonitrile-4-nitrobenzylide to a,b-unsaturated epoxy ketones, Khimiya Geterotsykl. Soed., 5, 630-633, (1998). 3. Barbera, N., Bulla, G., and Romano, G. A fatal case of benzene poisoning. JOURNAL OF FORENSIC SCIENCES 43[6], 1250-1251. 1998. 4. Chiacchio, Ugo, Corsaro, Antonio, Pistara, Venerando, Purrello, Giovanni, and Rescifina, Antonio. The reaction of unsaturated carbonyl compounds with \"activated\" sulfur. II. Formation of cyclic disulfide and polysulfides. Heterocycles 48[1], 41-51. 1998. 5. Corsaro, Antonino and Pistari, Venerando. Conversion of the thiocarbonyl group into the carbonyl group. Tetrahedron 54[50], 15027-15062. 1998. 6. A. M. Zvonok, V. Librando, E.B. Okaev, and S.G. Mikhalyonok, Synthesis of epoxycarbonyl pyrroline derivatives by cycloaddition of benzonitrilio p-nitrophenylmethanide to α,β-unsaturated epoxy Ketones, Chem. Heterocycl. Compd., 34(5), 554-557 (1998). 7. Corsaro, Antonio, Buemi, Giuseppe, Chiacchio, Ugo, Pistara, Venerando, and Rescifina, Antonio. Cycloadditions of mesitonitrile oxide with hydroxy- and methoxy-substituted stilbenes. A directing hydrogen bonding model. Heterocycles 48[5], 905-918. 1998. 8. Librando, Vito, Chiacchio, Ugo, Corsaro, Antonio, Pistara, Venerando, and Romano, Laura. Microwaveheating-assisted and conventional syntheses of polycyclic aromatic hydrocarbons. Acqua Aria [2], 79-83. 1998. 9. V. Librando, M. Forina, and G. Drava, 3-way Principal component analysis applied to the evaluation of the quality of underground waters in the industrial Syracuse area, Annali di chimica, 88 867-878 (1998). 10. V. Librando and L. Romano, Studio degli effetti di solventi e tensioattivi sulla stabilità e resa di estrazione di idrocarburi policiclici aromatici nelle acque, Boll. Chim. Igien., 49, 171-175 (1998). 1999 270 11. Castelli, F., Uccella, N., Trombetta, D., and Saija, A. Differences between coumaric and cinnamic acids in membrane permeation as evidenced by time-dependent calorimetry. Journal of Agricultural and Food Chemistry 47[3], 991-995. 1999. 12. Chiacchio, Ugo, Corsaro, Antonino, Gumina, Giuseppe, Rescifina, Antonio, Iannazzo, Daniela, Piperno, Anna, Romeo, Giovanni, and Romeo, Roberto. Homochiral .alpha.-D- and .beta.-D-Isoxazolidinylthymidines via 1,3-Dipolar Cycloaddition. Journal of Organic Chemistry 64[26], 9321-9327. 1999. 13. Chiacchio, Ugo, Corsaro, Antonino, Piperno, Anna, Rescifina, Antonio, Romeo, Giovanni, and Romeo, Roberto. Stereoselective synthesis of enantiomerically pure isoxazolidine-fused .delta.-lactams. Heterocycles 51[1], 37-49. 1999. 14. Librando, V., Corsaro, A., and Perrini, G. Comparison among active and passive samplers for monitoring polycyclic aromatic hydrocarbons. Polycyclic Aromatic Compounds 17[1-4], 241-254. 1999. 15. V. Librando, G. Perrini and C. Sgandurra, Environmental Impact and Monitoring of Polycyclic Aromatic Compounds in Landfill Emissions, Waste Management and Treatment of Municipal and Industrial WasteLandfill, Christensen, Cossu and Stegmann Editors, CISA Press, Vol V, 535-541 (1999) 2000 16. A. Corsaro, U. Chiachio, V. Librando, V. Pistarà and A. Rescifina, An unusual route for the regioselective acylation of Polycyclic Aromatic Hydrocarbons: Nitrile oxide addition followed by isoxazoline degradation, Synthesis, 10, 1469-1473 (2000). 17. Castelli, F., Giuffrida, N., Tringali, C., and Ruberto, G. Calorimetric evidence of differentiated transport of limonin and nomilin through biomembranes. Journal of Agricultural and Food Chemistry 48[9], 4123-4127. 2000. 18. Chiacchio, U., Rescifina, A., Corsaro, A., Pistara, V., Romeo, G., and Romeo, R. Diastereoselective and enantioselective synthesis of 4'-aza analogues of 2',3'-dideoxynucleosides. Tetrahedron: Asymmetry 11[10], 20452048. 2000. 19. Corsaro, Antonino, Chiacchio, Ugo, Pistara, Venerando, and Perrini, Giancarlo. 1,3-Dipolar cycloaddition reactions of benzonitrile oxide to 2(1H)-pyrazinone and its N- and O-methyl derivatives. Heterocycles 53[1], 6980. 2000. 20. Corsaro, Antonino, Chiacchio, Ugo, Pistara, Venerando, Rescifina, Antonio, Buemi, Giuseppe, and Romeo, Giovanni. Cycloadditions of mesitonitrile oxide with amino- and nitrostilbenes. Perkin 2 [8], 1761-1766. 2000. 21. Librando, Vito; Tringali, Giuseppe; Hjorth, Jens; Jensen, Niels R.; Sorensen, Soren; Mangoni, Monica, Reaction pathways of atmospheric oxidation of dimethylsulfide and corresponding aerosol formation, Prepr. Ext. Abstr., Am. Chem. Soc., Div. Environ. Chem., 40(1), 390-392 (2000) 22. Toma, Lucio, Quadrelli, Paolo, Perrini, Giancarlo, Gandolfi, Remo, Di Valentin, Cristiana, Corsaro, Antonino, and Caramella, Pierluigi. Cycloadditions of nitrile oxides to .alpha.,.beta.-unsaturated aldehydes. Frontier orbital interactions and secondary orbital interactions at work in determining regiochemistry. Tetrahedron 56[25], 42994309. 2000. 2001 23. A. Raudino, F. Castelli, G, Briganti, C. Cametti, Anomalous Dielectric Behaviour of Undulated Lipid Membranes. Theoretical Model and Dielectric Spectroscopy Measurements of the Ripple Phase of Phosphatidylcholine, J. Phys. Chem., 115 (2001) 8238-8250. 24. A. Raudino, F. Castelli. Modeling specific heat transient anomalies during permeation of liposomes by watersoluble substances, J. Colloid Interf. Sci, 200 (1998) 52-58. 25. Castelli, F., Caruso, S., and Uccella, N. Biomimetic transport of simple olive biophenol and analogues through model biological membranes by differential scanning calorimetry. Journal of Agricultural and Food Chemistry 49[11], 5130-5135. 2001. 26. Castelli, F., Librando, V., and Sarpietro, M. G. A calorimetric evidence of the interaction and transport of environmentally carcinogenic compounds through biomembranes. Thermochimica Acta 373[2], 133-140. 2001. 27. Librando, Vito, Castelli, Francesco, Sarpietro, Maria Grazia, and Aresta, Michele. Sequential reactivity studies of B[a]P and B[e]P by chemical and biological processes. International In Situ and On-Site Bioremediation Symposium, 6th, San Diego, CA, United States, June 4-7, 2001 3, 149-155. 2001. 271 28. Romano, G., Barbera, N., and Lombardo, I. Hair testing for drugs of abuse: evaluation of external cocaine contamination and risk of false positives. Forensic Science International 123[2-3], 119-129. 1-12-2001. 29. V. Librando, G. Tringali, J. Hjorth, N. R. Jensen, Reaction pathways in the atmospheric oxidation of DMS, Atmospheric Diagnostics in Urban Regions, Lay/Becker/Hauthal/Rindone/Zetsch (Ed.), Erich Schmidt Verlag, Berlin, pp. 43-50 (2001). 30. Vito Librando, Giuseppe Tringali, Jens Hjorth, Niels R. Jensen, Aerosol formation and reaction pathways of atmospheric oxidation of Dimethylsulfide, Annali di Chimica, 91, 415-424 (2001). Appendix 3 Journal Portfolio Analysis Name of the Unit: Environmental Processes and Transformations Research Director: Prof. Vito Librando Years included 1997-2001 Name of Journal Number Articles Acqua Aria 1 Boll. Chim. Igien. 1 Chem. Heterocycl. Compd. 1 Journal of Agricultural and 3 Food Chemistry Journal of Organic 1 Chemistry Journal of Chemical Physics 1 Tetrahedron: Asymmetry J. Phys. Chem Tetrahedron Synthesis Perkin 2 J. Colloid Interf. Sci Environmental Monitoring and Assessment JOURNAL OF FORENSIC Heterocycles Khimiya Geterotsykl. Soed. Thermochimica Acta Forensic Science International Annali di Chimica Polycyclic Compounds of Journal Factor 1.560 3.689 3.301 1 1 5 1 1 1 1 2.797 2.754 2.356 2.193 1.494 0.839 1 5 1 1 1 0.939 1.015 0.334 0.807 0.829 3 0.413 Aromatic 1 0.305 Papers that will appear on 2002 but already accepted during 2001 year Environmental Science and 1 Technology PCCP 1 1.787 Ozone Sci Eng. 1 0.683 Aromatic 1 0.305 Polycyclic Compounds 3.031 Impact Field(s) Ranking Order Agriculture, Multidisciplinary Chemistry, Organic 1/28 0.035 5/48 0.104 Physics, atomic, molecular and chemical Chemistry, Organic Chemical, physical Chemistry, Organic Chemistry, Organic Chemistry, Organic Chemical, physical Environmental Sciences Medicine, legal Chemistry, Organic Chemistry, Organic Chemical, physical Medicine, chemistry 5/30 0.167 9/48 18/91 15/48 16/48 22/48 42/91 63/127 0.187 0.198 0.312 0.333 0.458 0.461 0.496 5/9 31/48 31/48 67/91 7/9 0.555 0.646 0.646 0.736 0.777 Environmental Sciences Chemistry, Organic 104/129 0.806 45/48 0.937 Environmental Sciences CHEMISTRY, PHYSICAL Environmental Sciences Chemistry, Organic 3/127 0.023 35/93 0.376 77/127 0.596 45/48 0.937 272 Comments on: a) the method The articles are listed on the basis of the relative position (ranking) of the journals in which they are published. In our opinion the papers must be compared to member number of the unit. Further index can be obtained from the Average Ranking over the period 1997-2001 and over the year 2002 to take account of trend confirmation. The number of papers published for year is continuously increasing from 1997 to 2001. Apart from the peak of scientific production in 1998, it can be observed a 30% increase in each year compared to the previous years and an overall 600% increase in years 1997-2001 compared to 1997. The above annual increase trend has been confirmed in 2002, since one paper has been published on the top journal "Envir. Sci & Technol", six papers has been accepted for publishing, one of them on the top european journal "PCCP" and further four papers are waiting for referees advise. b) the results It can be calculated from the Journal portfolio analysis that 50% of the total number of publications (1997-2001) are published in the top 1/3 journals (33.33 %) and 80 % appear on the top 2/3 (66.66 %). Further the percentage of journals with ranking 20% is 23.33%. In the above analysis are missed extended papers of results presented in very important meetings in the field of Environmental Chemistry such ACS Symposium or Battelle Symposium and others listed in the Appendix I.2. This papers, in our opinion, have to considered of high quality typ 273 Appendix 4 Overview of Scientific Publications 2002 Due the fact that several papers accepted during 2001 and for editorial and referral delay they will appear on 2002 issues, for a complete evaluation of scientific output, in our opinion, must be considered also the seven accepted and the four submitted papers: 1. F Castelli, V. Librando, M.G. Sarpietro, Calorimetric approach of the interaction and absorption of Polycyclic Aromatic Hydrocarbons with model membranes. Environmental Science and Technology, 36 (2002) 2717-2723. 2. Paola Gramatica, Angela Santagostino, Ezio Bolzacchini , Vito Librando, Marco Orlandi and Bruno Rindone, Analysis in air and rain, toxicology and QSAR modelling with nitrophenols, AIR POLLUTION 2002, WIT Press, Southampton 2002, in press. 3. A. Raudino, F. Castelli, Transport through monolayers and bilayers at fluid-fluid interfaces. Encyclopedia Of Surface and Colloid Science, A.Hubbard Ed, Marcel Dekker (2002) 5441-5455. 4. Vito Librando, Francesco Castelli, M.G. Sarpietro and Michele Aresta, Sequential Reactivity Studies Of B[A]P And B[E]P By Chemical And Biological Processes, In situ and On-Site Bioremediation, Battelle Press, Columbus, 2002 5. Barbara Barletta, Ezio Bolzacchini, Vito Librando, Simone Meinardi, Marco Orlandi, Bruno Rindone*, Claudio Scicali, The Oxidation Of Some Azaarenes With Ozone, Ozone Sci Eng., in press. 6. V. Librando, G. Perrini and M. Tomasello, Biomonitoring of Suspended Particulate Matter PAHs by Evergreen Plants: An evidence of the correlation’s suitability, Polycyclic Aromatic Hydrocarbons, in press. 7. Vito Librando, Giuseppe Tringali, Jens Hjorth, Niels R. Jensen and Salvatore Coluccia, OH-initiated oxidation of DMS/DMSO: reaction products at high NOx levels, PCCP, in press 8. Ezio Bolzacchini, Vorne Gianelle , Vito Librando, Luca Pozzoli,Paola Gramatica , Simone Citterio, Grazia Perrone e Bruno Rindone, Linear correlations between particulate matter and some environmental parameters, Annali di Chimica, submitted. 9. F. Castelli, V. Librando and M. G. Sarpietro, Evidence of lipophilic medium importance in the absorption of polycyclic aromatic hydrocarbons by biomembranes, Environ. Toxicology and Chemistry, submitted 10. Renato Belloli, Ezio Bolzacchini∗, Laura Clerici, Bruno Rindone, Giulio Sesana, Vito Librando, Determination of nitrophenols in air and rain water using HPLC techniques, Atmospheric Environment, submitted. 11. V. Librando, G. A. Tomaselli and J. G. Tringali, OH-initiated oxidation of monoterpenes: reaction mechanism of a-pinene, Atmospheric Environment, submitted. 274 CATANIA 6 Name of the Research Unit CATANIA 6 Catalisi ambientale ed industriale Environmental and Industrial Catalysis University: Università di Catania University of Catania Department: Dipartimento Scienze Chimiche Department of Chemical Sciences Faculty: Facoltà di Scienze Matematiche, Fisiche e Naturali Faculty of Mathematical, Physical and Natural Sciences Research Leader Dr. Crisafulli Carmelo Contact Person Crisafulli Carmelo Dipartimento di Scienze Chimiche, Università di Catania Viale Andrea Doria 6 95125 CATANIA, Italy Phone: +39 095 7385036 Fax: +39 095 580138 E-mail: [email protected] Thematic Area Catalisi eterogenea per le sintesi ecosostenibili e la decontaminazione ambientale Heterogeneous catalysis for eco-compatible syntheses and environmental decontamination Introduction and Context Introduction to the Self-evaluation Report The Research Unit of Environmental and Industrial Catalysis is actually coincident with the research team named “Laboratorio di Petrolchimica” of the Department of Chemical Sciences of the University of Catania. This Laboratory was created in the early sixties with the purpose to prepare graduates able to satisfy the growing demand for specialized staff of the Refineries and the Petrochemical Industries which were establishing during that years in the eastern part of Sicily. All the members of this Unit have always worked in the field of the Industrial Chemistry, both from the didactic and the scientific point of view. This is well demonstrated by the didactic loads and the scientific publications of the members of the Units shown afterwards. The Research Unit owns several research equipment, such as FT-IR spectrophotometer, quadrupole gas analyzer, atomic adsorption spectrometer, BET surface area apparatus, NOx analyzer, gas-chromatographs, temperature programmed apparatus (for temperature programmed reduction, oxidation, desorption, etc.), apparatus for the catalytic activity tests, etc. Moreover the components of the Unit can have free access to the equipment available in the Department of Chemical Sciences (Mass Spectrometer, NMR, ESCA, XRD, XRF, etc.). The Department also provides the technical and administrative services, by employing funds of the research group. The University 275 The University of Catania is the 9th University in Italy, as far as student population is concerned. The total number of the students (Academic Year 2000-2001) is 53030; outs of these 5652 are enrolled in Courses offered by the Faculty of Mathematical, Physical and Natural Sciences. The University serves mainly five provinces (Catania, Enna, Caltanissetta, Siracusa and Ragusa). The high percentage of students coming from districts other than Catania’s induced the opening of courses in other cities in the nearby (Siracusa, Ragusa, Enna, Caltagirone). The University of Catania is the 2nd University of Italy to have filed a report for the Quality Audit Programme of the Conference of European Rectors. The University of Catania was also one of the first Universities to participate to the INCA consortium. The total teaching staff of the University is composed of 1506 members. 316 are members of the Faculty of Sciences. The Department of Chemical Sciences is the largest Department of the University of Catania in terms of staff, with 86 professors and researchers and 37 technicians and administratives. The research activities of the Department cover all the most important chemical areas (organic, inorganic, analytic, industrial, physical and biological). The Department is involved in several EU projects, in cooperative projects with national and international institutions and is strictly linked to the main local industries. The Department supports the research groups through its technical and administrative services, providing sophisticated equipment and a well-furnished library. The Unit Organization structure: The research unit of INCA directed by Dr. Carmelo Crisafulli is actually composed by 2 associated professors (Solarino Luigi, Toscano Giovanni), 2 researchers (Crisafulli Carmelo, Scirè Salvatore), 1 research fellow (Minicò Simona) 1 PhD student (Giuseppe Burgio) and a variable number of graduating students. It must be noted that Dr. Crisafulli became the new research leader of this Unit in March 2000 due to the sudden death of Prof. Rosario Maggiore, who was the former director. Teaching loads: All the members of the Unit are involved in the teaching of several courses for the Industrial Chemistry and Chemistry Degree and for the Environmental Chemistry short degree. Prof. Solarino: Laboratory of Industrial Chemistry: part I, for Industrial Chemistry Degree. Environmental Impact, for Environmental Chemistry short degree. Prof. Toscano: Industrial Chemical Plants: part I, for Industrial Chemistry Degree. Industrial Chemical Plants: part II, for Industrial Chemistry Degree. Laboratory of Industrial Chemical Plants, for Industrial Chemistry Degree. Dr. Crisafulli: Industrial Chemistry part I, for the Industrial Chemistry Degree. Chemistry and Technology of Catalysis for Industrial Chemistry Degree. Industrial Chemistry for Environmental Chemistry short degree. Dr. Scirè: Industrial Organich Chemistry, for Industrial Chemistry Degree. Chemistry and Technology of Petroleum for 1. Industrial Chemistry Degree and 2. for Chemistry Degree. Programme Description and Evaluation 1.Title Heterogeneous catalysis for environmental and industrial applications 2.Programme Director Dr. Crisafulli Carmelo 3.Composition of the scientific research staff of the unit per 1 January 2002 276 Name and Titles Year of Birth Rank Research Input in fte In 2001 Prof. Solarino Luigi Prof. Toscano Giovanni 1934 1940 Associated Prof. Associated Prof. 0.4 0.2 Dr. Crisafulli Carmelo Dr. Scirè Salvatore Dr. Minicò Simona Dr. Burgio Giuseppe Total research input 1952 1960 1968 1973 Researcher Researcher Research fellow PhD student 0.7 0.7 1 1 4.0 Remarks Director of the “University Bulletin” Comments Each year around 4-5 graduating students carry out the Master’s Thesis in the “Laboratorio di Petrolchimica” cooperating to the research activities of the Unit. However after the Degree it is unlikely that these students go on working in the University as PhD or grantee students for more than 6 months. In fact at the moment all the graduates in Industrial Chemistry get readily a working position in local industries. Moreover in the last years and probably in the near future the access to the university ranks is highly restricted. For these reasons no significant change in the Unit is expected. 1.Input of Academic Staff in fte Category Full Professors Associated Professors Ricercatori Post-docs PhD-students Research fellows Total 1997 1998 1999 2000 2001 Total 1.2 1.4 1.2 1.4 1.2 1.4 0.6 1.4 0.6 1.4 4.8 7.0 2.6 1 3.6 1 3.0 1 1 4.0 1 3 15.8 2.6 Comments The decrease in the input of associated professor observed after 1999 is related to the sudden death of Prof. Rosario Maggiore, who was the former director of this Unit. 1.Funding 5.1 Personnel (in fte) Source University CNR European Union Other Sponsors Total 1997 2.6 1998 2.6 1999 3.6 2000 3.0 2001 4.0 Total 15.8 2.6 2.6 3.6 3.0 4.0 15.8 1.3Materials and Equipment (in Million Lire) Source University – MURST CNR EU Other Sponsor Total 1.3Comments: 1997 26.0 10.0 1998 24.3 8.0 1999 89.0 8.0 2000 226.0 2001 191.2 Total 556.5 26.0 36 32.3 97.0 226.0 191.2 582.5 277 • On the figures All the staff is paid by the University. No administrative or technician personnel works specifically for the group. For this reason the academic staff has to take care also of technical and administrative matters. * On the funding policy Most of the funds came from the Minister of University and Scientific and Technological Research (MURST). A substantial increase in the funds obtained for materials and equipments can be observed along the 5 years considered. This is due to two projects of relevant national interest, funded respectively in 1999 and 2001, and one project in the framework of Act 488/96 coordinated by INCA (known as the Depressed Areas Law), funded during 2000-2001. Progress Report 1.3Mission Stateman The Unit works essentially in the fields of industrial and environmental catalysis. The research of the team is mainly devoted to applied topics, with a particular attention to the problems of the petrochemical industries located in the nearby. Often this cooperation allows several graduating students to carry out their Master’s Thesis directly in the Industries. Relating to the environmental applications of the catalysis the members of the Unit are actively involved in some projects of the INCA. 1.4The Research Over the last few years this Unit has been involved in several research topics, essentially concerning the heterogeneous catalysis field. The main topics, concerning environmental and industrial application of heterogeneous catalysis, that the Unit intends to further develop in the next future, are briefly discussed below. 1. Catalytic oxidation of CO and volatile organic compounds (VOCs) CO oxidation at room temperature is obtaining growing attention due to some important practical applications, such as CO and O2 recombination in close-cycle CO2 lasers and CO abatement in air purification systems. In this research the use of highly dispersed Au/Fe2O3 catalysts prepared by coprecipitation has been investigated. This system has been found to be one of the most active towards the CO oxidation with a complete conversion to CO2 even at –70°C. Au/Fe2O3 has been also used, with good results, in the oxidation of some volatile organic compounds (acetone, methanol, isopropyl alcohol, ethyl alcohol and toluene). For this reaction, however, the best catalytic performances have been found with Au/CeO2 catalysts. The high activity of this system has been related to the capacity of gold nanoparticles to weaken the surface Ce-O bonds adjacent to Au atoms, thus enhancing the reactivity of the CeO2 surface capping oxygen which is involved in the volatile organic compounds oxidation through a Mars-van Krevelen reaction mechanism. The catalytic combustion of chlorinated VOC has been also investigated over various supported Pt samples. It has been found that Pt/zeolite samples can be suitable catalysts for the combustion of chlorinated aromatics. In particular Pt/ZSM5 and Pt/ferrierite appears to be the best catalysts considering that on these system the formation of polychlorinated aromatics is hindered. 2. Alternative usage of CO2: CO2-reforming of methane and CO2 methanation Recently the recovery and the transformation of CO2 in useful industrial products attracted the attention of the researchers due to the strong increase in CO2 emissions from all combustion processes (power plants, car engines, etc.). CO2 is, in fact, one of the responsible of the greenhouse effect. In this laboratory the following two processes have been studied: a) the reforming of methane with CO2 (dry-reforming); b) the selective hydrogenation of CO2 to methane (methanation). In particular dry-reforming seems to be a very interesting reaction because it is possible to obtain a syngas with a CO/H2 ratio around 1, adapt for olefin hydroformylation. The catalytic systems used for these reactions have been Ru, Ni, Ir, Rh and Pt mono and bimetallic supported catalysts. The main goal of this research is to stabilize the catalytic system minimizing the formation of inactive carbonaceous species. 3. NOx Catalytic removal Recently selective catalytic reduction (SCR) of nitric oxide with reductants alternative to ammonia has attracted much attention both from an academic and an industrial point of view. The aim of the present research was to examine the use of hydrocarbons, such as propene, ethane and methane, as reductants in the SCR of NO over different catalysts. In particular several molybdates and different metals (Co, Cu, Rh, Pt) supported on ZSM5 zeolite and on activated carbons have been used as catalysts, with the purpose to improve the catalytic performance of the system both in terms 278 of activity under oxidizing conditions and stability in the presence of water and sulphur dioxide. Moreover the research intends to provide more insight into the broader question of the mechanism of the selective reduction of nitric oxide. 4. Selective hydrogenations of industrial interest a) hydrogenation of phenol to cyclohexanone Cyclohexanone is a very important intermediate in the production of ε-caprolactam, which is used in the manufacture of nylon 6. Nowadays the one-step process for the production of cyclohexanone by selective hydrogenation of phenol tends to replace the old two-step process via cyclohexanohol. The study is devoted to evaluate the effective role of alkali and alkali-earth promoters on the catalytic performance of supported palladium catalysts towards this reaction. Moreover the influence of the acid-base properties of the support have been taken into consideration in order to improve activity, selectivity to cyclohexanone and stability of the catalysts. b) hydrogenation of α,β-unsaturated aldehydes The selective hydrogenation of α,β-unsaturated aldehydes to the corresponding unsaturated alcohols is a reaction of great interest in Fine Chemistry due to the fact that unsaturated alcohols are valuable intermediates in the production of perfumes, flavourings and pharmaceuticals. It is well known that the selectivity to the unsaturated alcohol depends on the metal used. In particular Ir and Os are rather selective, whereas Pd, Rh and Ni are unselective. Pt, Ru and Co present an intermediate behaviour, which can be greatly influenced by various factors. In fact, the selectivity of Pt, Ru and Co can be strongly affected by the metal particles size, the characteristics of the support (steric or electronic effects), the solvent used (for liquid phase reactions), the presence of suitable promoters (Lewis acids and bases, metallic ions). In this context our research aim to investigate the relative importance of all the above discussed factors in order to elucidate the reaction mechanism. More recently we have investigated the possibility of using gold catalysts for this reaction. Preliminary results have shown that Au/metal oxides can present high selectivities to unsaturated alcohols, however depending on preparation and pretreatment conditions of the catalytic system. A detailed study for elucidating this aspect is now in progress. 5. Preparation, functionalization and applications of activated carbons In this research activated carbons have been prepared starting from different vegetable wastes, as peach stones, almond shell and exhausted olive husks. These activated carbons have been also modified through a functionalization process with acids or bases in order to obtain suitable materials for practical environmental applications such as adsorbents of specific pollutants (i.e. aflatoxins) or supports for catalysts to be used in the removal of gaseous pollutants. 6.1 Position in Networks The Unit collaborates with other research groups working in the same Department. This is confirmed by several publications written in collaboration with researchers working in Organic chemistry (Prof. G.Musumarra), Physical Chemistry (Dr. G.Compagnini) and Biochemistry (Prof. D.Condorelli). Active collaborations with other Italian research teams have been also established, in particular with the group of Prof. S.Galvagno (University of Messina), Prof. S.Cataliotti (University of Perugia) and Prof. G.Vasapollo (University of Lecce), confirmed by publications in collaboration. Moreover the Unit collaborates with the group of Prof. B.Corain (University of Padua), as confirmed by two projects of relevant national interest, funded respectively in 1999 and 2001. An international cooperation has been also established with the Catalysis Group of the Queen’s University of Belfast (U.K.) in particular with the head of the group, Prof. Robbie Burch. The Unit is also linked with several important local Industries located in the eastern Sicily in the industrial zone of Catania (Cyanamid), Siracusa (Enichem, Agip, Isab) and Gela (Enichem). One of the members of the group (Dr. Crisafulli) has been consultant, on behalf of the Department, for Enichem concerning problems of mercury in wastewaters and for Cyanamid concerning the optimization of separation and recovery of pharmaceutical compounds by means of polymeric resins. Dr. Scirè has been involved in a research project with ISAB concerning the application of multivariate analysis to the characterization of gasolines and gasoils through NIR spectroscopy. The cooperation with the local industry has permitted some students to work for the Master‘s thesis directly in the industry. 6.2 Societal Relevance and Impact The research topics carried out from the Unit of Environmental and Industrial Catalysis present a high relevance for a better quality of the environment. In fact, the study has been devoted both to the improvement of techniques of pollutants removal and to the introduction of newer and less polluting industrial chemical processes. The contribution of the Unit clearly appears in the Scientific Publications and the Master’s Thesis of the last five years, which are reported later on. 6.3 Further Indications of Quality and Reputation The major scientific and professional honours of the members of the Unit are listed below: Dr. C.Crisafulli: 279 - He is member of Italian Association of Zeolite and Italian Chemical Society. Dr. S.Scirè: - He earned a CNR grant in 1993, working for one year in the Catalysis Research Group laboratories, under the direction of Prof. Robert Burch at the University of Reading (GB), carrying out a research in the field of environmental catalysis. He is member of some scientific associations (Italian Association of Zeolite, Italian Chemical Society). From 1995 to 2000 he was member of the board of the Sicily Section of Italian Chemical Society, being the Secretary from 1998 to 2000. Since 1997 to now he is the Secretary of the Professional Order of Chemists of Catania. He is referee of some international journals dealing with catalysis (Appl. Catal., Catal. Lett.). Prof. G. Toscano: - He is the Director of the University Bulletin of Catania University 6.4 Key Publication 1.S.Minicò, S.Scirè, C.Crisafulli, S.Galvagno, “INFLUENCE OF CATALYST PRETREATMENTS ON VOLATILE ORGANIC COMPOUNDS OXIDATION OVER GOLD/IRON OXIDE ”, Appl.Catal. B: Environmental 34, 277 (2001). 2.S.Minicò, S.Scirè, C.Crisafulli, R.Maggiore, S.Galvagno, “CATALYTIC COMBUSTION OF VOLATILE ORGANIC COMPOUNDS ON GOLD CATALYSTS” Appl.Catal. B:Environmental 28, 245 (2000). 3.C.Crisafulli, S.Scirè, R.Maggiore, S.Minicò, S.Galvagno “CO2 REFORMING OF METHANE OVER Ni-Ru AND Ni-Pd BIMETALLIC CATALYSTS”, Catal.Lett. 591, 21 (1999). 4.S.Minicò, S.Scirè, C.Crisafulli, A.M.Visco and S.Galvagno, "FT-IR STUDY OF Au/Fe2O3 CATALYSTS FOR CO OXIDATION AT LOW TEMPERATURE", Catal. Lett. 47, 273 (1997). 5.R.Burch and S.Scirè, "SELECTIVE CATALYTIC REDUCTION OF NITRIC OXIDE WITH ETHANE AND METHANE ON SOME METAL EXCHANGED ZSM-5 ZEOLITES," Appl.Catal. B:Environmental 3, 295 (1994). 6.Scientific Output 6.3Publication Policy The scientific papers, all based on experimental researches, are published on relevant international journals specialized in the field of industrial physical chemistry. The great didactic and organizational effort made from all the members of the Unit, due to the rapid and deep change taking place in the italian universities, probably is responsible for a delay in the publication of all results collected during these years as pointed out from the large number of Master’s Thesis. Anyway it must be underlined that the productivity of the group is growing up as pointed out by the number of paper published during 2001 (6 papers) and in the first six months of 2002 (6 papers published or in press). 6.4Numerical data Category PhD-Dissertation 1997 1998 1999 2000 2001 Total ScientificPublications 1 4 1 2 6 14 3 6 4 6 4 23 Professional Publications Master’s Theses 280 1.Self-evaluation The major strength of the Unit is related to the long experience of each member in the field of the industrial catalysis. This gives to the Unit the right qualification to approach the most recent environmental problems. The scientific and technical know-how of the group covers several aspects of the industrial chemistry, ranging from the preparation and the physical–chemistry characterization of the catalysts to the set-up of pilot plants. For this reason the Unit is rather solid and able to give practical answers to a variety of applied questions. This aspect has been further strengthened by the presence of chemical industries in the local area. However it must be underlined that the technology transfer of the results is rather limited. The chemical companies seems to be, infact, more interested in the basic knowledge of the group and in the training of the chemistry graduates. The research Unit is composed by an average number of ten people (staff and graduating students). No change in the Unit is expected for the near future for the reasons discussed in the Comments of Section 3. During last three years the Unit established several collaborations with other Italian research teams (University of Messina, Perugia, Lecce, Palermo, Padua) which allowed some common research projects to be funded, thus resulting in a relevant increase in funds for materials and equipment and in the scientific productivity of the group. Appendix 1 Scientific Output I.1 Overview of Dissertation and Master’s Thesis (1997-2001) I.1.1 Dissertation I.1.2 Master’s Thesis Year Name Master’s student Title of the Dissertation Supervisor 1997 Lorenti Simona Dr. S.Scirè 1997 Campione Alberto 1997 Munafò Pietro 1998 Lo Faro Alessandro 1998 Blanco Ignazio 1998 Dragotta Salvatore 1998 Papale Francesco 1998 Nicolini Annalisa Spettroscopia FT-IR nello studio di catalizzatori bimetallici supportati. FT-IR spectroscopy for the study of supported bimetallic catalysts Ossidazione catalitica su catalizzatori Au/Fe2O3. Catalytic oxidation over Au/Fe2O3 catalysts. Idrogenazione di fenolo a cicloesanone: influenza delle proprietà acido-base del sistema catalitico. Phenol hydrogenation to cyclohexanone: influence of the acid-base properties of the catalytic system. Reforming del metano con CO2 su catalizzatori bimetallici a base di nichel Reforming of methane with CO2 on nickelbased bimetallic catalysts Abbattimento catalitico di NOx su Molibdato di magnesio Catalytic removal of NOx over magnesium molibdate Abbattimento catalitico di NOx su carboni attivi Catalytic removal of NOx on activated carbons Catalizzatori Au/Fe2O3 nell'ossidazione di VOC Au/Fe2O3 catalysts in VOC oxidation Catalizzatori bimetallici nell'idrogenazione selettiva di citrale e di aldeide cinnammica Bimetallic catalysts for the selective hydrogenation of citral and cynnamic aldehyde Dr. C.Crisafulli Dr. S.Scirè Dr. C. Crisafulli Prof. R. Maggiore Prof. R. Maggiore Dr. C. Crisafulli Dr. S. Scirè 281 1998 Solarino Gianfranco 1999 Lanza Amerigo 1999 Spadaro Michele 1999 Trovato Giuseppe 1999 Alba Fulvio 2000 Burgio Giuseppe 2000 Avarino Giovanna 2000 Messina Paolo 2000 Omeri Linda 2000 Gulino Giuseppe 2000 Ternullo Concetta 2001 Di Stefano Carmelo 2001 Battiato Salvatore 2001 Scicolone Gianfilippo Riduzione delle emissioni di NOx da forni di raffineria mediante l'impiego di bruciatori LowNOx LowNOx burners for the abatement of NOx emissions of refinery furnaces Effetto del pretrattamento in catalizzatori Au/Fe2O3 per l'ossidazione di VOC Pretreatment effect of Au/Fe2O3 catalysts towards VOC oxidation Carboni attivi ed abbattimento di ossidi di azoto Activated carbons and removal of nitric oxides Effetto dell'iniezione d'acqua sulla produzione di inquinanti allo scarico di un motore CFR Cetane Effect of water injection on pollutant production of a CFR Cetane engine Abbattimento catalitico di NOx su ossido di molibdeno Catalytic removal of NOx over molibdenum oxide Ossidazione catalitica di composti organici volatili Catalytic oxidation of volatile organic compounds Influenza del supporto nella reazione di dry reforming del metano Influence of the support on dry reforming of methane Caratterizzazione FT-IR di catalizzatori metallici supportati per reazioni di idrogenazione selettiva FT-IR characterization of supported metal catalysts for selective hydrogenation reactions Caratterizzazione di catalizzatori metallici supportati per l’idrogenazione selettiva di aldeidi α,β-insature Characterization of supported metal catalysts for the selective hydrogenation of α,β-unsaturated aldehydes Studio di catalizzatori metallici per l’idrogenazione selettiva di crotonaldeide Study of metal catalysts for the selective hydrogenation of crotonaldehyde Studio di compatibilità degli scarichi idrici di nuove utenze industriali con il sistema centralizzato di depurazione I.A.S. Study of compatibility between water industrial wastes and I.A.S. purification plant Catalizzatori a base di oro per applicazioni in campo ambientale Gold catalysts for environmental applications Rimozione di NOx su catalizzatori metallici supportati su carboni attivi NOx removal over metal catalysts supported on activated carbons Idrogenazione di aldeidi α,β-insature su catalizzatori metallici supportati su resine organiche di sintesi Hydrogenation of α,β-unsaturated aldehydes over metal catalysts supported on syntetic Prof. R. Maggiore Dr. C. Crisafulli Prof. R. Maggiore Prof. R. Maggiore Prof. R. Maggiore Dr. S. Scirè Dr. C. Crisafulli Dr. S. Scirè Dr. C. Crisafulli Dr. C. Crisafulli Prof. L. Solarino Dr. C. Crisafulli Dr. S. Scirè Dr. C. Crisafulli 282 2001 I.2 Gabriele Campisi Marcella organic resins Ossidazione catalitica di composti organici Dr. S. Scirè volatili su Au/ossidi metallici Catalytic oxidation of volatile organic compounds on Au/metal oxides Overview of Scientific Publications (since 1997) 1.S.Minicò, S.Scirè, C.Crisafulli, A.M.Visco, S.Galvagno, "FT-IR STUDY OF Au/Fe2O3 CATALYSTS FOR CO OXIDATION AT LOW TEMPERATURE", Catal. Lett. 47, 273 (1997). 2.S.Scirè, C.Crisafulli, R.Maggiore, S.Minicò, S.Galvagno “INFLUENCE OF THE SUPPORT ON CO2 METHANATION OVER Ru CATALYSTS: AN FT-IR STUDY”, Catal.Lett. 51, 41 (1998). 3.M.G.Musolino, G.Neri, C.Milone, S.Minicò, S.Galvagno “LIQUID CHROMATOGRAPHIC SEPARATION OF INTERMEDIATES OF THE CATALYTIC HYDROGENATION OF 2,4-DINITROTOLUENE“, J.Cromatography A 818, 123 (1998). 4.C.Milone, C.Gangemi, S.Minicò, S.Galvagno, G.Neri “SELECTIVE HYDROGENATION OF CITRONELLAL INTO MENTHOLS ON Ru SUPPORTED CATALYSTS“, in “Catalysis of Organic Reactions“ (Marcel Dekker Editor, New York, 1998) pag. 571. 5.S.Scirè, C.Crisafulli, R.Maggiore, S.Minicò, S.Galvagno “EFFECT OF THE ACID-BASE PROPERTIES OF Pd-Ca/Al2O3 CATALYSTS ON THE SELECTIVE HYDROGENATION OF PHENOL TO CYCLOHEXANONE”, Appl.Surf Sci. 136, 311 (1998). 6.C.Crisafulli, S.Scirè, R.Maggiore, S.Minicò, S.Galvagno “CO2 REFORMING OF METHANE OVER Ni-Ru AND Ni-Pd BIMETALLIC CATALYSTS”, Catal.Lett. 591, 21 (1999). 7.S.Minicò, S.Scirè, C.Crisafulli, R.Maggiore, S.Galvagno, “CATALYTIC COMBUSTION OF VOLATILE ORGANIC COMPOUNDS ON GOLD CATALYSTS” Appl.Catal. B:Environmental 28, 245 (2000). 8.G.Musumarra, D.F.Condorelli, S.Scirè, A.S.Costa, M.Fichera, “A MULTIVARIATE INSIGHT INTO THE IN VITRO ANTITUMOUR SCREEN NCI DATABASE”, Clinical Cancer Research 6, 155 Suppl. S (2000). 9.S.Scirè, S.Minicò, C.Crisafulli, S.Galvagno, “CATALYTIC COMBUSTION OF VOLATILE ORGANIC COMPOUNDS OVER GROUP IB METAL CATALYSTS ON Fe2O3”, Catal. Commun. 2, 229 (2001). 10.S.Minicò, S.Scirè, C.Crisafulli, S.Galvagno, “INFLUENCE OF CATALYST PRETREATMENTS ON VOLATILE ORGANIC COMPOUNDS OXIDATION OVER GOLD/IRON OXIDE ”, Appl.Catal. B: Environmental 34, 277 (2001). 11.R.S.Cataliotti, G.Compagnini, C.Crisafulli, S.Minicò, B.Pignataro, P.Sassi, S.Scirè, “LOW-FREQUENCY MODES AND ATOMIC FORCE MICROSCOPY FOR THE SIZE DETERMINATION OF THE CATALYTIC GOLD CLUSTERS SUPPORTED ON IRON OXIDE”, Surf.Sci. 494, 75 (2001). 12.G.Musumarra, S.Scirè, “MODDE 5.0 SOFTWARE REVIEW”, J.of Chemometrics, 15, 199 (2001). 1.G.Musumarra, D.F.Condorelli, S.Scirè, A.S.Costa, “SHORTCUTS IN GENOME-SCALE CANCER PHARMACOLOGY RESEARCH FROM MULTIVARIATE ANALYSIS OF THE NATIONAL CANCER INSTITUTE GENE EXPRESSION DATABASE”, Biochemical Pharmacology 62, 547 (2001). 2.S.Scirè, G.Musumarra, D.F.Condorelli, C.G.Fortuna, “POTENTIALITIES OF THE PLS APPROACH IN GENOME-SCALE CANCER PHARMACOLOGY RESEARCH”, Clinical Cancer Research Vol. 7, No 11 (2001). 3.C.Crisafulli, S.Scirè, S.Minicò, L.Solarino, “Ni-Ru BIMETALLIC CATALYSTS FOR THE CO2 REFORMING OF METHANE”, Appl.Catal A: General 225, 1 (2002). 283 4.V.Barresi, D.F.Condorelli, C.G.Fortuna, G.Musumarra, S.Scirè, “IN VITRO ANTITUMOR ACTIVITIES OF 2,6-DI-[2-(HETEROARYL)VINYL]PYRIDINES AND PYRIDINIUMS”, Biorg. & Med. Chem., 10, 2899 (2002). 5.S.Scirè, S.Minicò, C.Crisafulli, “SELECTIVE HYDROGENATION OF PHENOL TO CYCLOHEXANONE OVER SUPPORTED Pd AND Pd-Ca CATALYSTS AN INVESTIGATION ON THE INFLUENCE OF DIFFERENT SUPPORTS AND Pd PRECURSORS”, Appl. Catal. A: General, in press (2002). 6.S.Scirè, S.Minicò, C.Crisafulli, G.Burgio, V.Giuffrida, “CATALYTIC COMBUSTION CHLOROBENZENE OVER Pt/ZEOLITE CATALYSTS”, Stud. Surf. Sci. Catal., in press (2002). OF 7.S.Minicò, S.Scirè, C.Crisafulli, C.Satriano, A.Pistone, “CATALYTIC COMBUSTION OF VOLATILE ORGANIC COMPOUNDS ON GOLD/CERIUM OXIDE CATALYSTS”, Appl. Catal. B: Environmental, in press (2002). 8.A.M.Maffei, G.Mele, G.Ciccarella, G.Vasapollo, C.Crisafulli, S.Scirè, F.P. La Mantia, “CYCLOCARBONYLATION REACTIONS OF ALLYLPHENOLS AND ALLYLNAPHTOLS CATALYZED BY PD/C-DPPB”, Applied Organometallic Chemistry, in press (2002) Appendix II Journal Portfolio Analysis Name of the Unit: Environmental and Industrial Catalysis (Department of Chemical Sciences, University of Catania) Research Director: Dr. Crisafulli Carmelo Year included 1997-2001 Name of Journal Catalysis Letters Applied Catalysis B:Environmental Applied Surface Science Catalysis Communication Surface Science Journal of Chromatography A Journal of Chemometrics Clinical Cancer Research Biochemical Pharmacology Number Articles 3 2 1 1 1 1 1 2 1 of Journal Impact factor (2001) 1.852 3.643 1.068 2.189 2.793 1.845 5.076 3.340 Field(S) Ranking Chemistry Physical Chemistry Physical Chemistry Physical Chemistry Physical Chemistry Analytical Chemistry Analytical Oncology Biochemistry & Molecular Biology 33/93 13/93 58/93 28/93 6/68 19/68 9/107 81/308 Comments on: a) the method This method of evaluation of the scientific productivity can not be considered valid “per se”. However it is at the moment the only one which can supply an objective and homogeneous element of evaluation. b) the result 284 The average impact coefficient of the articles published during these 5 years is 2.85. All publications except one are in the first half of each specific field. It must be noted that Catalysis Communication do not yet possess an impact factor due to the fact that publication of this journal started in 2001. 285 CATANIA 7 Research Leader Prof Antonino Corsaro Name of the Research Unit (In Italian and English) Catania (Chimica Organica) Catania (Organici Chemistry) University (In Italian and English) Università degli Studi di Catania University of Catania Contact Person : Faculty (In Italian and English): Facoltà di Farmacia Name: Antonino Corsaro Mailing Address: Dipartimento di Scienze Chimiche Viale A. Doria, 6 – 95125 Catania Phone: 095 - 7385017 Fax: 095 - 580138 E-mail: [email protected] Faculty of Pharmacy Department (In Italian and English): Dipartimento di Scienze Chimiche Department of Chemical Science Thematic area • Sintesi ecosostenibili (solventi, fotochimica, catalisi, riciclo e altre). • Catalisi eterogenea per le sintesi ecosostenibili e la decontaminazione ambientale. • Chimica degli ecosistemi (chimica del suolo, delle acque e dell’aria; impatto dei prodotti di sintesi sull’ambiente). Introduction and Context Introduction to the Self-evaluation Report This report has been produced by two components of the unit. They have deduced information from the other components to whom the questionnaire, provided by Consortium, was submitted. The unit has proposed itself in environmental chemistry for a few years attending of researches within chemical properties of polycyclic aromatic compounds, recycling of agro-industrial wastes and recently, alternative energetic methods in organic syntheses. In the past years, the interest of the unit was focused on the syntheses of heterocyclic compounds with biological and pharmaceutical activities. The University of Catania is the 9th University in Italy, as far as student population is concerned. The total number of the students (Academic Year 2000-2001) is 53030; outs of these 5652 are enrolled in Courses offered by the Faculty of Mathematical, Physical and Natural Sciences. The University serves mainly five provinces (Catania, Enna, Caltanissetta, Siracusa and Ragusa). The high percentage of students coming from districts other than Catania has induced the opening of courses in other cities in the nearby (Siracusa, Ragusa, Enna, Caltagirone). The University of Catania is the 2nd university of Italy to have filed a report for the Quality Audit Programme of the Conference of European Rectors; moreover it was also one of the first universities to participate to the INCA consortium. The total teaching staff of the university is composed of 1506 members, of which 316 are members of the Faculty of Sciences. The Department of Chemical Sciences is the largest Department of the University of Catania in terms of staff, with 86 professors and researchers and 37 technicians and administratives. 286 The research activities of the Department cover all the most important chemical areas (organic, inorganic, analytic, industrial, physical and biological). The Department is involved in several EU projects, in cooperative projects with national and international institutions and is strictly linked to the main local industries. The Department supports the research groups through its technical and administrative services, providing sophisticated equipment and a well-furnished library. The Unit The reasearch unit of INCA is directed by Prof. Antonino Corsaro and it is actually composed by a full professor (Prof. Ugo Chiacchio), an associated professor (Prof. Antonino Corsaro), a researcher (Dr. Antonio Rescifina), an “assegnista” (Dr. Venerando Pistarà) and a variable number of PhD-students and graduating students. • teaching load Two professors and a researcher are involved in the teaching of several courses of organic chemistry concerning degree courses of pharmacy, pharmaceutical chemistry and technology, scientific information on drugs and environmental toxicology of the faculty of Pharmacy. • Numbers of PhD-students, etc. On the whole, the number of students is about 350 per annum. Programme Description and Evaluation 1 Title: Reactivity of polycyclic aromatic compounds and recycling of carbohydrates from the whey. 2 Research Leader: Prof. Antonino Corsaro 3 Composition of the scientific research staff of the unit per 1 January 2002 Remarks Names and Titles Year of Rank Research Birth Input in fte in 2001 Antonino Corsaro, Dr 1945 Asociated 0.5 Vice-Director of the Department Professor Ugo Chiacchio, Dr 1948 Full Professor 0.2 Antonio Rescifina, Dr 1965 ConfirmedRes 0.4 earcher Venerando Pistarà, Dr 1966 Assegnista 0.6 Roberto Adamo, Dr 1973 PhD Student 1.0 After 1997 Total research input 2.8 The unit has always been of the same consistency because new persons are followed one another to occupy the posts of PhD-students. Often, however, the number of PhD-students is become double, but someone of these has not concluded his period of doctorate because he has assumed a steady position or enter upon an industry. The unit relies on the increase of a persons the consistency of the group through a contract sponsored by INCA funds. 4 Input of Academic Staff in fte 1997 Category Full Professors Associated Professors 0.7 Ricercatori Post-docs PhD-students 0.8 1.5 1998 1999 2000 2001 Total 0.2 3.3 1.6 1.6 5.6 .7 0.4 .7 0.4 .7 0.4 0.2 .5 0.4 0.8 1.0 1.0 1.0 1.0 287 Borsisti/Assegnista Total 5 Funding 5.1 Personnel (in fte) Source University CNR European Union Other Sponsors Total 5.2 2.9 0.6 2.7 0.6 2.7 0.6 2.7 1.8 14.1 1997 3.1 1998 3.0 1999 2.8 2000 2.8 2001 2.8 Total 14.5 3.1 3.0 2.8 2.8 2.8 14.5 1999 29 2000 59 2001 61 34 Total 209 34 29 150 209 50 145 200 443 Materials and Equipment (in Million Lire) Source University - MURST CNR EU Other Sponsors Total 5.3 3 1997 32 32 1998 28 28 Comments: • On the figures: The majority of the staff is paid by the university, which supports PhD-students. No administrative personnel works specifically for the group and then the academic group is obliged to take care of administrative matter, since the department administrative personnel is not sufficient to take care of the research group. • On the funding policy: Every year the unit receives about the same consistent funds from the university in relation to its publications. Recently, other funds have come from CNR, MIUR for a program of scientific research of prominent national interest, the consultancy of Wyeth Lederle S.P.A. through Consorzio Interunivesitario Nazionale “Metodologie e Processi Innovativi di Sintesi” and finally from Consorzio INCA for a project within the framework of Act 488/96 (known as the Depressed Areas Law). For the next future the unit has applied for funds from the same institutes and it is expected to receive them. Please add a list of major sponsors and the character of the liaison with the major sponsors 1.Progress Report 1.3Mission Statement The mission statement of the unit concerns the definition of new methods for the exploitation and valorization of the sugar portion of agro-industrial wastes, such as the whey. Particularly, the unit intends to develop synthetic and eco-compatible methodologies to enter to several classes of drugs or their structural analogues in an economically competitive way. The development of synthetic methods for new derivatives of polycyclic aromatic hydrocarbons is an other theme of interest since several years. Inside INCA, the ambition of the unit is promote this type of research, which attracts scant attention, integrating this with appropriate technological knowledge in order to interest other groups of research. Outside INCA, the unit is always present and very active with its programs on sustainable chemistry proposed to regional and national authorities and industries, with its educational and training programs and its consultancy. 1.4The Research Programme The principal theme of the research concerns the chemical valorization of the agro-industrial wastes. In this theme, the unit ha considered the possibility to use greater amounts of lactose, present in the whey, to increase its market value and then to extend, optimize and to generalize the recycling processes of the whey and to reduce notably the negative 288 environmental effects. The annual production of the lactose in the EC is estimated in half million tons approximately, and its market price is very cheap (about 600 ECU/ton). The industrial use of the lactose, currently limited to pharmaceutical industry, is developed into two directions: as such, as excipient and diluent for capsules in the drug production, and as hepatoprotector and laxative, after chemical transformation in lactulose and lactilol, respectively. In comparison with other industrially produced disaccharide, such as cellobiose and maltose, containing only D-glucopyranose moiety, the presence of an axial hydroxyl group in the 4’position of the D-galactopyranoside moiety, facilitates the processes of selective protection and functionalization, even if until today, these processes have been study rarely and without the indispensable method. On the basis of these premises, the following general objectives for the chemical valorization of the lactose can be defined: 2.transformation of lactose into complexes di- and oligosaccharides with biological and pharmaceutical interest; 3.simplification of the lactose hyperfunctionality and synthesis of chiral derivatives with different substituents as chiral building blocks for the fine chemistry; 4.increment of the hydrosolubility of compound with hydrophobic property diffusely used in industrial processes, by conjugation to the lactose through the formation of specific covalent bond For these reasons, the research activity of the group has been devoted to the realization and the optimization of a new synthetic approach for the hydrolysis of a totally protected lactose derivative, which affords L-arabino-aldohexos-5ulose, a monosaccharide belonging to one class of carbohydrate which has received poor attention. This derivative through an intermolecular aldol condensation affords one inosose that by stereoselective reduction gives two rare and unnatural inositols, muco- and epi-inositol, a group of carbocyclic analogues of monosaccharides with remarkable importance for their biological property. Subsequently has been lead a study about the epimerization of the 4,5-unsaturated intermediate of the lactose which affords L-lixo-aldohexos-5-ulose, through a protection/deprotection and oxidation/reduction sequences. L-Lixoaldohexos-5-ulose was then subjected to intramolecular aldol condensation and successive stereoselective reduction, to give allo- (a exclusively synthetic inositol) and D-chiro-inositol. The future objectives regard the possibility to extend the aldol condensation to the others two series of the 1,5dicarbonil derivative, obtainable from the protected lactose derivative through an epimerization process, in order to verify the selectivity of the condensation and the possibility to obtain others inososes and from everyone of these the corresponding two inositols by stereoselective reduction. Also, the transformation of inosose into inosamine for reaction with hydroxylamine hydrochloride and successive reduction of the intermediate oxime will be studied, together with the enzymatic desimmetrization of the symmetrical inososes. Moreover, will be examined the reactivity of the double bond in 4,5-position, in cyclopropanation and 1,3dipolar cicloaddition reactions in comparison with that one of the double bond in 1,2-position that has been extensively studied. Finally, within research program regarding the synthesis of modified nucleosides in the sugar moiety, carried out from several years with success, the unit will be defined intramolecolar 1,3-dipolar cycloaddition processes of unsaturated nitrile oxides or nitrones, starting from lactose and using the opening reaction of the sugar ring in an olefinic aldehyde with the Vasella’s method, followed by the conversion of the aldehyde in the corresponding oxime. These processes leads to enantiomerically pure polyhydroxylated cyclopentanes, or cyclopentanes with an aminic group instead of hydroxyl group, by hydrogenolysis of the isoxazolidine bicyclic derivative obtained by 1,3-dipolar cycloaddition reaction. The second theme of research rests in the reactivity of polycyclic aromatic hydrocarbons (PAHs). In the last years we are interested in the study of the reactivity of PAHs towards 1,3-dipolar systems in order to find their new derivatives for their potential use in the environmental chemistry. While the reactivity of PAHs as 4?-components in the DielsAlder reactions has been extensively studied, their dipolarofihicity has attracted scant attention. Recently, our interest focused in reactions of some PAHs with nitrile oxides under classical heating. We found that, in contrast with an predictable chemical inertia towards the 1,3-dipolar cycloaddition reaction owing to the loss of aromaticity, PAHs add nitrile oxides to give mono- and bis-cycloadducts with moderate yields. When the same reactions were performed under microwave irradiation in the absence of solvents, yields of cycloadducts increased of a 2-7.5 factor. More recently, our researches have been extended to aza- and diaza-analogues of PAHs towards nitrile oxides with the aim at comparing their reactivity with that of PAHs and examining the regiochemistry of the cycloaddition in relation to the position of nitrogen atom(s) in the ring. Next researches of the unit will be devoted to the study of reactions relative to the same and other PAHs and aza-PAHS with other different 1,3-dipolar systems such as carbonyl ylides, imines and oxides. 4.3Position in Networks • Intra-university co-operation 289 For the development of this program of research, collaborations already exist with research groups of Department Farmaco-Chimico, Department of Microbiology and that one of Pharmacology of the university of Catania, where all the obtained compounds will be tested for their biological and pharmaceutical activities. Particularly, in the Department Farmaco-Chimico studies will be devoted to the evaluation of the different methodologies exploited for their vehiculation. 5.Regional co-operation The unit collaborates with the university of Messina which has all the necessary competences, but in the next future the unit foresees a further enlargement of this regional collaborations. • National co-operation (including INCA) The unit partecipates to a Programma di Ricerca di Interesse Nazionale with other universities of several cities and to the programs of INCA consortium. • International co-operation The unit collaborates with the university of Saragoza (Spain) in the research project on the synthesis of modified nucleosides and the unit is a component of an European network on nucleosides and nucleotides which sees the participation of 15 European universities. 6.4 Societal Relevance and Impact The social relevance of the research che svolge the unit emerge chiaramente dalle linee del 5 prgramma quadro della European Community in which the enviromental studies are considered of fondamentale importance. The impact of the unit is documented by the grants obtained from local industries and from MIUR The results of the unit research are important within the world of the environmental impact and human health because of the harmful effects of polycyclic aromatic hydrocarbons and serious problems which are producing agro-industrial wastes, which open new pathways for, not only, their reduction, but also for their use in the pharmaceutical field with the return of huge benefits. The training of young graduates aimed at working and proposing solutions in order to minimize the impact of PAHs, because of their carcinogenic activity and to reduce the agro-industrial wastes, the controlled disposal of which represents an important ecological problem. 5.3Key Publications 1. A New Route for the Chemical Valorisation of Lactose, A. Corsaro, G. Catelani, F. D’Andrea, S. Fisichella, M. Mariani, and V. Pistarà, J. Environ. Sci. Poll. Res., DOI: http://dx.doi.org/10.1065/espr2001,12.104.2. 2. A New Highly Diasterereoselective Synthesis of epi-Inositol from D-Galactose, V. Pistarà, P. L. Barili, G. Catelani, A. Corsaro, F. D'Andrea, and S. Fisichella, Tetrahedron Lett., 2000, 41, 3253. 3. An Unusual Route for the Regioselective Acylation of Polycyclic Aromatic Hydrocarbons: Nitrile Oxide Addition Followed by Isoxazoline Degradation, A. Corsaro, U. Chiacchio, V. Librando, V. Pistarà, and A. Rescifina, Synthesis, 2000, 1469. 4. Homochiral ?-D- and ?-D-Isoxazolidinyl Thymidines Via 1,3-Dipolar Cycloaddition. U. Chiacchio, A. Corsaro, G. Gumina, A. Rescifina, D. Iannazzo, A. Piperno, G. Romeo, and R. Romeo, J. Org. Chem., 1999, 64, 9321. 5. Steroselective Synthesis of 2’-Amino-2’,3’-dideoxynucleosides by Nitrone 1,3-Dipolar Cycloadfdition: a New Efficient Entry toward d4T and its 2-Methyl Analogue, U. Chiacchio, A. Rescifina, D. Iannazzo, G. Romeo, J. Org. Chem. 1999, 64, 28. 7. Scientific Output 7.1 Publication Policy In its publication policy, the unit has privileged quality over quantity. Then, the unit has tried to publish its results in international journals of high scientific reputation and of broad readership. A little production concerning specific themes of the environment and particularly, chemical properties of polyarenes and the recycling of the whey, has regarded journals with lower impact factor. Recently, the unit has undertaken new applicatory projects which will lead, with good probability, to some results that will be protected by filing patent. The research activities are developed in connection with graduate theses and in these cases the student who performed the work is co-author of the paper. In terms of number of dissertations of PhD-students, the productivity is poor. The reason is that many students take the way of the work and don not conclude the doctorate period. 290 7.2 Numerical data Category PhD-Dissertations 1997 1 1998 1999 2000 1 2001 Total 2 Scientific Publications 7 6 5 6 10 34 Professional Publications Master’s Theses 3 2 3 4 2 13 8 Self-evaluation The unit is a small one in terms of number of staff components in the steady position. All the members of the staff have a strong organic chemistry background with somebody who is differentiating for devoting himself to physical organic and computational chemistry and some others to more applied research in fundamental aspects of the environmental area. The transformation into a group partially involved in the development of methodologies for environmental chemistry is, however, still in progress. Connections with other researchers, both at national and international level, have been developing and the wish of the unit is that these will have a future growth in order to have the possibility to exchange information and experience. Moreover, the unit holds that it is very important to improve the interactions with other chemical companies in order to transfer the results to a large scale production. The strength of the unit can be found in the number and quality of the scientific production. Publications are the expressions of a valid and faithful organization of the unit. Now, financial support is good and derives prevalently from the public. New funding must be searched and devoted to the acquisition of new instrumentations. Appendix I Scientific Output I-1 Overview of Dissertations and Master's Thesis (1997-2001) I.1.1 Dissertations Year 1997 Ph.D Student Giuseppe Gumina Title of dissertation Sintesi di derivati purinici e pirimidinici a potenziale azione antivirale 2000 Sonia Pedotti Impiego ciclodestrine quali carriers per la realizzazione di prodrugs I.1.2 Master's Thesis Year 1999 Master’s Student Debora Carla Pergolizzi Maria Grazia Saita 1999 1999 2000 2000 2000 2000 Title of dissertation Reazioni di cicloaddizione 1,3-dipolare del benzonitrilossido con il 2(1H)pirazinone e con i suoi derivati N- ed O-metilici Sintesi enantioselettiva e diastereoselettiva di 4’-aza analoghi di 2’,3’dideossinucleosidi Guglielma Vecchio Sintesi stereoselettiva di isossazolidiniltimine per cicloaddizione 1,3dipolare Monica Lupo Reazioni di cicloaddizione 1,3-dipolare di nitrilossidi con aza-fenantreni e reazioni di apertura del nucleo diidroisossazolico dei corrispondenti addotti Roberto Adamo Sintesi di inositoli pre reazione di condensazione alcolica di composti 1,5dicarbonilici Maria Concetta Rita Sintesi stereoselettiva di 4’-aza analoghi di 2’,3’-dideossinucleosidi Siciliano Giovanni Gambera Sintesi di nuovi ausiliari chinali analoghi al sultame di Oppolzer Supervisor Prof. U. Chiacchio Prof. A. Corsaro Supervisor Prof. A. Corsaro Prof. U. Chiacchio Prof. U. Chiacchio Prof. A. Corsaro Prof. A. Corsaro Prof. Chiacchio Prof. Chiacchio U. U. 291 2001 2001 Maurizio Platania Reazioni di cicloaddizione 1,3-dipolare di nitrilossidi con acridina Prof. A. Corsaro Rossella Anita Esaidroisotiazolo[4,5-c]isossazolo-4,4-diossidi e loro utilizzo nella sintesi Prof. U. Sanfilippo asimmetrica Chiacchio Please list the PhD-dissertation and Master's thesis supervised by the Unit. If the dissertation or theses title is written in Italian, please add an English translation I-2 Overview of Scientific Publications (1997-2001) per year 1997 1.Comparison among active and passive samples for monitoring polycyclic aromatic hydrocarbons - V. Librando, A. Corsaro and G. Perrini - Proceedings J. of Polycyclic Aromatic Compounds, Charlotte Meeting USA 1997, 16th Symposium, Part III 17, pp 241-254. 2.1,3-Dipolar Cycloaddition Reactions of Polycyclic Aromatic Hydrocarbons with Nitrile Oxides under Microwave Irradiation in the Absence of Solvent. A. Corsaro, U. Chiacchio, V. Librando, S. Fisichella, and V. Pistarà, Heterocycles, 1997, 45, 1567. 3.Stereoselective Synthesis of Isoxazole and Pyrazole Annulated Sultams Via Intramolecular 1,3-Dipolar Cycloaddition Reactions, U. Chiacchio, A. Corsaro, G. Gumina, V. Pistarà, A. Rescifina, M. Alessi, A. Piperno, G. Romeo, and R. Romeo Tetrahedron, 1997, 53,13855. 4.Monitoring Studies of Augusta Bay Marine Waters. Chiacchio, U.; Librando, V.; Magazzù, G. Enviromental Monitoring and Assessment. 1977, 44, 383. 5.Ring-Opening of Carboxysubstituted Isoxazolidines: Synthesis of lactones and ?-hydroxy-?-lactams. Chiacchio, U.; Rescifina, A.; Casuscelli, F.; Di Bella, M. R.; Ficarra, P.; Melardi, S.; Romeo, G. Gazz. Chim. Ital. 1997, 121, 367. 6.Stereoselective Synthesis of Functionalized Five-, Six- and Seven-Membered Heterocyclic System Via Intramolecular Cycloaddition of C-Alkenyl Nitrones and Nitrile Oxides. Chiacchio, U.; Rescifina, A.; Romeo, G.. Targets in Heterocyclic Systems. Chemistry and Properties, Vol. 1, p 1997, 225-227. 7.Biomimetic Supramolecular Biophenol-Carbohydrate and Biophenol-Protein Models by NMR Experiments. Bianco, A.; Chiacchio, U.; Rescifina, A.; Romeo, G.; Uccella, N. J. Agr. Food Chem. 1997, 45, 4281. 1998 1.The Reaction of Unsaturated Carbonyl Compounds With “Activated Sulfur” (II). Formation of Cyclic Disulfide and Polysulfides, U. Chiacchio, A. Corsaro, V. Pistarà, G. Purrello, and A. Rescifina, Heterocycles, 1998, 48, 41. 2.Cycloadditions of Mesitonitrile Oxide with Hydroxy- and Methoxy-Substituted Stilbenes. A Directing Hydrogen Bonding Model, A. Corsaro, G. Buemi, U. Chiacchio, V. Pistarà, and A. Rescifina, Heterocycles, 1998, 48, 905. 3.Cycloaddition of Nitrile Oxides to Aza-Analogues of Phenanthrene, A. Corsaro, V. Librando, U. Chiacchio, V. Pistarà, and A. Rescifina Tetrahedron, 1998, 54, 9187. 4.Conversion of the Thiocarbonyl Group into the Carbonyl Group, A. Corsaro and V. Pistarà, Tetrahedron, 1998, 54, 15027 5.The Reaction of Unsaturated Carbonyl Compounds with "Activated Sulfur". Part 3. Reaction Course, U. Chiacchio, A. Corsaro, V. Pistarà, A. Rescifina, and G. Purrello, Phosphorus, Sulfur and Silicon,1998, 134/135, 463. 6.A General Synthetic Approach to 5-Alkyl-2(5H)furanones Via 1,3-dipolar Cycloaddition. Chiacchio, U.; Piperno, A.; Rescifina, A.; Romeo, G.; Uccella, N. Tetrahedron, 1998, 54, 5695. 1999 1.Stereoselective Synthesis of Enantiomerically Pure Isoxazolidine-Fused ?-Lactams. U. Chiacchio, A. Corsaro, A. Piperno, A. Rescifina, G. Romeo, and R. Romeo, Heterocycles, 1999, 51, 37. 2.Synthesis and Biological Activity of 1-, 2- or 3-Substituted Benzothieno[2,3d]triazole Derivatives Structurally Related to Trazolone. F. Guerrera, C. Salerno, M. C. Sarvà, M. A. Siracusa, A. Corsaro, V. Pistarà, R Capasso, and G. M.Raso, J. Heterocyclic Chem., 1999, 36, 549. 3.Stereoselective Synthesis of 2’-Amino-2’,3’-Dideoxynucleosides by Nitrone 1,3-Dipolar Cycloaddition: A New Efficient Entry Towards d4T and 2-Methyl Analog. Chiacchio, U.; Iannazzo, D.; Rescifina, A.; Romeo, G. J. Org. Chem. 1999, 64, 28. 4.Homochiral ?-D- and ?-D-Isoxazolidinyl Thymidines Via 1,3-Dipolar Cycloaddition. U. Chiacchio, A. Corsaro, G. Gumina, A. Rescifina, D. Iannazzo, A. Piperno, G. Romeo, and R. Romeo, J. Org. Chem., 1999, 64, 9321. 292 5.Comparison among Active and Passive Samplers for Monitoring Polycyclic Aromatic Hydrocarbons, V. Librando, A. Corsaro, and G. Perrini, Polycyclic Aromatic Compounds, 1999, 17, 241-254. 2000 1.1,3-Dipolar Cycloaddition Reactions of Benzonitrile Oxide to 2(1H)-Pyrazinone and its N- and O-Methyl Derivatives. A. Corsaro, U. Chiacchio, V. Pistarà, and G. Perrini, Heterocycles, 2000, 53, 69. 2.A New Highly Diasterereoselective Synthesis of epi-Inositol from D-Galactose, V. Pistarà, P. L. Barili, G. Catelani, A. Corsaro, F. D'Andrea, and S. Fisichella, Tetrahedron Lett., 2000, 41, 3253. 3.Diastereoselective and Enantioselective Synthesis of 4’-Aza Analogues of 2’,3’-Dideoxynucleosides, U. Chiacchio, A. Rescifina, A. Corsaro, V. Pistarà, G. Romeo, and R. Romeo, Tetrahedron: Asymmetry, 2000, 11, 2045. 4.Cycloadditions of Nitrile Oxides to ?,?-Unsaturated Aldehydes. Frontier Orbital Interactions and Secondary Orbital Interactions at Work in Determining Regiochemistry. L. Toma, P. Quadrelli, G. Perrini, R. Gandolfi, C. Di Valentin, A. Corsaro, and P. Caramella, Tetrahedron, 2000, 56, 4299. 5.Cycloadditions of Mesitonitrile Oxide with Amino- and Nitrostilbenes, A. Corsaro, U. Chiacchio, V. Pistarà, A. Rescifina, and G. Buemi, J. Chem. Soc., Perkin Trans. 2, 2000, 1761. 6.An Unusual Route for the Regioselective Acylation of Polycyclic Aromatic Hydrocarbons: Nitrile Oxide Addition Followed by Isoxazoline Degradation, A. Corsaro, U. Chiacchio, V. Librando, V. Pistarà, and A. Rescifina, Synthesis, 2000, 1469. 2001 1.Diastereoselective Synthesis of N,O-Psiconucleosides via 1,3-Dipolar Cycloaddition, U. Chiacchio, A. Corsaro, D. Iannazzo, A. Piperno, A. Rescifina, R. Romeo, and G. Romeo, Tetrahedron Lett., 2001, 42, 1777-1780. 2.Stereoselective Synthesis of Homochiral Annulated Sultams via Intramolecular Cycloaddition Reactions, U. Chiacchio, A. Corsaro, A. Rescifina, M. Bkaithan, A. Piperno, T. Privitera, and G. Romeo, Tetrahedron, 2001, 57, 3425-3433. 3.A Stereoselective Approach to Isoxazolidinyl Nucleosides, U. Chiacchio, A. Corsaro, A. Rescifina, D. Iannazzo, A. Piperno, and G. Romeo, Eur. J. Org. Chem., 2001, 1893-1898. 4.Regeneration of Carbonyl Compounds from the Corresponding Oximes, A. Corsaro, U. Chiacchio, and V. Pistarà, Synthesis, 2001, 13, 1903-1931. 5.Biomembrane Model Interaction and Percutaneous Absorption of Papaverine Throught Rat Skin. Effects of Cyclodextrins as penetration Enhancers, C. A. Ventura, M. Fresta, S. Pedotti, A. Corsaro, and G. Puglisi, J. Drug Targeting, 2001, 9, 379-393 6.A New Route for the Chemical Valorisation of Lactose, A. Corsaro, G. Catelani, F. D’Andrea, S. Fisichella, M. Mariani, and V. Pistarà, J. Environ. Sci. Poll. Res., DOI: http://dx.doi.org/10.1065/espr2001,12.104.2. 7.Enantioselective Synthesis of 4-Hydroxy-Dpyroglutamic Acid Derivatives by an Asymmetric 1,3-dipolar Cycloaddition. Pedro Merino, Julia Revuelta, Tomas Tejero, Ugo Chiacchio, Antonio Rescifina, Anna Piperno, Giovanni Romeo Tetrahedron Asymmetry 2002, 13, 167-172 8.Experimental and Theoretical Study of 1,3-dipolar Cycloadditio between D-Glyceraldehyde Nitrones and Acrylates. Diastereoselective Approach to 4-Hydroxy Pyroglutamic Acid Derivatives. Pedro Merino, Juan Mates, Julia Revuelta, Tomas Tejero, Ugo Chiacchio, Daniela Iannazzo, Giovanni Romeo Tetrahedron Asymmetry 2002, 13, 173-190. 9.Chemo-,regio, and steroselective Mitsunobu reaction of unprotected pyrimidine bases with hydroxypyrrolidines. Barbara Richichi, Stefano Cicchi, Ugo Chiacchio, Giovanni Romeo, Alberto Brandi, Tetrahedron Letters, 2002, 43, 4013-4015. 10.Modified Nucleosides. A General and Diastereoselective Approach to N,O-Psiconucleosides, D. Iannazzo, A. Piperno, V. Pistarà, A. rescifina, R. Romeo,Tetrahedron, 2002, 58, 581-587. Appendix 3 Journal Portfolio Analysis Name of the Unit: Research Director: Years included Catania (Organic Chemistry) Prof. Antonino Corsaro 1997 - 2001 293 Name of Journal J. Org. Chem. Number Articles 2 Tetrahedron 7 Tetrahedron Asymmetry of Journal Factor 3.689 Impact Field(s) Ranking Organic Chemistry 5/37 2.356 Organic Chemistry 11/37 3 2.797 Organic Chemistry 9/37 Tetrahedron Letters 3 2.558 Organic Chemistry 8/37 Eur. J. Org. Chem. 1 2.150 Organic Chemistry Synthesis 2 2.193 Organic Chemistry 10/37 J. Chem. Soc., Perkin Trans. 1 2 Heterocycles 5 1.770 Organic Chemistry 13/37 1.015 Organic Chemistry 24/37 J. Heterocyclic Chem. 1 0.781 Organic Chemistry 29/37 Polycyclic Aromatic Compounds Phosphorous, Sulfur and Silicon J. Environ. Sci. Poll. Res. Gazz. Chim. Italiana Envir. Monitoring and Assessment J. Drug Targeting 2 1 Environmental Chemistry 0.308 Organic Chemistry 31/37 1 1 1 0.792 0.526 Environmental Chemistry Chemistry Environmental Chemistry 51/110 67/105 1 2.186 Medicinal Chemistry Comments on: a) the method: This method of evaluation of the scientific productivity can not be considered valid in absolute. However it is, at the moment, the only one, which can supply an objective and homogenous element of evaluation b) the results: The average impact coefficient of the articles published is 1.946. Only, some publications of the unit have not cited impact factors because they fall in scientific areas of environment very specific. For this reason, the unit’s publications in the examined years rank in journals of organic chemistry, and only very little areas are of environmental chemistry. 294 COSENZA 1 Name of the Research Unit Membrane e Processi a Membrana Membrane and Membrane Processes Research Leader Prof. Enrico Drioli Contact Person University: Università degli Studi della Calabria University of Calabria Faculty: Facoltà di Ingegneria Faculty of Engineering Department: Dipartimento di Ingegneria Chimica e dei Materiali Department of Chemical and Materials Engineering Name: Prof. Molinari Raffaele Mailing Address: Dipartimento di Ingegneria Chimica e dei Materiali – Università della Calabria. I-87036 Arcavacata di Rende (CS) Italy Phone: ++39-984-492090 Fax: ++39-984-492058 E-mail: [email protected] Thematic area Please indicate to which thematic area of INCA the unit belong (in priority order): • Tecnologie di depurazione (membrane, sonochimica, fotocatalisi, elettrochimica e altre). • Catalisi eterogenea per le sintesi ecosostenibili e la decontaminazione ambientale. Introduction and Context Introduction to the Self-evaluation Report The University, the Faculty and the Department University of Calabria born in 1972. It is localized in South Italy, in Rende, province of Cosenza. The University is composed of six Faculties: Economy, Political Sciences, Pharmacy, Engineering, Humanity, Matemathics, Physic and Natural Sciences. The number of students grow in the years reaching now about 30.000 that is the full capacity of the University campus. The Faculty of Engineering has eigth courses of Degree (Civil, Environment, Chemical, Management, Informatic, Mechanical, Electronic, Building), master and PhD courses. The Department of Chemical and Materials Engineering is one of the 23 Departments of the University of Calabria. The Department was born in 1994 from the Department of Chemistry of which was the Chemical Engineering Section. The personnell is devided in: teaching/research staff: 5 full professors; 6 associate professors; 4 researchers. technical staff: 7 technicians. administrative staff: 5 employees. There are also various fellowships, external collaborators, students in thesis (for graduation and for PhD graduation) and visiting research associates. There is a library, the biggest in South Italy, with books and Journals in the various fields. The Department participate to the Erasmus and Socrates projects and has several collaborations with international research groups. The economical balance (payments) of the 2001 was about 1.350.000 of Euros. In the Department there are several research groups working on various themes: Membrane Processes, Development of new zeolite catalysts, Characterization of complex reological systems, Simulation of chemical plants, Development of bioartificial organs, Purification of industrial wastes, Study of fluidized bed systems. 295 The Unit The Research Unit is formed by 3 teaching-research staff , 2 technician, 1 Researcher of CNR, 2 PhD students, several student in thesis (degree), visiting researchers, 2 external collaborators. The teaching staff is involved in the courses of Chemistry for the Faculty of Engineering for more than 1000 students per year, and in the course of “Chimica II” for about 15 students per year. Major durable equipments existing in the group are: spectrophotometers, HPLC, GC, fast-flow slab electrophoresis, pH-stat, contact angle measurement, UF flat, membrane characterization plant, RO single- spiral module plant, UF single cylindrical geometry module, PSI 500 Permporometer. Other equipments available in the Department are: Xray, SEM, Thermal analysis, Differential Calorimetry, Particles distribution, Optical microscopes. Programme Description and Evaluation 1 Title Membrane preparation and Molecular separations and Conversions by using Membrane Processes 2 Research Leader Prof. Enrico Drioli 2a Sub-programme titles and sub-programme leaders 3 Composition of the scientific research staff of the unit per 1 January 2002 Names and Titles Year of Rank Birth Drioli Enrico, Prof. Molinari Raffaele, Prof. 1941 1953 Golemme Giovanni, Dr. 1960 Cassano Alfredo, Dr. 1965 Buonomenna Maria 1975 Giovanna, Dr. Augurio Pietro, Dr. Ing. 1973 Pirillo Fabrizio, Dr. Ing. 1972 Poerio Teresa, Dr. 1970 Regina Angelo, Dr. 1956 Grandinetti Massimo, Mr. 1954 Full Professor Associated Professor Researcher UNICAL Researcher ITM-CNR PhD-student PhD-student Contractor INCA Contractor CNR Graduate Tecnician Diplomate Technician Research Input Remarks in fte in 2001 0.4 0.5 0.6 1.0 1.0 1.0 1.0 1.0 1.0 0.4 Total research input 10 7.9 Note: The Research Unit is formed also by other Researcher of the ITM-CNR (more than 15) but only that involved in INCA Projects have been included in the Table. 4 Input of Academic Staff in fte Category Full Professors Associated Professors Ricercatori Post-docs PhD-students 1997 0.4 / 5.2 1.8 3.2 1998 1999 2000 2001 0.4 0.5 3.0 / 2.0 Total 296 Borsisti and Contracts Total 5 Funding 5.1 Personnel (in fte) Source University CNR European Union Other Sponsors Total 5.2 4.6 15.2 1997 5.8 6.0 1.0 2.4 15.2 2.0 7.9 1998 1999 2000 2001 4.9 2 / 1 7.9 Total 1999 2000 2001 Total 5 year 350 700 100 Materials and Equipment (in Million Lire) Source 1997 1998 University - MURST CNR EU Other Sponsors Total 5.3 1150 Comments: List of major sponsors: ESF (European Science Foundation), CAS (Chinese Academy of Science), EU, MURST, ENEA, PASTIS (Centro Nazionale per la Ricerca e lo Sviluppo dei Materiali (Brindisi), CNR, Regione Calabria, Concia Ricerche, INTAS, KTI, Tecnoprogetti Industriali, etc. 6. Progress Report 6.1 Mission Statement The research area and the mission of the research unit is the development of new type of membranes (mainly polymeric) and new membrane separation processes. The researches are divided in fundamental (such as preparation and characterization of membranes and characterization of transport properties of membranes) and applied (application of membrane separation processes to specific separation problems of industrial and civil interest) The clients are the international scientific community, practitioners in the field, regional and national authorities, regional, and national industries, educational and training programmes, consultancy, etcetera. 6.2 The Research Programme Some research themes, close to the environmental sector, are: 1) Rationalization of energy and material consumption in industrial cycles using membrane processes study of traditional cycles and determination of mass and energy fluxes; determination of the new mass and energy fluxes after the introduction of the membrane process; energy and exergy analyses of the cyles using the concept of direct and indirect energy and substitution coefficient; experimental tests on membranes to evaluate possibility of using membrane operations, chemical interaction of 297 components to separate and membrane, chemical conditions for cleaning the membranes , etc. 2) Degradation of pollutants using heterogeneous photocatalysis on membranes checking the type of polymeric membrane; study of kinetics and configuration of photocatalytic membrane reactors; application of photoreactors in the photodegradation of pollutants present in low concentration in aqueous solutions. 3) Removal of pollutants in waters by means controlled complexation and precipitation together membrane technology separation of specific pollutants (iron, manganese, silica, humic acids, bacteria, etc) from water of various sources; potabilization of waters, recycle and reuse in industrial processes; finding of precipitants/complexants and of the chemical conditions for removing specific components from water; checking and characterization of various type of membranes and their efficiency in the removal of pollutants chosen as models; study of the interactions pollutants – membrane (fouling, concentration polarization) and of the cleaning techniques and type of chemicals to be used; comparison of the proposed processes with the conventional treatment processes; use of water from various sources to validate the new process. 4) Chromium (III) recovery from waste waters in the tanning industry checking the type of membranes and of the operating conditions to maximize chromium (III) recovery from exhaust tanning baths ; purification of the recovered chromium (e.g. reduction of fat substances contained in the wastewater); study of supported liquid membranes (transport mechanism, equilibrium conditions at the interfaces, chemicalphysical conditions of the complexation-decomplexation reactions, etc.) to obtain an high recovery efficiency and an high purification degree of the chromium (III) by using specific carriers. 5) Combined use of sorbent particles and membranes in the recovery and purification of chemical species from solutions. recovery, purification, separation and concentration of chemical species (e.g. metal ions, dyes, etc.) from various waste waters; finding the type of membranes, type of sorbent particles; study of the chemical-physical operating conditions and of the fluid dynamic conditions related to membrane and particles. Some of the most impressive results in the past five years are: - Development of a combined process UF/NF for the purification and recycling of Cr(III) from waste water of chromium tanning. - Development of a nanofiltration process for recovering and recycling tannins from spent tanning liquors. -Development of a new rapid method for tannin analysis in tanning baths. -Stabilization of liquid membranes by a new type of sandwich liquid membrane. -Development of a configuration of Photocatalytic Membrane Reactor interesting for industrial applications. -Development of the Polymer Assisted ultrafiltration process (PAUF) for metal ions recovery from waste water. The programme development for the future (the coming 5 years) foresee: - study of the Photocatalytic Membrane process using new type of catalysts (e.g. nanoparticles) to improve reactor performance. - research and/or synthesis of new selective carriers to be used in (supported)liquid membranes. - reserarch and /or synthesis of new selective polymers to be used in the PAUF process. - study of new hybrid membrane processes in water treatment. 6.3 Position in Networks 298 • Intra-university co-operation Department of Chemistry Department of Physics ITM- CNR (Rende (CS)-I) • Regional co-operation Consorzio Sibarit APOA (Corigliano Calabro-I) Emmegi agro-ind. (Rossano Calabro-I) Ist. di Medicina Sperimentale e Biotecnologia del CNR (Cosenza-I) • National co-operation (including INCA) University of Bologna (Bologna-I) University of Genova (Genova-I) CNR-Dip. di Calcolo Parallelo (Naples-I) Stazione Sperimentale per la Cellulosa, Carta e Fibre Tessili Vegetali ed Artificiali (Milan-I) Istituto di Ozono Elettronica (Milan-I) Stylfil (Pordenone-I) PASTIS - CNRSM (Centro Nazionale per la Ricerca e lo Sviluppo dei Materiali)- (Brindisi-I) ISCOM CNR Production S.r.l. (Carpi-I) Separem S.p.A. (Biella-I) ITS-ARTEA (Milan-I) University of Pisa (Pisa-I) Consorzio Recupero Cromo (Pisa-I) Department of Engineering Chemistry, Processes and Materials – University of Palermo. KTI (Rome-I) Tecnoprogetti Industriali (Bergamo-I) INCA: The research unit started research programme in co-operation with INCA structure. Projects L.488 (Membrane Photoreactors) and Sisifo (Polymer assisted Ultrafiltration). • International co-operation University of Glascow (Glascow-UK) Res. Inst. of Petroleum Processing (Pechino-China) Topchiev Institute (Moscow-RU) University of Salford (Salford-UK) Nat. Chemical Lab. for Industry (Tsukuba-JP) Institute of Chemistry, Academia Sinica (Pechino-China) Baetens (Belgium) Centexbel (Belgium) Lis Lieve (Belgium) Hilature de Portolin (Spain) INSA (Toulouse-F) Middle East Desalination Research Center (Muscat - Oman) Valle Ballina Y Fernandez (Spain) Lund University (Lund-SW) ATO-DLO (The Netherlands) Universidad de Oviedo (Oviedo-S) Inst. of Phys. Org. Chem. (Minsk-Belarus) University of Twente (Enschede-NL) Department of Chemical and Biochemical Engineering – Slovak Technical University (Bratislava) Institute of Chemistry – University of Sciences and Technology “Houary Boumediene”- Algier – Algerie. Univ. Sidi Mohamed Ben Abdellah, Faculty of Sciences, Fès - Morocco 6.4 Societal Relevance and Impact 299 The relevant importance of Membrane and Membrane Processes is today well consolidated with many applications in numerous fields and new applications are adding day to day. The unit has contributed in this area for what concerns membrane preparation and characterization and possibility of application of some membrane processes in separations of industrial interest. The unit received funding also from private companies for exploring applications of membrane operations. The about 30 year activity in the field, the numerous publications (more than 320), participation and organization of seminars, congresses (national and international), schools and participation to several membrane networks justify the contribution of the unit in this area. 6.5 Further Indications of Quality and Reputation The research leader of the unit received various types of scientific honours: Dean of the School of Engineering of the University of Calabria (1982-1985). • Director of the Institute on Membranes and Chemical Reactors of the National Research Council (since 1993). • President of the European Society of Membrane Science and Technology (1982 - 1998). • Chairman of the Working Party on Membranes of the European Federation of Chemical Engineering (since 1985). • Doctorate Honoris Causa in Chemistry and Chemical Technology from Russian Academy of Science (February 1992). • Honorary Professor at the China Northwest University in Xi'an, Shaanxi, People's Republic of China (Sept. 1991). • Honorary Founding President of the European Membrane Society (from 1999). • Honorary Member of the A. V. Topchiev Institute of Petrochemical Synthesis at the Russian Academy of Sciences, Moscow (from 1999). • Patron Member of the Indian Membrane Society. • Member of the Advisor Board of the UNESCO Center on Membrane Science and Technology at the New South Wales University, Australia. • Member of the European Communities Chemistry Council (E.C.C.C.). • Member of Executive Council of the European Federation of Chem. Engineering (from 1996) • Member of the Interim Board of Governors of the Middle East Desalination Research Center, Oman, Muscat (1994 - 1996); Member and Moderator of the Research Advisory Council of the Middle East Desalination Research Center , Oman, Muscat (from May 1997) • Member of the NATO/CCMS Pilot Study on "Clean Products and Processes" • International Scientific Counselor of the Membrane Industry Association of China • Member of the ASME Industrial Water Treatment Committee • Director of Research Projects on Membrane Science and Technology sponsored by the C.N.R., M.U.R.S.T., E.N.E.L.-C.R.I.S., E.N.E.L.-G.R.E., F.I.A.T., Montedison, Assoreni, S.A.M.I.M., U.S.A.F., Committee Energy Atomique (France), DGXII - E.U., Progetto Finalizzato Chimica Fine, Progetto Finalizzato Energia II, Tecnofarmaci, Unioncamere, Parmalat, Technip Italia, Biofil, TecnoProgetti, Tecnomare, ABB and other National and International Agencies and Industries, etc. • Director and/or lecturer in various postdoctoral Schools on Membrane Science and Technology sponsored by CESVITEC, Italian Chemical Society, FAST, FORMEZ, Plastic Institute of America, NATO Advanced Study Institute, European Society of Membrane Science and Technology, Comm. Eur. Communities, FOIST, etc. • Director of various international bilateral research programs (USA/Italy, France/Italy, Korea/Italy, China/Italy, Egypt/Italy, Japan/Italy, Russia/Italy, etc.). • Author of more than 320 scientific papers and 14 patents in the field of Membrane Science and Technology. • Member of the Editorial Boards of the: Chemical Engineering and Processing - Elsevier Desalination - Elsevier Journal of Membrane Science – Elsevier Journal of Molecular Catalysis (1982–1992) - Elsevier Chemical Engineering and Technology Journal - Wiley-VCH; Industrial & Engineering Chemistry Research (from Jan. 2002) – American Chemical Society; Journal of Clean Products and Processes - Springer-Verlag; Acqua-Aria – Arti poligrafiche europee; Chimica Oggi - TeknoScienze; 300 La Chimica e L’Industria - Editrice di chimica; Orizzonti Tecnologici - CESVITEC; Water Treatment - China Ocean Press; Anales de Fisica - La Sociedad; Russian Journal of Physical Chemistry - MAIK Nauka, Interperiodica Publ.,; Journal of Separation and Purification Technology - Childwall University Press; • Member of the Scientific Committee of ENICHEM S.p.A., Milan (1985-87), Tecnofarmaci S.p.A. (Rome); Member of the Technical Committee of CESVITEC (Naples); Concia Ricerche (Milan), etc. • Served as expert or consultant of various National and International Organizations as U.N.D.P.; Economic Council of EUROPE, UN, Geneve; Commission of the European Community; DG XII, Brussels, Belgium; Nat. Science Foundation, Washington, USA; Australian Research Council, Canberra, Australia; Swedish Research Council for Engineering Science, Sweden; NATO (Science for Peace Program); Ministero dell'istruzione, dell'università e della ricerca, Ministero per le attività produttive (Italy); etc. • Member of the National Committee for Chemistry of the Ministry for University and Scientific Research (1988). • Served as Member of the Commission for the Evaluation of Doctorate Thesis in Chemical Engineering at the University of Twente (The Netherlands), at the University of New South Wales (Sydney, Australia), at the Ecole Polytechnique Federale de Lausanne (Lausanne, Switzerland), at Dept. of Food Eng. University of Lund (Sweden), at Dept. of Chemistry, Glascow University (U.K.), at Indian Institute of Technology, (Kanpur, India), at ENSIC - University of Nancy (France); at University of Paul Sabatier of Toulouse (France); etc. • Chairman or Co-chairman of various International Conference on Membranes (e.g., Ravello Conference in 1977 and 1988; Europe-Japan Conference in 1984 - Stresa; ICOM in Tokyo 1987; International Conference on Membranes for gas and vapor separation, Suzdal, USSR, 1989; World Desalination in 1991 - Malta; Int'l symposium on Membranes and Membrane Processes, Hangzhou, China, 1994, etc.); Summer Schools (E.E.C.China in Lanzhou, 1986; and in Nantong, 1988) and Workshops (e.g. Workshop on Membrane Distillation, Rome), EC-Indian Workshop on Membranes, New Delhi, 1991; EEC China Workshop on Preservation of Cultural Heritages, Xian, Shaanxi, P. R. of China (1991); EC-Brazil Workshop on Membranes, Rio de Janeiro, 1992, etc); International Symposium on Membranes and Membrane Processes, Hangzhou, China (1994); ASEANEU, Workshop on Membrane Technology in Agro-Based Industry, Kuala Lumpur, Malaysia (1994); International Conference on Membrane Science and Technology (ICMST ’98); Ravello Conference on “Catalysis in Membrane Reactors, New Frontiers for Catalytic Membrane Reactors & Other Membrane Systems”, organized with the European Science Foundation of Strasbourg (France) and the Kenan Inst. for Engineering, Technology & Science (USA) (1999); 2001 International Conference on Membrane Technology Application, Shanghai & Hangzhou, P. R. China (2001); China - Italy Workshop on Membrane Process for Clean Production and for sustainable Growth, Beijing, P. R. China (2001); Engineering Foundation Conference on Advanced Membrane Technology, Barga, Italy (2001); etc. • Visiting scientist at the Max Plank Institut für Biophysic, Frankfurt a.m.; at the Chemical Engineering Department of the North Carolina State University, Raleigh, USA; at The Bend Research, USA; at the Institute of Membrane Science and Technology, Lanzhow, R.P.China; at the Demokritos Nuclear Research Center, Athens, Greece, etc. • Invited lecturer at various Universities, Scientific Institutions and Industrial Research Groups in Australia, Austria, Bahrain, Belgium, Bielorussia, Brazil, Czechoslovakia, Demark, Egypt, Finland, France, Greece, Holland, Israel, Japan, Jordan, Kuwait, Malesia, Malta, Norway, Oman, P.R. China, Poland, Portugal, Russia, Singapore, Slovakia., Spain, Sweden, Switzerland, UK,USA, USSR, West Germany. • Member of A.I. Ch. E., ACS, Soc. Chim. Ital., European Membrane Society, NAMS, etc. 6.6 Key Publications 1) A. Cassano, A. Criscuoli, E. Drioli, R. Molinari, Clean operations in the tanning industry: aqueous degreasing coupled to ultrafiltration. Experimental and theoretical analysis, Clean Products and Processes, 1(4), 257-263 (1999). 2) R. Molinari, M. Mungari, E. Drioli, A.Di Paola, V. Loddo, L. Palmisano, M. Schiavello, Study on a photocatalytic membrane reactor for water purification, Catalysis Today, 55, 71-78 (2000). 3) A. Gherrou, H. Kerdjoudj, R. Molinari, E. Drioli, Facilited co-transport of Ag(I), Cu(II) and Zn(II) ions by using DB18C6 and DA18C6 crown ethers as carriers: Interface behaviour on the ion transport, Sep. Sci. & Technol., 36(10), 2289-2304 (2001). 4) R. Molinari, M.G. Buonomenna, A. Cassano, E. Drioli, Rapid determination of tannins in tanning baths by adaptation of BSA method, Annali di Chimica 91, 2001, 255-263. 301 5) R. Molinari, C. Grande, E. Drioli, L. Palmisano, M. Schiavello, Photocatalytic Membrane Reactors for Degradation of Organic Pollutants in Water, Catalysis Today, 67(1-3), 273 – 279 (2001). 7. Scientific Output 7.1 Publication Policy In all the years of his activity the unit published more than of 320 papers, participated to national and international meetings and conferences contributing with oral and poster presentation (not included in the list below) and also in the organisation of several of them included Schools and Membrane Courses. 7.2 Numerical data Category PhD-Dissertations 1997 3 1998 / 1999 / 2000 1 started 2001 5 started Total 3 + 6 started Scientific Publications 6 12 18 16 22 74 Professional Publications Master’s Theses (Tesi di Laurea) 6 4 8 8 3 29 Appendix I Scientific Output I-1 Overview of Dissertations and Master's Thesis (1997-2001) I.1.1 Dissertations Year Name PhD-student I.1.2 Master's Thesis (1997 – 2001) Year Title of the Dissertation Supervisor Title of the Dissertation Name Master’s student Supervisor 1996-97 Fenomeni di Polarizzazione Trasporto 1996-97 Chiarificazione e Deamarizzazione di 1996-97 Sintesi della Faujasitica 1996-97 Steam Reforming del Metano in un 1996-97 Concentrazione alimentari 1997-98 Produzione di Syngas mediante Reattori Luca Paturzo a Angelo Basile, Enrico Drioli 1997-98 Reattori Catalitici a Membrana per Angelo Basile, Enrico Drioli 1997-98 Preparazione di Membrane Polimeriche e Gabriele Clarizia Enrico Drioli 1998-99 Applicazione dei Reattori a Membrana Giovanni Pietro Enrico Drioli, Angelo Basile, Silvano Zeolite spinta a e di Lucio Cicerelli Patrizia Tallarico Struttura Vincenzo Durante di Giuseppe Salvatore succhi Fortunato Laganà Sergio Antonio Enrico Drioli, Vincenza Calabrò Enrico Drioli, Silvestro Todisco Rosario Aiello, Fortunato Crea Enrico Drioli, Giuseppe Barbieri Enrico Drioli, Giuseppe Barbieri 302 nel Tosti, 1998-99 Operazioni a Membrana in Reazioni Alessandra Criscuoli Enrico Drioli 1998-99 Studio dell'Estrazione con Solvente in Luigi Leva Enrico Drioli 1998-99 Modellistica di Membrane Polimeriche Elena Tocci Enrico Drioli 1998-99 Studio Teorico-Sperimentale sulle Efrem Curcio Enrico Drioli, Giuseppe Barbieri Fausto Gallucci A. Basile, E. Drioli 1999/2000 Produzione di Metanolo da CO2 e H2 1999-00 Reattore a membrana per la produzione Antonino Vazzana di Angelo Basile 19992000 Reattori catalitici a membrana per lo Perri Giovanni steam Drioli Enrico, Barbieri Giuseppe 20002001 Aspetti Sperimentali e di Modellistici Angelo della Famà 20002001 Day reforming del metano mediante Davide A. Basile, E. Drioli Calabrò Giuseppe E. Drioli, A. Basile 13) Impiego di particelle adsorbenti e di tecniche a membrana nella rimozione dell'amaro da succhi di agrumi. Candidato: Brancaccio Vittoria (A.A. 1995/96 -Laurea maggio 1997) Relatori: G. Martino, R. Molinari 14) Flocculazione controllata ed ultrafiltrazione nella potabilizzazione delle acque. Candidato: Sottile Sandra (A.A. .1996/97 - Laurea maggio 1998) Relatori: R. Molinari, G. De Munno 15) Tecnologie pulite a membrana nel disinquinamento delle acque: processi di osmosi inversa e di ultrafiltrazione. Candidato: Romeo Leonardo (A.A. 1997/98 - Laurea maggio 1999) Relatore: R. Molinari 16) Caratterizzazione di diverse configurazioni di reattori fotocatalitici a membrana. Candidato: Mungari Gennaro Milo (A.A. 1997/98 - Laurea maggio 1999) Relatore: R. Molinari 17) Reattori fotocatalitici a membrana con biossido di titanio intrappolato e in sospensione nella degradazione di inquinanti di natura organica in soluzioni acquose. Candidato: Grande Cesare (A.A. 1998/99 - Laurea luglio 1999) Relatore: R. Molinari 18) Stabilizzazione di membrane liquide supportate da impiegare in separazioni chirali. Candidato: Argurio Pietro (A.A. 1998/99 - Laurea febbraio 2000) Relatore: R. Molinari 19) Studio sperimentale di un reattore fotocatalitico a membrana nella degradazione di inquinanti organici in soluzioni acquose. Candidato: Borgese Michelangelo (A.A. 1998/99 - Laurea aprile 2000) Relatore: R. Molinari 20) Flocculazione-precipitazione combinata con ultrafiltrazione nell’abbattimento di ioni Ca2+, Mg2+, Fe2+ e Mn2+ nelle acque. Candidato: Di Sanzo Giuseppe (A.A. 1999/00 - Laurea luglio 2000) Relatore: R. Molinari 303 21) Rimozione dei componenti dell’amaro da succhi di agrumi mediante estrazione liquido-liquido in sistemi a membrana. Candidato: Madia Edoardo (A.A. 1999/00 - Laurea luglio 2000) Relatore: R. Molinari 22) Studio di diverse operazioni a membrana nel recupero e riciclo di bagni tannici esausti del’industria conciaria. Candidato:Scicchitano Gianluca (A.A. 1999/00 - Laurea luglio 2000) Relatore: R. Molinari 23) Studio teorico e sperimentale di membrane liquide supportate: stabilità e modellistica del traporto di materia. Candidato: Pirillo Fabrizio (A.A. 1999/00 - Laurea maggio 2001) Relatore: R. Molinari 6 I-2 Overview of Scientific Publications (1997-2001) per year I-3 Overview of Professional Publications (1997 - 2001) per year 1997 258) Giorno, L., Molinari, R., Natoli, M., Drioli, E., Hydrolysis and regioselective transesterification catalyzed by immobilized lipases in membrane bioreactors, Journal of Membrane Science, 125 (1997) 177-187 259) Giorno, L., Drioli, E., Catalytic behaviour of lipase free and immobilized in biphasic membrane reactor with different low water-soluble substrates, J. Chem. Tech. Biotechnol., 1997, 69, 11-14 260) Bouma, R.H.B., Checchetti, A., Chidichimo, G., Drioli, E., Permeation through a heterogeneous membrane: The effect of the dispersed phase, Journal of Membrane Science, 128 (1997) 141-149 261) Barbieri, G., Violante, V., Di Maio, F.P., Criscuoli, A., Drioli, E., Methane steam reforming analysis in a palladium-based catalytic membrane reactor, Industrial & Engineering Chemistry Research, 36(8), 3369-3374, 1997 262) Natoli, M., Pagliero, C., Trotta, F., Drioli, E., A study of catalytic ?-cyclodextrin carbonate membrane reactor performance in PNPA hydrolysis, Journal of Molecular Catalysis A: Chemical, 121, 179-186, 1997 263) Cassano, A., Drioli, E., Molinari, R., Recovery and reuse of chemicals in unhairing, degreasing and chromium tanning processes by membranes, Desalination, 113 (1997), 251-261 1998 264) Alentiev, A., Drioli, E., Gokzhaev, M., Golemme, G., Ilinitch, O., Lapkin, A., Volkov, V., Yampolskii, Yu., Gas permeation properties of phenylene oxide polymers, J. Membr. Sci., 138 (1998) 99-107 265) Giorno, L., Donato, L., Todisco, S., Drioli, E., Study of fouling phenomena in apple juice clarification by enzyme membrane reactor, Sep. Sci. & Techn., 33(5), pp.739-756, 1998 266) Todisco, S., Tallarico, P., Drioli, E., Modelling and analysis of ultrafiltration effects on the quality of freshly squeezed orange juice, Italian Food & Beverage Technology, XII (1998), pp. 1 – 8. 267) Laganà, F., Barbieri, G., Drioli, E., Il Processo di distillazione a membrana per la concentrazione di succhi alimentari, ICP, Luglio/Agosto 1998, pp. 161- 166 268) Giorno, L., Donato, L., Drioli, E., Study for enzyme membrane reactor for apple juice clarification, Fruit Processing, 6, 1998, pp. 239-241 269) Cassano, A., Drioli, E., Molinari, R., Integration of ultrafiltration into unhairing and degreasing operations, Journal of the Society of Leather Technologists and Chemists, 82, pp- 130-135, 1998. 270) Giorno, L., Molinari, R., Drioli, E., Experimental studies on enzyme membrane reactors in oil treatment, Emerging Technologies, Current Practices, Quality Control, Technology Transfer, and Environmental Issues, Vol. I, (S.S. Koseoglu, K.C. Rhee, R.F. Wilson, Ed.), pp. 91-94, 1998. 271) Trotta, F., Drioli, E., Moraglio, G., Baima Poma, E., Sulfonation of polyetheretherketone by chlorosulfuric acid, J. Appl. Polym. Sci., 1998, 70(3), 477-482 272) De Bartolo, L., Drioli, E., Membranes in artificial organs, Biomed. Health Res., 1998, 16, 167-181 273) Donato, L., Checchetti, A., Drioli, E., Assorbimento di acqua liquida e vapore in pietre microporose protette da membrane polimeriche di CoPVDF, Proc. “1st Int. Congress on: Science and Technology for the 304 Safeguard of Cultural Heritage in the Mediterranean Basin”, Nov. 27 – Dec. 2, 1995, Catania, pp. 899-902, 1998. 274) Golemme, G., Drioli, E., Polyphosphazene Membrane Separations – Review, Journal of Inorganic and Organometallic Polymers, 6(4), 1996, 341-365 275) Tomaselli, M., Cassano, A., Drioli, E., Processi a membrana nell’industria conciaria: potenzialità e prospettive, CPMC, 74(4), 1998, pp. 149-167. 1999 276) Bove, L., Clarizia, G., Golemme, G., Drioli, E., Development and characterization of PPO composite membranes for gas separation, Macromolecular Symposia, 138, 93-7 (1999). 277) Golemme, G., Facchin, G., Gleria, M., Guarino, L., Drioli, E., Preparation and characterization of hybrid polyphosphazene-silica gel membranes, “Phosphorus Res. Bull.”, 10, 736-41 (1999). 278) De Bartolo, L., Catapano, G., Della Volpe, C., Drioli, E., The effect of surface roughness of microporous membranes on the kinetics of oxygen consumption and ammonia elimination by adherent hepatocytes, J. Biomater. Sci., Polymer. Edn., 10(6), pp. 641-655, 1999 279) Laganà, F., Drioli, E., Criscuoli, A., Barbieri, G., Integrated membrane operations in desalination processes, Desalination, 122 (1999) 141- 145 280) Cassano, A., Molinari, R., Drioli, E., Saving of water and chemicals in tanning industry by membrane processes, Water Science & Technology, 40/4-5 (1999) 443-450 281) Cassano, A., Criscuoli, A., Drioli, E., Molinari, R., Clean operations in the tanning industry: aqueous degreasing coupled to ultrafiltration. Experimental and theoretical analysis, Clean Product and Processes, 1999, 1(4), 257-263. 282) Tavolaro, A., Drioli, E., Zeolite Membranes, Advanced Materials, 1999, 11(12), pp. 975-996 283) Molinari, R., Mungari, M., Drioli, E., Di Paola, A., Loddo, V., Palmisano, L., Schiavello, M., Study on a photocatalytic membrane reactor for water purification, Catalysis Today, 55 (2000), pp. 71-78. 284) Muzzalupo, R., Ranieri, A.G., Golemme, G., Drioli, E., "Self diffusion measurements of organic molecules in PDMS and water in sodium alginate membranes"; J. Appl. Polym. Sci., 74 (5) 1119-28 (1999) 285) Laganà, F., Barbieri, G., Drioli, E., "Direct contact membrane distillation:modelling and concentration experiments", J. Mem. Sci., 2000, 166, pp. 1-11. 286) Drioli, E., Todisco, S., I processi a membrana nella moderna enologia, VIGNEVINI; n. 1/2, 1999, pp. 31-45. 287) Trotta, F., Drioli, E., Gordano, A., Nitro derivative of PEEK-WC, Journal of Applied Polymer Science, 80, 2001, 1037-1045 288) Gordano, A., Clarizia, G., Tocci, E., Drioli, E., Arcella, V., Arrigoni, S., Colaianna, P., Brinati, G., Hydrophobic Membranes of Tetrafluoroethylene and 2,2,4 Trifluoro 5 Trifluorometoxy 1,3 Dioxole, Korean Membrane Journal, 1999, 1(1), pp. 50-58. 289) Madia, G.S., Barbieri, G., Drioli, E., Theoretical and experimental analysis of methane steam reforming in a membrane reactor, The Canadian Journal of Chemical Engineering, 77 (1999), 698-706 290) Cassano, A., Drioli, E., Molinari, R., Grimaldi, D., La Cara, F., Rossi, M., "Enzymatic membrane reactor for eco-friendly goat skins unhairing", Journal of the Society of Leather Technologists and Chemists, 2000, 84, 205-211. 291) Criscuoli, A., Drioli, E., “Energetic and exergetic analysis of an integrated membrane desalination system”, Desalination, 124 (1999) 243-249 292) Basile, A., Fasson, S., Vitulli, G., Drioli, E., An experimental study of the partial oxidation of methane in a membrane reactor, in Studies in surface science and catalysis: Natural Gas Conversion V, A. Parmaliana et al. (Eds), N. 119, 1998, pp. 453-458. 293) Arcella, V., Colaianna, P., Maccone, P., Sanguineti, A., Gordano, A., Clarizia, G., Drioli, E., A study on a perfluoropolymer purification and its application to membrane formation, Journal of Membrane Science, 163 (1999) 203 – 209 2000 294) Tocci, E., Hofmann, D., Paul, D., Russo, N., Drioli, E., A molecular simulation study on gas diffusion in a dense poly(ether ether ketone) membrane, Polymer, 42 (2001) 521-533 295) Criscuoli, A., Basile, A., Drioli, E., An analysis of the performance of membrane reactors for the watergas shift reaction using gas feed mixture, Catalysis Today, 56 (2000), 53-64 305 296) Drioli, E., Criscuoli, A., “Microporous inorganic and polymeric membranes as catalytic reactors and membrane contactors” in “Recent Advances in Gas Separation by Microporous Ceramic Membranes” N.K. Kanellopoulos (Ed), Elsevier Science B.V., Amsterdam, 2000, 497-510 297) Drioli, E., Criscuoli, A., Molero, L.P.,“Membrane distillation”, EOLSS Encyclopedia, 1999, in press 298) Tavolaro, A., Julbe, A., Guizard, C., Basile, A., Cot, L., Drioli, E., Synthesis and Characterization of a Mordenite on an alfa-Al2O3 Tubular Support, J. of Materials Chemistry, 2000, 10, 1131-1137 299) Todisco, S., Drioli, E., La Sala G., Guerriero, R., Simulazione e ottimizzazione di un impianto industriale di microfiltrazione in flusso tangenziale per le operazioni di chiarificazione della nuova industria enologica, Industria delle Bevande, XXIX (2000) febbraio, 1-13. 300) Giorno, L., Drioli, E., Enantiospecific membrane processes. Review, Membrane Technology, 1999, 106, 6-11. 301) Criscuoli, A., Drioli, E., Membrane contactors for water carbonation, Korean Membrane Journal, 1(1), 1999, pp. 59-64 302) Curcio, E., Barbieri, G., Drioli, E., Operazioni di distillazione a membrana nella concentrazione dei succhi di frutta, Industrie delle Bevande, XXIX (2000) aprile, 113-121 309) Drioli, E., Basile, A., Criscuoli, A., High temperature membrane reactors for clean productions, Clean Products and Processes, 2(3), 2000, 179-186. 304) Capuano, A., Memoli, B., Andreucci, V.E., Criscuoli, A., Drioli, E., Membrane distillation of human plasma ultrafiltrate and its theoretical applications to haemodialysis techniques, The International Journal of Artificial Organs, 23(7), 2000, 415-422. 305) Alvarez, S., Riera, F.A., Alvarez, R., Coca, J., Cuperus, F.P., Bouwer, S.Th., Boswinkel, G., van Gemert, R.W., Veldinsk, J.W., Giorno, L., Donato, L., Todisco, S., Drioli, E., Olsson, J., Tragardh, G., Gaeta, S.N., Panyor, L.,A New integrated membrane process for producing clarified apple juice and juice aroma concentrated, Journal of Food Engineering 46 (2000) 109-125. 306) Giorno, L., Drioli, E., Biocatalytic membrane reactors: applications and perspectives, Trends in Biotechnology, 2000, 18, 339-348 /73/ R. MOLINARI, C. GRANDE, Membrane separation processes for chiral resolution of racemic mixtures. Comparison with conventional techniques. Energy and exergy analyses of racemic amino acids resolution, Editoriale Progetto 2000, Cosenza (Italy), April 2000, pp. 1-80, ISBN 88-8276-052-9. /74/ R. MOLINARI, M.G. BUONOMENNA, E. DRIOLI, Supported Liquid Membranes in metals recovery and concentration, in: P. Massacci (Ed.), Development in Mineral Processing, 13, Elsevier, Amsterdam (The Netherlands), 2000, pp. A6-95 – A6-102. ISBN 0 444 50283 1. /76/ R. MOLINARI, C. GRANDE, Processi innovativi a membrana nel trattamento delle acque, in L. Palmisano (Ed.), Processi e metodologie per il trattamento delle acque, Edizioni Spiegel, Abbiategrasso (MI), Chap. 9, pp. 159-186, October 2000. ISBN 88-7660-159-7. 2001 307) Giorno, L., Drioli, E., Carvoli, G., Cassano, A., Donato, L., Study of an enzyme membrane reactor with immobilized fumarase for production of L-malic acid, Biotechnol. Bioeng., 72(1), 2001, 77-84 308) Sakaki, K., Giorno, L., Drioli, E., Lipase-catalyzed optical resolution of racemic naproxen in biphasic enzyme membrane reactors, J. Membr. Sci. 184(2001), 27-38 303) Gherrou, A., Kerdjoudj, H., Molinari, R., Drioli, E., Effect of thiourea on the facilitated transport of silver and copper using a crown ether as a carrier, Sep. Sci. & Techn., 2001, 22-23, 571-581 310) Cassano, A., Molinari, R., Romano, M., Drioli, E., Treatment of aqueous effluents of the leather industry by membrane processes. A review, Journal of Membrane Science, 181(1), 2001, 111-126. 311) Romano, M., Drioli, E., Analisi energetica ed exergetica nei processi a membrana, ICP, Marzo 2000, 76-79. 312) Criscuoli, A., Basile, A., Drioli, E., Loiacono, O., An economic feasibility study for water gas shift membrane reactor, Journal of Membrane Science 181(1), 2001, 21-27 313) Tocci, E., Drioli, E., Hofmann, D., Russo, N., A molecular simulation study on ?-cyclodextrins included in PEEK membrane, Journal of Molecular Structure (Theochem), 540, 2001, 15-21 314) Molinari, R., Borgese, M., Drioli, E., Palmisano, L., Schiavello, M., Photocatalytic membrane processes for degradation of various types of organic pollutants and micropollutants in water, Annali di Chimica, 91, 2001, 197-202 315) Drioli, E., Romano, M., Progress and new perspectives on integrated membrane operations for sustainable industrial growth, Ind. Eng. Chem. Res., 40, 2001, 1277-1300 306 316) Curcio, E., Criscuoli, A., Drioli, E., Membrane Crystallizers, Ind. Eng. Chem. Res. 2001, 40, 2679-2684 317) Gherrou, A., Kerdjoudji, H., Molinari, R., Drioli, E., Modelization of the transport of Silver and copper in acidic thiourea medium through a supported liquid membrane, Desalination, 139 (2001), 317-325 318) Gherrou, A., Kerdjoudj, Molinari, R., Drioli, E., Facilitated CO-transport of Ag(I), Cu(II) and Zn(II) ions by using DB18C6 and DA18C6_crown ethers as carriers: interface behaviour on the ion transport, Sep. Sci. & Techn., (36)10, 2001, 2289-2304. 319) Marigliano, G., Barbieri, G., Drioli, E., Effect of energy transport on a palladium-based membrane reactor for methane steam reforming process, Catalysis Today, 67(2001), 85-99 320) Molinari, R., Grande, C., Drioli, E., Palmisano, L., Schiavello, M., Photocatalytic membrane reactors for degradation of organic polluttants in water, Catalysis Today, 67 (2001), 273-279 321) Molinari, R., Buonomenna, M.G., Cassano, A., Drioli, E., Rapid determination of tannins in tanning baths by adaptation of BSA method, Annali di Chimica 91, 2001, 255-263 322) Barbieri, G., Marigliano, G., Perri, G., Drioli, E., Conversion-Temperature Diagram for a Palladium Membrane Reactor. Analysis of an Endothermic Reaction: Methane Steam Reforming, Ind. Eng. Chem. Res. 2001, 40, 2017-2026 /80/ A. CASSANO, R. MOLINARI, E. DRIOLI, Processi a membrana per il trattamento degli effluenti esausti dell’industria conciaria, Chim. & Indust. (Italy), 83 (2), 53-59 (2001). /81/ M.A. ARTALE, V. AUGUGLIARO, E. DRIOLI, G. GOLEMME, C. GRANDE, V. LODDO, R. MOLINARI, L. PALMISANO and M. SCHIAVELLO, Preparation and Characterization of Membranes with Entrapped TiO2 and Preliminary Photocatalytic Tests, Ann.Chim. (Rome), 91(3-4), 127-136 (2001). /82/ R. MOLINARI, P. ARGURIO, Supported Liquid Membrane Stability In Chiral Resolution by Chemically and Physically Modified Membranes, Ann.Chim. (Rome), 91(3-4), 191-196 (2001). //84/ R. MOLINARI, P. ARGURIO, L. ROMEO, Studies on interactions between membranes (RO and NF) and pollutants (SiO2, NO3-, Mn++ and Humic Acid) in water, Desalination, 138, 271-281 (2001). /87 bis/ R. MOLINARI, M. G. BUONOMENNA, A. CASSANO, E. DRIOLI, Determinazione rapida dei tannini in bagni tannici mediante adattamento del metodo della BSA, C.P.M.C., 77(3), 91-97 (2001). /88/ R. MOLINARI, P. ARGURIO, L. ROMEO, Behaviour of RO and NF membranes in the separation of some pollutants in water, In A. Noworita, A. Trusek-Holownia (Eds), Using membranes to assist of cleaner processes, Agencja Wydawnicza “ARGI”, Wroclaw, 2001, pp. 55-60. (ISBN 83-913887-4-3). I-4 Other Scientific Output Reports related to research activity done were sent to clients that committed the research. 307 FERRARA 1 Name of the Research Unit Ferrara 1 Research Leader Maldotti Andrea Contact Person Name: Maldotti Andrea Mailing Address: Dipartimento di Chimica Università di Ferrara, Via L. Borsari 46, 44100 Ferrara. Faculty: Facoltà di Scienze Matematiche Fisiche e Naturali/ Faculty Phone: + 39 0532 291147 Fax: +39 0532 240709 of Mathematical Physical and Natural Sciences E-mail: [email protected] Department: Dipartimento di chimica/ Department of Chemistry University: Università di Ferrara/ University of Ferrara Thematic area • Sintesi ecosostenibili (solventi, fotochimica, catalisi, riciclo e altre). •Tecnologie di depurazione (membrane, sonochimica, fotocatalisi, elettrochimica e altre). Introduction and Context Introduction to the Self-evaluation Report We have been one of the founding groups of INCA, as we are firmly convinced that our research on oxidation photo(electro)catalysis for clean syntheses and pollution degradation is relevant in the field of chemistry for the environment. In the following we try to present a critical self-analysis of the progress done after the previous research and management evaluation of INCA. Great attention is devoted to suggestions and criticisms which, at that time, were raised by the Review Committee. We think that this is a very good oppurtunity for us to verify progress of our activity within INCA. The University, the Faculty and the Department No significant changes have taken place since 1998 The Unit The Research Unit (UdR) of Ferrara has acquired a considerable expertise in the preparation and characterisation of inorganic systems able of performing photo(electro)catalytic processes. Recent research has developed along: i) tailoring the reactivity of photoactive semiconductors through surface functionalization and control of the operative conditions (including the effect of applied potential); ii) heterogenisation of molecular photocatalysts and their use in collectively organised systems; iii) biomimetic systems as models of natural hemoproteins. The UdR is composed of the following researchers. - Andrea Maldotti. He is associate professor of General and Inorganic Chemistry at the Faculty of Science of the University of Ferrara since 1992. His teaching load includes courses of General and Inorganic Chemistry, Laboratory of Chemistry, Bioinorganic Chemistry, graduate theses and PhD theses, coordination of Erasmus-Socrates Programmes. His current research interest is mainly focused on homogeneous and heterogeneous photocatalysis with particular interest to molecular oxygen activation and oxidation reactions (including biomimetic processes). He participated as invited speaker in many national and international meetings of chemistry and he is author of over 90 papers and review articles. - Rossano Amadelli. He received his Ph.D. Degree in Chemistry from the Case Western Reserve University, Cleveland. Since 1991 he holds the position of research executive at the Ferrara Section of the ISOF Institute of C.N.R.. His current research activities focuses on photoelectrocatalysis on semiconductors, especially for the degradation of pollutants and on electrocatalytic processes (ozone formation, oxidation of organic compounds). He participated as 308 invited speaker in many national and international meetings of chemistry and he is author of over 70 papers and review articles. He is a member of the international Committee on “Environmental conscious construction materials and systems” for the part deals on photocatalysis for self-cleaning surfaces. - Alessandra Molinari. She is at the Chemistry Department of the University of Ferrara as a post-doc fellow since 1999. Her current research field is heterogeneous photocatalysis based on the use of semiconducting oxides, polyoxometallates and metalloporphyrins, covering aspects dealing with preparation of the photocatalytic systems and with their characterization by ESR spectroscopy. A. Molinari is coauthor of 26 articles. She received an Enichem Award in 1994 and a Federchimica Award in 1995. - L. Samiolo. He is a PhD student. His research activity regards the preparation of collectively organized photocatalysts. Particular attention is devoted to their use for self-cleaning surfaces. - I. Vitali. She has a research fellowship from INCA. She is mainly interested in the photocatalytic tests of heterogeneous catalysts and in tailoring their activity using biomimetic systems. - The group considerably benefits for discussion, suggestions and organization activity of Prof. Graziano Varani (Associate Professor), who is especially dedicated to didactics. In 2001, Prof. V. Carassiti deceases. For his unceasing guidance and encouragement we remember him with gratitude and affection. Our UdR has always been a part of a CNR Center within the Department of Chemistry. The intrinsic nature of the CNR Centers within Universities favours a strong integration among researchers of the two formally different administrations. Accordingly, during the last thirty years, researchers from CNR and from University in Ferrara have been carrying out a common activity which still now goes on. Altogether we have access to several large-scale facilities such as: Laser flash photolysis equipments (including femtosecond spectroscopy), NMR spectrometer, ESR and FTIR spectrometers with the possibilities of performing photochemical experiments in situ. Programme Description and Evaluation 1 Title Photocatalysis and Photoelectrocatalysis in Oxidation Processes. 2 Research Leader Prof Andrea Maldotti 3 Composition of the scientific research staff of the unit per 1 January 2002 Names and Titles Prof. Andrea Maldotti Prof. Graziano Varani Dr. Rossano Amadelli Dr. Alessandra Molinari Dr. Luca Samiolo Dr. Irene Vitali Total research input Year of Rank Birth 1950 associate professor 1940 associate professor 1950 director of research (C.N.R.) 1968 Post doc fellowship (assegnista 1975 PhD student 1975 INCA fellowship Research Input in fte in 2001 0.5 0.2 0.7 0.9 0.6 1.0 4.1 Remarks Finish 2003 Began 2001 Began 2001 Comments The major changes in the composition of the research group during the previous five years are the following. - Prof. Carlo Bartocci retired . - Dr. Leonardo Andreotti attended our laboratory for three years and finished his PhD thesis. 309 - Dr. Luca Samiolo has attended our laboratory for one year in the framework of a common project with Italcementi S.p.A. and now he started researches for his doctoral thesis, partially sponsored by Italcementi . - Dr Jerome Spengler attended our laboratory for six months in the framework of a common project with researchers of French CNRS (Erasmus Socrates Programme). - Dr. Alexander Timonov from the University of S. Petersburg spent a period of one month in our laboratory as visiting professor. - Dr. A. Velichenko from the University of Kiev spent a period of one month in our laboratory as visiting professor. - Dr. Giovanni Maria Mura from the University of Sassari spent a period of one month in our laboratory as visiting professor. - Dr. Irene Vitali spent a period of 3 months at the Departement of Chemistry of the University of Sassari as master student. - Dr. Irene Vitali received a fellowship sponsored by INCA. - The master student Grazia Totaro spent a period of 6 months at the University Paris V in the framework of an Erasmus Socrates Programme. - Dr. Luca Antolini spent a period of 12 months in our laboratory with a fellowship from Italcementi SpA. - The master students Luca Ferrari and Marco Spiazzi spent a period of one month at the Plataforma Solar de Almeria in the framework of a TMR-LSF Programme for studies on the scaling up of our photocatalytic systems. - The master student Massimiliano Bacilieri spent a period of one month at the solar facilities in Odeillo (France) in the framework of a TMR-LSF programme to prepare nanostructured TiO2. Prof Carlo Bartocci decided to retire in 2000. This influenced only partially the scientific activity of the group since his main activity during the last five years before retiring was especially dedicated to didactics. We have reason to believe that the research fellowships reported in the table will be maintained, if not extended, in the future for other young researchers. A significant contribution to our activity will also be given by a number of students (at least four per year) preparing their master theses in our laboratory (one year duration). Finally, we expect visiting professors and PhD students both from the Russian Federation within the framework of collaborations which have been going on for several years, and of the Erasmus-Socrates Programme. 4 Input of Academic Staff in fte Category Full Professors Associated Professors Researchers (C.N.R.) Post-docs PhD-students Felloship owners Total 1997 1998 1999 2000 2001 Total 1 0.7 1 0.7 0.8 1.6 0.6 3.9 .7 0.7 0.9 0.8 0.6 3.7 .7 0.7 0.9 0.8 0.8 3.9 .7 0.7 0.9 0.6 1 3.9 4.1 3.5 2.7 4.6 3 17.9 2.5 Comments The Research Unit still misses possible benefits of a full professor member with the excellent managerial expertise of Prof. Vittorio Carassiti. This situation, which also depends on a number of variables that we can not control, may have some negative effects on the possibility to have new people with permanent academic positions within our group. On the other hand, as research leader of this UdR, I can claim that the scientific quality of my work and its recognition is on the increase within the scientific community working in this research area, as witnessed, for example, by an invitation to write an article on Chemical Reviews, now in press on the special issue “Recoverable Catalysts and Reagents”. The quality of my research allowed me to receive funding from MIUR (60% and COFIN), C.N.R., European Union. It is also noteworthy that one of the component of the Research Unit, Dr Rossano Amadelli, is research executive (Direttore di Ricerca) at C.N.R., a position which is equivalent to full professorships at the University. Considering the relatively small size of our group, we have addressed our efforts towards the optimization of the balance between people with permanents positions and young researchers with fellowships. Moreover, co-operation with other INCA Units on common research projects to which we can contribute with our knowledge and experience has been strongly boosted. In this regard, I mention the collaboration with the Units of Pavia 1 (Prof. A. Albini), Parma 2 (Prof. G. Sartori) and l’Aquila 1 (Prof. G. Cerichelli), which allowed us to publish several works and to obtain 310 commmon funding for the research. Finally, an effort has been done for obtaining more consistent funding for fellowships by C.N.R., European Union and Industry. The national policy on research seems to favour at present temporary positions for research activity. Nevertheless, we hope that at least one permanent position will come from MIUR or CNR shortly. 5 Funding 5.1 Personnel (in fte) Source University CNR European Union Other Sponsors Total 5.2 1998 2.7 0.7 2.7 0.6 4.1 1999 1.4 0.7 0.1 (TMRLSF) 0.5 3.9 2000 1.4 0.7 0.1 (TMRLSF) 0.7 4.1 2001 1.4 0.7 Total 10.8 3.5 0.2 1.6 4.1 3.4 18.9 Materials and Equipment (in Million Lire) Source University - MURST CNR EU Other Sponsors Total 5.3 1997 1.7 0.7 1997 25 15 1998 20 15 1999 83 60 2000 25 60 2001 18 60 Total 171 210 40 30 65 30 173 30 115 50 128 140 521 Comments: Funds from University include: i) salaries for the permanent staff, 80% of one postdoctoral position (assegno di ricerca) and a grant for a PhD student; ii) the government grants named “ex 60 %”, used for equipment, material and for paying 20% of the postdoctoral position (assegno di ricerca); iii) 60 million lire come from a COFIN project coordinated by Prof. Angelo Albini titled: “Cleaner Syntheses – Molecular oxygen and sunlight in oxidation reactions with heterogeneous integrated catalysts” used for equipment and material. Funds from C.N.R. consist in part (about 15 million lire per year) of the grant for all the researchers of the Center of Study on Photoreactivity and Photocatalysis. 45 million lire per year come from CNR through “Assegnazione straordinaria legge 95/95; Tecnologie non convenzionali per la sintesi di intermedi per la chimica fine; ossidazioni catalizzate da materiali inorganici fotosensibili” from 1999 to 2001. All funds from CNR have been employed for equipment and materials. 30 million lire per year come frm the industry Italcementi SpA in the framework of a common project on “Photoactive surfaces on TiO2 in cement matrices” from 1998 to 2001. These funds have been used for equipment, material and for paying a PhD grant (20 million lire in 2001). In 2001 we have had funds from INCA (20 million lire) in the framework of the “Piano Nazionale INCA” for a research fellowship on the “Chemistry of the clean reactions and processes”. The European Union sponsored three stages of young researchers at the Plataforma Solar de Almeria and at Odeillo (France) in the framework of TMR-LSF programmes, to test the possibility of employing our photocatalytic systems under large scale conditions and to prepare nanostructured TiO2 respectively. Other funds have been available for student mobility through the Erasmus-Socrates programme. On the figures. The University-payed personnel includes the permanent staff, a postdoc researcher and a PhD student. From 1999, part of the money for paying fellowships comes from “other sponsors”. We think that the possibility to have other grants from such sources for young researchers should be increased in the future. On the funding policy. From 1999 there has been an evident increase in available funding. In the next two years, funds (50.000 Euro) will come from the European Union in the framework of the PICADA project titled: “ Photocatalytic innovative covering applications for depollution assessment”. GROWTH project GRD12001-40449”, where we are subcontractors of Italcementi SpA. An application (national coordinator: Prof. A. Albini) for COFIN grant has been presented together with the UdRs, of Pavia 1 and Parma 2. Other funds are expected in the framework of the “Piano Nazionale INCA” on the “Chemistry of the clean reactions and processes” (responsible: Prof. P. Tundo). 311 We consider that an additional effort should be done in order to have more grants from “other sponsors” such as industry and European Union. We also realise that our relatively small group can hope to obtain funding from European Union only through strong co-operation with other partners having similar or complementary research interest. Co-operation among the Research Units of INCA for participation in international projects may be favoured by the coordination activity of INCA. 6. Progress Report 6.1 Progress analysis The research interest of our unit continues to be focused on the synthesis and characterization of collectively organized systems able of catalysing the oxidation of organic substrates with clean and cheap reagents such as molecular oxygen and sunlight. The main strategies followed are: - surface derivatization of inorganic semiconductors, - use of composite systems based on polyoxoaniones and metalloporphyrins (biomimetic), - preparation of nanostructurated materials, - control of the operative conditions by applied potential, - electrochemical processes at high anodic potentials (including ozone evolution). The final goal is to perform oxidation with of poorly reactive organic substrates in view of realising: - clean selective syntheses, - efficient oxidative degradation of pollutants, - conversion of pollutants into useful products. ESR, electrochemistry, laser flash photolysis techniques are successfully employed for the optimisation of the investigated photocatalytic systems. In the last years, a considerable effort has been done in order to increase co-operation with other INCA UdRs’. In this regard, I mention the collaborations with the Units of Pavia 1, Parma 2 and l’Aquila 1, which allow us to broaden the scope of the research, to publish several works and to obtain funding. Our research activity concerning the use of heterogenised polyoxotungstates is carried out in collaboration with the Unit of Parma 2 (Prof. G. Sartori), which has acquired a consolidated experience in the preparation and characterisation of mesoporous silica materials. The Unit of Pavia 1 (Prof. A. Albini) is interested to test the ability of our organized systems in photoinduced alkylation processes. In the framework of this collaboration our contribution also derives from our experience in the investigation of mechanisms and kinetics of single steps of photocatalytic processes. Thanks to the co-operation with the Unit of l’Aquila 1 (Prof. G. Cerichelli) we could exploit the photocatalytic properties of iron porphyrins in micelles dispersed in aqueous medium. Scientific collaborations with other research groups are currently carrying on: University of S. Petersburg (Prof. V. Vasil’ev) for preparing heterogenised photosensitizers able to generate singlet oxygen; French CNRS (Dr. D. Mansuy) for studying new biomimetic oxidation photocatalysts; University of Kiew (Prof. A. Velichenko) for the electrocatalytic evolution of O3; University of Milano (prof. S. Tollari) for the photoindiuced formation of C-N bonds; University of Sassari (Dr. G.M. Mura) for the use of the composite system TiO2/glucose oxidase. Italcementi SpA (L. Cassar) for the application of photocatalysis for preserving cementitious materials. 6.2 Position within INCA A positive role of INCA in the development of the research quality of our group is that of improving the degree of our collaboration with other UdRs’, promoting internal contacts and links and providing funds. This effort of INCA allows our group to work in a wide research context, which is a necessary condition to participate to national and international networks. We believe that INCA should continue to boost the quality of the research of the single units. Therefore it is expected i) to favour future collaboration among other units; ii) to allow access to large scale facilities of the Consortium; iii) to provide funds to single units through both research fellowships and scientific equipment. Moreover, INCA is expected to favour the diffusion of our research to possible “clients” of industry and environmental agencies. 6.3 Key Publications 1) A. Maldotti, A. Molinari, R. Amadelli, “Photocatalysis with organized systems for the oxofunctionalization of hydrocarbons by O2”. Chem. Rev., in press on the special issue “Recoverable Catalysts and Reagents” . 312 2) A. Molinari, R. Amadelli, V. Carassiti, A. Maldotti, “ Photocatalyzed oxidation of cyclohexene and cyclooctene with (nBu4N)4W10O32 and (nBu4N)4W10O32/Fe(III)mesotetrakis (2,6-dichlorophenyl) porphyrin in homogeneous and heterogeneous systems”. European Journal of Inorganic Chemistry, 91-96, 2000., 3) A. Maldotti, L. Andreotti, A. Molinari, G. Varani, G. Cerichelli, M. Chiarini, “Photocatalytic properties of iron porphyrins revisited in aqueous micellar environment: oxygenation of alkenes and reductive degradation of carbon tetrachloride”. Green Chemistry, 3, 42-46, 2001. 4) A. Maldotti, L. Andreotti, A. Molinari, S. Borisov, V. Vasil’ev “Photoinitiated catalysis in Nafion membranes containing palladium(II) meso-tetrakis(N-methyl-4-pyridyl)porphyrin and Iron(III)meso-tetrakis-(2,6-dichlorophenyl)porphyrin oxidations of alkenes”; Chem. Eur. J., 7 (16), 3564- 3571, 2001. for O2-mediated 5) A. Maldotti, A. Molinari G. Varani, M. Lenarda, L. Storaro, F. Bigi, R. Maggi, A. Mazzacani, G. Sartori, “Immobilization of (n-Bu4N)4W10O32 on mesoporous silicas for photocatalytic oxidation of cycloalkanes with molecular oxygen”. J. Catal., (209), 210-216, 2002. 7. Scientific Output 7.1 Publication Policy Dissertations and pubblications reported are all relevant to the the mission of our UdR . The number of PhD and Master theses is adequate to the size of our group. The trend of the scientific publication is positive. We intend to continue to publish the results of our research on international journals with good impact factors in the scientific community. We consider that the diffusion of our research results to other possible “clients” such as industries and agencies for the environment should be strengthened. Therefore, we intend to increase the number of professional publications. 7.2 Numerical data Category PhD-Dissertations 1997 1998 1 1999 2000 1 2001 Total 2 Scientific Publications 4 7 7 9 11 38 4 1 5 1 22 Professional Publications Patent Master’s Theses 4 4 5 8 Self-evaluation The use of solarlight and molecular oxygen as reagents brings about some important benefits in the development of innovative chemical methodologies that are promising for the welfare and growth of the chemical industry, accomplishing both pollution prevention and environment clean up. In this framework, the research of our Unit has a fundamental chemistry character with a view, however, to practical applications. On the basis of the comments reported in the above sections, and in line with criticisms and suggestions of the Review Committee of the previous assessment, we now report an evaluative description of the Unit’s strong and weak points, and the action undertaken to further improve quality and to strengthen viability. Considerable efforts have been done towards the optimisation of the balance between people with a permanent position and young researchers with fellowships. In doing this, we have realized that the research activity of two associate 313 professors (one retired in 2000) contributed only partially to the scientific productivity of the group, since their activity was mainly dedicated to didactics. We have reason to believe that the fellowships obtained in recent years will be maintained, if not extended, in the future for other young researchers. A significant contribution to the research will also be given by a number of master students and from foreign visiting professors and PhD students. The national research policy on research seems to favour at present temporary positions for research activity. Nevertheless, we hope that at least one permanent position will come from MIUR or CNR shortly. The Research Unit still misses possible benefits of a full professor member with the excellent managerial expertise of Prof. Vittorio Carassiti. This situation, which also depends on a number of variables that we can not control, may have some negative effects on the possibility to have new people with permanent academic positions within our group. On the other hand, as research leader of this UdR, I can claim that the scientific quality of my work and its recognition is on the increase within the scientific community working in this research area. Accordingly, I have received funding from MIUR (60% and COFIN), C.N.R., European Union. It is also noteworthy that one of the component of the Research Unit, Dr Rossano Amadelli, is research executive researcher at C.N.R., a position which is equivalent to full professorships at the University. Co-operation with other INCA Units on common research projects to which we can contribute with our knowledge and experience has been strongly boosted. In this regard, we mention the collaborations with the Units of Pavia 1 (Prof A. Albini), Parma 2 (Prof. G. Sartori) and l’Aquila 1 (Prof G. Cerichelli), which allowed us to publish several works and to obtain common funding for the research. Co-operation with foreign groups (CNRS, Universities of S. Petersburg and Mosca), with industry (Italcementi SpA) has been also strongly developed. From 1999 there has been a significant increase in funding. In the next two years, funds (50.000 Euro) will come from the European Union in the framework of a project where we are subcontractors of Italcementi SpA. An application for COFIN funding has been presented together with the UdRs, of Pavia 1 and Parma 2. Other funds are expected in the framework of the “Piano Nazionale INCA”. We think that our relatively small Unit can hope to increase the amount of funds from “other sponsors” such as Industry and European Union only through strong cooperation with partners having similar or complementary research interests. A positive role of INCA in the development of the research quality of our group is that of improving the degree of our collaboration with other UdRs’, promoting internal contacts and links and providing funds. This effort of INCA allows our group to work in a wide research context, which is a necessary condition to participate to national and international networks. We believe that INCA should continue to boost the quality of the research of the single units. Therefore it is expected i) to favour future collaboration among other units; ii) to allow access to large scale facilities of the Consortium; iii) to provide funds to single units through both research fellowships and scientific equipment. Moreover, INCA is expected to favour the diffusion of our research to possible “clients” of industry and environmental agencies. We can state that on the whole our scientific production is relevant to our mission. The number of PhD and Master theses is adequate to the size of our group. The number of publications is positive. We intend to continue to publish the results of our research on international Journals with good impact factors in the scientific community. We consider that the diffusion of our research results to other possible “clients” such as industries and agencies for the environment should be strengthened. Indeed our recent patent is promising in this respect. Appendix I Scientific Output I-1 Overview of Dissertations and Master's Thesis (1997-2001) I.1.1 Dissertations Year 1998 Name Master’s Title of the Dissertation student Alessandra Molinari Composite systems based on metal-oxide and ironporphyrins Maldotti 2000 Leonardo Andreotti Maldotti I.1.2 Master's Thesis Oxidative photocatalysis in organized inorganic systems Supervisor 314 Year 1997 Name Master’s Title of the Dissertation student Anna Sgobino Photoredox properties of composite polyoxotungstates/iron porphyrins Monica Alebbi Biomimetic photocatalysis in heterogeneous Systems. 1997 Luca Antolini Photoredox properties of iron porphyrins on colloidal TiO2 Maldotti/Amadelli 1997 Leonardo Andreotti O2 activation with photoexcited iron porphyrins within Nafion. Maldotti 1998 Jacopo Volpe 1998 Luca Goldoni 1998 Paola Villani Heterogenization of polyoxotungstates on SiO2 for photocatalytic Maldotti oxidations. Control of the photocatalytic properties of TiO2 for synthetic Maldotti/Amadelli purposes: Functionalization with iron porphyrins. Photoxidation of p-chloro-phenol on TiO2 and TiO2/Mg . Maldotti/Amadelli 1998 Cristian Bardella 1999 Silvia Magon 1999 Luca Ferrari 1999 Alberto Pezzoli 1999 Eva Carli 1999 2000 Massimiliano Bacilieri Stefano Billo 2000 Marco Spiazzi 2000 Andrea Buzzoni 2000 Luca Samiolo 2001 Barbara Falcone 2001 Leonardo Barbieri 2001 Irene Vitali 2001 Stefano Carboni 2001 Luca Borgatti 1997 I-2 Supervisor systems Maldotti Maldotti/Amadelli Formation and reactivity of synglet oxygen with Pd tetra-methylpyrydil-porphyrin caged in Nafion membranes. Photocatalytic properties of iron and manganese tetraazaporphyrins: alkane oxidation. Biomimetic redox processes induced by photoexcited iron porphyrins. Photocatalytic properties of composite systems Pd(II)/ Fe(III) porphyrins within Nafion: Biomimetic oxidation of cyclohexene. Oxidation of organic substrates in aqueous medium with photoexcited iron porphyrins. Photodegradation of trans-3,4-dihydroxicinnamic on TiO2. Maldotti Maldotti/Amadelli Nitroaromatic reduction on semiconductors Maldotti/Amadelli Oxygenation of cycloalkenes with composite systems: Pd(II)/Fe(III) porphyrin in polymeric matrices Effect of the counter-cation on the photocatalytic properties of W10O324-. Photo-electrochemical investigation of TiO2 modified with vanadyl. Photo-electrocatalysis with TiO2 in the presence of Glucose Oxidase. Photoxidation of alkanes catalysed by W10O324-immobilized on SiO2 and MCM-41. Reduction of O2 to H2O2 catalysed by Glucose Oxidase in the presence of TiO2 photoexcited. Model Systems of NO-syntase: oxidation of N-(4-chlorophenyl)N’-hydroxyguanidine with photoexcited iron porphyrins. Photocatalytic oxidation of cycloalkenes with W10O324immobilized on silica materials. Maldotti/Molinari Bartocci Maldotti Maldotti Maldotti Maldotti/Molinari Maldotti/Molinari Maldotti/Amadelli Maldotti/Molinari Maldotti/Molinari Maldotti Maldotti/Molinari Overview of Scientific Publications (1997-2001, including accepted papers ) per year All the reported works are directly related to the main topics of the Consortium activity. We omit to report the numerous proceedings of national and international congresses. 1997 A. Maldotti, R. Amadelli, V. Carassiti, A. Molinari, “Catalytic oxygenation of cyclohexane by photoexcited (nBu4N)4W10O32: The role of radicals”. Inorg. Chim. Acta, 256, 309-312, 1997. 315 E. Albizzati, U. Giannini, G. Balbontin, I. Camurati, J.C. Chadwick, T. Dall’occo, Y. Dubitsky, M. Galimberti, G. Morini, A. Maldotti, “Propylene polymerization with catalysts containing divalent titanium”. J. Pol. Sci. Pol. Chem., 35, 2645-2652, 1997. R. Amadelli, A. Maldotti, V. Carassiti, “Inorganic Membranes as Photo- and Electrocatalysts”. Chim. Ind., 79, 885-891, 1997. A. Maldotti, C. Bartocci, R. Amadelli, A. Molinari, V. Carassiti, “Metal porphyrin based photocatalysts in organized and constrained systems in Synthesis and methodologies in inorganic chemistry”. Da Olio S., Tondello E., Vigato P.A., 21-31, Eds. 1997. 1998 A. Molinari, A. Maldotti, R. Amadelli, V. Carassiti, “Integrated Photocatalysts for Hydrocarbon oxidation: Polyoxotungstates/Iron-porphyrin systems in the reductive activation of molecular oxygen”. Inorg.Chim.Acta, 272, 197-203, 1998. A. Maldotti, A. Molinari, L. Andreotti, M. Fogagnolo, R. Amadelli, “Novel reactivity of photoexcited iron porphyrins caged into a polyfluorosulphonated membrane in catalytic hydrocarbon oxygenation”. Chem. Commun. 507-508, 1998. P. Boarini, V. Carassiti, A. Maldotti, R. Amadelli, “Photocatalytic oxygenation of cyclohexane on titanium dioxide suspensions: effect of the solvent and of oxygen”. Langmuir, 14, 2080-2085, 1998. A. Molinari, L. Andreotti, L. Antolini, A. Maldotti, “Solar photooxidation of hydrocarbons by some types of inorganic photocatalysts”. In Proceedings of the 2nd users workshop of the TMR programme at Plataforma Solar de Almeria, 129-134, 1998. A. Babak, R. Amadelli, V.N. Fateev, “Effect of perfluoro compounds on kinetics of the oxygen and ozone formation on the platinum anode”. Russian J. Electrochem., 34, 149-151,1998. A.B. Velichenko, D.V. Girenko, S.V. Kovalyov, A.N. Gnatenko, R. Amadelli, F.I. Danilov, “Lead dioxide electrodeposition and its application: influence of fluoride and iron ions”. J.Electroanal.Chem., 454, 203-208, 1998. R. Amadelli, A.B. Velichenko, E. Tondello, L. Armelao, S. Daolio, M. Fabrizio, “Ion bombardment of PbO2 films: water influence of cluster production”. International J. of Mass Spectroscopy and Ion Processes, 179, 309-317, 1998. R. Amadelli, T. Bonato, A. De Battisti, A. Babak, A. Velichenko, “A comparative study of the electrooxidation of some phenolic compounds by electrogenerated O3 and by direct electrolysis at PbO2 anodes”. The Electrochemical Society Inc., PV 97-28, 51-60, 1998. 1999 C. Sabbioni, M.A. Raggi, G. Casamenti, Q. Zini, G. Varani, “Comparison of fluorimetric reagents for the analysis of aluminium in mineral waters”. Anal. Lett., 32, 123-137, 1999. M.A. Raggi, C. Sabbioni. R. Mandrioli, Q. Zini, G. Varani, “Spectrophotometric determination of silicate traces in hemodialysis solutions”. J. Pharm. Biom. Anal., 20, 335-342, 1999. A. Molinari, R. Amadelli, L. Andreotti, A. Maldotti, 316 “Heterogeneous photocatalysis for synthetic purposes: oxygenation of cyclohexane with H3PW12O40 and (nBu4N)4W10O32 supported on silica”. Journal of Chemical Society, Dalton Transaction, 1203-1204, 1999. A. Maldotti, L. Andreotti, A. Molinari, V. Carassiti, “Photochemically driven models of oxygenases based on the use of iron porphyrins”. Journal of Biological Inorganic Chemistry, 154-161,1999. A. Maldotti, L. Andreotti, A. Molinari, “Iron porphyrin based photocatalysts mimicking cytochrome P450 oxygenases: effect of reaction environment”. In Coordination Chemistry at the Turn of the Century, G. Ondrejovic, A. Sirota (Eds), Slovak Technical University Press, Bratislava, 191-202, 1999. R. Amadelli, L. Armelao, E. Tondello, S. Daolio, M. Fabrizio, C. Pagura, A. Velichenko, “A sims and xps study about ions influence on electrodeposited PbO2 films”. Applied Surface Science, 142, 200-203, 1999. R. Amadelli, L. Armelao, A.B. Velichenko, N.V. Nikolenko, D.V. Girenko, S.V Kovalyov. , F.I Danilov, “Oxygen and ozone evolution at fluoride modified lead dioxide electrodes”. Electrochimica Acta, 45, 757-765, 1999. 2000 A. Molinari, R. Amadelli, V. Carassiti, A. Maldotti, “Photocatalyzed oxidation of cyclohexene and cyclooctene with (nBu4N)4W10O32 and (nBu4N)4W10O32/Fe(III)mesotetrakis (2,6-dichlorophenyl) porphyrin in homogeneous and heterogeneous systems”. European Journal of Inorganic Chemistry, 91-96, 2000. A. Maldotti, R. Amadelli, A. Molinari, V. Carassiti, “Cyclohexane oxygenation with inorganic photocatalysts”. in “Green Chemistry: Challenging Perspectives”; P. Tundo, P.T. Anastas (Eds), Oxford Science Publications, 124-143, 2000. A. Molinari, R. Amadelli, L. Antolini, A. Maldotti, P. Battioni, D. Mansuy, “Photoredox and photocatalytic processes on Fe(III)-porphyrin surface modified nanocrystalline TiO2 “. Journal of Molecular Catalysis A: Chemical, 521-531, 2000. A. Maldotti, L. Andreotti, A. Molinari, S. Tollari, A. Penoni, S. Cenini, “Photochemical and photocatalytic reduction of nitrobenzene in the presence of cyclohexene”. J. Photochem. Photobiol. Chemistry, 129- 133, 2000. G. Varani, A. Molinari, A. Maldotti, C. Bartocci, “Oxidation of L-arginine to citrulline and nitrate induced by photoexcitation of a Fe-porphyrin cysteinate complex”. Inorganica Chimica Acta, 122-124, 2000. A.B. Velichenko, R. Amadelli, G.L Zucchini, D.V. Girenko, F.I. Danilov, “Electrosynthesis and physicochemical properties of Fe-doped lead dioxide electrocatalysts”. Electrochimica Acta, 4391, 4350, 2000. A.B. Velichenko, N.V. Girenko, N.V. Nikolenko, R. Amadelli, E.A. Baranova, F.I. Danilov, “Oxygen evolution on lead dioxide modified with fluorine and iron”. Russian J. Electrochem., 36, 1216-1220, 2000. A. Maldotti, atti della scuola di Pavia "Seminari di fotochimica molecolare e applicata", 2000. R. Amadelli , A. De Battisti, D.V. Girenko, S.V. Kovalyov, A.B. Velichenko, “Electrochemical oxidation of trans-3,4-dihydroxycinnamic acid at PbO2 electrodes: direct electrolysis and ozone mediated reactions compared”. Electrochimica Acta, 46, 341-347, 2000. 2001 R. Amadelli, A.B. Velichenko, 317 “Lead dioxide electrodes for high potential processes”. J. Serb. Chem. Soc., 66, 803-813, 2001. A. Maldotti, L. Andreotti, A. Molinari, G. Varani, G. Cerichelli, M. Chiarini, “Photocatalytic properties of iron porphyrins revisited in aqueous micellar environment:oxygenation of alkenes and reductive degradation of carbon tetrachloride”. Green Chemistry, 3, 42-46, 2001. A. Maldotti, L. Andreotti, A. Molinari, S. Borisov, V. Vasil’ev, “Photoinitiated catalysis in Nafion membranes containing palladium(II) meso-tetrakis(N-methyl-4-pyridyl)porphyrin and Iron(III)meso-tetrakis-(2,6-dichlorophenyl)porphyrin oxidations of alkenes”. Chem. Eur. J., 7 (16), 3564- 3571, 2001. for O2-mediated A. Maldotti, A. Molinari, G. Varani, “Biomimetic photocatalysis: iron porphyrins in heterogeneous and organized systems”. Int J. Med. Biol. Environ., 29, 7-17, 2001. L. Ferrari, M. Spiazzi, A. Molinari, R. Amadelli, A. Maldotti, “Selective photoreduction of p-nitrobenzaldehyde with TiO2 and CdS”; Proceedings of the 1st Users Workshop at the Plataforma Solar de Almeria, p. 51-55, Series Ponencias, 2001. A. Maldotti, A. Molinari G. Varani, M. Lenarda, L. Storaro, F. Bigi, R. Maggi, A. Mazzacani, G. Sartori, “Immobilization of (n-Bu4N)4W10O32 on mesoporous silicas for photocatalytic oxidation of cycloalkanes with molecular oxygen”. J. Catal., 209, 210-216, 2002. A. Maldotti, A. Molinari, R. Amadelli, “Photocatalysis with organized systems for the oxofunctinalization of hydrocarbons by O2”; Chem. Rev., in press on the special issue“Recoverable Catalysts and Reagents” R. Amadelli , A. Maldotti, A. Molinari, F.I. Danilov, A.B.Velichenko, “Influence of the electrode history and effects of the electrolyte composition and temperature on O2 evolution at βPbO2 anodes in acid media”. J. Electroanal. Chem., in press. A.B. Velichenko, R. Amadelli, A. Benedetti, D.V. Girenko, S.V. Kovalyov , F.I. Danilov , “Electrosynthesis and physicochemical properties of PbO2 films”. J. Electrochem. Soc. , in press. A.B. Velichenko, R. Amadelli, E.A. Baranova, D.V. Girenko, F.I Danilov. “Electrodeposition of Co-doped Lead Dioxide and its physicochemical properties”. J. Electroanal. Chem., in press. A. Molinari, R. Amadelli, A. Mazzacani, G. Sartori, A. Maldotti, “Tetralkylammonium and Sodium Decatungstate Heterogenized on Silica: Effects of the Nature of Cations on the Photocatalytic Oxidation of Organic Substrates”. Langmuir 18, 5400-5405, 2002. I-4 Other Scientific Output R. Amadelli, L. Cassar, C. Pepe, “Use of photocatalytic preparations of colloidal titanium dioxide for preserving the original appearance of cementitious, stone, or marble products”. PCT Int. Appl. 2001 Patent No. WO 2001000541 Appendix 3 318 Journal Portfolio Analysis Name of the Unit: Research Director: Years included Name of Journal Chem. Rev. Chem Commun Chem. Eur. J. Green Chem. Langmuir Ferrara 1 Maldotti Andrea 1997-2001 including papers accepted for pubblication Number of Journal Impact Field(s) Articles Factor 1 20.036 Chemistry: Multidisciplinary 1 3.695 Chemistry: Multidisciplinary 1 4.698 Chemistry: Multidisciplinary 1 2.111 Chemistry: Multidisciplinary 2 3.045 Chemistry, Physical Applied Surf. Science 1 1.222 J. Chem. Soc. Dalton Trans. 1 2.502 Eur. J. Inorg. Chem. 1 2.222 J. Biol. Inorg. Chem. 1 3.045 Inorg. Chim. Acta 3 1.200 J. Catalysis J. Mol. Catal. A: Chemical J. Photochem. Photobiol. A: Chemistry J. Pol. Sci. Pol. Chem. Electrochimica Acta Russian J. Electrochem. J. Electroanal. Chem J. Electrochem. Soc. Intern. J. Mass Spectr. and Ion Processes Anal. Lett. J. Phar. Biom. Anal. 1 1 1 3.030 1.744 0.940 1 3 2 3 1 1 1.711 1.597 0.110 1.700 2.293 1.923 1 1 0.968 1.013 Ranking 1/118 11/118 10/118 20/118 13/91 Physics, Condensed Matter Chemistry inorganic and Nuclear Chemistry Inorganic and Nuclear Chemistry Inorganic and Nuclear Chemistry Inorganic and Nuclear Chemistry, Physical Chemistry, Physical Chemistry, Physical 17/54 Polymer Science Electrochemistry Electrochemistry Electrochemistry Electrochemistry Physics, Atomic, Molecular, Chemical Chemistry, Analytical Chemistry, Analytical 6/69 7/16 15/16 6/16 2/16 9/30 11/38 12/38 7/38 18/38 15/91 30/90 57/91 42/65 41/65 Comments on: a) the method The Citation Index method is a suitable mean to assess the contribution of the UdR to the international scientific community. b) the results The above table clearly indicates that our research in the field of photo(electro)catalysis are mainly published on highrank journals in chemistry, inorganic chemistry and physical chemistry. A common characteristic, in any case, is the interest for the possible application in catalysis. In addition to the articles reported in the previous table we have some other papers that are not included in the Citation Index (for example chapters on books). 319 FIRENZE Unità di ricerca: Università di Firenze Dipartimento di Chimica Prof. Andrea Scozzafava: Name Andrea Scozzafava Mailing Address Dipartimento di Chimica, via della Lastruccia 3, Polo Scientifico 50019 Sesto Fiorentino Phone 055/4573273 Fax 055/5473363 E-mail [email protected] Aree Tematiche • • • • Processi chimici e tecnologie pulite Trasformazioni nell’ambiente: 1 Metodologie analitiche avanzate: 3 Disinquinamento: 2 SCIENTIFIC LEADER Prof. Andrea Scozzafava OTHER MEMBERS OF THE RESEARCH GROUP Name Institution Position 1. Fabrizio Briganti Department of Chemistry University of Florence Associate Professor 2. Marta Ferraroni Department of Chemistry University of Florence Researcher 3. Silvia Tilli Department of Chemistry University of Florence Technician 4. Demetrio Randazzo Department of Chemistry University of Florence Technician 5. Ilaria Duchi Department of Chemistry University of Florence Ph.D. student UNIVERSITY OR INSTITUTIONS INVOLVED IN THE RESEARCH GROUP Department CHEMISTRY, Laboratory of BIOINORGANIC CHEMISTRY University of FLORENCE City FLORENCE - ITALY Experience The present research unit has acquired more than 12 years of experiences in the study of a range of enzymatic systems involved in the biodegradation processes of organic substances by soil microorganisms. Our workgroup is involved in the isolation and purification of different oxygenases specific for mono- and polyaromatics from bacteria such as Pseudomonas, Alcaligenes, Rhodococcus, Streptomyces, Acinetobacter and in their structural and mechanistic characterization, at the molecular level, using kinetic, spectroscopic and crystallographic techniques. Both the purification and the following characterization of such enzymatic systems are fundamental for the 320 comprehension of the mechanism