IMPP-2 2015 - Dipartimento di Scienze e Tecnologie Chimiche
Transcript
IMPP-2 2015 - Dipartimento di Scienze e Tecnologie Chimiche
IMPP-2 2015 The I talian Meeting on P orphyrins and P hthalocyanines-2 6 – 8 July, 2015 Rome IMPP-2 2015 The Italian Meeting on Porphyrins and Phthalocyanines-2 6 – 8 July 2015 CNR-Aula Marconi P.le Aldo Moro 7, 00185 Rome Abstract Book 2 Contents Welcome 5 General Information 7 Scientific Programme 9 Oral Communications 13 Posters 47 List of Participants 63 3 Sponsors 4 Welcome to IMPP-2 2015 Every two years the Italian porphyrinoid community meets to share, collaborate and discuss all aspects of porphyrinoid science at the 'Italian Meeting on Porphyrins and Phthalocyanines'. The organising committee, in conjunction with the delegates, decided to convene this conference in Rome due to its convenient proximity thus making it easier for all representatives to attend. The meeting has reached its second edition and we trust that this union of porphyrinoid minds will bring multiple benefits: Organisation: The primary purpose of this gathering is to consolidate and streamline our porphyrinoid community to create unity within our field and within Italy and, by doing so, we create a united front in the international scientific society of porphyrinoids. Knowledge: Sharing knowledge could lead to new opportunities and new opportunities could lead us to greater progress and success. Collaboration: Bringing together the best of Italian expertise could be the key to higher quality research ideas and results. As a community we should share our resources and our intellectual capital to ensure excellent quality output. In addition, there is the advantage of collective financial resources as well as greater strength in tendering for local and international funding. Cross-bordering: Interdisciplinary scientific sharing could expand the scope of our research thus opening doors to new prospects for fruitfull scientific projects. Friendship: Last but not least, we hope that IMPP will be the place to create new friendships as well as build on new ones, giving opportunity to grow human and scientific partnerships! Benvenuti a Roma!! The Organising Committie 5 Maps of Meeting Venue and Social Event Ristorante “Al Chiostro” Social Dinner 6 General Information LOCATION The conference takes place at CNR-Aula Marconi (P.le Aldo Moro 7, 00185 Rome) located near the Rome Termini train station. From the rail station Roma-Termini you go to Piazza dei Cinquecento, take the bus 492 (direction: Stazione Tiburtina) and after 6 stops you reach Via dei Marrucini bus stop. Then, you walk for 100 meters to arrive at piazzale Aldo Moro, 7. ORAL AND FLASH COMMUNICATIONS The lecture hall is equipped with a projector and Windows computers. Microsoft Power Point facilities will be available. Memory key is preferred instead of a personal laptop computer. POSTER PRESENTATIONS The poster section will take place on Tuesday 7th at 12:40 during the lunch time. A number has been assigned to each poster and it will appear on the allotted poster place. All posters will be on view throughout the conference. SOCIAL EVENTS The Social Dinner will take place on Tuesday 7th at 20:30 in ‘Ristorante Al Chiostro’, Via Paolina, 31 -Roma. 7 8 Scientific Program MONDAY AFTERNOON, 6th JULY 12:00 14:00 Registration Opening Ceremony Chairperson: Roberto Paolesse 14:20 M.L. Naitana ([email protected]) Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata” A New Sulfonation Strategy for Corroles: the Key Role of Phosphorus 14:40 S. Banfi ([email protected]) Dipartimento di Scienze Teoriche ed Applicate (DiSTA), Università degli Studi dell’Insubria Fotosensibilizzatori Cationici Antitumorali e Antibatterici 15:00 S. Belviso ([email protected]) Dipartimento di Scienze, Università della Basilicata Thioalkyl-Porphyrazines for Electronic Materials 15:20 C. D. Calvano ([email protected]) Dipartimento di Chimica e Centro Interdipartiment. di Ricerca S.M.A.R.T., Università degli Studi di Bari Characterization of Cyclic Tetrapyrroles and Related Compounds by Maldi TOF/TOF Mass Spectroscopy 15:40 D. M. Carminati ([email protected]) Dipartimento di Chimica, Università degli Studi di Milano Synthesis of Iron(III) Porphyrin Complexes to Promote the Regioselective Cyclopropanation of Olefins” 16:00 Coffee Break Chairperson: Maria Elena Fragalà 16:20 M. A. Castriciano ([email protected]) I.S.M.N. – C.N.R. Dipartimento di Scienze Chimiche, Università di Messina Composite Nafion and Speek-Porphyrin Membranes 16:40 D. Monti ([email protected]) Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata” Effect of Chiral Surfactants on the Sterespecific Aggregation of Chiral Amphiphilic Porphyrin Derivatives 17:00 A. D’Urso ([email protected]) INSTM UdR - Dipartimento di Scienze Chimiche, Università di Catania Supramolecular Porphyrins Systems: Chiroptical Probe, Building Block for Multicomponent Arrays and Chiral Assemblyes 17:20 G. Manca ([email protected]) Istituto di Chimica dei Composti OrganoMetallici, ICCOM-CNR, Firenze Mechanistic Investigation of the Ruthenium Porphyrin Catalysed Aziridination of Olefins by Aryl Azides 9 TUESDAY MORNING, 7th JULY Chairperson: Alessandro D’Urso 9:00 L. Monsù Scolaro ([email protected]) I.S.M.N. – C.N.R. Dipartimento di Scienze Chimiche, Università di Messina Reversible Aggregation/Deaggregation of Porphyrin J-Aggregates Induced by Silver(I) Cations 9:20 M. Gobbo ([email protected]) Dipartimento di Scienze Chimiche, Università di Padova Chiral Assemblies of Porphyrins Linked to -Helical Peptides is Controlled by the Stereochemistry of the First Amino Acid 9:40 E. Iengo ([email protected]) Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Trieste Tetrahedral Arrays of Metallo-Porphyrins 10:00 M.E. Fragalà ([email protected]) INSTM UdR - Dipartimento di Scienze Chimiche, Università di Catania Spontaneous Deposition of Water-Soluble Porphyrins on Glass: a Big Challenge or a “Green” Opportunity?” 10:20 G. Smulevich ([email protected]) Dipartimento di Chimica “Ugo Schiff”, Firenze Conformational Changes of Cardiolipin-Bound Cytochrome C: a Spectroscopic Study 10:40 Coffee Break Chairperson: Sara Nardis 11:00 M. Stefanelli ([email protected]) Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata” -Alkynylcorrole Derivatives via Stille Cross-Coupling Reaction 11:20 P. Mineo ([email protected]) Dipartimento di Scienze Chimiche, Università di Catania Action of an Asymmetric Heat Source on the Mirror-Symmetry Breaking of Porphyrin Aggregates 11:40 A. Mazzaglia ([email protected]) I.S.M.N. – C.N.R. Dipartimento di Scienze Chimiche, Università di Messina Cyclodextrins/Porphyrinoids Supramolecular Assemblies Tailored by Receptor Targeting Groups as Potentially Cell-Selective Nano-Phototherapeutics 12:00 M. Bischetti ([email protected]) Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata” Mesoscopic Structures by Langmuir-Blodgett Deposition of Steroid-Porphyrins 12:20 C. Di Natale ([email protected]) Dipartimento di Ingegneria Elettronica, Università di Roma “Tor Vergata” Photo-Assisted Chemical Sensors Based on Porphyrins Coated ZnO 12:40 Lunch Break / Poster Session 10 TUESDAY AFTERNOON, 7th JULY Chairperson: Roberto Purrello 14:00 B. Berionni Berna ([email protected]) Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata” Expanded Corroles by -Fused Aromatic Rings 14:20 P. Galloni ([email protected]) Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata” Assessment in Electronic Interactions in Mono-Oxidated Tetraferrocenylporphyrins 14:40 E. Reddi ([email protected]) Dipartimento di Biologia, Università di Padova Porphyrins and Antimicrobial Peptides for Photodynamic Therapy of Cancer” 15:00 N. Russo ([email protected]) Dipartimento di Chimica e Tecnologie Chimiche, Università della Calabria Photodynamic Therapy: Good News from Computational Approaches 15:20 P. Tagliatesta ([email protected]) Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata” Synthesis and Characterization of New Ferrocene, Porphyrin and C60 Triads, Connected by Triple Bonds” 15:40 Coffee Break 16:00 Round Table: Valutazione, finanziamento e didattica: quale futuro per l’Università 20:30 Social Dinner, Ristorante “Al Chiostro”, Via Paolina, 31 - Rome 11 WEDNESDAY MORNING, 8th JULY Chairperson: Maria Pia Donzello 9:00 E. Gallo ([email protected]) Dipartimento di Chimica, Università degli Studi di Milano Ruthenium Porphyrin Complexes as Efficient Catalysts of Biological Aza-Derivatives 9:20 F. Tessore ([email protected]) Dipartimento di Chimica, Università degli Studi di Milano The Fascinating World of -Pyrrolic Substituted Zn(II)-Tetraarylporphyrinates for Dye-Sensitized Solar Cells” 9:40 M. Trotta ([email protected]) IPCF-CNR, Università degli Studi di Bari Photosynthetic Bacteria Play Heavy Metals 10:00 E. Viola ([email protected]) Dipartimento di Chimica, Università di Roma “La Sapienza” Porphyrazines in Combined Photo - and Chemio- Anticancer Therapies: Recent Results in Water Solution” 10:20 G. Zanotti ([email protected]) CNR – ISM, Roma Fluorescence Enhancement in an Unsymmetrically-Substituted Copper Phthalocyanine 10:40 Coffee Break Chairperson: Emma Gallo 11:00 A. Peluso ([email protected]) Dipartimento di Chimica e Biologia, Università di Salerno Genetrating Function Approach to the Calculation of Spectral Band Shapes 11:20 M. Di Valentin ([email protected]) Dipartimento di Scienze Chimiche, Università di Padova The Porphyrin in the Triplet State as a Potential Spin Label for Nanometer Distance Measurements by EPR Spectroscopy 11:40 M.E. Crestoni ([email protected]) Dipartimento di Chimica e Tecnologie del Farmaco, Università di Roma “La Sapienza” Metal-Oxo Porphyrin Complexes: Catalytic Intermediates in the Gas Phase 12:00 L. Guidoni ([email protected]) Dipartimento di Scienze Fisiche e Chimiche, Università degli Studi dell’Aquila The Special Pair of Chlorophylls in Photosynthesis. Insights by Computer Simulations 12:20 Conclusions and Perspectives 12 ORAL COMMUNICATIONS 13 OC01 A NEW SULFONATION STRATEGY FOR CORROLES: THE KEY ROLE OF PHOSPHORUS Mario NAITANA, Fabrizio CAROLEO, Sara NARDIS, Roberto PAOLESSE Department of Chemical Science and Technologies, University Of Rome Tor Vergata, Via della Ricerca Scientifica 1, 00133 Rome, Italy. [email protected] One of the most interesting features of porphyrins is represented by the possibility of modulating their properties and reactivity exploiting, for instance, a wide coordination chemistry developed through the years 1. In these last few years, the relatively new member of this family of molecules, corrole, has been the main character for a sort of “gold rush”, with the main goal to synthesize metal and main group complexes and enrich the macrocycle with new functional groups. In particular non-metals complexes of amphiphilic porphyrinoid have obtained high attention, due to their biological and optical properties, which are very promising for the utilization in different technology fields, such as dyes for photodynamic therapy, solar cells, supramolecular chemistry and organic catalysis 2. One of the main route to obtain an amphiphlic porphyrinoid is the sulfonation reaction with the best example of this strategy given by 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS4). Therefore all the applications that have involved the use of the TPPS4 are enough to justify the efforts that are involving the synthesis of analogues corrole derivatives3. In this work we present a novel and efficient strategy to obtain new sulfonato corrole derivatives, showing peculiar properties that can be exploited in all the fields that have made TPPS 4 very popular. N OCH3 N P O3S N OH SO3 ______________ References: 1. Aviv-Harel, I.; Gross, Z. Coord. Chem. Rev, 2011, 7, 717. 2. Aviv-Harel, I.; Gross, Z. Chem. Eur. J, 2009, 15, 8382. 3. Naitana, M. L.; Nardis, S.; Lentini, S.; Cicero, D.; Paolesse, R. J. Porphyrins and Phtalocyanines, 2015, 19, 1. 14 OC02 FOTOSENSIBILIZZATORI CATIONICI ANTITUMORALI E ANTIBATTERICI 1 1 1 1 Stefano BANFI , Enrico CARUSO , Viviana ORLANDI , Paola BARBIERI , Amedea MANFREDI 2 1 Dipartimento di Scienze Teoriche ed Applicate (DiSTA), Università degli Studi dell’Insubria, via 2 JH Dunant, 3 – Varese. Dipartimento di Chimica, Università Statale di Milano, Via Golgi 19 – Milano La terapia fotodinamica (PDT) è una metodologia di cura applicabile contro i tumori solidi o per debellare le infezioni batteriche localizzate. Il processo richiede la somministrazione di un fotosensibilizzante (PS), in modo che possa raggiungere efficacemente la zona malata, seguita da irraggiamento della zona interessata con una radiazione elettromagnetica a bassa energia, cioè luce visibile. Il PS assorbe l’energia della radiazione e la trasmette all’ossigeno molecolare che in questo modo genera radicali dell’ossigeno (ROS) e ossigeno singoletto (1O2). Entrambe queste specie sono forti ossidanti che attaccano le molecole organiche presenti nelle vicinanze così causando la morte della cellula. Nel nostro laboratorio ci occupiamo di due classi di PS, le porfirine e i borodipirrometeni (BODIPY), di cui la prima è una delle famiglie di molecole storicamente più studiata nella terapia fotodinamica che trova applicazione a livello clinico mentre la seconda comprende fotosensibilizzanti che stanno riscontrando un discreto interesse in vitro per la loro applicazione nella PDT. In questo convegno presentiamo due recenti risultati del nostro lavoro di ricerca. Il primo riguarda porfirine diariliche simmetriche (dicationiche), la cui struttura è stata ideata con l’obiettivo di facilitarne la somministrazione oltre alla possibilità di applicare lo stesso PS sia in campo antitumorale che in campo antibatterico semplicemente modificando le condizioni sperimentali quali iltempo di incubazione e di illuminazione. Le molecole sintetizzate sono state testate in vitro su cellule tumorali del colon (HCT116) in differenti condizioni sperimentali di incubazione e di illuminazione. In seguito sono state eseguite prove preliminari di attività fotodinamica su due ceppi batterici, uno Gram negativo (Escherichia coli) e uno Gram positivo (Staphilococcus aureus). Il secondo lavoro riguarda lo studio dell’attività fotodinamica antibatterica ottenuta per azione combinata di un BODIPY cationico con polimeri policationici appartenenti alla famiglia delle poliammidoammine (PAA), quest’ultimi caratterizzati da un numero crescente di cariche in funzione del peso molecolare del polimero stesso. Per questo studio si sono scelti gli stessi ceppi batterici modello indicati sopra. Nella valutazione dell’efficacia del trattamento si è preso in considerazione: 1) la fototossicità del BODIPY da solo; 2) la tossicità intrinseca dei polimeri e 3) la fototossicità ottenuta in presenza di entrambe le molecole. 15 OC03 THIOALKYL-PORPHYRAZINES FOR ELECTRONIC MATERIALS Sandra BELVISO Dipartimento di Scienze - Università della Basilicata, via dell'Ateneo Lucano 10, I-85100, Potenza, IT [email protected] Our research is mainly directed to the synthesis and characterization of porphyrazines, tetrapyrrole macrocycles which are “structural hybrids” of the more well known porphyrins and phthalocyanines. In particular we are studying symmetrically and non-symmetrically substituted thioalkyl-porphyrazines for applications in material chemistry. Thanks to the presence of the sulfur atoms on the peripheral positions these molecules display discotic columnar mesophases1 and peculiar spectroscopic and electrochemical properties, such as an UV-visible spectrum with very broad and intense absorption bands, well overlapping the solar emission spectrum. Moreover, the possibility to selectively remove one thioalkyl chain in these macrocycles 2 has allowed to disclose a new procedure for the synthesis of non-symmetrically substituted thioalkylporphyrazines from the symmetric parent. This opened the way to the easy insertion on the macrocycle periphery of substituents suitable to tune its spectroscopic and self-aggregation properties, as well as HOMO-LUMO values.3 In particular, mono-aryl substituted derivatives provided unconventional “push-pull” systems suitable for non-linear optics.3 Taking into account the great interest of tetrapyrrole macrocycles as light acceptors in organic photovoltaic (OPV) devices, our recent studies focused on the synthesis of novel thioalkyl-porphyrazine dyes for either dye-sensitized (DSSC) or bulk heterojunction (BHJ) solar cells. To this end, perfluorinated thio-alkylporphyrazines endowed with liquid-crystalline and spectro-electrochemical properties interesting for potential applications in electronic materials were prepared.4 Moreover, the insertion of a pyrene unit on the macrocycle periphery provided a dye able to interact non covalently with acceptor systems like carbon nanotubes (SWNTs) and graphene, making these molecules promising chromophoric/donor units for OPV. Preliminary experiments on photoconduction of nanohybrids of 1-pyrene-thioalkyl-porphyrazine with both SWNTs and graphene nanoflakes (GNF) have been carried out. ______________ References: 1. Belviso, S.; Ricciardi, G.; Lelj, F. J. Mater. Chem. 2000, 10, 297. 2. a) Belviso, S. ; Ricciardi, G. ; Lelj, F. ; Monsù Scolaro, L. ; Bencini, A. ; Carbonera, C. J. Chem. Soc., Dalton Trans., 2001, 1143. b) Belviso, S.; Giugliano, A.; Amati, M.; Ricciardi, G.; Lelj, F.; Monsù Scolaro, L. Dalton Trans. 2004, 305. 3. a) Belviso, S.; Amati, M.; De Bonis, M.; Lelj, F. Mol. Cryst., Liq. Cryst. 2008, 481, 56. b) Belviso, S.; Amati, M.; Rossano, R.; Crispini, A.; Lelj, F. Dalton Trans. 2015, 44, 2191. 4. Belviso, S.; Cammarota, F.; Rossano, R.; Lelj, F. Tetrahedron 2015, submitted. 16 OC04 CHARACTERIZATION OF CYCLIC TETRAPYRROLES AND RELATED COMPOUNDS BY MALDI TOF/TOF MASS SPECTROSCOPY C.D. CALVANO 1,2 3 3 1 1,2 , M. TROTTA , F. ITALIANO , G. VENTURA , T.R.I. CATALDI , F. PALMISANO 1 1,2 2 Dipartimento di Chimica & Centro Interdipartimentale di Ricerca S.M.A.R.T. - Università degli Studi di 3 Bari Aldo Moro, Via Orabona 4, 70126 Bari, Italy CNR, Istituto per i Processi Chimico-Fisici, Sezione di Bari, Via Orabona, 4, 70126 Bari, Italy [email protected] Tetrapyrrole derivatives are a large family of molecules containing four pyrrole rings held together by direct covalent bonds or by one-carbon bridges with a resultant linear or cyclic structure. The most common macrocycles, usually coordinating a metal ion into the conjugated ring system, include porphyrins (e.g., hemes), chlorins (e.g., pheophytins, chlorophylls and bacteriochlorophylls), corrins (e.g., cobalamins, vitamins B12), and phthalocyanines (Figure 1). These macrocyclic substructures are present in many natural compounds as green pigments in chloroplasts of algae, plants and bacteria (chlorophylls or bacteriochlorophylls) [1, 2] or red pigments in hemoglobin, myoglobin (heme b) and cytochrome c (heme c) [3]. Porphyrins, phthalocyanines, and corroles complexes are also efficient catalysts for many reactions [4, 5]. A B C D Figure 1. Structures of basic tetrapyrrole macrocycle for (A) porphyrins, (B) chlorins, (C) corrins and (D) phthalocyanines. High performance liquid chromatography coupled with mass spectrometry (LC-MS) is a versatile tool to investigate and identify cyclic tetrapyrroles and closely related compounds [6] even if, due to the necessary sample treatment, it could be less suitable for routine analyses of large numbers of samples. Fast and selective identification of these compounds may be accomplished by matrix-assisted laser desorption ionization (MALDI) time-of-flight (ToF) MS because of well-recognized features, such as rapid and easy sample preparation, tolerance to salts, and high sensitivity. Yet, the analysis of cyclic tetrapyrrole-derivatives by MALDI-MS technique has not been fully established. Considering that proton affinities and ionization energy of a MALDI matrix affect energy transfer involved in proton- and electron-transfer, a possible way to successfully attain structural information on these compounds may be the choice of a proton-transfer or an electron-transfer matrix [7], depending on the nature of the metal cation and/or the surrounding substituents. Here, we report the characterization of some representative cyclic tetrapyrrole-derivatives by MALDI-ToF/ToF MS analyses, including chlorophylls (a and b), bacteriochlorophylls, vitamins B12, etc., upon proper matrix selection. References: 1. Ballschmiter K, Katz JJ. Nature, 1968, 220, 1231. 2. Scheer, H. Chlorophylls and bacteriochlorophylls: biochemistry, biophysics, functions and applications, 2006, 25, 1. 3. Kim T, Lee J, Kim J. Int. J. Mass Spectrom., 2015, 376, 13. 4. Costas, M. Coord. Chem. , 2011, 225, 2912. 5. Sorokin, A. B. Chem. Rev., 2013, 113, 8152. 6. Luo X, Chen B, Ding L, Tang F, Yao S. Anal. Chim. Acta, 2006, 562,185. 7. Calvano CD, Ventura G, Cataldi TRI, Palmisano F. Anal. Bioanal. Chem., 2015, doi: 10.1007/s00216-015-87289. 17 OC05 SYNTHESIS OF IRON(III) PORPHYRIN COMPLEXES TO PROMOTE THE REGIOSELECTIVE CYCLOPROPANATION OF OLEFINS. 1 1 2 2 Daniela M. CARMINATI, Daniela INTRIERI, Stéphane LE GAC, Bernard BOITREL, Emma GALLO 1 1 2 Università degli Studi di Milano, Milan, Italy. Institut des Sciences Chimiques de Rennes, UMR CNRS 6226, Université de Rennes 1, France, e-mail: [email protected] Cyclopropanes are important three-member carbon rings which often represent the active part in biological and/or pharmaceutical compounds.1-2 Catalytic diastereo- and enantioselective olefin cyclopropanations have been extensively explored and among all the available synthetic methodologies to synthesise cyclopropanes, the one pot reaction of diazocompounds with olefins represents a sustainable and atom-efficient strategy due to the formation of N2 as the only stoichiometric by-product. Considering that metal porphyrins represent a very competent and stereoselective class of catalysts, we are currently studying the catalytic activity of iron derivatives which display a good sustainability for the presence of the eco-friendly, cheap and very efficient metal centre. Thus, we synthesised the new iron(III) complex 1Fe starting from the porphyrin ligand 13 (scheme 1) which has one C2 axis within the porphyrin plane and exhibits an open space on each side for the substrate access. Complex 1Fe demonstrated a very high catalytic activity in cyclopropanations which occurred with excellent transdiastereoselectivities (94-99%). Since positive data, we employed ligand 1 to synthesise the chiral derivative 2, which shows a steric chiral bulk surrounding the Ncore of the porphyrin. The free porphyrin 2 was then reacted with iron bromide, in the presence of methanol, to yield the relative iron(III) complex 2Fe (scheme 1) which was completely characterised.4 Complex 2Fe showed a very high catalytic efficiency; excellent trans-diastereoselectivities, good enantioselectivities and outstanding TON and TOF values were observed in the reaction of cyclopropanation of several olefins by differently substituted diazo compounds (scheme 1).4 References: 1. C. A. Carson, M. A. Kerr, Chem. Soc. Rev. 2009, 38, 3051-3060. 2. A. K. Kumar, Int. J. Pharm. Pharm. Sci. 2013, 5, 467-472. 3. A. Didier, L. Michaudet, D. Ricard, V. Baveux-Chambenoît, P. Richard, B. Boitrel, Eur. J. Org. Chem. 2001, 1927-1926. 4. D. Intrieri, S. Le Gac, A. Caselli, E. Rose, B. Boitrel, E. Gallo, Chem. Commun. 2014, 50, 1811-1813. 18 OC06 CHIRALITY IN PORPHYRIN AGGREGATES 1 1 2 Maria Angela CASTRICIANO, Roberto ZAGAMI, Mario SAMPERI, Andrea ROMEO, 1,2 SCOLARO 1,2 Luigi MONSU’ 1 Istituto per lo Studio dei Materiali Nanostrutturati, c/o Dipartimento di Scienze Chimiche, V.le F. Stagno 2 D'Alcontres n.31, 98166 Messina, Italy. Dipartimento di Scienze Chimiche, University of Messina, V.le F. Stagno D'Alcontres n.31, 98166 Messina, Italy. [email protected] Reports of optical activity for assemblies of achiral entities in the absence of templates were greeted at first with skepticism. However, now that these findings have been confirmed, considerable attention has been focused on this phenomenon. The possibility that what is being observed in these systems is a spontaneous mirror-symmetry breaking has led to speculation about the relationship of these processes to those responsible for the ubiquitous homochirality in our universe. Achiral chromophores, especially porphyrins, have been of some considerable importance for such symmetry-breaking studies due to their rich spectral properties and their ability (under appropriate conditions) to self-assemble into chiral supramolecular structures. In particular, meso-tetrakis4-sulfonatophenyl (TPPS) and aryl-substituted porphyrins have been widely used as starting materials. TPPS J-aggregates, obtained in aqueous solution in the absence of any added chiral templating agent, show an unpredictable chirality, resulting in controversial proposals for their basis. Recently, we demonstrated the fundamental role of kinetic parameters in the expression and transmission of chirality in this supramolecular system.1 Whatever the source of the chiral bias promoting such symmetry breaking, the rate of the aggregation process leading to the formation of J-aggregates strongly affects the size of these nanoassemblies and the chiral induction. With the aim to resolve some of the confounding issues still open in literature related to the TPPS J-aggregate optical activity, here we report on detailed kinetic investigation on selfassembly processes induced by different inorganic achiral acid in the absence of an added chiral template and in presence of various chiral acids opportunely selected to have variability in terms of structure and strength. The results obtained have allowed to gain important information in the field of supramolecular architectures, highlighting the importance of the role of experimental parameters such as concentration and/or mixing order of the reagents. We anticipate that, depending on the overall rate of the process, a distinctive kinetic difference, together with a difference variance in the extent of the chiral transfer, is evident for the various acids and strictly connected with medium properties. ______________ References: 1. Romeo, A.; Castriciano, M.A.; Occhiuto, I.; Zagami, R.; Pasternack, R.F.; Monsù Scolaro, L. J. Am. Chem. Soc. 2014, 136, 40-43. 19 OC08 SUPRAMOLECULAR PORPHYRINS SYSTEMS: CHIROPTICAL PROBE, BUILDING BLOCK FOR MULTICOMPONENT ARRAYS AND CHIRAL ASSEMBLYES Alessandro D’URSO, Maria Elena FRAGALA’, Roberto PURRELLO University of Catania, Viale A. Doria 6, 95125 Catania, Italy. [email protected] Porphyrins are quite versatile molecules successfully used in many fields: from nanotechnology to biomedicine. These hetero-aromatic macrocycles present remarkable electronic properties which bring to attractive spectroscopic features. The non-covalent interactions of water-soluble achiral porphyrins with chiral templates have been exploited to transfer, detect and/or amplify the matrix handedness. As chiral templates we used biopolymers such aminoacid or DNA sequences, even if more challenging was the induction of chirality with single molecules as Ruthenium phenantroline. Interestingly, for some of such systems the chiral memory phenomenon has been observed.1 Porphyrins are used also as chiroptical probe for polynucleotides conformation. Cationic and anionic metalloporphyrins, have shown to be excellent chiroptical probes for detecting Z-DNA (an intriguing DNA structure which vital role in vivo is still unknown) not only in polynucleotides entirely converted in Z form but also under highly competitive conditions as in BZB sequence.2 We are involved also in non-covalent syntheses of multi-porphyrin supramolecular species in aqueous solution.3 In particular, calixarene–porphyrin species represents concrete evidence of a quantitative complexation, governed by precise hierarchical rules, which together with a rational functionalization of the molecular components leads to supramolecular entities of well-defined and tunable stoichiometry. Herein, we will propose an overview of our recent developments in porphyrin systems mentioned above. ______________ References: 1. a) Mammana A.; D’Urso A.; Lauceri R.; Purrello R. J. Am. Chem. Soc. 2007, 129, 8062–8063; b) Randazzo R.; Mammana A.; D’Urso A.; Lauceri R.; Purrello R. Angew. Chem. 2008, 120, 10027–10030. 2. a) Balaz M.; De Napoli M.; Holmes A.E.; Mammana A.; Nakanishi K.; Berova N.; Purrello R. Angew Chem Int Ed 2005, 44, 4006-4009; b) D'Urso A.; Choi J.K.; Shabbir-Hussain M.; Ngwa F.N.; Lambousis M.I,.; Purrello R.; Balaz M. Biochem Biophys Res Comm 2010, 397,329–332; d) D'Urso A.; Mammana A.; Balaz M.; Holmes A.E.; Berova N.; Lauceri R.; Purrello R. J Am Chem Soc 2009, 131, 2046–2047; e) D'Urso A.; Holmes A.E.; Berova N.; Balaz M.; Purrello R. Chem As J 2011, 6, 3104–3109; f) Holmes A.E.; Choi J.K.; Francis J.; D’Urso A.; Balaz M. J Inorg Biochem, 2012, 110, 18–20. 3. D’Urso A., Fragalà M. E.; Purrello R. Chem. Commun., 2012, 48, 8165–8176. 20 OC09 MECHANISTIC INVESTIGATION OF THE RUTHENIUM PORPHYRIN CATALYSED AZIRIDINATION OF OLEFINS BY ARYL AZIDES a b Emma GALLO , Gabriele MANCA , Carlo MEALLI a b b Dep. of Chemistry, University of Milan, Via Golgi 19, I-20133 Milan (Italy). Istituto di Chimica dei Composti OrganoMetallici, ICCOM-CNR, Via Madonna del Piano 10, I-50019 Sesto Fiorentino. [email protected] Aziridines are important building blocks in organic synthesis because their highly strained three-membered ring affords an epoxide-like reactivity through an easy C-N bond cleavage. 1 The relevant biological activity of these heterocycles, which are present in several natural compounds and antitumor/antimicrobial agents 2 suggests their usage as precursors of important aza-compounds. Hence, efficient aziridine synthetic strategies have become of importance. A mechanism for the aziridination of olefins by aryl azides (ArN 3), promoted by ruthenium(II) porphyrin complexes, is proposed on the basis of a combined experimental/theoretical approach. Aryl azides are efficient nitrogen sources with the eco-friendly N 2 elimination. All the recorded data support the involvement of a monoimido ruthenium complex as the active intermediate in the transfer of the nitrene moiety “ArN” to the olefin. The DFT study highlights the importance of an accessible triplet ground state of the intermediate ruthenium mono-imido complex [Ru](NR)(CO) to allow the evolution of the aziridination process in presence of an olefin. A similar intermediate has been recognized by us to play a central role also in the amination reactions in presence of organic azides and olefin with a hydrogen atoms. 3 The diradical mono-imido nitrogen is able to transfer spin density to the olefin carbon atom, providing a metastable triplet N-C-C open chain, which is the subject of a triplet singlet, before the final achievement of three-membered ring. The analysis of Minimum Energy Crossing Point (MECP) has been also provided. The selectivity of the azidirination vs. the uncatalysed triazoline formation has been also addressed in terms of electronic features of the porphyrin ligand and olefin/azide catalytic ratio. ______________ References: 1.a) Sweeney, J. B. Chem. Soc. Rev., 2002, 31, 247; b) Hu, X. E., Tetrahedron, 2004, 60, 2701; c) Sweeney, J. B.; Yudin, A., Aziridines and Epoxides in Organic Synthesis, Wiley-VCH Verlag GmbH & Co. KGaA, 2006. 2. a) Ismail, F. M. D.; Levitsky, D. O.; Dembitsky, V. M., Eur. J. Med. Chem., 2009, 44, 3373; b) Tsuchida, T. ; Sawa, R.; Takahashi, Y.; Inuma, H.; Sawa, H.; Naganawa, H.; Takeuchi, T., J. Antibiot., 1995, 48, 1148. 3. Manca, G.; Gallo, E.; Intrieri, D.; Mealli, C., ACS Catal., 2014, 4, 823. 21 OC10 REVERSIBLE AGGREGATION/DEAGGREGATION OF PORPHYRIN J-AGGREGATES INDUCED BY SILVER(I) CATIONS 1 2 2 Ilaria Giuseppina OCCHIUTO, Mariachiara TRAPANI, Maria Rosaria PLUTINO, Giovanna DE LUCA, 1,2 Luigi MONSU’ SCOLARO 3 1 Dipartimento di Scienze Chimiche, University of Messina, V.le F. Stagno D'Alcontres n.31, 98166 2 Messina, Italy. Istituto per lo Studio dei Materiali Nanostrutturati, c/o Dipartimento di Scienze Chimiche. 3 V.le F. Stagno D'Alcontres n.31, 98166 Messina, Italy. Dipartimento di Scienze del Farmaco e dei Prodotti per la Salute, University of Messina, V.le Annunziata, 98166 Messina, Italy. [email protected] Porphyrin J-aggregates have been largely investigated due to their remarkable structural, electronic and chiral properties. Much of these studies have been carried out on water soluble tetra-anionic tetrakis(4-sulfonato-phenyl)porphyrin (H2TPPS4). In the presence of added salts or at high acid concentration the diacid H4TPPS4 self-assembles into J-aggregates stabilized primarily by electrostatic interactions between the positive protonated core of the macrocycle and the negatively charged sulfonate groups of adjacent porphyrins. The kinetics of supramolecular assembling of these nanoaggregates are characterized by a sigmoidal profile with an initial lag period.1 Detailed kinetic studies on the reverse reaction for J-aggregates , i.e. the disassembly process, are far less frequent. Quite recently, we reported that for the metallation of the acidic form of H2TPPS4 (di-anionic H4TPPS4) by copper(II), the order of reagent mixing determines the rate and mechanism of CuTPPS 4 formation. When copper salts are added last, the kinetic profile is fit as a (pseudo)-first order process. However, J-aggregates of the di-anionic H4TPPS4 porphyrin are rapidly formed at pH ~ 3 when copper(II) salts are incorporated in solution prior to porphyrin addition. The subsequent metallation of the porphyrin units leads to the disassembling of these arrays via a pseudo-zero order kinetic profile, suggesting an attack of the metal ion at the rims of the nanostructure.2 Here we report on the aggregation of H4TPPS4 under acidic pH in the presence of excess silver(I) ions. The formed J-aggregates under light irradiation undergo to the formation of the silver(II) metal derivative of the porphyrin, that in the dark slowly interconverts back to the J-aggregated species. Based on previous literature reports,3 a mechanism has been proposed. ______________ References: 1. Micali, N.; Mallamace, F.; Romeo, A.; Purrello, R.; Scolaro, L. M. J. Phys. Chem. B 2000, 104, 5897−5904. 2. Occhiuto, I.; De Luca, G.; Trapani, M.; Monsù Scolaro, L. and Pasternack, R.F. Inorg. Chem., 2012, 51, 10074−10076. 3. Krishnamurthy, M. Inorg. Chem. 1978, 17, 2242. 22 OC11 CHIRAL ASSEMBLIES OF PORPHYRINS LINKED TO α-HELICAL PEPTIDES IS CONTROLLED BY THE STEREOCHEMISTRY OF THE FIRST AMINO ACID Francesca BISCAGLIA, Elisa FREZZA, Alberta FERRARINI, Marina GOBBO Department of Chemical Sciences – University of Padua [email protected] Supramolecular assemblies of porphyrins have been received increasing interest in recent years due to potential applications in optoelectronic and photovoltaic devices as models of the light harvesting complexes and redox enzymes in living systems. Achiral porphyrins can self-assembly in chiral supramolecular aggregates under the influence of different stimuli as complexation with chiral guest, mechanical effects (such as swirling, stirring) or aggregation on chiral templates such as helical peptides and DNA.1 In the last few years the synthesis of several porphyrin-peptide conjugates,2-3 for studies in photodynamic therapy, allowed us to observe aggregation behavior of these compounds in water-organic mixture, suggesting that the peptide secondary structure can influence growing of chiral aggregates. In particular the conjugate between meso-tetraphenylporphyrin and the α-helical peptide [Leu21]magainin (see the sequence below) self-assemblies in water in chiral supramolecular aggregates, as suggested by the CD spectrum that shows an intense positive couplet in the porphyrin region, with a zero point crossing at 422 nm. The reproducible sign of the Cotton effect suggests a preferential right-handed twist between porphyrins in aggregates. By synthetizing two model peptides, adopting in organic solvent right-handed or left-handed helical conformation, and their porphyrin conjugates, we found that chiral preferences exhibit by supramolecular aggregates are independent by the screw sense of the α-helical peptide. On the contrary, alanine scan on selected positions of the magainin sequence pointed at the importance of the first amino acid residue, connecting the peptide to the porphyrin system, in determining chiral preferences of supramolecular aggregates. This result could shed light on assembling of natural peptide-containing porphyrin systems. ______________ References: 1. D’Urso, A.; Fragalà, M. E.; Purrello, R.; Chem. Commun. 2012, 48, 8165-8176. 2. Dosselli,R., Tampieri, C., Ruiz-Gonzalez,.R, De Munari, S, Ragàs,.S, Sánchez-García, D, Agut, M, Nonell, S, Reddi, E., Gobbo, M. J. Med. Chem. 2013 , 56, 1052-1063. 3. Dosselli, R.; ,. R. ; Moret,. F. ; Agnolon,. V. ; Compagnin, C.; Mognato,. M.; Sella,. V. ; Agut,. M. ; Nonell,. S. ; Gobbo, M.;. Reddi , E. J. Med. Chem. 2014 , 57, 1403-14153. 23 OC12 TETRAHEDRAL ARRAYS OF METALLO-PORPHYRINS a b c c Alessandra LUISA, Nicola DEMITRI, Giacomo BERGAMINI, Marianna MARCHINI, Massimo c c a BARONCINI, Paola CERONI, Elisabetta IENGO a Dep. Chemical and Pharmaceutical Sciences, University of Trieste, Via L. Giorgieri 1, 34127 Trieste (IT); b Elettra – Sincrotrone Trieste, S.S. 14 Km 163.5 in Area Science Park, 34149 Basovizza Trieste (IT); c Dep. of Chemistry “G. Ciamician” and Interuniversity Center for the Chemical Conversion of Solar Energy, University of Bologna, Via Selmi 2, 40126 Bologna (IT). [email protected] Artificial photosystems mimicking the natural occurring ones [1] play a prominent role in the contemporary research [2]. In particular, the study of multichromophoric systems with a shapepersistent arrangement of the chromophores has gained increasing relevance since new properties may emerge from the interaction between the spatially organized units. The group of Anderson has very elegantly achieved the template-directed synthesis of fully conjugated zincporphyrin nanorings (containing up to twelve Zn-porphyrin units), by axial coordination of appropriate oligo-pyridyl scaffolds to the zinc centers of linear Zn-porphyrin oligomers, followed by covalent coupling and removal of the templating scaffold [3]. Herein, we describe two H O acetone H CH novel rutheniumCH py porphyrin tetra-cationic py Ph Ph py py arrays obtained by D = 5.9510 cm s coordination of four Rur = 11.6 Å porphyrin units to the +4 pyridylpyridinium arms of a tetrahedral core (Figure). The arrays, that differs in the substituents on the Ru-porphyrins, have been fully characterized in solution and, in one case, also in the solid state (X-ray δ (ppm) structure). The dendritic core serves as scaffold, but most importantly it posses unique luminescent properties on its own, deriving from the rigid spatial arrangement of the four pyridylpyridinium units [4]. Modulation of the emission and electrochemical properties of the peripheral Ruporphyrins and of the core unit within the arrays, with respect to those of the parent components and/or of smaller model compounds, and possible inter-component photo-induced processes occurring between the peripheral and the inner chromophores, have also been investigated. 2 meso 3 2 2 1 3 4 1 2 coeff -6 2 -1 Diffusion Coeffcient (cm2 s-1) h ______________ References: 1. In “Electron Transfer in Chemistry” Balzani, V., Ed.; Wiley-VCH: Weinheim (Germany) 2001: Gust, D. et al. Vol. III, Part 2, Chapter 2, pp 273−336 and Fukuzumi, S. et al. Vol. II, Part 2, Chapter 8, pp 927−966. 2. Scholes, G. D.; Fleming, G. R.; Olaya-Castro, A.; van Grondelle, R. Nat. Chem., 2011, 3, 763. 3. O’Sullivan, M. C.; Sprafke, J. K.; Kondratuk, D. V.; Rinfray, C.; Claridge, T. D. W.; Saywell, A.; Blunt, M. O; O’Shea, J. N.; Beton, P. H; Malfois, M; Anderson, H. L. Nature, 2011, 469, 72. 4. Bergamini, G.; Fermi, A.; Marchini, M.; Locritani, M.; Credi, A.; Venturi, M.; Negri, F.; Ceroni, P.; Baroncini, M. Chem. Eur. J., 2014, 20, 7054. 24 OC13 SPONTANEOUS DEPOSITION OF WATER-SOLUBLE PORPHYRINS ON GLASS: A BIG CHALLENGE OR A “GREEN” OPPORTUNITY? Maria Elena FRAGALÀ, Alessandro D’URSO, Domenico A. CRISTALDI, Rosalba RANDAZZO and Roberto PURRELLO Università di Catania, Dipartimento di Scienze Chimiche and INSTM UdR Catania Viale A. Doria 6, 95100 Catania, Italy Porphyrins represent a multitopic class of chromophores largely used as functional overlayer in hybrid organic-inorganic materials. These versatile macrocycles, in fact, are often grafted to inorganic nanostructures for applications in sensing, energetics, medicine, catalysis and many other technological fields. An interesting functional aspect of porphyrins is their dichotomous behaviour: in fact, by a proper derivatization of periphery (meso and beta positions) it is possible to make them water soluble despite the intrinsic solvophobic nature. Accordingly, porphyrin based supramolecular chemistry in aqueous solutions paves the wave to a plethora of noncovalent self-assembled architectures with specific optical, electronic and chemical properties. Since chemistry in water represents, nowadays, an eco-friendly and harmless synthetic and material fabrication approach we focus our efforts in optimization and control of noncovalent surface functionalization strategies to graft porphyrin overlayers onto inorganic surfaces. In fact, immobilization of porphyrin onto surface of inorganic materials and nanostructures has become a fundamental process in the development of advanced devices. Aware of the importance of electrostatic and related interaction in formation of supramolecular assemblies, we remark the importance of the porphyrin chemistry in solution- and its associated hierarchical rules- to trigger the spontaneous deposition of water soluble porphyrin derivatives on oppositely charged surface as well as to determine the layer stability and process reliability. The possibility to control spontaneous deposition process in a reproducible manner represents an easier and greener alternative to covalent approaches extensively used to develop functional materials and systems. 25 OC14 CONFORMATIONAL CHANGES OF CARDIOLIPIN-BOUND CYTOCHROME C: A SPECTROSCOPIC STUDY Lisa MILAZZO, Lorenzo TOGNACCINI, Barry D. HOWES, and Giulietta SMULEVICH Dipartimento di Chimica “Ugo Schiff”, Via della Lastruccia 3-13, Sesto Fiorentino (Fi). [email protected] Interaction of cytochrome c (Cyt c) with cardiolipin (CL) is important for its apoptotic function. CL binding activates a peroxidase function in Cyt c by promoting protein unfolding. Peroxidation of CL decreases the strength of the Cyt c-CL interaction, facilitating protein detachment from the mitochondrial membrane leading to initiation of apoptosis (1,2). Many attempts have been made to obtain a consistent structural description of the CL-bound Cyt c species; however, the protein conformational heterogeneity has hindered the analysis of the different forms. A consensus view is that upon formation of the Cyt c-CL complex the Fe-Met80 coordination is ruptured followed by changes in heme ligation. Using different approaches, it has been concluded that i) His33, His26 or water (3), ii) Lys or OH- (4) can replace Met80, or iii) that both His-Fe-His and Lys-Fe-His species can be formed in the complex (5). The puzzling disparity in binding modes may be due to the different experimental conditions used (6). In the present work we have studied the interaction using horse heart Cyt c which, unlike yeast Cyt c, has pro-apoptotic activity (7). Ferric Cyt c has been titrated with bovine CL. The final complex, corresponding to a CL/Cyt c ratio of 30:1, is characterized by the disappearance of the 695 nm CT, the presence of a new band at 625 nm, and the overall blue shift of the electronic absorption spectrum compared to the native Cyt c. These changes, together with a curve-fitting analysis of the corresponding resonance Raman (RR) spectra, indicate that upon complexation the lack of the Met80 ligand gives rise to the formation of at least four different forms: two minor HS species (a 5-coordinated HS and an aquo 6-coordinated HS) and two misligated forms. A His-FeHis species is the first misligated state to be formed, at low CL concentration (when the CT at 695 nm, indication of the presence of the Fe-Met ligation, is still present in the UV-Vis spectra), followed by the formation of a Lys-Fe-His species, for higher CL ratios. In the final complex, the proximal Fe-His bond is strong, as suggested by the fairly high RR frequency of the (Fe-Im) stretching bond, whereas the distal cavity is open, since CO binds to the Fe atom in an upright conformation with no polar interactions with the distal residues. In agreement with previously reported UV-RR data (8), we suggest that the first event of the interaction between Cyt c and CL is the rupture of the critical His26-Pro44 hydrogen-bond. Pro44 bridges the 20s and the 40s -loops in the polypeptide chain stabilizing the protein tertiary conformation. This event induces increased flexibility of the Met80-containing loop, disrupting the Met80-heme ligation followed by the formation of the His-Fe-His species. Subsequently, a nearby Lys residue possibly binds the heme. ______________ References: 1. Kagan V.E.; Tyurin, V.A.; Jiang, J.; Tyurina, Y.Y.; Ritov, V.B.; Amoscato, A.A.; Osipov, A. N., Belikova, N. A., Kapralov, A.A., Kini, V., Vlasova, I. I., Zhao, Q., et al., Nat. Chem .Biol., 2005, 1, 223. 2.Ott, M.; Robertson, J.D.; Gogvadze, V.; Zhivotovsky, B.; Orrenius, S. PNAS, 2002, 99, 1259. 3. Oellerich, S.; Wackerbarth, H.; Hildebrandt, P.,. Eur. Biophys J., 2003, 32, 599. 4. Bradley, J.M.; Silkstone, G.; Wilson, M.T.; Cheesman, M.R.; Butt, J.N. J. Am. Chem. Soc., 2011, 133, 19676. 5. Sinibaldi, F.; Howes, B.D.; Droghetti, E.; Polticelli, F.; Piro, M.C.; Di Pierro, D.; Fiorucci, L.; Coletta, M.; Smulevich, G., Santucci, R.. Biochemistry, 2013, 52, 4578. 6. Muenzner, J.; Pletneva, E.V. Chemistry and Physics of Lipids 2014, 179, 57. 7. Kluck R.M.; Ellerby L.M.; Ellerby H.M.; Naiem S.; Yaffe M.P.; Margoliash E.; Bredesen D.; Grant Mauk A.; Sherma F.; Newmeyer D.D. J. Biol. Chem. 2000, 275, 16127. 8. Balakrishnan, G.; Hu, Y.; Spiro, T. G. J. Am. Chem. Soc., 2012, 134, 19061. 26 OC15 β-ALKYNYLCORROLE DERIVATIVES VIA STILLE CROSS-COUPLING REACTION a a b a b Manuela STEFANELLI , Mario Luigi NAITANA , Marco CHIARINI , Sara NARDIS , Antonella RICCI , b a Claudio LO STERZO , Roberto PAOLESSE a Dipartimento di Scienze e Tecnologie Chimiche Università di Roma “Tor Vergata” Via della Ricerca b Scientifica snc, 00133 Roma, Italy E-mail:[email protected]. Facoltà di Bioscienze e Tecnologie Agro-Alimentari e Ambientali, Università degli Studi di Teramo, Via Carlo R. Lerici 1, 64023 Mosciano Sant’Angelo (Teramo), Italy The remarkable photophysical and photochemical properties exhibited by corroles accounted for their potential use as photo- and electro-active building blocks in the realization of multicomponent arrays where these tetrapyrroles and other cromophores or electron acceptors are linked.1Frequently, synthetic methodologies for the peripheral functionalization of corrole macrocycle are developed with the aim to further amplify these appealing features, for example allowing for the introduction of functional groups that increase the electronic conjugation along the corrole skeleton. Regarding this, recently we have been interested to the insertion of alkynyl groups at the corrole β-pyrrolic positions, they being commonly used in the organic synthetic materials fabrication, where high exciton and electron coupling between the units are required.2 The alkynylation of corrole periphery can be performed by metal-catalyzed reactions on halogenated corrole derivatives. We have recently developed a bromination protocol leading selectively to a silver 3,17-dibrominated corrolate in very high yield. This compound gave entry to both free base and the corresponding copper complex, which were used as substrates for the cross coupling reactions tested. Although unsatisfactory results were obtained applying the Sonogashira reaction conditions, the use of Stille methodology allowed the achievement of the novel β-alkynylcorrole derivatives reported in Figure from good to excellent yields. These studies are extremely important in corrole field and will be discussed in detail during this communication. ______________ References: 1. Flamigni, L; Gryko, D.T., Chem. Soc. Rev., 2009, 38, 1635. 2. Bottari G.; Diaz, D.D; Torres, T., J. Porphyrins Phtalocyanines, 2006, 10, 1083.b) Tanaka, T.; Osuka, A., Chem. Soc. Rev., 2015, 44, 943. 27 OC16 ACTION OF AN ASYMMETRIC HEAT SOURCE ON THE MIRRORSYMMETRY BREAKING OF PORPHYRIN AGGREGATES a,b CD (mdeg) a b b a Placido MINEO , Norberto MICALI , Valentina VILLARI , Emilio SCAMPORRINO b Dipartimento di Scienze Chimiche, Università di Catania, Viale Andrea Doria 6, I-95125 Catania. CNRIPCF Istituto per i Processi Chimico-Fisici, Viale F. Stagno d’Alcontres 37, I-98158,Messina. [email protected] The spontaneous symmetry breaking (SSB) is one of the most strange and exciting natural phenomenon. It, from the macroscopic to the microscopic world, finds an evidence (often without any plausible explanation) in several scientific fields, as for example: in astronomy, the spiral galaxies have, generally, a left-handed motion; in nuclear physic, the β-particles, emitted from radioactive nuclei, have an intrinsic asymmetry; in biochemistry, L-amino acids and Dsugars are the essential elements of the origin of the life. For a simple approach to the study of the mirror-symmetry breaking, the aggregation of non-chiral molecules should be considered. Commonly used dyes can be some water soluble porphyrinic systems which exhibit some peculiar properties: i) a high molar absorption; ii) a water solubility, generally due to the presence of suitable charged peripheral groups or peripheral hydrophilic branches; iii) a capability to form self-assembled systems that can be tuned acting on the solution properties. The self-aggregation of porphyrin systems can lead to the formation of H-type and/or J-type structures, whose formation can be easily evidenced by examining the visible region of their extinction spectra. However, these mesoscopic aggregates, generated from achiral buildingblocks, should not show chiral properties because the aggregation process, generally, is a random phenomenon leading to an achiral or racemic mixture. Nevertheless, it has been shown that the mirror-symmetry of a such system can be 100 "broken" by means of an enantiomeric enrichment Figure 1 induced by a chemical (through chiral templates) 50 heating CD@25 C and/or a physical (through asymmetric fields) perturbation. Surprisingly, in several cases, also 0 without the application of an external perturbation, the appearance of a CD signal, in correspondence of -50 cooling CD@25 C porphyrin H- or/and J-band, has been observed. Concerning this, we have recently demonstrated1 that, -100 in a stagnant aqueous solution, a self-assembled 360 380 400 420 440 460 480 500 achiral porphyrin can exhibit an induced l (nm) supramolecular chirality, if subjected to a weak temperature gradient able to give rise to a thermophoretic chiral force, inducing an enantiomeric enrichment with the appearance of circular dichroism signals, as consequence of an unexpected asymmetric external force. In the present communication, we show that, in a stagnant water solution of porphyrin-based molecular aggregates, the symmetry breaking, caused by a temperature gradient (due to an asymmetric heat source), can be controlled in sign. In particular, the optical activity (evidenced by CD signal) can be increased and reversed only acting on the thermal ramp direction (Figure 1). These data can be considered a further evidence about the origin of mirror-symmetry breaking phenomena, suggesting as also weak natural events could be responsible of a chirality selection in animal and vegetal environment. _____________ References: 1. Mineo, P.; Villari, V.; Scamporrino, E.; and Micali, N. Soft Matter, 2014, 10 (1), 44-47. 28 OC17 CYCLODEXTRINS/PORPHYRINOIDS SUPRAMOLECULAR ASSEMBLIES TAILORED BY RECEPTOR TARGETING GROUPS AS POTENTIALLY CELL-SELECTIVE NANO-PHOTOTHERAPEUTICS 1 2 2 3 Giuseppe SORTINO , Anna PIPERNO , Angela SCALA , Valentina RAPOZZI , Luigi MONSU’ 1,2 1 SCOLARO and Antonino MAZZAGLIA 1 CNR-Istituto per lo studio dei Materiali Nanostrutturati, CNR-ISMN c/o Dip. di Scienze Chimiche, dell’ 2 Università di Messina, Viale Ferdinando Stagno D’Alcontres 31, 98166, Messina, Italy. Dip. di Scienze 3 Chimiche, Università di Messina, Viale Ferdinando Stagno D’Alcontres 31, 98166, Messina, Italy. Dip. di Scienze Mediche e Biologiche, Università di Udine, P.le Kolbe 4, 33100 Udine, Italy [email protected] Over the past two decades, scientists focused their interests on design of novel nanotherapeutic tools, prompt to actively deliver drugs in tumor tissue. One of the most used strategies relies on the functionalization of carrier system with receptor targeting groups such as folate, antibody, saccharides and peptides. Folate receptor-α (FR-α) is over-expressed in different cancer cell lines, thus the modification of nanosystem with folate group, represents a well-established strategy for tumor targeting. Cyclodextrins (CyDs), a well-known class of macrocyclic carriers, have been modified with folate group to deliver anticancer drug in (FR-α) cell positive.1 Here, we exploit the host−guest interaction of non ionic amphiphilic cyclodextrins (ACyDs, SC6OH)2 with a folate–adamantanyl derivative (Ada-Fol) to design a novel tailored drug delivery system. Ada-Fol was newly synthesized by coupling of the adamantanyl-carboxylate and the carboxylic group of folic acid to a diamine spacer, and characterized by 1H-NMR and MALDIMS. Nanoassemblies of SC6OH@Ada-Fol loaded with Pheophorbide (Pheo),3 a photosensitiser with high PDT efficacy were produced and fully characterized. SC6OH@Ada-Fol system has been prepared by adding PBS (10 mM, pH 7.4) to a mixed (organic) film of SC6OH and AdaFol at 2.5:1 SC6OH/Ada-Fol molar ratio. This dispersion has been used to dissolve Pheo at 2.5:1:1 SC6OH:Ada-Fol:Pheo molar ratio. Pheo-loaded SC6OH@Ada-Fol nanoassemblies were investigated by complementary techniques such as UV-Vis, steady-state fluorescence and characterized to elucidate size, drug loading and to get insight on the sites of entrapped photosensitizer interaction. In order to verify the biological properties, we have begun to evaluate in vitro the effectiveness of SC6OH@Ada-Fol/Pheo on cell growth on different breast cancer cell lines (MCF-7, MD-231). Preliminary data indicate that the nanoassemblies, upon light irradiation, inhibit cell proliferation depending on the expression of folate receptor. Other biological studies in this direction are in due course. Webpage:http://www.ismn.cnr.it/index.php?option=com_cnrprofile&view=profile&profileid=73 5&lang=it ______________ References: 1. Onodera, R.; Motoyama, K.; Okamatsu, A.; Higashi, T.; Arima, H.; Scientific Reports .2013, 3, 1104. 2. Mazzaglia, A.; Bondì M. L.; Scala, A.; Zito, F.; Barbieri, G.; Crea, F.; Vianelli, G.; Mineo, P.; Fiore, T.; Pellerito, C.; Pellerito, L.; Costa. M. A. Biomacromolecules, 2013, 14, 3820. 3. Rapozzi ,V.; Zorzet, S.; Zacchigna, M.,; Drioli, S.; Xodo, L. Invest. new drugs, 2013; 31, 192. 29 OC18 MESOSCOPIC STRUCTURES BY LANGMUIR-BLODGETT DEPOSITION OF STEROID-PORPHYRINS a a a b Martina BISCHETTI, Raffaella LETTIERI, Antonio PALLESCHI, Ernesto PLACIDI, Lenka CARDOVA, c a a Pavel DRASAR, Donato MONTI, Mariano VENANZI a c b Dept. of Chemical Sciences and Technologies, and CNR-ISM, Dept. of Physics, University of Rome b ‘Tor Vergata’, 00133 Rome (Italy). Institute of Chemical Technology, 166 28, Praha, Czech Republic [email protected] Porphyrin aggregation is primarily dictated by non-covalent and non-specific interactions established between the large macrocycles (π-π and London dispersion). However, the presence of substituents with particular chemical and structural characteristics can modulate the extent and type of noncovalent interactions.1 Exploiting hierarchical self-assembly, porphyrin aggregation can be driven to generate ordered nano- and meso-structures of well-defined topology, such as nanoparticles, nanorods, molecular wires and ordered monolayers. The aggregation properties in solution and the formation of nano- and mesoscopic structures on solid substrates of a cholic acid disubstituted porphyrin (H2Ch2P) were investigated by spectroscopy (UV-Vis absorption, steady-state fluorescence, circular dichroism), microscopy (fluorescence, scanning electrons, atomic force) and molecular mechanics calculations. Monoand multilayer films of H2Ch2P have been obtained by Langmuir-Blodgett (LB) deposition on quartz supports, and their features at the air/water interface were characterized by pressure-area isotherms. Interestingly, it was found that LB deposition, carried out at a surface pressure above the liquid-expanded to liquid-condensed phase transition, gave rise to the formation of mesoscopic rod-like structures, the morphology of which is modulated by the interactions established by the chiral steroid units functionalizing the porphyrin macrocycle. In Figure 1 the micrometric fibers formed by H2Ch2P by LB deposition are clearly imaged by fluorescence microscopy. Fig. 1. Fluorescence microscopy imaging of H2Ch2P mesoscopic fibers formed by LangmuirBlodgett deposition. ______________ References: 1. Lorecchio, C.; Venanzi, M.; Mazzuca, C.; Lettieri, R.; Palleschi, A.; Thi, N. H. N.; Cardova, L.; Drasar, P.; Monti, D. Org. Biomol. Chem. 2014, 12, 3956-3963. 30 OC19 PHOTO-ASSISTED CHEMICAL SENSORS BASED ON PORPHYRINS COATED ZnO a a a a Corrado DI NATALE , Gabriele MAGNA, Francesco MOSCIANO, Eugenio MARTINELLI, Roberto b PAOLESSE a b University of Rome Tor Vergata, Department of Electronic Engineering, Rome, 00133, Italy. University of Rome Tor Vergata, Department of Chemical Science and Technologies, Rome, 00133, Italy [email protected] Hybrid materials formed by a layer of dye molecules over a wide-band gap semiconductor, are widely studied mainly for optoelectronics and photovoltaic applications. However, besides the conversion of visible photons into an excess of carriers, the combination of organic-inorganic materials offers other additional properties such as chemical sensing. ZnO and porphyrins are a good example of the combination of a metal oxide semiconductor and a dye molecule. We have investigated different routes for the preparation of the hybrid materials. To this regard we found that porphyrin-ZnO materials can be obtained from a one-pot growth method where porphryins are directly added to the precursor solution of the hydrothermal growth of ZnO. Porphyrins interfere with the ZnO growth altering the morphology of the materials. Interestingly, the sensing properties of the one-pot material are different from those of the material prepared growing the porphyrin onto the yet formed ZnO nanorods1 and they offer a further degree of freedom for the design of sensor arrays extending the properties and the capabilities of porphyrins based sensor array in particular for medical diagnosis, the quality and control of the foods and the detection of compounds signalling harmful or dangerous substances. The enhanced catalytic properties of porphyrins coated ZnO were studied in the past as electrochemical sensors for the detection of compounds in solution. Recenty we found that the exposure to visible light enhances both the sensitivity and the selectivity with respect to the detection of L-cysteine in water where the porphyrin coated ZnO is used as the work electrode of a voltammetric setup.2 The sensing properties of layers of porphyrins onto ZnO nanostructures offer a further degree of freedom for the design of sensor arrays extending the properties and the capabilities of porphyrins based sensor array in particular for medical diagnosis, the quality and control of foods and the detection of compounds signalling harmful or dangerous substances. ______________ References: 1. Magna, G.; Sivalingam, Y.; Martinelli, E.; Pomarico, G.; Basoli, F.; Paolesse, R.; Di Natale, C. Anal Chim Acta 2014, 810, 6-93. 2. Sivalingam, Y.; Pudi, R.; Lvova, L.; Pomarico, G.; Basoli, F.; Catini, A.; Legin A.; Paolesse, R.; Di Natale, C. Sens Actuators B 2015, 209, 613-621. 31 OC20 EXPANDED CORROLES BY β-FUSED AROMATIC RINGS Beatrice Berionni BERNA, Sara NARDIS, Federica MANDOJ, Roberto PAOLESSE Department of Chemical Science and Technology, University of Rome “Tor Vergata” [email protected] Among the different corrole functionalizations, we focused our interest on the fusion of aromatic substituents at the macrocyclic β-positions. It is well-known that an expansion of porphyrinoids core aromaticity results in a remarkable modification of the optical features of the chromophore, making them particularly interesting for potential applications in fields ranging from PDT to chemical sensors, and especially as sensitizer in dye-sensitized solar cells (DSSC)[1]. Taking into account such a consideration, we investigated novel and straightforward synthetic approaches for the preparation of expanded corroles using pyrazino units as linking bridges. [2-(NH2)-3-(NO2)-triarylcorrolato]Cu has been chosen as starting material[2]: the reduction of the nitro group to amino and the further condensation have been carried out by an one-pot procedure, using different diones. The condensed compounds exhibited some intriguing spectroscopic features; their application is currently under investigation. X-ray structure of Cu-2,3-[9',10'-phenanthrene(b)-pirazino]-5,10,15-tris(4-tert-butylphenyl)corrolato ____________ References: 1. H. Imahori, K. Kurotobi, M. G. Walter, A. B. Rudine, and C. C. Wamser, in “Handbook of Porphyrin Science”, K. M. Kadish, K. M. Smith, and R. Guilard, eds., World Scientific, Singapore, 2012, Vol. 18, Chapter 80, pages 58-123. 2. Stefanelli, M.; Mandoj, F.; Mastroianni, M.; Nardis, S.; Mohite, P.; Fronczek, F. R.; Smith, K. M.; Kadish, K. M.; Xiao, X.; Ou, Z.; Chen, P.; Paolesse, R. Inorg. Chem. 2011, 50, 8281–8292 32 OC21 ASSESSMENT IN ELECTRONIC INTERACTIONS IN MONO-OXIDATED TETRAFERROCENYLPORPHYRINS a a b a Pierluca GALLONI, Andrea VECCHI, Andrea MARRANI, Daniel O. CICERO, Valeria CONTE, a c d Barbara FLORIS, Victor NEMYKIN, Alessandro BAGNO a a Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata, Via della Ricerca b Scientifica, 00133, Roma, Italia. Dipartimento di Chimica, Università degli Studi di Roma “La Sapienza”, c P. Aldo Moro 5, 00185 Roma, Italia. Department of Chemistry & Biochemistry, University of Minnesotad Duluth, Duluth, Minnesota 55812, USA. Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova, Italia. We recently characterized metal free and metallated 5,10,15,20-tetraferrocenylporphyrin (H2TFcP and MTFcP), which showed reversible electrochemical behavior and mixed-valence states.1,2 Moreover interesting results were obtained using this macrocycle on gold surface.3 The easy accessibility to the monocationic porphyrin (TFcP+) is of particular interest because of the long-range electronic communication among ferrocenyl units, which gives rise to an intense inter-valence charge transfer (IVCT) band in the NIR region of the spectrum. This peculiar absorption can be used in the construction of redox-driven optical sensors and switches in the NIR. Both mono-oxidized TFcPs free-base and zinc complex were prepared in good yields and characterized by XPS and NMR spectroscopy. Experimental data as well as theoretical calculations support the idea that the oxidation process involves a hydrogen atom abstraction, and the effects are very different between metallated and free base derivatives. ______________ References: 1. Nemykin, V. N.; Rohde, G. T.; Barrett, C. D.; Hadt, R. G.; Bizzarri, C.; Galloni, P.; Floris, B.; Nowik, I.; Herber, R. H.; Marrani, A. G.; Zanoni, R.; Loim, N. M. J. Am. Chem. Soc. 2009, 131, 14969. 2. Rhode, G. T.; Sabin, J. R.; Barret, C. D.; Nemykin, V. N. New J. Chem. 2011, 35, 1440. 3. Vecchi, A.; Gatto, E.; Floris, B.; Conte, V.; Venanzi, M.; Nemykin, V. N.; Galloni, P. Chem. Commun. 2012, 48, 5145. 33 OC22 PORPHYRINS AND ANTIMICROBIAL PEPTIDES FOR PHOTODYNAMIC THERAPY OF CANCER 1 2 Francesca MORET , Marina GOBBO , Elena REDDI 1 1 University of Padova, Department of Biology, Via U. Bassi 58/B, 35121, Padova, 0498276335. University of Padova, Department of Chemical Sciences, Via Marzolo 1, 35121, Padova, 0498275741 2 [email protected] Some antimicrobial peptides (AMPs) have the ability to penetrate and kill not only pathogenic microorganisms but also cancer cells while are less active toward normal eukaryotic cells 1. Thus, we investigated the potential of three AMPs, namely apidaecin 1b (Api), magainin 2 (Mag) and buforin II (Buf), as carriers of photosensitizers for cancer photodynamic therapy (PDT) by using the hydrophobic 5-(4-carboxyphenyl)-10,15,20-triphenylporphyrin (cTPP) as model porphyrin conjugated to the N-terminus of the peptides. The delivery efficiency and photo-toxicity of the conjugates (T-Buf, T-Mag, T-Api) were compared to that of the un-conjugated cTPP in A549 lung cancer cells in vitro. Flow cytometry experiments showed that the kinetic of cellular uptake of the conjugates was very rapid and, after 5 h of incubation, the uptake of T-Mag, T-Buf and TApi was respectively 32, 8.5 and 6.5-fold higher than that of cTPP. In vitro PDT experiments showed that, after cells irradiation with 1.5 J cm-2 of blue light, comparable photo-killing was measured with AMP-porphyrin conjugates at nanomolar concentrations instead of micromolar concentrations required for the un-conjugated cTPP. Investigations on the mechanisms by which the cells die after PDT treatments showed that the exclusive mechanism of cell death was necrosis. Confocal microscopy revealed that the intracellular localization of the porphyrin was changed by using the AMPs as delivery systems, since while the unconjugated cTPP accumulated in Golgi apparatus and in endoplasmic reticulum, all the conjugates showed a predominantly punctuated and cytoplasmic localization, without co-localizing with mitochondria or lysosomes. Serum proteins interacted with cTPP conjugated to Buf and Api and slightly interfered with cellular uptake of these conjugates but not with that of Mag. The mechanisms of cellular uptake is based on electrostatic interactions of the conjugates with sialic acid and gangliosides rich domains, as lipid rafts of the plasma membrane followed by internalization via non-caveolar dynamin-dependent endocytosis. Our study demonstrated that the three AMPs investigated, Mag in particular, have the ability to carry a hydrophobic cargo inside cancer cells and may therefore represent useful carriers of anticancer drugs especially those with poor capacity to penetrate inside the target cells. ______________ References: 1. Gaspar, D.; Veiga, A.S.; Castanho M.A.R.B. Front. Microbiol., 2013, 4, 294-310. 34 OC23 PHOTODYNAMIC THERAPY: GOOD NEWS FROM COMPUTATIONAL APPROACHES Nino RUSSO, Marta E. ALBERTO, Gloria MAZZONE, Bruna C. DE SIMONE, Tiziana MARINO, Emilia SICILIA Dipartimento di Chimica e Tecnologie Chimiche, Università della Calabria, I-87036 Rende, Italy. [email protected] Recent developments in design new photosensitizers active in photodynamic therapy starting from computed electronic and geometrical properties by using density functional theory should be presented. In particular, we will show as the main photophysical properties that a drug active in photodynamic therapy must possess (absorption wavelengths shifted in the Near Infrared Region, singlet-triplet energy gaps and spin-orbit matrix elements large enough to allow an efficient intersystem spin crossing) can be reliably predicted by modern density functional methods. The studied systems include a series of free porphyrin-like and metallated porphyrinlike systems able to activate singlet O2 excited state (Type II reactions)1. ______________ References: 1 G. Mazzone, N. Russo, E. Sicilia, Can. J. Chem. 91(2013)902–906; M. E. Alberto, C. Iuga, A. D. Quartarolo, and N, Russo, J. Chem. Inf. Model., 53 (2013) 2334−2340; M. E. Alberto, T. Marino, A. D. Quartarolo, N. Russo, Phys.Chem. Chem. Phys., 15 (2013)16167; A. D. Quartarolo, D. Pérusse, F. Dumoulin, N. Russo, E. Sicilia, J. Porphyrins Phthalocyanines, 17(2013) 980–988; Marta E. Alberto, Bruna C. De Simone, Gloria Mazzone, Angelo D. Quartarolo, and Nino Russo, J. Chem. Theory Comput, 10 (2014) 4006−4013; M. E. Alberto, G. Mazzone, A. D. Quartarolo, F. Fortes Ramos Sousa, E. Sicilia, N. Russo, Journal of Computational Chemistry 35 (2014) 2107–2113. 35 OC24 SYNTHESIS AND CHARACTERIZATION OF NEW FERROCENE, PORPHYRIN AND C60 TRIADS, CONNECTED BY TRIPLE BONDS Pietro TAGLIATESTA Dipartimento di Scienze e Tecnologie Chimiche. Universita' di Roma-Tor Vergata [email protected] Electron and energy transfer are important topics in the chemistry of biological and artificial systems and have been extensively studied over the past twenty years.1 Photosynthesis in plants and bacteria is based on chemical reactions induced by the electron-transfer phenomena between natural tetrapyrrolic pigments, such as chlorophyls and related molecules, and quinones, both embedded in a protein matrix.2 The entire process is not yet well understood and more information can be obtained by the use of synthetic models.3 During our studies on the possibility to use molecular wires to connect to the beta-pyrrole positions of the porphyrins one C60 unit through the assembling of one or more triple bond, we found that it was very convenient and important to have a large delocalization of the π electrons between the donor and the acceptor moieties of the models.4 Recently we have reported the beta functionalization of H2TPP by one or two ferrocene molecules in the 2 and 3 positions through ethynyl or phenylethynyl groups, applying a new approach of the Sonogashira reaction, never used before in the case of porphyrins.5 In this communication we report on the synthesis of four new triads, useful as a model for investigating the electron-transfer processes, connecting ferrocene and C60 to the 2,12 pyrrole positions of H2TPP through ethynyl bonds. In Figures 1 and 2 the structures of the free bases and their zinc complexes are reported. We will also show the fluorescence spectra of the triads compared to the related reference compounds. Ph N Ph N N CH3 Fe N M N Ph Ph Figure 2: M=2H, M=Zn Figure 1: M= 2H, M=Zn ______________ References: 1. (a) Marcus, R. A. J. Phys. Chem., 1968, 72, 891; (b) Gust, D; Moore, T. A.; Moore A. L., Acc. Chem. Res., 2009, 42, 1890. 2. Gregory, R. L. Biochemistry of photosynthesis, New York: Wiley-Interscience, New York, 1971. 3. (a) Wurfel, P., Physics of Solar Cells in Basic Principles to Advanced Concepts, 2nd edn, Wiley-VCH Verlag GmbH, Weinheim, 2009; (b) Wenham, S. R.; Green, M. A.; Watt M. E.; Corkish, R. Applied Photovoltaics, 2nd edn, Earthscan Publications Ltd., London, 2007; (c) Green, M. T. Generation Photovoltaics in Advanced Solar Energy Conversion, Springer Series in Photonics, Springer, Heidelberg, 2005. 4. Lembo, A.; Tagliatesta, P.; Guldi, D. M. J. Phys. Chem. A, 2006, 110, 11424; (b) Lembo, A.; Tagliatesta, P.; Guldi, D. M.; Wielopolski, M.; Nuccetelli M. J. Phys. Chem. A, 2009, 113, 1779; (c) Guldi, D. M.; Lembo, A.; Tagliatesta, P. ECS Transactions, 2007, 2, 3. 5. Tagliatesta, P.; Lembo, A.; Leoni, A. New J. Chem., 2013, 37, 3416 36 OC25 RUTHENIUM PORPHYRIN COMPLEXES AS EFFICIENT CATALYSTS OF BIOLOGICAL AZA-DERIVATIVES Emma GALLO, Paolo ZARDI, Daniela Maria CARMINATI, Daniela INTRIERI Chemistry Department of Milan University; Via Golgi 19, 20133 Milan (Italy) [email protected] The direct amination of hydrocarbons is a reaction of great synthetic interest because of the biological and pharmaceutical relevance of aza-derivatives. For several years we have studied the formation of C-N bonds using aryl azides (ArN3)1 as nitrogen sources and metal porphyrins as catalysts. Amongst all the metal porphyrin catalysts,2 ruthenium porphyrins show a good catalytic activity in both inter- and intramolecular transfer of a nitrene functionality “ArN” from aryl azides into C-H bonds. The sustainability of the synthetic procedure is related to the high atom efficiency of azides which insert the aza-fragment into the organic skeleton with the formation of benign molecular nitrogen as the only stoichiometric side product. Herein we report the use Ar NH [Ru] of ruthenium porphyrins CH2 CH2 COOMe COOMe Ph Ph +ArN3 to promote the synthesis N2 -amino esters of biologically interesting a) O compounds such us: a) αAr O Ar NH O [Ru] N COMe CH2 and β-amino esters3 by CH COMe Ph +ArN3 Ph Ph amination of benzylic OMe N2 OMe OMe -amino esters -lactames C−H bonds. The methodology was also R3 R4 R3 2 3 3 4 R R effective in synthesizing R C3-N R2 [Ru] 2 R 4 NH R two derivatives of methyl N b) cleavage +ArN3 R1 R1 L-3-phenyllactate in 1 N2 R R order to convert one of 2,5-dihydro-1H-benzo[b]azepines R them into the Ar Ar R R corresponding β-lactam; [Ru] 3 + c) b) benzoazepines4 by R' -N2 2 N N3 R' aza-[3,3]-Claisen H indoles rearrangement of N-aryl2-vinylaziridines derived from the reaction of aryl azides with diene substrates; c) C3functionalized indoles5 by an intermolecular reaction of aryl azides with alkynes. Several derivatives were synthesized with yields up to 95%, high regioselectivity, and without requiring the time consuming prefunctionalisation of reagents and the addition of oxidants and/or additives. ______________ References: 1. a) S. Cenini, E. Gallo, A. Caselli, F. Ragaini, S. Fantauzzi, C. Piangiolino Coord. Chem. Rev. 2006, 250, 1234; b) D. Intrieri, P. Zardi, A. Caselli, E. Gallo Chem. Commun., 2014, 50, 11440. 2. S. Fantauzzi, A. Caselli, E. Gallo Dalton Trans, 2009, 5434. 3. P. Zardi, A. Caselli, P. Macchi, F. Ferretti, E. Gallo Organometallics 2014, 33, 2210. 4. a) C. Piangiolino, E. Gallo, A. Caselli, S. Fantauzzi, F. Ragaini S. Cenini Eur. J. Org. Chem. 2007, 743; b) S. Fantauzzi, E. Gallo, A. Caselli, C. Piangiolino, F. Ragaini, N. Re, S. Cenini Chem. Eur. J. 2009, 15, 1241. 5. P. Zardi, A. Savoldelli, D. M. Carminati, A. Caselli, F. Ragaini, E. Gallo ACS Catal. 2014, 4, 3820. 37 OC26 THE FASCINATING WORLD OF -PYRROLIC SUBSTITUTED Zn(II)-TETRAARYLPORPHYRINATES FOR DYE-SENSITIZED SOLAR CELLS a b a Gabriele DI CARLO, Alessio ORBELLI BIROLI, Giulia MAGNANO, Maddalena PIZZOTTI, a Francesca TESSORE a a b Dipartimento di Chimica, Università degli Studi di Milano, via C. Golgi 19, 20133 Milano; Istituto di Scienze e Tecnologie Molecolari del CNR (CNR-ISTM), via C. Golgi 19, 20133 Milano. [email protected] In the last few years porphyrins attracted considerable attention as sensitizers in DSSCs, because of their strong electronic absorption bands up to the NIR region and their long-lived * singlet excited states.1 In particular, mesodisubstituted push-pull Zn(II)-porphyrinates were deeply investigated thanks to their directional electronic charge transfer process,2 and a well engineered derivative reached photovoltaic performances comparable to those of the benchmark Ru(II) dye N719.3 However, meso-disubstituted Zn(II)-porphyrinates suffer of time consuming and low yield syntheses. -pyrrolic Zn(II)-tetraarylporphyrinates are much more convenient because the preparation of the core requires a one pot reaction and the functionalization of the porphyrin ring is readily achievable by selective mono or di-bromination reaction under mild conditions.4 The sterically hindered architecture of -pyrrolic derivatives lowers -stacking aggregation phenomena and the enhancement of solubility in most common organic solvents allows to obtain very pure compounds.5 Although the HOMO-LUMO energy gap of -pyrrolic systems is higher in comparison to that of the meso analogues, the -mono or disubstituted Zn(II)-tetraarylporphyrinates show comparable or even better photovoltaic performances as dyes in DSSCs, because they offer a superior screening effect against detrimental charge recombination processes.6 Moreover, the replacement in the side aryl rings of tert-butyl groups with octyloxy chains in ortho position allows an almost 80% increase of the power conversion efficiency, making this class of green dyes particularly attractive for technological applications.7 ______________ References: 1. Urbani, M.; Grätzel, M.; Nazeeruddin, M. K.; Torres, T. Chem. Rev., 2014, 114, 12330. 2. De Angelis, F.; Fantacci, S.; Sgamellotti, A.; Pizzotti, M.; Tessore, F.; Orbelli Biroli, A. Chem. Phys. Lett., 2007, 447, 10. 3. Mathew, S.; Yella, A.; Gao, P.; Humphry-Baker, R.; Curchod, B. F. E.; Ashari-Astani, N.; Tavernelli, I.; Rothlisberger, U.; Nazeeruddin, M. K.; Grätzel, M. Nat. Chem., 2014, 6, 242. 4. Di Carlo, G.; Orbelli Biroli, A.; Tessore, F.; Rizzato, S.; Forni, A.; Magnano, G.; Pizzotti, M. J. Org. Chem., 2015, DOI: 10.1021/acs.joc.5b00367. 5. a) Di Carlo, G. ; Orbelli Biroli, A. ; Pizzotti, M. ; Tessore, F. ; Trifiletti, V. ; Ruffo, R. ; Abbotto, A. ; Amat, A. ; De Angelis, F. ; Mussini, P. R. Chem. Eur. J., 2013, 19, 10723. b) Di Carlo, G. ; Orbelli Biroli, A. ; Tessore, F. ; Pizzotti, M. ; Mussini, P. R. ; Amat, A. ; De Angelis, F. ; Abbotto, A. ; Trifiletti, V. ; Ruffo, R. J. Phys. Chem. C, 2014, 118, 7307. 6. Di Carlo, G. ; Caramori, S. ; Trifiletti, V. ; Giannuzzi, R. ; De Marco, L. ; Pizzotti, M. ; Orbelli Biroli, A. ; Tessore, F. ; Argazzi, R. ; Bignozzi, C. A. ACS Appl. Mater. Interfaces, 2014, 18, 15841. 7. Orbelli Biroli, A. ; Tessore, F. ; Vece, V. ; Di Carlo, G. ; Mussini, P. R. ; Trifiletti, V. ; De Marco, L. ; Giannuzzi, R. ; Manca, M. ; Pizzotti, M. J. Mater. Chem. A, 2015, 3, 2954. 38 OC27 PHOTOSYNTHETIC BACTERIA PLAY HEAVY METALS Massimo TROTTA and Angela AGOSTIANO Istituto per i Processi Chimico Fisici – Consiglio Nazionale delle Ricerche Università degli Studi di Bari [email protected] Purple photosynthetic bacteria as tool for remediation of environmental sites polluted by heavy metals have been explored in the last 10 years. In selecting these microorganisms for bioremediation one of the most stringent parameter, beside lack of pathogenicity, is the energy source required for their growth and for driving their metabolism: photosynthetic microorganisms rely on solar light, a cheap and largely available energy supplement, which makes them very appealing. Among photosynthetic microorganisms, purple photosynthetic bacteria represent a small group, well characterized by the ability of using different energy sources, which allows them to switch metabolism if the environmental condition changes. Photosynthetic metabolism, which is the sturdiest one that the bacterium can employ to survive to the nastiest environment, is based on a molecular machinery that relies on a careful spatial organization of bacteriochlorophylls, the well-known photosynthetic reaction center. A story of how such bacterium copes with heavy metals under photosynthetic conditions will be presented, along with successful and unsuccessful attempts to employ them as bioremediators. ______________ References: 1. L. Giotta, F. Italiano, F. Milano, A. Agostiano and M. Trotta (2006) Chemosphere 62, 1490-1499. 2. A. Buccolieri, F. Italiano, A. Dell’atti, G. Buccolieri, L. Giotta, A. Agostiano, F. Milano and M. Trotta (2006) Annali di Chimica 96, 195-203 3. M. Trotta e L. Fanizzi (2006) L’Ambiente XII(2), 14-17. 4. F. Pisani, F. Italiano, F. De Leo, R. Gallerani, S. Rinalducci, L. Zolla, A. Agostiano, L. R. Ceci and M. Trotta Journal of Applied Microbiology (2009) 106 338–349. 5. F. Italiano, A. Buccolieri, L. Giotta, A. Agostiano, L. Valli, F. Milano and M. Trotta. International Biodeterioration & Biodegradation, (2009) 63(7), 948-957 6. Losurdo L., Italiano F., Trotta M., Gallerani R. Ceci L. R., De Leo F. Journal of Basic Microbiology, (2010) 50, 1–4. 7. E. Asztalos, F. Italiano, F. Milano, P. Maróti, and M. Trotta (2010) Photochem. and Photobiol. Sci. 9 12181223. 8. L. Giotta, D. Mastrogiacomo, F. Italiano, F. Milano, A. Agostiano, K. Nagy, L. Valli, and M. Trotta (2011) Langmuir 27 (7), 3762–73. 9. F. Italiano, GM D’Amici, S Rinalducci, F De Leo, L Zolla, R Gallerani, M Trotta and LR. Ceci (2011) Res. Microbiology, 162 (5) 520-7. 10. E. Asztalos, G. Sipka, M. Kis, M. Trotta, P. Maróti (2012) Phototosynthesis Research. 112(2), 129-140. 11. F. Italiano, S. Rinalducci, A. Agostiano, Lello Zolla, F. De Leo, L.R. Ceci and M. Trotta. (2012) BioMetals Volume 25(5), 939-949, DOI: 10.1007/s10534-012-9561-7. 12. Benny D. Belviso, Francesca Italiano, Rocco Caliandro, Benedetta Carrozzini, Alessandra Costanza, Massimo Trotta. (2013) BioMetals 26(5): 693-703. DOI: 10.1007/s10534-013-9641-3. 13. Calvano C.D., F. Italiano, L. Catucci, A. Agostiano, Tommaso R.I. Cataldi, F. Palmisano, M. Trotta (2014) BioMetals 27 65–73. 14. Volpicella, M.; Costanza, A.; Palumbo, O.; Claudia, L.; Italiano, F.; Placido, A.; Picardi, E.; Carella, M.; Trotta, M.; Ceci, L. (2014) FEMS Microbiology Ecology 88(2):345-57 DOI: 10.1111/1574-6941.12303. 39 OC28 PORPHYRAZINES IN COMBINED PHOTO- AND CHEMIOANTICANCER THERAPIES: RECENT RESULTS IN WATER SOLUTION a a a b Maria Pia DONZELLO , Elisa VIOLA , Fabiola SCISCIONE , Giuseppe TRIGIANTE , Claudio a ERCOLANI a b Università La Sapienza, P.le A. Moro 5, 00185 Roma, Italy, Centre for Cutaneous Research, Queen Mary University of London, 4 Newark Street London E1 2AT, U.K. [email protected] During the last ten years, our group has been directing some of its efforts to synthesize novel water-soluble porphyrazine species, multicharged [1] and neutral [2], in view of their promising potentialities as photo/chemioactive drugs for biomedical applications, and a wide general characterization of these materials has been carried out in the solid state and in solution. Among the studied species, the mononuclear octacationic Zn(II) (Figure 1-A) and the binuclear hexacationic Zn(II)/Pt(II) related species, this latter carrying one exocyclic cis-platin-like functionality (Figure 1-B), proved in DMF solution to be excellent photosensitisers for the generation of singlet oxygen, the main citotoxic agent in photodynamic therapy (PDT). It has been recently shown that both mentioned species when dissolved in water solution: (a) bind to a telomeric G-quadruplex structure, favoring its parallel conformation [3a], (b) interact non covalently with a synthetic double strand as model for B-DNA.[3c], (c) show a high photoactivity for the generation of singlet oxygen. Tests in vitro conducted using the melanoma C8161 tumor cells indicate a strong anticancer action of both the octacationic and the hexacationic compounds (Figure 1), with an increased cytotoxic activity toward cancerous cells for the hexacation presumably due to the presence of the external cis-platin-like functionality. N + +N N + H3C N N N N + N N+ + N H3C N N N N + N N N N CH3 + CH3 N N H3C N M N N N N N H3C CH3 N N N N N N N N + + CH3 N M N H3C +N H3C N N N N + CH3 N N + N H3C CH3 N + N CH3 N N Pt Cl Cl A B Figure 1. Schematic formulations of the ZnII octacation (A) and the ZnII/PtII hexacation (B) (both neutralized by I- ions). _____________ References: 1. Donzello, M. P.; Viola, E.; Mannina, L.; Barteri, M.; Fu, Z.; Ercolani, C. J. Porphyrins Phthalocyanines, 2011, 15, 984 and refs.therein. 2. Donzello, M. P. et al. submitted to E. J. Inorg. Chem. 3. a) Manet, I.; Manoli, F.; Donzello, M. P.; Ercolani, C.; Vittori, D.; Cellai, L.; Masi, A.; Monti, S. Inorg. Chem. 2011, 50, 7403; b) Manet, I; Manoli, F.; Donzello, M. P.; Viola, E.; Masi, A.; Andreano, G.; Ricciardi, G.; Rosa, A.; Cellai, L.; Ercolani, C.; Monti, S. Inorg. Chem., 2013, 52, 321. 40 OC29 FLUORESCENCE ENHANCEMENT IN AN UNSYMMETRICALLYSUBSTITUTED COPPER PHTHALOCYANINE a b a a Nicola ANGELINI , Daniela CASCHERA ,Sara NOTARANTONIO , Anna Maria PAOLETTI , Giovanna a a a PENNESI , Gentilina ROSSI , Gloria ZANOTTI a b CNR – ISM, Via Salaria km 29.500, Monterotondo Scalo (Rm), 00015 – Italy. CNR - ISMN, Via Salaria km 29.500, Monterotondo Scalo (Rm), 00015 - Italy [email protected] Amongst all the properties that phthalocyanines possess, their photochemical behavior is extremely peculiar and useful for an extremely wide range of applications such as photodynamic therapy and photovoltaics. During the last years we have synthesized and tested a considerable number of new macrocyclic-based dyes for Dye-Sensitized Solar Cells bearing zinc in the central cavity. We have recently chosen to change the central ion to investigate the potentialities of other metals and we have focused our attention on copper derivatives because of their extremely high stability, fundamental for a long lifetime of the solar cell, and color intensity which is needed in order to maximize the light harvesting properties of the device. Even if Cu(II) is a well known fluorescence quencher because of its capability to induce an intersystem crossing in the molecular systems that interact with it, a consistent number of copper chlorines, porphyrins and corroles have been reported as photosensitizers1,2 showing interesting results in terms of efficiencies. Our contribution will deal with the fluorescence properties of some copper phthalocyanines with increasing degree of substitution synthesized as potential photochemical sensitizers, analyzed both with steady-state and time-resolved measurements. The results will be compared with those of the corresponding free-base and, when possible, zinc derivatives and in one specific case the evidence of a consistent fluorescence in a copper derivative has been highlighted. N -C(CH3 )3 N N N -COOH N M N R= N N COOH COOH R M = Cu, Zn, H2 ______________ References: 1. Kay, A.; Grätzel, M. J. Phys. Chem. 1993, 97, 6272-6277 2. Calogero, G.; Citro, I.; Crupi, C.; Di Marco, G. Spectrochim. Acta A: Molecular and Biomolecular Spectroscopy 2014, 132, 477–484 41 OC30 GENETRATING FUNCTION APPROACH TO THE CALCULATION OF SPECTRAL BAND SHAPES Raffaele BORRELLI, Amedeo CAPOBIANCO, Amalia VELARDO, Andrea PELUSO di Torino, I-10095 Grugliasco (TO). [email protected] Figure 1. Lowest energy tautomer of free-base chlorin. The calculation and the analysis of absorption and emission band shapes of molecules from first principles is a fundamental problem of modern physical chemistry, with a widespread range of applications, extending from the understanding of the basic aspects of light-matter interaction to the development of organic dyes with tailored spectroscopic properties. Herein, we present a generating function approach to the calculation of spectral band shapes including Duschinsky and Herzberg−Teller effects,1,2 together with an application to the computation of the free-base chlorin Q absorption bands, using molecular geometries and normal vibrations obtained by density functional theory computations.3 The results clearly show that non-Condon effects can significantly affect the relative intensities of the weakest Qy and, to a lesser extent, Qx bands. The proposed approach is extremely powerful and can be used in the cases where the molecular size makes the direct calculation of Franck−Condon integrals by recurrence formulas prohibitive. ______________ References: 1. Kubo, R.; Toyozawa, Y. Prog. Theor. Phys. 1955, 13, 160−182 2. Borrelli, R.; Peluso, A. Phys. Chem. Chem. Phys. 2011, 13, 442 3. Borrelli, R.; Capobianco A.; Peluso, A. J. Phys. Chem. A 2012, 116, 9934−9940. 42 OC31 THE PORPHYRIN IN THE TRIPLET STATE AS A POTENTIAL SPIN LABEL FOR NANOMETER DISTANCE MEASUREMENTS BY EPR SPECTROSCOPY Marilena DI VALENTIN, Marco ALBERTINI, Enrico ZURLO, Maria Giulia DAL FARRA, Laura ORIAN, Antonino POLIMENO, Marina GOBBO and Donatella CARBONERA Department of Chemical Sciences, University of Padova, Italy [email protected] Pulsed electron-electron double resonance (PELDOR/DEER) is a pulsed EPR spectroscopy that measures, via the dipolar electron-electron coupling between two paramagnetic species, distances in the nanometer range (currently 15-80 Å) with high precision and reliability. This technique is complementary to the methods of X-ray crystallography, NMR and FRET and it is becoming a powerful method for structural determination of biomolecules. Conventionally, PELDOR/DEER measurements are performed between two nitroxide spin labels which have been attached to biological molecules either by site-directed spin labelling or by chemical modification. In recent years, numerous efforts have been devoted to the development of alternative spin labels, featuring more attractive properties than conventional nitroxide radicals, despite the widespread employment of the latter for distance measurements. This work demonstrates the feasibility of distance measurements between a porphyrin in the photoexcited triplet state and a nitroxide spin label chemically incorporated in a small helical peptide [1]. We have constructed a porphyrin-based molecular ruler where the nitroxide spin label is attached to different positions along the peptide sequence in the range from 15 to 60 Å. We have demonstrated that high sensitivity, and consequently high accuracy, is acquired in the distance measurements due the spectroscopic properties of the porphyrin molecule in the photoexcited triplet state. The methodology has been extended from the peptide model system to paradigmatic proteins, where the porphyrin derivative probe is endogenously bound, in order to prove that this labelling approach has a high potential for measuring nanometer distances in more complex biological systems. ______________ Reference: 1. Di Valentin, M.; Albertini, M.; Zurlo, E.; Gobbo,M.; Carbonera, D.; Journal of the American Chemical Society Communication, 2014, 136, 6582. 43 OC32 METAL-OXO PORPHYRIN COMPLEXES: CATALYTIC INTERMEDIATES IN THE GAS PHASE Francesco LANUCARA, Maria Elisa CRESTONI, Simonetta FORNARINI Dipartimento di Chimica e Tecnologie del Farmaco, Università di Roma “La Sapienza”, P.le A. Moro 5, Roma, I-00185, Italy [email protected] High-valent transition metal-oxo complexes are active intermediates involved in many metal catalyzed biological and industrial oxidation processes. High-valent iron porphyrin complexes, namely the iron(IV)-oxo porphyrin cation radical oxidant or Compound I, are frequently invoked as the competent catalysts of monooxygenase heme enzymes. Biomimetic studies in the gas phase may allow to reveal the inherent reactivity of these active species by disclosing the specific contributions of solvent and environmental effects. The preparation of functional models of the Compound I, namely [(TPFPP)·+FeIV=O]+ and [(TPFPP)MnV=O]+ (TPFPP = meso-tetrakis (pentafluorophenyl)porphyrinato dianion) is achieved by controlled oxidation of [MeIII(TPFPP)]Cl (Me= Fe, Mn) either in solution, by using different oxidants, including H2O2 and iodosyl benzene, or in the gas-phase, using ozone.1-3 Electrospray ionization (ESI) in combination with Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry is used to explore (under carefully controlled experimental conditions) the underlying factors that govern the reaction routes in the catalytic activity of these high-valent oxo-metal intermediates. Patterns of ionic products, involving: (i) addition; (ii) oxygen atom transfer; (iii) formal hydride transfer; (iv) electron transfer, and thermal rate constants were determined and found to depend on the nature of the metal, the axial ligands trans to the oxo-function, and the specific substrate. The selected substrates include (aromatic) hydrocarbons, olefins, thiols, amines, and phosphites.4-6 [(TPFPP)MeIII]Cl + oxidant ESI [(TPFPP)MeIV=O]+ solution Ft-icr Products gas-phase The kinetic acidity towards selected reference bases of putative hydroxo intermediates, playing a role in catalytic oxidations, [(TPFPP)FeIVOH]+ and [(TPFPP)MnIVOH]+, has been examined as well. ______________ References: 1. Crestoni, M. E.; Fornarini, S. Inorg. Chem., 2005, 44, 5379. 2. Crestoni, M. E.; Fornarini, S. Inorg. Chem., 2007, 46, 9018. 3. Chiavarino, B.; Cipollini, R.; Crestoni, M. E.; Fornarini, S.; Lanucara, F. Lapi, A. J. Am. Chem. Soc., 2008, 130, 3208. 4. Crestoni, M. E.; Fornarini, S.; Lanucara, F. Chem. Eur. J. 2009, 15, 7863.(5. Lanucara, F.; Crestoni, M. E. Chem. Eur. J., 2011, 17, 12092. 6. Sainna, M. A.; Kumar, S.; Kunar, D.; Fornarini, S.; Crestoni, M. E.; de Visser, S. P. Chem. Science, 2015, 6, 1516. 44 OC33 THE SPECIAL PAIR OF CHLOROPHYLLS IN PHOTOSYNTHESIS. INSIGHTS BY COMPUTER SIMULATIONS Daniele BOVI, Daniele NARZI, and Leonardo GUIDONI Dipartimento di Scienze Fisiche e Chimiche, Università degli studi dell’Aquila [email protected] Chorophylls and bacterio-chlorophylls molecules are at the basis of the photosynthetic energy conversion mechanisms in algae, green plants and many bacteria. In this respect, they serve to different roles: as light-capturing chromophores and excitation transporters in light harvesting antennas, and as primary electron donors in the photo-induced charge separation occurring in reaction centres. In the oxygen-evolving reaction centre Photosystem II, the photo-produced electrons leave a special pair of chlorophylls (named PD1 and PD2) that becomes cationic. This oxidizing pair (PD1PD2)+ in turn, triggers a cascade of oxidative events, eventually leading to water splitting and oxygen evolution. Two different oxidative pathways start from the special pair: an active channel, which is gated by PD1 and leads to water oxidation, and an alternative channel, likely starting from PD2, that is supposed to be related to photo-protective mechanisms [1]. Ab initio Molecular Dynamics simulations using a Quantum Mechanics / Molecular Mechanics approaches and based on the high-resolution crystal structure of Photosystem II [2] have been recently carried out by us to describe the catalytic mechanisms of Photosystem II complex along the water-splitting cycle [3-4]. In the present work, using these techniques we have investigated the electronic structure and the dynamics of the special pair of chlorophylls in both its oxidised (PD1PD2)+ and reduced (PD1PD2) states. In agreement with previously reported static calculations [4] we have found that the symmetry between the two chlorophylls is broken, the positive charge being preferentially located on PD1. This is consistent with the fact that PD1 chlorophyll is the gate for the active channel for water oxidation. The simulation reveals that large charge fluctuations occur along dynamics, temporarily inverting the charge preference for the two branches. A vibrational analysis of the computational data has also pinpointed that such charge fluctuations are strongly coupled to specific modes of the special pair with frequency below 500 cm-1. Webpage: http://bio.phys.uniroma1.it ______________ References: 1. Styring S.; Sjöholm J.; Mamedov F. BBA-Bioenergetics, 2012, 1817, 16. 2. Umena, Y.; Kawakami, K.; Shen, J.-R.; Kamiya, N. Nature, 2011,473, 7345. 3. Bovi, D.; Narzi.D.; Guidoni L. Angewandte Chemie, 2013, 125, 11960. 4. Narzi, D.; Bovi, D.; Guidoni L. P.N.A.S., 2014, 111, 8723. 5. Saito, K. et al. J.A.C.S., 2011, 133, 14379. 45 46 POSTERS 47 P01 COMPOSITE NAFION AND sPEEK-PORPHYRIN MEMBRANES 1 1 1 1 Alessandra CARBONE, Ada SACCA’, Rolando PEDICINI, Irene GATTO, Massimiliano GAETA, 2,3 2,3 2 Andrea ROMEO, Luigi MONSU’ SCOLARO, Maria Angela CASTRICIANO 2 1 Istituto di Tecnologie Avanzate per l’Energia “Nicola Giordano”, via S. Lucia sopra Contesse 5, 98126 2 Messina, Italy. Istituto per lo Studio dei Materiali Nanostrutturati, c/o Dipartimento di Scienze Chimiche, 3 V.le F. Stagno D'Alcontres n.31, 98166 Messina, Italy. Dipartimento di Scienze Chimiche, University of Messina, V.le F. Stagno D'Alcontres n.31, 98166 Messina, Italy. [email protected] The ability to control the spatial arrangement of porphyrins, through non covalent intermolecular interactions, is very important for accessing advanced functional materials with peculiar properties. Recently, we reported on the ability to easily tune porphyrin J-aggregates optical features using inner channels of Nafion membranes as confined environment to arrange and orient the chromophores.1 Since Nafion is usually involved as electrolyte in fuel cells applications, also the contribution of the porphyrin aggregates on the membranes proton conduction mechanism has been investigated. Furthermore, in order to overcome the Nafion limitations such as high production cost and low performance at low temperature, pressure and humidity we explored porphyrin modified sulphonated polyetheretherketone (sPEEK) membranes. Generally, sPEEK-membranes possess good mechanical properties, reduced hydrogen cross-over, similar unit area resistance to Nafion, improved stability to radical species and reduced production cost. Opportunely selected porphyrins embedded in the membranes allowed to increase the proton transmissibility of the material forming a hydrogen ion sieve structure.2 Here, we report on composite membranes based on highly sPEEK and different weight percentage (0 - 5wt%) of 5,10,15,20-tetra(4-pyridyl)porphyrin (TPyP)3 and meso-tetrakis(4sulfonatophenyl)porphyrin (TPPS) developed and tested for their use in portable applications. The aim is to exploit the ability of two different porphyrins, containing polar functional groups, to create specific interactions in a polymeric matrix, in order to stabilize the membranes maintaining a proton path for the conduction mechanism. The membranes have been obtained by a standardized doctor-blade method, thermally and chemically treated. UV-Vis and Fluorescence emission were carried out to investigate the porphyrin aggregation state. Physical-chemical characterizations in terms of ionic exchange capacity, water uptake, dimensional variations and swelling, structural and morphological analyses have been performed. Proton conductivity measurements at low temperatures allowed to investigate the role of the interaction between polymer and porphyrin on the proton transport mechanism. Furthermore, the composite membranes were tested in a PEFC 25 cm2 single cell to verify the electrochemical performance at the selected operative conditions. We anticipate that sPEEK-TPPS membranes operating at 30°C, dry H2/ 100%RH air and 1 abs. bar showed the best fuel cell performance with a limiting current approaching 1A/cm2. ______________ References: 1. Castriciano, M.A.; Carbone, A.; Saccà, A.;Donato M.G.; Micali, N.; Romeo, A.; De Luca, G.; Monsù Scolaro, L. J. Mater. Chem.,, 2010, 20, 2882-2886. 2. Fei, Y.; Zhen-Tao, Z.; Ge, Z. G. Patent CN 102020781 B, 2012. 3. Carbone, A.; Saccà, A.; Pedicini, R.; Gatto, I.; Romeo, A.; Monsù Scolaro, L.; Castriciano, M.A. Int. J. Hydrogen Energy, 2015, submitted. 48 P02 INTERACTION OF ZnTCPPSpm4 WITH DNA. IN A SINGLE MOLECULE: PROBE, CATALYTIC & STABILIZING EFFECT TOWARD Z-FORM. a,b b a a Chiara M. A. GANGEMI , Nina BEROVA , Alessandro D’URSO , Gaetano A. TOMASELLI , Roberto a PURRELLO a Dipartimento di Scienze Chimiche, Università di Catania, Viale Andrea Doria 6, 95125 Catania (Italy). b Department of Chemistry, Columbia University, 3000 Broadway, NY, 10027 (USA). [email protected] DNA containing an alternation of purine and pyrimidine repeats has the potential to adopt the Z structure, a left-handed double helix characterized by a high-energy structure.1 It has been shown that Z-DNA can exist in vivo under physiological conditions as a transient structure, occasionally induced by a biological process. Therefore, tracts of Z-DNA can exist within a single duplex of segments of right-handed B-DNA if the conditions and sequences are appropriate.2 Several research groups have studied the possible correlation between chromosomal breakpoints in human tumours with potential Z-DNA forming sequences.3 For these reasons the possibility to recognize, to induce or in some cases to stabilize this conformation could represent an important goal to understand the mechanism of action of this important structure of DNA. Porphyrinoids are ideal compounds to interact with DNA due to their peculiar characteristics.4 In this work, we developed a new achiral zinc-spermine-porphyrin conjugate that shows a catalytic and a stabilizer effect toward the changing of B-DNA into Z-DNA of poly(dG-dC) sequence. In addition, it works as probe, showing an intense ICD signal. ______________ References: 1. a) Herbert, A.; Rich, A. J. Biol. Chem., 1996, 271 , 11595. b) Herbert, A.; Rich, A. Genetica, 1999, 106, 37. c) Wang, A. H.; Quigley, G. J.; Kolpak, F. J.; Crawford, J. L.; van Boom, J. H.; van der Marel, G.; Rich, A. Nature, 1979, 282, 680. 2. a) Jovin, T. M.; Soumpasis, D. M.; McIntosh, L. P. Annu. Rev. Phys. Chem., 1987, 38, 521. b) Rich, A.; Nordheim, A.; Wang, A. H. J. Annu. Rev. Biochem., 1984, 53, 791. 3. a) Adachi, M; Tsujimoto, Y. Oncogene, 1990, 5, 1653. b) Boehm, T.; Mengle-Gaw, L.; Kees, U. R.; Spurr, N.; Lavenir, I.; Forster, A.; Rabbitts, T. H. EMBO Journal, 1989, 8, 2621. 4.a) Balaz, M.; De Napoli, M.; Holmes,A.E.; Mammana, A.; Nakanishi,K.; Berova, N.; Purrello, R. Angew. Chem. Int. Ed. 2005, 44, 4006-4009; b) D’Urso, A.; Nardis, S.; Pomarico, G.; Fragala, M. E.; Paolesse, R.; Purrello, R.; J. Am. Chem. Soc., 2013, 135, 8632-8638. 49 P03 CYCLODEXTRIN POLYMER/PORPHYRINS ASSEMBLIES AS CAPPING AGENTS FOR METAL NOBLE NANOPARTICLES WITH POTENTIAL IN DUAL PHOTOTHERAPY 1 1 1 2 Antonino MAZZAGLIA , Mariachiara TRAPANI , Maria Angela CASTRICIANO , Bernard MARTEL , 1,3 1,3 Andrea ROMEO , and Luigi MONSU’ SCOLARO 1 CNR-Istituto per lo studio dei Materiali Nanostrutturati, CNR-ISMN c/o Dip. di Scienze Chimiche, dell’ 2 Università di Messina, Viale Ferdinando Stagno D’Alcontres 31, 98166, Messina, Italy. Université de Lille - Sciences et Technologies UFR de Chimie, UMET CNRS 8207 59655 Villeneuve d'Ascq – France. 3 Dip. di Scienze Chimiche, Università di Messina, Viale Ferdinando Stagno D’Alcontres 31, 98166, Messina, Italy [email protected] Nowadays, researchers are interested to design and investigate multifunctional metal noble nanoparticles (NPs) with high potential in biomedical applications. The utilize of agents which acts simultaneously as reductants and stabilizers of metal nanoparticles is a well- established procedure. -Cyclodextrin (CD) polymers bearing citrate and cyclodextrin functionalities have been extensively used as coatings of a wide range of biomaterials for drug delivery.1 Nanoassemblies based on CD were used as shell entrapping photosensitisers (PSs) to cover metal noble NPs for photothermal and photodynamic combined therapy (PTT-PDT).2 Here we report an one-pot synthesis of gold and silver NPs, respectively, covered by water-soluble cyclodextrins polymer entrapping photosensitisers based on porphyrins. CD polymer was produced by condensation between hydroxypropylated CD (HPCD) and citric acid (CTR), named polyCTR-HPCD, according to a previously reported method.2 AuNPs@ polyCTRHPCD have been prepared by addition of the polymer suspension to a HAuCl4 solution at reflux and under stirring, thus the polymer acts as both reductant and stabilizing agent. The synthesis of AgNPs@ polyCTR-HPCD has been carried out at room temperature by addition of NaBH4 to a stirred solution of AgNO3 previously mixed to polyCTR-HPCD, using NaBH4 as reductant and polyCTR-HPCD as capping agent to avoid agglomeration. Au and Ag core-shell NPs have been characterized by UV-Vis, DLS, TEM and STEM to elucidate size and confirm the presence of the polymeric cover. The non-covalent interaction between core-shell NPs with water-soluble anionic porphryin (tetrakis(4-sulfonatophenyl) porphyrin (H2TPPS4) and the positively charged meso-tetrakis(N-methylpyridinium-4-yl)porphine (H2T4), respectively, was studied in aqueous solution by complementary techniques such as UV-Vis, fluorescence emission and circular dichroism. Our data evidence as H2T4 interacts more strongly with polymeric shell than H2TPPS4, pointing to the both electrostatic and hydrophobic effects which can address the porphyrin entrapment. This approach consents a control of the PS content in core-shell NPs with the aim to design novel nanophotherapeutics with dual action. Webpage:http://www.ismn.cnr.it/index.php?option=com_cnrprofile&view=profile&profileid=73 5&lang=it ______________ References: 1. Sobocinski, J.; Laure, W.; Taha, M.; Courcot, E.; Chai, F.; Simon, N.; Addad, A.; Martel, B.; Haulon, S.; Woisel, P.; Blanchemain, N.; Lyskawa, J. ACS Appl. Mater. Interface, 2014, 6, 3575-3586. 2. Trapani, M.; Romeo, A.; Parisi, T. Sciortino, M. T.; Villari, V. ; Mazzaglia, A. RSC Adv., 2013, 3, 5607–5614. 3. Martel, B.; Ruffin, D.; Morcellet, M.; Weltrowski, M.; Lechiri, Y.; J Appl Poly Sci, 2005; 97, 433–442. 50 P04 ZINC-PHTHALOCYANINE AS PRECURSOR FOR PREPARATION OF EXTREMELY HIGH SURFACE AREA N-DOPED CARBON FOR POTENTIAL APPLICATIONS IN ELECTROCHEMICAL DEVICES Luigi OSMIERI, Alessandro H. A. MONTEVERDE VIDELA, Reza ALIPOUR MOGHADAM ESFAHANI, Svetoslava VANKOVA, Marco ARMANDI, Stefania SPECCHIA Politecnico di Torino – DISAT – Corso Duca degli Abruzzi, 24 – 10129 – Torino – Italy [email protected] The development of non-precious metal catalysts and/or ultra-low Pt loading catalysts with improved performance and durability is essential in order to reduce the use of Pt as catalyst for the oxygen reduction reaction (ORR) in PEMFCs, making their large-scale commercialization possible in the future [1]. Different types of C-N-Me (Me = mainly Fe or Co) electrocatalysts for ORR have been developed so far. Me(II)-phthalocyanines (Me-Pc) have been proved to be suitable precursors to produce active ORR catalysts [2]. However, to our knowledge the use of Zn(II)-Pc for this purpose has not been investigated so far. Moreover, the use of N-doped carbon based materials as support for Pt catalysts should increase the stability of Pt particles preventing sintering, and have a synergistic effect on ORR activity [3]. An important interaction between Pt clusters and N atoms on the C support has also been found to increase the catalyst mass activity [4], allowing to significantly reduce the Pt loading [5]. In addition, C materials with a high amount of N doping atoms (≈10%) have been found to have interesting properties for applications in the field of Li-ion batteries [6]. In our work, Zn(II)-Pc is dissolved in ethanol-water solution and impregnated on SBA-15 ordered mesoporous silica [7]. Afterwards, a heat treatment under inert atmosphere at 800 °C is performed. Finally, the silica template is removed by HF washing. The resulting material was characterized by BET-porosimetry, XPS, FTIR, XRD, SEM-EDX and FESEM analyses. It is a highly Ndoped carbon material, with some Zn still present on the surface. The survey surface atomic chemical composition (by XPS) is 89% C, 8.3% N, 2.2% O, 0.5% Zn. The Zn amount is also confirmed by EDX. In addition, this material exhibits a surprisingly high surface area of ≈1850 m2 g–1. These properties make it a potential candidate to be used as non-precious metal ORR catalyst in alkaline membrane fuel cells, as well as support for ultra-low Pt loading ORR catalysts. Fig. 1 - Isotherm linear plots and SEM Electrochemical tests were performed in order to image for Zn(II)-Pc. investigate the activity towards ORR using a Rotating Disk Electrode (RDE) under acid (0.5 M H2SO4 electrolyte) and alkaline conditions (0.1 M KOH electrolyte). Potential applications as electrode material for Li-ion batteries have also been tested. ___________ References: 1. Feng, Y. ; Alonso-Vante, N. ; Physica Status Solidi (b), 2008, 245, 1792-1806 2. Othman, R.; Dicks, A.L.; Zhu, Z., International Journal of Hydrogen Energy, 2012, 37, 357-372 3. Chen, Y.; Wanga, J.; Liu, H.; Li, R.; Sun, X.; et al.; Electrochemistry Communications, 2009, 11, 2071-2076. 4. Ma, J.; Habrioux, A.; Luo, Y.; et al.; J. Mater. Chem. A, 2015, DOI: 10.1039/C5TA01285F 5. Vinayan, B.P.; Nagar, R.; Rajalakshmi, N.; et al.; Advanced Functional Materials, 2012, 22, 3519-3526 6. Zheng, F.; Yang, Y.; Chen, Q.; Nature communications, 2014, 5, 5261. 7. Monteverde Videla, A.H.; Osmieri, L.; et al.; Electrochim. Acta, 2015, DOI: 10.1016/j.electacta.2015.01.165 51 P05 SUNTHESIS OF FUNCTIONALIZED TETRAFERROCENYLPORPHYRINS Fabio POSSANZA, Andrea VECCHI, Barbara FLORIS, Valeria CONTE, Pierluca GALLONI Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata, via ricerca scientifica snc, 00133 Rome, Italy [email protected] Metallocenyl porphyrins are of great interest for their electrochemical and photophysical properties and for possible application in different fields such as energy conversion, memory devices and elctrochemical capacitors.1,2 In our group we studied the tetraferrocenylporphyrins showing interesting features in terms of electrochemical processes and photoelectrochemical catalysis.3 We recently investigated the mono-functionalized derivatives bearing an acetyl group on one ferrocenyl moiety that showed interesting features in terms of electronic interactions. 4 With the aim to analyze the effects of 4 acetyl groups on the electronic properties of this class of macrocyle, we synthetized a tetrasubstitutedferrocenyl porphyrins. The compounds obtained have been characterized by electrochemical and spectroscopic techniques, and the quite unexpected effects of the acetyl groups will be discussed in comparison with the classical tetraferrocenylporphyrin. ______________ References: 1. Vecchi, A.; Galloni, P.; Floris, B.; Dukin, S. V.; Nemykin, V. N. Coord. Chem. Rev. 2015, 291, 95. 2. Bucher, C.; Devillers, C. H.; Moutet, J.-C.; Royal, G.; Saint-Aman, E. Coord. Chem. Rev. 2009, 253, 21. 3. Vecchi, A.; Gatto, E.; Floris, B.; Conte, V.; Venanzi, M.; Nemykin, V. N.; Galloni, P. Chem. Commun. 2012, 48, 5145. 4. Vecchi, A.; Erickson, N. R.; Sabin J. R.; Floris, B.; Conte, V.; Venanzi, M.; Galloni, P.; Nemykin, V. N. Chem. Eur. J. 2015, 21, 269. 52 P06 SYNTHESIS OF NEW GLICOPORPHYRIN LIGANDS FOR HOMOGENEOUS CATALYSIS Paolo ZARDI, Giorgio TSEBERLIDIS, Daniela Maria CARMINATI, Luigi LAY, Emma GALLO Università degli Studi di Milano, Milan, Italy. [email protected] Glycoporphyrins are generated by the conjugation of saccharide units with a porphyrin molecule. These compounds have several biological applications due to the good activity of carbohydrates in ligand-acceptor interaction and recognition, and also because the porphyrin ligand is a biocompatible scaffold1. Since metallo-porphyrins are active in promoting nitrene and carbene transfer reactions2, glycoporphyrin complexes can be a new class of catalysts. Taking advantage of the chiral and hydrophilic nature of saccharide units, this class of compounds can be used either for asymmetric synthesis or to develop new sustainable water-soluble catalysts. We synthesised glycoporphyrin derivatives following two synthetic strategies (Scheme 1): a) Aromatic nucleophilic substitution using F20-TPPH2 (tetra-(pentafluoro)phenyl-porphyrin) and a sugar carrying an unprotected OH group. b) Copper catalyzed azide-alkyne cycloaddiction (CuAAC), starting from TAPPH2 (tetra(amino)phenyl-porphyrin) and a sugar functionalised with a propargyl moiety. We were able to synthesise the corresponding iron(III), cobalt (II) and ruthenium(II)-carbonyl complexes of the obtained glycoporphyrins. A preliminary study concerning the photochemical properties of the free-base compounds and the catalytic activity of the metal complexes was performed. ____________________ References: 1) Top. Heterocycl. Chem. 2007 ,7 , 179-248. 2) S. Fantauzzi, A. Caselli, E. Gallo, Dalton Trans, 2009, 28, 5434. b) D. Intrieri, A. Caselli A, E. Gallo , Eur. J. Inorg. Chem., 2011, 33, 5071-5081. 53 P07 OPTICAL SENSORS CROSS-SENSITIVITY AMENDMENT: THE CASE STUDY OF HEAVY METALS CSPT DETECTION 1,2, Larisa LVOVA 1 1 1 3 4 , Pierluca GALLONI , Barbara FLORIS , Corrado DI NATALE , Ingemar LUNDSTRÖM , 5 5 1 Vito LIPPOLIS , Alessandra GARAU , Roberto PAOLESSE 2 Department of Chemical Science and Technologies, University “Tor Vergata”, Rome, ITALY. Faculty of 3 Biology and Soil Science, St. Petersburg State University, St. Petersburg, RUSSIA. Department of 4 Electronic Engineering, University “Tor Vergata”, Rome, ITALY. IFM, Linköping University, SWEDEN. 5 Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari,Monserrato, ITALY The application of optical sensors has recently spread in many fields, such as environmental analysis, industrial control, and routine laboratory testing1. Being non invasive, easy to handle, and possessing the notable selectivity, optical chemical sensors have been previously utilized for the analysis of several hazardous compounds in aquatic environments, and in particular for the transition metal ions detection2,3. Recently we reported novel optical sensors based on the mixed aza-thioether macrocycles bearing coumarin pendant arm, [4] and tetraferrocenylporphyrin PFc4 [5] chromophores for the selective fluorimetric detection of Hg(II) and Pb(II) respectively; the former increases the fluorescence with the analyte concentration growth, while TFc4 fluorescence quenches under exposure to analyte, Figure 1. The possibility to substitute fluorimetric signal detection of the developed optodes with the Computer Screen Photo-Assisted Technique (CSPT), applying a computer monitor screen as polychromatic light source and a webcam as optical response detector, have been also demonstrated. In this contribution we propose the simple, fast and effective method to tune the cross-sensitivity of optical sensors for multisensory CSPT analysis of heavy metals in complex liquid samples. Figure 1: The chemical structures and fluorimetric response of PFc4 and L3 chromoinophores. ______________ References: 1. B.A. McKinley, Chem. Rev. ,108 (2008) 826 2.M. Shamsipur, M. Hosseini, K. Alizadeh, N. Alizadeh, A. Yari, C. Caltagirone, V. Lippolis, Anal. Chim. Acta 533 (2005) 17. 3. D. Monti, M. Venanzi, M. Russo, G. Bussetti, C. Goletti, M. Montalti, N. Zaccheroni, L. Prodi, R. Rella, M.G. Manera, G. Mancini, C. Di Natale, R. Paolesse, New J. Chem., 28 (2004) 1123 4. Z. Cao, L. Lvova, C. Di Natale, I. Lundström, R. Paolesse, A. Garau, V. Lippolis, Fluorimetric Chemosensors Combined with Familiar CSPT Devices for the Selective Detection of Mercury(II) Ions, Proc. Eurosensors XXVI, September 9-12, 2012, Krakow, Poland. 5. R. Paolesse, L. Lvova, P. Galloni, B. Floris, C. D.Natale, A. D’Amico, Porphyrin-Ferrocene conjugate based hyphenated opto-electroche-mical sensors for transition metals detection, IMCS 14, July 11-14, 2010, Perth, Australia. 6. D. Filippini, C. Di Natale, R. Paolesse, A. D’Amico, I. Lundstrom, Sens.Act B, 121 (2007) 93 54 P08 FOUR METAL IONS FOR ONE MACROCYCLE: FERROCENYL-CORROLE METAL COMPLEXES Giuseppe POMARICO, Pierluca GALLONI, Federica MANDOJ, Andrea VECCHI, Sara LENTINI, Roberto PAOLESSE Università di Roma “Tor Vergata”, Dipartimento di Scienze e Tecnologie Chimiche, Via della Ricerca Scientifica 1, 00133 Roma. [email protected] Among the different polypyrrolic macrocycles, corrole is one of the more intriguing compounds due to its particular reactivity and to its non-innocent behaviour as ligand. Several modifications of corrole backbone have been investigated to fit its properties with those needed for the application in the field of material science. For example, the introduction of ferrocenyl moieties may led to the formation of the so called mixed-valence states [1], of potential interest for optoelectronic applications. We recently reported the first example of triferrocenylcorrole as Cu derivative [2]. Now a series of corrole bearing one or two ferrocene units, or different metal ions in the inner core have been prepared and fully characterized by UV-vis, NMR, electrochemical and DFT technique. ______________ References: 1. Nemykin, V. N.; Galloni, P.; Floris, B.; Barrett, C. D.; Hadt, R. G.; Subbotin, R. I.; Marrani, A. G.; Zanoni, R.; Loim, N. M. Dalton Trans. 2008, 4233-4246. 2. Pomarico, G.; Vecchi, A.; Mandoj, F.; Bortolini, O.; Cicero, D. O.; Galloni, P.; Paolesse, R. Chem. Commun. 2014, 50, 4076-4078. 55 P09 IRON-PORPHYRIN ELECTROPOLYMERS FOR MULTITRANSDUCTION ANALYSIS APPLICATIONS a a b c a Rajesh PUDI , Larisa LVOVA , Corrado DI NATALE , Ingemar LUNDSTRÖM , Roberto PAOLESSE a b Department of Chemical Science and Technologies, University “Tor Vergata”, Rome, Italy. Department c of Electronic Engineering, University “Tor Vergata”, Rome, Italy. IFM, Linköping University, Sweden The comparative study of the optical and electrocatalytic activity of the electrochemically generated Fe-porphyrin polymeric films I, II (semiconductive and intrinsically conductive respectively) was performed [1,2]. Opto-electrochemical sensors were then developed, employing the combination of two transduction principles in the same Fe-porphyrin-based sensing layer, and they have been applied for the analysis of foodstuffs, namely for the detection of forbidden diazo-conjugated Sudan dye additives [3]. The Computer Screen Photoassisted Technique, CSPT, was employed as an optical method, while Differential Pulse Voltammetry, DPV, was applied for the reduction of Sudan I and Sudan IV analytes, catalyzed by polymeric ironporphyrin films I, II, Fig.1. The fusion of DPV and CSPT data has permitted to improve significantly the diazo-conjugated colorants classification and aided to distinguish between Sudan I and IV. Figure 1. The principle of multi-transduction sensing on Fe-porphyrin electropolymers for Sudan dyes forbidden food additives PCA discrimination; A-= ClO4-. ______________ References: 1. Y. Wu, Food Chem., 121 (2010) 580. 2. P.A. Liddell, M. Gervaldo, J.W. Bridgewater, A.E. Keirstead, S. Lin, T.A Moore, A.L Moore, D. Gust, Chem. Mater., 20 (2008) 135. 3. Z. Cao, L. Lvova, R. Paolesse, C. Di Natale, I. Lundström, A.D’Amico, Lect.Notes Electr. Eng., 162 (2014) 49 56 P10 SYNTHESIS OF CHROMOPHORE-MODIFIED GRAPHENE 1 1 1 1 Michele RAGGIO , Sara NARDIS , Mario Luigi NAITANA , Alessandra D’EPIFANIO , Saisameera 2 2 3 3 1 MITTA , Anna SGARLATA , Santodh Kiran BALIJEPALLI , Saulius KACIULIS , Roberto PAOLESSE 1 Department of Chemical Science and Technology, University of Rome “Tor Vergata” 00133, Rome, Italy. 2 3 Department of Physics, University of Rome “Tor Vergata” 00133, Rome, Italy. CNR – ISMN, P.O. Box 10, 00015 Monterotondo Stazione, Rome, Italy Email: [email protected] Since the first successful exfoliation of single-layer graphene from graphite in 2004 [1], this twodimensional sp2-hybridized carbon material has been deeply investigated due to its unique properties ranging from high surface area to high thermal and electronic conductivity. Many efforts have been made to enable this material to be processed by solvent-assisted techniques, like layer-by-layer assembly, spin-coating and filtration, with the aim to use graphene as a versatile material for the fabrication of electrochemical devices such as supercapacitors, fuel cells, drug delivery system, memory devices, transistor devices, biosensors, solar cells, etc. Functionalization with organic functional groups can be performed by covalent and noncovalent modification techniques on both graphene oxide (GO) and reduced graphene oxide (rGO) [2], to prepare processable graphene, preventing agglomeration and facilitating the formation of stable dispersions in organic solvents. This is a crucial move towards nano composite materials and moreover represents a way to introduce new properties that can be combined with those of graphene. For this purpose we studied the interactions of both GO and rGO with a tetrapyrrolic chromophore: different triarylcorroles have been used to covalently functionalize GO or to enhance the solubility of rGO in polar solvents. The acylation reaction on GO allowed to perform the coupling with an amminoarylcorrole through the formation of an amide bond. On the other hand the intermolecular interactions between GO and corrole derivatives bearing polar groups have been investigated. The reduction reaction to obtain rGO was carried out in the presence of such corroles affording an increased dispersibility of graphene in polar solvents. The materials have been characterized through XPS technique, IR and Raman spectroscopy. Several microscopy techniques (AFM, STM, SEM) have been used to analyze GO, rGO and modified graphene on gold substrate. ______________ References: 1. K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, S. V. Dubonos, I. V. Grigorieva, A. A. Firsov, Science, 2004, 306, 666-669. 2. V. Georgakilas, M. Otyepka, A. B. Bourlinos, V. Chandra, N. Kim, K. C. Kemp, P. Hobza, R. Zboril, K. S. Kim, Chem. Rev., 2012, 112, 6156−6214. 57 P11 LIGHT-INDUCED REGIOSPECIFIC BROMINATION OF MESO-TETRA(3,5-DI-TERT-BUTYLPHENYL)PORPHYRIN ON 2,12 -PYRROLIC POSITIONS a b a b Gabriele Di Carlo, Alessio ORBELLI BIROLI, Silvia RIZZATO, Alessandra FORNI, Giulia MAGNANO, a a Maddalena PIZZOTTI, Francesca TESSORE a a b Dipartimento di Chimica, Università degli Studi di Milano, via C. Golgi 19, 20133 Milano; Istituto di Scienze e Tecnologie Molecolari del CNR (CNR-ISTM), via C. Golgi 19, 20133 Milano. [email protected] The antipodal introduction of two bromine atoms on 2,12 -pyrrolic position of 5,10,15,20-tetra(3,5-di-tertbutylphenyl)porphyrin was successfully achieved by a light-induced reaction of the substrate with excess NBS. Complexation with NiII of the major regioisomer led to good quality crystals, suitable for X-ray structure determination with unprecedented probability levels. The regiospecific character of the synthetic procedure and the exactness of the bromine atom position assignment were thus confirmed, suggesting also an unexpected electrophilic aromatic substitution pathway rather than a freeradical halogenation process. A QTAIM topological analysis on the DFT optimized wavefunction of the monosubstituted free-base porphyrin intermediate carrying a bromine atom in C2 -pyrrolic position confirmed the largest negative charge for the C12 carbon atom in antipodal position, in agreement with the proposed electrophilic aromatic substitution mechanism. ______________ Reference: Di Carlo, G.; Orbelli Biroli, A.; Tessore, F.; Rizzato, S.; Forni, A.; Magnano, G.; Pizzotti, M. J. Org. Chem., 2015, 80, 4973 58 P12 Effetto di polimeri cationici sulla foto-inattivazione antimicrobica indotta da BODIPY 1 1 1 1 1 Stefano BANFI , Enrico CARUSO , Viviana ORLANDI , Paola BARBIERI , Barbara LEVA , Stefano 1 2 FERRARA , Amedea MANFREDI 1 Dipartimento di Scienze Teoriche ed Applicate (DiSTA), Università degli Studi dell’Insubria, via JH 2 Dunant, 3 – Varese. Dipartimento di Chimica, Università Statale di Milano, Via Golgi 19 – Milano I metodi antimicrobici tradizionali risultano spesso inefficaci in ambito ambientale e clinico, di conseguenza, negli ultimi anni, sono stati sviluppati nuovi sistemi per rimuovere la contaminazione microbica. La Terapia Fotodinamica Antimicrobica (APDT) sembra essere promettente per debellare contaminazioni batteriche localizzate su superfici biologiche o inerti. Nella APDT il fotosensibilizzante (PS) e una sorgente di luce a bassa energia, inducono uno stress ossidativo nei batteri. Recentemente, il nostro gruppo di ricerca si è interessato dell’uso di boro-dipirrometeni, generalmente denominati BODIPY, come PS in ambito antimicrobico. Questa classe di composti presenta una proprietà chimico-fisica (alta resa quantica di fluorescenza, Φfl) che li rende adatti per un’applicazione come sonde diagnostiche in campo oncologico. E’ noto che l’elevata Φfl dei BODIPY pregiudica il loro impiego come fotosensibilizzanti, per cui si rende necessaria un’opportuna modifica strutturale per inibire la perdita di energia attraverso la fluorescenza, favorendo il processo di “intersystem crossing” che, in ultima analisi, incrementa la produzione dell’ossigeno singoletto essenziale per l’efficacia fotodinamica. Sulla base di queste premesse abbiamo sintetizzato alcuni BODIPY iodurati e che presentano anche una carica cationica necessaria per l’interazione con la parete batterica. In questo lavoro abbiamo analizziamo l’influenza di alcuni polimeri cationici sullo stress fotodinamico antibatterico indotto da un BODIPY cationico. I polimeri appartengono alla famiglia delle poli-amidoamine (PAA), macromolecole biocompatibili caratterizzate da un elevato numero di cariche cationiche in funzione della struttura, del peso molecolare e del pH. Per questo tipo di studio abbiamo scelto due microorganismi modello rappresentativi di batteri Gram-negativi e Gram-positivi (Escherichia coli e Staphylococcus aureus) per i quali si è valutato l’efficacia della foto-inattivazione ottenuta per l’azione del solo BODIPY, a bassa concentrazione, e per effetto del sistema composto da BODIPY e PAA, quest’ultima a concentrazione non tossica per i microorganismi. I risultati indicano che, in generale, i polimeri incrementano l’azione fotodinamica del BODIPY di circa 2 unità logaritmiche, e, in particolare, i polimeri più corti hanno evidenziato incrementi superiori. 59 P13 METALLOPORPHYRINS AS PHOTOSENSITIZER FOR MULTICOMPONENT PHOTOACTIVE SYSTEMS a b Paolo CAVIGLI, Maria Teresa INDELLI, Elisabetta IENGO a a Dep. Chemical and Pharmaceutical Sciences, University of Trieste, Via L. Giorgieri 1, 34127 Trieste (IT); b Dep. Chemical and Pharmaceutical Sciences, University of Ferrara, Via Fossato di Mortara 17, 44121 Ferrara. [email protected] Artificial systems mimicking the natural photoinduced processes are an important topic for the research activity. In many of these artificial systems, metalloporphyrins play an important role as photosensitizers. Indeed, besides their well-known chemical resemblance to the chlorophylls of the natural systems, porphyrins can be considered as ideal components for the construction of antennas for photoinduced processes [1, 2], and/or photocatalytic purposes triggered by visible light, such as photoreduction of CO2 to CO when the chromophore is coupled with a Re(CO)3(bipy) catalyst [3]. Recently, we have exploited a metal-mediated approach that led us to the obtainment of multicomponent photoactive systems based on metalloporphyrins that behaves as photosensitizers. Two examples are reported in the Figure: on the left a Zn(II)-porphyrin is and a C60 are connected to a central Re(CO)3(bipy) unit [4]; on the right an Al(III)-porphyrin play the pivotal role for the self-assembling of photoactive units. For both systems, the formation of charge separated states initiated by visible light was proven. An outlook on the synthetic strategy, characterization, and kinetic study of the electron transfer processes occurring upon selective visible excitation of the porphyrin unit, will be presented. ______________ References: 1. Gatti, T.; Cavigli, P.; Zangrando, E.; Iengo, E.; Chiorboli, C.; Indelli, M. T. Inorg. Chem., 2014, 52, 3190. 2. Iengo, E.; Pantoş, G. D.; Sanders, J. K. M.; Orlandi, M.; Chiorboli, C.; Fracasso, S.; Scandola, F. Chem. Sci., 2011, 2, 676. 3. Windle, C. D.; Câmpian, M. V.; Duhme-Klair, A.-K.; Gibson, E. A.; Perutz, R. N.; Schneider J. Chem. Commun., 2012, 48, 8189. 4. Cavigli, P.; Da Ros, T.; Kahnt, A.; Gamberoni, M.; Indelli, M. T.; Iengo, E. Inorg. Chem,. 2015, 54, 280. 60 P14 PORPHYRIN NANO-ASSEMBLIES ONTO GOLD NANORODS 1 2 Mariachiara TRAPANI, Giovanna DE LUCA, Andrea ROMEO, 1,3 MONSU’ SCOLARO 1,3 1 Maria Angela CASTRICIANO, Luigi 1 Istituto per lo Studio dei Materiali Nanostrutturati, c/o Dipartimento di Scienze Chimiche, V.le F. Stagno 2 D'Alcontres n.31, 98166 Messina, Italy. Dipartimento di Scienze del Farmaco e Prodotti per la Salute, 3 Viale SS. Annunziata, 98168, Messina, Italy. Dipartimento di Scienze Chimiche, University of Messina, V.le F. Stagno D'Alcontres n.31, 98166 Messina, Italy. Gold nanoparticles (AuNPs) have attracted large interest due to their relatively easy syntheses and their peculiar shape and size dependent optical properties, which make them interesting nanomaterials for a variety of applications. In particular, gold nanorods (AuNRs) have been extensively explored in several fields, such as in catalysis, sensing, optoelectronics and biomedicine. Ordered assemblies in which electronic, magnetic and optical properties could be tailored through coupling among neighboring nanorods have been investigated in order to improve the properties of these nanomaterials.1 Self-assembling can be accomplished via supramolecular approach by functionalization with organic or inorganic components as well as biomolecules.2,3 The facile fabrication of linear chains of AuNRs and bifurcated junctions of nanorods/nanospheres has been achieved through crosslinking of AuNPs with a water soluble anionic porphyrin.3 Here, we report the interaction between tetrakis-(4-sulphonatophenyl) porphyrin (TPPS) and AuNRs in aqueous solution. This porphyrin shows the peculiar ability to self-aggregate forming extended J-type nano-assemblies which exhibit interesting nonlinear optical and optoelectronic properties mainly related to their structure.4,5,6 At rather mild acidic conditions nanohybrid assemblies composed of TPPS porphyrin J-aggregates and AuNRs has been obtained. Kinetics for the growth of AuNRs assemblies evidence dependence on porphyrin concentration. In particular, at high porphyrin load a fast process, i.e. a more pronounced shift of the longitudinal plasmonic absorption band of AuNRs, have been observed. A detailed spectroscopic investigation has been carried out using a combination of UV/Vis absorption, resonance light scattering and fluorescence emission techniques. ______________ References: 1. Fan, H.; Yang, K.; Boye, D.M.; Sigmon, T.; Malloy, K.J.; Xu, H.; López, G.P.; Brinker, C. J. Science, 2004, 304, 567. 2. Fava, D.; Nie, Z.; Winnik, M. A.; Kumacheva, E. Adv. Mater., 2008, 20, 4318. 3. Zhang, L.; Chen, H.; Wang, J.; Li, Y. F.; Wang, J.; Sang, Y.; Xiao, S. J.; Zhan, L.; Huang, C. Z. Small, 2009, 18, 2001-2009. 4. Collini, E.; Ferrante, C.; Bozio, R. J. Phys. Chem. B, 2005, 109, 2. 5. Micali, N.; Villari, V.; Castriciano, M.; Romeo, A.; Monsù Scolaro, L. J. Phys. Chem. B, 2006, 110, 8289. 6. Villari,V.; Mazzaglia, A.; Trapani, M.; Castriciano, M. A.; De Luca, G.; Romeo, A.; Monsù Scolaro, L.; Micali, N. J. Phys. Chem. C, 2011, 115, 5435. 61 62 List of Participants Banfi Stefano [email protected] Dipartimento di Scienze Teoriche ed Applicate (DiSTA), Università degli Studi dell’Insubria Belviso Sandra [email protected] Dipartimento di Scienze, Università della Basilicata Berionni Berna Beatrice [email protected] Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata” [email protected] Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata” Calvano Cosima Damiana [email protected] Dipartimento di Chimica e Centro Interdipartiment. di Ricerca S.M.A.R.T., Università degli Studi di Bari Carminati Daniela Maria [email protected] Dipartimento di Chimica, Università degli Studi di Milano Carofiglio Tommaso [email protected] Dipartimento di Scienze Chimiche, Università di Padova [email protected] I.S.M.N. – C.N.R. Dipartimento di Scienze Chimiche, Università di Messina Crestoni Maria Elisa [email protected] Dipartimento di Chimica e Tecnologie del Farmaco, Università di Roma “La Sapienza” Di Valentin Marilena [email protected] Dipartimento di Scienze Chimiche, Università di Padova Di Natale Corrado [email protected] Dipartimento di Ingegneria Elettronica, Università di Roma “Tor Vergata” Donzello Maria Pia [email protected] Dipartimento di Chimica, Università di Roma “La Sapienza” D'Urso Alessandro [email protected] INSTM UdR - Dipartimento di Scienze Chimiche, Università di Catania Bischetti Martina Castriciano Maria Angela 63 Floris Barbara [email protected] Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata Fragalà Maria Elena [email protected] INSTM UdR - Dipartimento di Scienze Chimiche, Università di Catania Gallo Emma [email protected] Dipartimento di Chimica, Università degli Studi di Milano Galloni Pierluca [email protected] Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata” Gangemi Chiara M. A. [email protected] Dipartimento di Scienze Chimiche, Università di Catania Gobbo Marina [email protected] Dipartimento di Scienze Chimiche, Università di Padova Guidoni Leonardo [email protected] Dipartimento di Scienze Fisiche e Chimiche, Università degli Studi dell’Aquila Iengo Elisabetta [email protected] Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Trieste Intrieri Daniela [email protected] Dipartimento di Chimica, Università degli Studi di Milano larisa.lvova@uniroma2 Department of Chemical Science and Technologies, University “Tor Vergata”, Rome and Faculty of Biology and Soil Science, St. Petersburg State University, St. Petersburg [email protected] Istituto di Chimica dei Composti OrganoMetallici, ICCOM-CNR, Firenze Mandoj Federica [email protected]. Department of Chemical Science and Technology, University of Rome “Tor Vergata” Mazzaglia Antonino [email protected] I.S.M.N. – C.N.R. Dipartimento di Scienze Chimiche, Università di Messina Mineo Placido [email protected] Dipartimento di Scienze Chimiche, Università di Catania Lvova Larisa Manca Gabriele 64 [email protected] I.S.M.N. – C.N.R. Dipartimento di Scienze Chimiche, Università di Messina Monti Donato [email protected] Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata” Naitana Mario [email protected] Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata” Nardis Sara [email protected]. Department of Chemical Science and Technologies, University of Rome Tor Vergata Notarantonio Sara [email protected] CNR – ISM, Monterotondo Scalo, Rome Osmieri Luigi [email protected] Politecnico di Torino – DISAT, Torino Paolesse Roberto [email protected] University of Rome Tor Vergata, Department of Chemical Science and Technologies Paoletti Anna Maria [email protected] CNR – ISM, Monterotondo Scalo, Rome Peluso Andrea [email protected] Dipartimento di Chimica e Biologia, Università di Salerno Pennesi Giovanna [email protected] CNR – ISM, Monterotondo Scalo, Rome Pomarico Giuseppe [email protected] Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata” Possanza Fabio [email protected] Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata Pudi R. Rajesh [email protected] Department of Chemical Science and Technologies, University “Tor Vergata”, Rome Purrello Roberto [email protected] Department of Chemical Science, University of Catania Monsù Scolaro Luigi 65 Raggio Michele [email protected] Department of Chemical Science and Technologies, University “Tor Vergata”, Rome Reddi Elena [email protected] Dipartimento di Biologia, Università di Padova Romeo Andrea [email protected] Istituto per lo Studio dei Materiali Nanostrutturati, c/o Dip. di Scienze Chimiche, University of Messina Russo Nino [email protected] Dipartimento di Chimica e Tecnologie Chimiche, Università della Calabria Smulevich Giulietta [email protected]) Dipartimento di Chimica “Ugo Schiff”, Università di Firenze [email protected] Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata” Tagliatesta Pietro [email protected] Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata” Tessore Francesca [email protected] Dipartimento di Chimica, Università degli Studi di Milano Trotta Massimo [email protected] IPCF-CNR, Università degli Studi di Bari [email protected] Dipartimento di Ingegneria dell'Innovazione, Università del Salento Venanzi Mariano [email protected] Dept. of Chemical Sciences and Technologies, and CNR-ISM, Dept. of Physics, University of Rome ‘Tor Vergata’ Viola Elisa [email protected] Dipartimento di Chimica, Università di Roma “La Sapienza” Zanotti Gloria [email protected] CNR – ISM, Roma Stefanelli Manuela Valli Ludovico 66 ISBN 978–88–7959–879–8 9 788879 598798