Relazione ScientificaAprile2010
Transcript
Relazione ScientificaAprile2010
Università di Trieste Scuola di dottorato di ricerca in Nanotecnologie Resoconto dell’attività 2009 Sommario 1. 2. 3. Relazione scientifica riassuntiva .................................................................................................. 3 Elenco dottorandi, supervisori e titolo delle tesi .......................................................................... 5 Schede attività dottorandi............................................................................................................. 7 Dottorandi del 22 ciclo:.................................................................................................................... 8 Dottorandi del 23 ciclo:.................................................................................................................. 33 Dottorandi del 24 ciclo: • ............................................................................................................... 53 Research activity ............................................................................................................................ 58 Research activity ............................................................................................................................ 83 4. Progetti Dottorandi del 25 ciclo: ................................................................................................ 89 5. Pubblicazioni dei dottorandi. ................................................................................................... 119 6. Giudizi della commissione d‟esame finale 2009 ..................................................................... 127 7. Elenco dei componenti del collegio docenti ............................................................................ 130 8. Pubblicazioni rappresentative del collegio docenti .................................................................. 133 9. Criteri di valuatazione delle scuole di dottorato ...................................................................... 205 10. Valutazione da parte del nucleo di valutazione dell‟Ateneo ................................................. 209 11. Giudizi dei referee esterni per dottorandi ammessi all‟esame finale .................................... 210 12. Presentazioni dei dottorandi al congesso del 2009 ............................................................... 211 Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 1 Attività della scuola: situazione ad aprile 2010. Questo documento contiene il dettaglio dell‟attività didattico scientifica della scuola di dottorato in nanotecnologie svolto durante l‟anno 2009 fino ad aprile del 2010. Il documento si compone delle seguenti parti: 1. Relazione scientifica riassuntiva (Executive summary) 2. Elenco dei dottorandi, supervisori e titolo tesi in corso. 3. Schede di attività dei dottorandi che hanno svolto attività continuativa nell‟anno 2009. Questa attività è stata presentata nel congresso di gennaio 2010 (vedi slides su CD allegato) ed è riassunto per ogni dottorando nelle seguenti schede. Le schede si riferiscono ai dottorandi in corso dei cicli 22, 23 e 24, non essendo nesssun dottorando del ciclo 21 in proroga. 4. Progetti dei dottorandi nuovi entrati nella scuola (25 ciclo). Questa attività non è stata presentata in gennaio 2010 poiché non ancora definiti gli accoppiamenti dottorando – tema di ricerca. 5. Riassuntivo delle pubblicazioni dei dottorandi.. 6. Giudizi della commissione d‟esame finale 2010. 7. Elenco dei componenti collegio docenti. 8. Pubblicazioni rappresentative del collegio docenti. 9. Criteri di valutazione delle scuole di dottorato. 10. Valutazione della scuola da parte del nucleo di valutazione riassunta in una tabella e rimandi ad (allegati). 11. Giudizi dei reviewer esterni per i dottorandi ammessi all‟esame finale (allegati). 12. Presentazioni dei dottorandi al congresso del 2010 (allegati). Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 2 1. Relazione scientifica riassuntiva La missione della scuola di dottorato è di migliorare le conoscenze ed educare studenti nel campo delle nanotecnologie al fine di formare scienziati e tecnici per il 21° secolo. La caratteristica della Scuola è l‟interdisciplinarità: sugli argomenti di ricerca attivi lavorano in sinergia fisici, chimici, biologi, ingegneri, medici, farmacologi, odontoiatri, biotecnologi e laureati in Agraria, mantenendo e rafforzando la specificità della cultura di provenienza ed acquisendo la capacità di sviluppare la propria ricerca in un quadro più ampio. L‟obiettivo principale della Scuola è di formare Ricercatori che sappiano progettare, costruire, utilizzare e sottoporre a prove di funzionalità strumenti e dispositivi nano tecnologici, in grado di rispondere alle crescenti e diversificate esigenze delle applicazioni. L'allievo “dottorato” di questa Scuola sarà un professionista della ricerca e dello sviluppo tecnologico che sappia applicare le proprie conoscenze, con capacità di valutazione critica, allo sviluppo di metodi di progettazione, produzione e valutazione di nuovi materiali e al miglioramento di quelli esistenti. Questo anche mirato ad una produzione industriale più efficace, economica e sostenibile dal punto di vista delle risorse e dell'ambiente. La scuola è stata fondata nel 2006 a partire da un dottorato in nanotecnologie. Gli obiettivi delle ricerche sono i seguenti: Sviluppo di nuove tecniche sperimentali per lo studio, la lavorazione, la manipolazione e la visualizzazione su scala nanometrica di materiali nanostrutturati. Sviluppo di tecniche spettroscopiche di rivelazione di singola molecola su substrati nanostrutturati. Studio delle relazioni tra la microstruttura e le proprietà dei materiali e ingegnerizzazione di materiali nanostrutturati. Sintesi di nanostrutture. Applicazioni delle nanotecniche e nanostrutture a ricerche di interesse biomedico ed energetico. Modellizzazione molecolare multiscala di materiali e di fenomeni di interesse attraverso tecniche di simulazione computazionale. Salute umana con particolare attenzione allo studio ed al trattamento di tumori e malattie degenerative. Applicazione delle nanotecnologie nei settori medico, farmacologico e biomedico Questi obiettivi sono perseguiti avvalendosi delle attrezzature d'avanguardia disponibili nei laboratori dell'Università di Trieste e degli Enti di ricerca pubblici e privati convenzionati con l‟Università di Trieste: il centro internazionale di ingegneria genetica e Biotecnologie (ICGEB), il Sincrotrone TS, il CRO di Aviano ed il laboratorio nazionale TASC- INFM- CNR. Di seguito alcuni numeri rappresentativi dell‟attività della scuola: n. di studenti (ad aprile 2010): 32 Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 3 Numero di diplomati nel 2010: 7 Numero di diplomati nel 2009: 6 Numero di diplomati nel 2008: 9 Numero di diplomati nel 2007: 14 Membri del collegio docenti: 48 Enti di ricerca coinvolti nel dottorato: o Dipartimenti dell‟Università di Trieste: 10 o Enti di ricerca esterni: 5 o Altre Università: 5 Numero di pubblicazioni degli studenti (anno 2009): 83 (comprese di brevetti e presentazioni a convegni) di cui 5 brevetti e 47 pubblicazioni su riviste internazionali Numero di pubblicazioni di supervisori e tutors (2004-09): 1002 Risorse finanziarie (per anno): 520.000 euro Ultima valutazione complessiva del nucleo dell‟Università di Trieste: A+ (Ottimo) I criteri usati per la valutazione interna sono stati quelli suggeriti dal Ministero, accompagnati da criteri interni all‟Ateneo. Questi criteri sono descritti di seguito in questo documento in modo dettagliato. I principali indicatori utilizzati dal nucleo che hanno permesso la valutazione in classe A+ sono: produzione scientifica del Collegio Docenti; congruo numero di docenti dell‟Ateneo coinvolti nel collegio; rapporto del dottorato con il mondo del lavoro; attrattività del dottorato nelle precedenti edizioni; livello di soddisfazione dei dottorandi; produzione scientifica dei dottorandi ed iniziative esistenti di pubblicizzazione e referaggio delle tesi di dottorato; adeguata formulazione delle tematiche scientifiche e degli obiettivi formativi, riduzione della frammentazione dei corsi di dottorato; accuratezza delle informazioni fornite per la valutazione. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 4 2.Elenco dottorandi, supervisori e titolo delle tesi Dottorando Ciclo Supervisore FRAGKOU Effrosyni GANAU Mario 25 STANTA Giorgio 25 SCOLES Giacinto GIORGIS Valentina AMBROSINI Stefano CHEN Yan Xin 25 ROMANATO Filippo 25 RUBINI Silvia SAMMITO Davide LUCAFO' Marianna PERONIO Angelo MARSICH Lucia BIDOGGIA Silvia CARGNELLO Matteo D'ESTE Elisa ERA Daniel ELIA Caterina PAKDAST Hossein SCIUTO Giacomo COZZARINI Luca ZANUSSO Chiara TAVANO Federica 25 FORNASIERO Paolo 25 ROMANATO Filippo 25 SAVA Gianni 25 COMELLI Giovanni 25 SERGO Valter SSD Titolo Tesi MED/08 Nanobiotechnologies for Dermatological Applications FIS/03 Nanotechnology applications in quantitative neuroscience: proteomics assessment of astrocyte stressing and neuronal plasticity FIS/03 Development, design and characterization of Metamaterials with negative refractive index FIS/01 Sintesi di nanostrutture di semiconduttori e loro studio mediante luce di sincrotrone. CHIM/03 Nanostructured Titanium Dioxide Based Materials for Photocatalysis and Phototelectrocatalysis FIS/03 Design, Fabrication and Characterization of Plasmonic Nanostructures for Solar Cells Light Harvesting Enhancement. BIO/14 Study of carbon nanostructures as carriers for drugs for cancer chemotherapy. FIS/03 Single-molecule heterogeneous catalysis INGIND/22 Design and synthesis of functionalized metal nanoparticles for bio-analysis with Surface-Enhanced Raman Scattering (SERS) 25 PASQUATO CHIM/06 Gold nanoparticles as carriers for drug delivery Lucia applications 24 FORNASIERO CHIM/03 Rare earths oxides based nanostructures as Paolo heterogeneous catalysts 24 MORGANTE FIS/01 Bio-sample environment manipulation using advanced Alberto microscopy techniques 24 GIRALDI Tullio BIO/14 Nanotechnology application in pharmacogenetic research 24 TOFFOLI BIO/14 Molecular Interaction on Nanoscale in Cancer Therapy Giuseppe 24 LAZZARINO FIS/01 Single Molecule Detection with Advanced MEMS Marco Resonators 24 MUSCIA INGInnovative LHTS Elements Based on Nanotechnologies Roberto IND/15 24 SERGO Valter INGQuantum dot-based materials IND/16 24 TOFFOLI BIO/14 Nanotechnologies and oncology: Giuseppe pharmacokinetics and pharmacogenomics to optimize the antitumor therapie 24 BONIN Serena MED/35 Cell mobility and metastatic spreading: a study on human neoplastic cells using optical tweezer Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 5 Dottorando Ciclo Supervisore SSD FIOR Raffaella 24 SBAIZERO Orfeo INGIND/22 LANZILOTTO Valeria LUISI Immacolata MIGLIORINI Elisa 24 MORGANTE Alberto 24 MARZARI Roberto 24 LAZZARINO Marco FIS/01 MARINI Monica ASTOLFO Alberto SANTARELLI Xenja BELLOMO Francesca RAMPINO Antonio SOVERNIGO Enrico MARCHESI Giulio BIRARDA Giovanni 24 FIRRAO AGR/12 Giuseppe 23 ARFELLI Fulvia FIS/07 FONTANIVE Luca 23 ROSEI Renzo BIO/06 FIS/01 FIS/03 Titolo Tesi Ionic channel behavior: development of a novel, non destructive method for mechanical and electrical analysis of a single cell Self assembly and charge transfer properties of thin organic films at metal surfacese Identification of novel protein scaffolds for binding of small molecules Characterization of nanostructured substrates which control the Embryonic Stem Cells differentiation into neurons Implementation of simple logics in bioinorganic hybrid nanosensors Development of novel experimental methods for cell tracking using nanoparticles Correlation between structure and reactivity for nanostructured catalysts Biopolymer based scaffold for tissue engineering 23 PAOLETTI BIO/10 Sergio 23 CESARO Attilio CHIM/04 Polysaccharide based nanoparticles for drug delivery 23 MORGANTE Alberto 23 BRESCHI Lorenzo 23 FRANCIOSI Alfonso FIS/01 Influence of nanostructure on the electronic properties of heterojunctions in photovoltaic cells MED/28 Analysis of aging and stability of bonded interface in dentistry FIS/01 Development of microfluidic devices for biomedical applications of Synchrotron Radiation FTIR Microspectroscopy 23 CESARO Attilio CHIM/04 Nanoscale interaction for higher efficiency of contrast media Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 6 3.Schede attività dottorandi Questo allegato contiene le schede dei dottorandi della scuola di nanotecnologia così come sono pervenute al 31 gennaio 2009. Sono quindi incluse le schede dei dottorandi dei cicli 22, 23 e 24. Dottorandi del 22 ciclo: DAL MIGLIO Matteo Maria, LACOVIG Paolo, LORENZUT Barbara, PAVAN Giovanni Maria, POSOCCO Paola, TRAVAN Andrea, UMERI Andrea. Dottorandi del 23 ciclo: ASTOLFO Alberto, BELLOMO Francesca, BIRARDA Giovanni, FONTANIVE Luca, MARCHESI Giulio, RAMPINO Antonio, SANTARELLI Xenja, SOVERNIGO Enrico Dottorandi del 24 ciclo: CARGNELLO Matteo, COZZARINI Luca, D‟ESTE Elisa, ELIA Caterina, ERA Daniel, FIOR Raffaella, LANZILOTTO Valeria, LUISI Immacolata, MARINI Monica, MIGLIORINI Elisa, PAKDAST Hossein, SCIUTO Giacomo, TAVANO Federica, ZANUSSO Chiara. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 7 Dottorandi del 22 ciclo: Candidate Matteo Maria Dalmiglio Title of the thesis: Reactivity and oxidation properties of catalytic supported nanoclusters Supervisor: Luca Gregoratti Tutors (if any): Research Activity The research activities performed in this 3 years were focused on studying the reactivity and oxidation properties of catalytic supported nanocluster on oxide films and carbon nanotubes (CNTs), by means of different chemical and structural characterization techniques; in particular the main technique used was the scanning photoemission spectromicroscopy (SPEM) available at the EscaMicroscopy beamline of the Elettra Synchrotron Light Source. This novel experimental technique allows sample‟s chemical mapping with a spatial resolution of 100nm and the acquisition of photoemission spectra on regions with the same dimension. In particular we studied PtRh cluster deposited by PLD (pulsed laser deposition) on a tungsten single crystal (W(110)) covered by a thin magnesium oxide film (MgO). The starting of the research activities related to this project was preceded by a training aimed to become familiar with the experimental setup and data acquisition procedures. During this time I participated to several user beamtime. The first action strictly related to my thesis was focused on the realization of a setup for the coverage of a micron-sized region of a single MCNT by using commercial and home-made masks. This setup was used to produce nanoclusters covered patches as model systems to investigate surface and bulk diffusion, mass transport, etc. The cluster‟s characterization and study was performed with AFM (atomic force microscope) and SEM (scanning electron microscope) in collaboration with other laboratory at Elettra and TASC. Afterwards different experiments were made with the aim to understand the nanoclusters catalytic activity during oxidation and reduction conditions. It was demonstrated that under an atomic oxygen flux a selected oxidation occurs: rhodium atoms undergo stronger and faster oxidation than platinum ones. Furthermore, the oxidation process is composed by many intermediate steps, in which metastable oxides are formed. Very small cluster‟s oxidation (<10nm diameter) is significantly faster then the bigger one (>100nm). Some morphological and structural clusters‟ modifications after long oxidation treatments were also investigated using a high resolution SEM (<2nm lateral resolution). In this last third year the nanocluster reactivity towards redox reactions after many reaction cycles has been investigated in detail; the chemical characterizations have been carried out on the as Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 8 deposited particles and on the same particles after many reactions cycles in order to probe the modifications of the catalysts. The results obtained confirm some previous evidences on the decreasing oxides‟ stability. In fact after the same oxidation rate the “aged” particles are easily reduced; sometimes the photon beam intensity was enough to reduce the samples in a spectra acquisition time. Some other measurements were performed at the Nanospectroscopy beamline where it‟s possible to use a LEEM microscope ((Low Energy Electron Microscope) that combines a high spatial resolution (<5nm) to a high sensitivity to surface structural modifications. In particular the behaviour of the clusters‟ polycrystalline structure was studied during oxidation-reduction treatments. It was shown that the clusters‟ surface is polycrystalline: the nano crystals on the surface had different orientation from region to region of the sample and undergo different oxidation rate. The diffraction pattern revealed that after a long oxidation all the informations on the long range order are completely lost. Other experiments were realized with SEM and AFM for studying the clusters‟ morphology and behaviour at different annealing temperature. The results showed structural and surface morphology changes on the clusters‟ facets. Along this year a peer review paper that summarizes the main results obtained during this PhD has been submitted to the Journal of Physical Chemistry . Other time was dedicated to prepare posters and presentations for conferences and a summer school on reactivity of nanoparticles in different European countries. - - - Publications on scientific journals (printed or in press) Barinov, A., Malcioǧlu, O.B., Fabris, S., Sun, T., Gregoratti, L., Dalmiglio, M., Kiskinova, M. Initial stages of oxidation on graphitic surfaces: Photoemission study and density functional theory calculations, 2009, Journal of Physical Chemistry C 113 (21), pp. 90099013 Bozzini, B., Dalmiglio, M., De Gaudenzi, G.P., D'Urzo, L., Gregoratti, L. An investigation of the corrosion of WC-Co cermets in CN--containing aqueous solutions. Part II: Synchrotron-based high lateral-resolution XPS study, 2009, Corrosion Science 51 (8), pp. 1675-1678 M. Dalmiglio, M. Amati, L. Gregoratti, T. O. Menteş, M. A. Niño, L. Felisari and M. Kiskinova, Catalytic activity of PtRh particles, submitted to Journal of Physical Chemistry Publications/abstracts in conferences/congresses (national or international) Books /Chapters and sections of books Other publications Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 9 Participation to conferences (as speaker) - First common workshop of the 'Scuola di Dottorato di Ricerca in Nanotecnologie' and the 'Nano-IMPRS' in Halle on July 15-16, 2009. Educational Activity - Periods abroad (date and place) 14-17/07/2009: Halle, Max Plank Institute - 21-29/08/2009: Sonderborg (DK), Summer School on 'Reactivity of nanoparticles for more efficient and sustainable energy production' - 09-11/09/2009: Wittenberg, Joint Workshop of SFB762 & IMPRS Classes followed (date, course, professor, type of course) Conferences, seminars, advanced courses and other didactic activities Congresso scuola di dottorato di gennaio X-ray microscopy: dealing with real-life complexities Modelling reactions at the nanoparticle scale, Prof. Phillip R. Westmoreland Dept of Chemical Engineering, University of Massachusetts Amherst Low-dimensional oxide structures on metal surfaces Stress-induced Mesoscopic Patterns on a Single Crystal Surface, Tevfik Mentes Chimica fisica delle interfasi in sistemi nano strutturati, Dr Italo Colombo Summer School on 'Reactivity of nanoparticles for more efficient and sustainable energy production' in Sonderborg (DK) XPS Measurements for Probing Dynamics of Chargin How to write (and manage) a research project Support educational activity and teaching Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 10 Candidate PAOLO LACOVIG Title of the thesis: Electronic structure, morphology and chemical reactivity of nanoclusters and low-dimensional systems: fast photoemission spectroscopy studies Supervisor: Dr. Alessandro BARALDI (Physics Department – Uni TS) Tutors (if any): Dr. Silvano LIZZIT (Sincrotrone Trieste S.C.p.A.) Research Activity During the three-year PhD research project Paolo Lacovig was involved in the development of innovatory instrumentation for high energy- and high temporal-resolution acquisitions of photoemission spectra and its applications. From the latter point of view the experimental activity hinged on the study of several physical systems for which the characteristics of the new experimental set-up have been fully exploited. The first year activity was focused on the hardware and software development for the new electron energy analyser installed on the SuperESCA beamline at the Elettra synchrotron light source. The analyser commissioning phase focused on the estimation of the energy (25 meV) and temporal resolution (80 ms) achievable with the new instrumentation in synchrotron radiation photoemission experiments. The innovative properties of this novel instrument have been exploited for investigations on the electronic structure, morphology and chemical properties of low-dimensional systems. One of the most significant results concerns the understanding of the modifications in the chemical reactivity of bimetallic interfaces due to the different thickness of the pseudomorphically grown overlayer. In the case of Pd-Ru bimetallic interface, we found out how the surface electronic structure, and its chemical properties as a consequence, can be tuned by varying the number of Pd atomic layers grown on the Ru(0001) surface. The temporal resolution achieved with the new electron energy analyser allowed studies on dynamical processes up to now inaccessible; in particular the investigation of the the graphene growth process at high temperature on transition metal surfaces (Ir, Pt and Rh) and the study of the chemical reactivity of Pt nanoclusters supported on MgO. In the first case, we discovered that graphene formation proceeds via preliminary nucleation of dome-shaped C nano-islands. In the second case, we succeded in following both the dynamics of CO adsorption process and the CO+O2→CO2 reaction on Pt nano-clusters grown on a ultra-thin film of magnesium oxide. Finally, the morphology of Pd, Pt, Rh and Au nanoclusers grown on different carbon-based substrates (namely graphite, single-walled carbon nanotubes and graphene) has been characterized. Among the most interesting results we report the understanding of the dependence of the metalsubstrate interaction on the cluster size and the role of defects in the nucleation and intercalation processes. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 11 Publications on scientific journals (printed or in press) 1. G. Cautero, R. Sergo, L. Stebel, P. Lacovig, P. Pittana, M. Predonzani, S. Carrato, A twodimensional detector for pump-and-probe and time resolved experiments, Nucl. Instrum. Methods A 595, 447-459 (2008) 2. P. Lacovig, M. Pozzo, D. Alfè, P. Vilmercati, A. Baraldi, S. Lizzit, Growth of Dome-Shaped Carbon Nanoislands on Ir(111): The Intermediate between Carbidic Clusters and QuasiFree-Standing Graphene, Phys. Rev. Lett. 103, 166101 (2009) 3. E. Golfetto, A. Baraldi, M. Pozzo, D. Alfè, A. Sala, P. Lacovig, E. Vesselli, S. Lizzit, G. Comelli, R. Rosei, Determining the chemical reactivity trends of Pd/Ru(0001) pseudomorphic overlayers: core level shift measurements and DFT calculations, J. Phys. Chem. C, in press DOI: 10.1021/jp908568v Other publications 1. G. Cautero, R. Sergo, L. Stebel, P. Lacovig, P. Pittana, M. Predonzani, S. Carrato, “A twodimensional detector for pump-and-probe and time resolved experiments”, Highlights 2007-2008, 110 (2008) Elettra Participation to conferences (as speaker) 1. POSTER - P. Lacovig, M. Pozzo, D. Alfè, P. Vilmercati, A. Baraldi, and S. Lizzit, Graphene Growth on Ir(111): A Fast XPS Study - CINF-DTU Summer School on “Reactivity of nanoparticles for more efficient and sustainable energy production”, Sandbjerg Gods (Denmark), 2009 2. POSTER – P. Lacovig, A. Baraldi, S. Lizzit, Chemical reactivity of nanoclusters deposited on solid surfaces: new time-domain and enhanced surface-sensitivity of photoelectron spectroscopy - Joint Workshop of SFB762 & IMPRS on “Magnetic properties of oxidic and multiferroic systems”, Wittenberg (Germany), 2009 Educational Activity Classes followed (date, course, professor, type of course) COURSE: “Advanced microscopy”, April-June, 2007 (C. Africh, V. Grillo) - 20 hours COURSE: “Photoemission Spectroscopy and Spectro-Microscopy”, February-March, 2008 (A. Baraldi, A. Goldoni, A. Locatelli) - 25 hours REVIEW ARTICLE: B. Hammer, J.K. Norskov, “Theoretical Surface Science and Catalysis – Calculation and Concepts”, Advances in Catalysis 45, (2000) 71-128 BOOK CHAPTER: C.S. Fadley, “Basic Concepts of X-Ray Photoelectron Spectroscopy” in C.R. Brundle, A.D. Baker (Eds.), “Electron Spectroscopy: Theory, Techniques and Applications”, Pergamon Press, New York, 1978, 1-156 BOOK: M. Cardona, L. Ley (Eds.), “Photoemission in Solids I: General Principles”, Springer-Verlag, Berlin, 1978, 1-288 Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 12 REVIEW ARTICLE: D.P. Woodruff, A.M. Bradshaw, “Adsorbate structure determination of surfaces using photoelectron diffraction”, Rep. Prog. Phys. 57 (1994) 1029-1080 REVIEW ARTICLE: J. Libuda, H.-J. Freund, “Molecular beam experiments on model catalysts”, Surf. Sci. Rep. 57 (2005) 157-298 REVIEW ARTICLE: C.T. Campbell, “Ultrathin metal films and particles on oxide surfaces: structural, electronic and chemisorptive properties”, Surf. Sci. Rep. 27 (1997) 1111 REVIEW ARTICLE: M. Baumer, H.-J. Freund, “Metal deposits on well-ordered oxide films”, Progr. Surf. Sci. 61 (1999) 127-198 LABORATORY: “Operation of the SuperESCA beamline: alignment and calibration procedure; introduction to the main beamline instrumentation”, February, 2007 (S. Lizzit, S. Gardonio) – 16 hours LABORATORY: “Sample mounting techniques and cleaning procedures for transition metal single crystals”, April, 2007 (S. Lizzit) – 12 hours LABORATORY: “Growth of oxide layers on transition metal”, May, 2007 (A. Baraldi) – 10 hours LABORATORY: “Evaporator assemblies and chemical vapor deposition of transition metal nanoclusters ”, June, 2007 (S. Lizzit) – 16 hours LABORATORY: “Data analysis techniques”, October, 2007 (S. Lizzit, A. Baraldi, S. Gardonio) – 12 hours Conferences, seminars, advanced courses and other didactic activities CONFERENCE - Nanotech Conference 2008 – Trieste – January 15th-17th, 2008 CONFERENCE - Nanotech Conference 2009 – Trieste – January 13th-15th, 2009 CONFERENCE - Joint Workshop SFB762 & IMPRS on “Magnetic properties of oxidic and multiferroic systems” – Wittenberg, Germany – September 10th-11th, 2009 SEMINAR – Confined and composite soft matter on the nanoscale (M.L. Saboungi) – Trieste – April 11th, 2008 SEMINAR – Modeling reactions at the nanoparticle scale (P.R. Westmoreland) – Trieste – May 8th, 2009 SEMINAR – Chimica fisica delle interfasi in sistemi nanostrutturati (I. Colombo) – Trieste – May 15th, 2009 SEMINAR – How to write (and manage) a research project (C. Blasetti, V. Sergo, M. Fermeglia) – October 16th, 2009 MEETING – Collegamento VPN e nuovo portale della Scuola di Dottorato (M. Fermeglia) – Trieste – March 20th, 2009 MEETING – Panoramica delle nuove modalità di comunicazione scientifica (S. Arabito, A. Bonazza, J. Piščanc) – Trieste – June 30th, 2009 SCHOOL – ARS 2 – Synchrotron radiation applications for nanostructured material and thin film investigations – Trieste – April 23rd-26th, 2007 SCHOOL – Summer School 2009 - Reactivity of nanoparticles for more efficient and sustainable energy production (CINF, DTU) – Sandbjerg Gods, Denmark – August 22nd27th, 2009 WORKSHOP – Bio Meets Nano: a surface scientist approach to bio-organic interfaces – Trieste – March 16th, 2007 SEMINAR – Nanoscale Fermi systems: Structure and dynamics of metal clusters (B. von Issendorf) – Trieste – March 7th, 2007 Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 13 SEMINAR – Reaction kinetics on nanostructured materials (J. Libuda) – Trieste – March 26th, 2007 SEMINAR – Ultrathin ordered titanium oxide films on Pt(111) properties and perspectives (F. Sedona) – Trieste – March 28th, 2007 SEMINAR – Quasi 1-D Metal Oxide and Phthalocyanine Nanostructures as Gas Sensors: Fabrication, Characterization and Prototype Devices (A. Kolmakov) – Trieste – June 20th, 2007 SEMINAR – Time resolved photoemission on Mott insulators and High Temperature Superconductors (L. Perfetti) – Trieste – July 17th, 2007 SEMINAR – X-ray micro- and nano-spectroscopies at ESRF (M. Salome) – Trieste – September 26th, 2007 SEMINAR – Electron-phonon interaction in graphene: non-adiabatic Kohn anomalies and electron-mass enhancement (F. Mauri) – Trieste – October 25th, 2007 SEMINAR – XAS measurements under extreme conditions at third generation synchrotron sources (S. De Panfilis) – Trieste – December 6th, 2007 SEMINAR – X-ray absorption spectroscopy and high pressure science at ESRF: techniques, results, and future opportunities (G. Aquilanti) – Trieste – December 6th, 2007 SEMINAR – Studies of carbon nanotubes and nano-crystalline Silicon under high pressures (S.M. Sharma) – Trieste – December 14th, 2007 SEMINAR – The power of SAXS: exploration of the magic world of biomaterials (M. Rappolt) – Trieste – February 1st, 2008 SEMINAR – Electron-Phonon Superconductivity in graphite (L. Boeri) – Trieste – February 5th, 2008 SEMINAR – X-ray study of MEMS structures (A. Dommann) – Trieste – February 18th, 2008 SEMINAR – First-Principle investigations of intrinsic and Si-doped GaAs nanowires (N. Gaderi) – Trieste – February 29th, 2008 SEMINAR – Spatially resolved spectroscopic characterization of cluster assembled nanocomposite films (M. Amati) – Trieste – March 7th, 2008 SEMINAR – Unravelling the electronic structure of intercalated graphite: a key to graphene and single-wall carbon nanotubes (A. Gruneis) – Trieste – March 12nd, 2008 SEMINAR – Characterization and manipulation of single molecules and molecular complexes by Low-Temperature Scanning Tunneling Microscopy (C. Dri) – Trieste – April 2nd, 2008 SEMINAR – Bacterial protein crystals as pure biomimetic nanomolecules and other biophysical issues (J.L. Toca-Herrera) – Trieste – April 4th, 2008 SEMINAR – Some new directions in materials and nanostructure studies with photoemission and x-ray emission:instrumentation, standing waves and hard x-rays (C. Fadley) – Trieste – April 14th, 2008 SEMINAR – Catalytic model systems studied by STM and photoemission (C. Blasetti) – Trieste – April 16th, 2008 SEMINAR – Celle fotovoltaiche organiche nanostrutturate: prime misure e primi risultati (E. Sovernigo) – Trieste – April 16th, 2008 SEMINAR – Evaporation driven self assembly of colloidal/nano particles during spray drying: A SAXS investigation (D. Sen) – Trieste – April 18th, 2008 SEMINAR – Photoelectron spectroscopy of reactive intermediates with synchrotron radiation (F. Innocenti) – Trieste – April 24th, 2008 SEMINAR – Magnetism atom by atom: Magnetic states where you would not expect them (S. Modesti) – Trieste – May 7th, 2008 Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 14 SEMINAR – Molecular motors at surfaces (P. Rudolf) – Trieste – May 8th, 2008 SEMINAR – Catalyst assisted and catalyst free growth of GaAs nanowires by molecular beam epitaxy (MBE) (F. Jabeen) – Trieste – May 8th, 2008 SEMINAR – Electronic states of Cu vicinal surface nanopatterned by oxygen-induced reconstruction (C.E. Viol Barbosa) – Trieste – June 11th, 2008 SEMINAR – Catalytic combustion of methane. A case study: Pd/CeO2 catalysts (S. Colussi) – Trieste – June 23rd, 2008 SEMINAR – Mechanisms of high-order photoemission from metal surfaces (F. Bisio) – Trieste – June 24th, 2008 SEMINAR – Covalent connection of organic molecules on Au(111) (L. Lafferentz) – Trieste – July 4th, 2008 SEMINAR – Imaging and force spectroscopy by AFM on DNA (G. Di Santo) – Trieste – July 7th, 2008 SEMINAR – Polyoxometalates: from Molecular Catalysts to Nanostructures, towards Innovative Materials (M. Bonchio) – Trieste – July 9th, 2008 SEMINAR – Nanofabrication strategies for the development of new tools for biosensing (G. Rius Suñé) – Trieste – July 14th, 2008 SEMINAR – Growth, Properties Measurements and Nanodevices Applications of 1D Nanoclusters (J. Tian) – Trieste – September 12th, 2008 SEMINAR – Production and characterization of 3D metal nanoparticle films (S. D‟Addato) – Trieste – November 17th, 2008 SEMINAR – Bulk and supported oxides as catalysts for gas-phase reactions: Characterization and reactivity of surface species (F. Cavani) – Trieste – February 24th, 2009 SEMINAR – Low-dimensional oxide structures on metal surfaces (S. Surnev) – Trieste – March 6th, 2009 SEMINAR – Transducing biomolecular interactions into nanomechanics (P. Bergese) – Trieste – March 10th, 2009 SEMINAR – Linear and nonlinear spectroscopy of a single metal nanoparticle (N. Del Fatti, F. Vallée) – Trieste – April 16th, 2009 SEMINAR – Nanothermodynamics applied to the local thermal properties of disordered materials (R.V. Chamberlin) – Trieste – May 14th, 2009 Support educational activity and teaching Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 15 Candidate Barbara Lorenzut – [email protected] Title of the thesis: “Development of nanostructured catalysts for hydrogen production and purification” Supervisor: Prof. Paolo Fornasiero Tutor: Dr. Tiziano Montini Research Activity During the three years of PhD, catalytic systems for hydrogen production and purification were synthetized and characterized. In the first year, catalysts based on transition metal supported on ZnO/Al2O3 were developed for methanol and ethanol steam reforming. The activity was carried out in collaboration with ACTA s.p.a.. This collaboration was continued during the second year, when the research activity was directed to the development of systems based on ruthenium embedded into porous oxides for hydrogen production from ammonia cracking reaction. Finally, during the last year, the complete characterization of the developed catalysts confirmed that the embedded approach leads to nanostructured catalysts with very good catalytic activity and high thermal stability. Moreover, with the scientific collaboration of ACTA s.p.a, non noble metal catalysts (Fe and Mo based) were synthesized for ammonia cracking. These Fe-Mo based catalysts were prepared by classical impregnation method with great attention to the role of either the metal and the support. The effect of K doping on the catalytic activity and stability was considered on the most active systems for NH3 cracking; enhancement of the catalytic activity was observed only for catalyst prepared by co-impregnation with salt of potassium at low concentration (< 0.5%). During the third PhD year, a new project concerning the development of catalysts for glycerol reforming was also started. Pt based catalysts supported on Al2O3 were developed, characterized and tested. The introduction of CeO2 and La2O3 as dopants increases the H2 yields and the thermal stability in reaction conditions. Part of the results obtained in collaboration with ACTA s.p.a. is still confidential and it will not be presented during the final examination. Publications on scientific journals (printed or in press) Italian Patent FI2007A0000179 “Catalizzatori per la produzione di gas di sintesi da reforming di idrocarburi o alcoli comprendenti un supporto in ZnO e loro uso” ; Inventors: Paolo BERT, Stefano CATANORCHI, Paolo FORNASIERO, Mauro GRAZIANI, Barbara LORENZUT, Hamish MILLER, Tiziano MONTINI, Marina RAGNOLI, Adriana SCAFFIDI, Alessandro TAMPUCCI. Loredana De Rogatis, Tiziano Montini, Barbara Lorenzut and Paolo Fornasiero, Energy Environ. Sci., 2008, 1, 501 – 509 “NixCuy/Al2O3 based catalysts for hydrogen production”. T. Montini, A. Speghini, L. De Rogatis, B. Lorenzut, M. Bettinelli, M. Graziani and P. Fornasiero, “The identification of the structural phases of CexZr1-xO2 by Eu(III) luminescence studies.”, Journal of the American Chemical Society 131 (2009), 13155-13160 Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 16 S. Specchia, L. D. Vella, B. Lorenzut, T. Montini, V. Specchia and P. Fornasiero, “Effect of the catalyst load on syngas production in SCT-CPO reactors.”, Industrial and Engineering Chemistry Research (2009), accepted for publication, doi:10.1021/ie900695j. L. De Rogatis, M. Cargnello, V. Gombac, B. Lorenzut, T. Montini and P. Fornasiero, “Embedded phases: a way to active and stable catalysts”, ChemSusChem (2009), accepted for publication Publications/abstracts in conferences/congresses (national or international) Meeting ACTA, 25 th -27 th October 2007, Lavoria (PI)- Presentation of obtained results “Development of nanostructured catalysts supported on ZnO for H2 production from ethanol steam reforming” XII National Congress of Industrial Chemistry – “Energy, materials and products from ecosustainable technologies and processes” – Genova 30 th June-3 th July 2008. Oral communication “H2 production from ethanol and methanol steam reforming over Co, Ni, Cu based catalysts”. Catalysis interdivisional Group School of Italian Chemical Society “From catalyst to process: principles, strategies and ways”– Certosa di Pontignano (SI) 3 th -6 th November 2008 – Poster communication “Influence of preparation method on performance of Co, Ni, Cu based catalysts for methanol and ethanol steam reforming for H2 production” Meeting ACTA, 12 th November 2008, Lavoria (PI)- Presentation of obtained results “Development of Ru embedded nanostructured catalysts for ammonia decomposition”. CLEAR Summer School in Catalysis 2009 “Catalysis Lectures for Environmental Applications & Renewables”- Porto Carras, Chalkidiki, Greece, May 24 th -29 th, 2009. Poste communication “Ruthenium nanoparticles embedded catalysts for hydrogen production from ammonia decomposition” Round table partecipation “Hydrogen production”. Meeting ACTA, 24 th July 2009, Trieste- Presentation of obtained results “Development of biomimetic catalysts Fe/Mo based for ammonia decomposition”. Meeting ACTA, 4 th November 2009, Trieste- Final presentation on results obtained in collaboration with ACTA S.p.a. during ammonia cracking project. Educational Activity Periods abroad (date and place) CLEAR Summer School in Catalysis 2009 “Catalysis Lectures for Environmental Applications & Renewables”- Porto Carras, Chalkidiki, Greece, May 24 th -29 th, 2009 Classes followed (date, course, professor, type of course) “ARS2 II School: “ Sinchrotron radiation applicated on the nanostructured materials and thin films characterization” Trieste, Adriatico Guesthouse, 22 th -26 th April 2007 Course of “Eterogeneous catalysis” Prof. Paolo Fornasiero (4CFU -36 h) Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 17 Course of “Inorganic chemistry I” Prof. Mauro Graziani (8CFU -64 h) Course of “Advanced microscopies” at TASC laboratories Dr. Vincenzo Grillo – (6 h) School of catalysis of the Italian Chemical Society- Certosa di Pontignano (SI), 3-6 November 2008 Course of “Structural chemistry” Prof. Lucio Randaccio (4CFU -36 h) Course of “Synchrotron light characterization techniques” Prof. G. Vlaic Course of “Inorganic chemistry II” Prof. M. Graziani Conferences, seminars, advanced courses and other didactic activities Conference: “Molecular Printboards, from supramolecular chemistry to nanofabrication”- Prof. David N. Reinhoudt-Supramolecular Chemistry and Tecnology, Faculty of Science and Tecnology, University of Twente, Olanda - il 5 th March 2007 - University of Trieste Conference:” La sfida del secolo- Energia” –Dott. Piero Angela and Alberto Pinna - University of Trieste Conference: “ Per fortuna si innalza il prezzo del petrolio. Così la chimica riparte”- Prof. Ferruccio Trifirò Industrial and materials chemistry Department, University of Bologna and journal editor of “La Chimica e l‟Industria” University of Trieste Conference: “Funcionalized gold nanoparticles: synthesis and applications”-Prof. Lucia Pasquato- Chemical Sciences Department- University of Trieste Conference: “ Carbonylation reaction in supercritical carbon dioxide”- Dr. Anna M. MasdeuBultò- Department de Quimica Fisica Inorganica, Universitat Rovira i Virgili, Terragona ( Spagna)- Chemical Sciences Department- University of Trieste Conference: “Methane clatrate: an energy storage”- Prof. Giacomo Costa, Prof. Iginio Marson, Dr. Umberta Tinivella, Prof. Lino Santoro, Dr. Fabio Pagan - University of Trieste Congress Nanotech 2008 “Nanotechnology for Industry 2015” – Venice 10 th -13 th March 2008 “Workshop safety” organized by VWR - University of Trieste, 20 th May 2008 Conference: “Paints: Applied chemistry”- Dr. Gianpaolo Vicario – Elacrom Udine - 26 th March 2008 - Chemical Sciences Department- University of Trieste Conference: “Electronic Spin resonance Spectroscopy in Supramolecolar Chemistry” – Prof. Marco Lucarini – Organic Chemistry Department “A. Mangini” University of Bologna – 4th April 2008 - Chemical Sciences Department- University of Trieste. Conference: “ Confined and composite soft matter on the nanoscale”- Prof. Marie Luise Saboungi- CRMD, CNRS-Universitè d‟Orléans- 11 th April 2008 - University of Trieste Conference: “Nanomaterials in catalysis: problems and possible solutions”- Dr. Massimiliano Comotti – Acta s.p.a. – 21 th April 2008 - Chemical Sciences Department- University of Trieste Conference: “Theoretical simulation of condensed systems XAS spectra” - Prof. Giovanna Fronzoni – Chemical Sciences Department- University of Trieste Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 18 Formative lecture: “Safety practice in the gas employment”- organized by Sapio group - 26 th November 2008 - Chemical Sciences Department- University of Trieste Annual meeting PhD School in Nanotechnology, 13 th -15 th January 2009, “Information meetings for doctoral students”, 30 th June 2009, “Seminar on writing (and managing) a research project”, 16 th October 2009 Annual meeting PhD School in Chemical and Pharmaceutical Sciences and Technologies, 21th -23 th January 2009.- University of Trieste Conference: “Modelling reactions at the nanoparticle scale”, Prof. P. Westmoreland, 8 th May 2009 - University of Trieste Conference: “Physical Chemistry nanostructured systems interphases”, Dr. I. Colombo, 15 th May 2009- University of Trieste Conference: “Penta coordinated Pd complexes and bi-functional effects in organometallic chemistry”, Prof. F. Ragaini, 30 th June 2009 - University of Trieste Conference “NMR Techniques for Investigating the Supramolecular Structure in Solution”, Prof. Alceo Macchioni, 17 th September 2009 - University of Trieste Conference. “Nanoparticles dissolution and absorption: biopharmaceutics, physical pharmacy and simulation”, Prof. Michael B. Bolger, 25 th September 2009 Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 19 Candidate GIOVANNI MARIA PAVAN Title of the thesis: structural and energetic analysis of organic and inorganic systems. The molecular modelling potentiality. Supervisor: Prof. Sabrina Pricl Tutors (if any): Research Activity During the first year of activity, the subject of the study has been the “target therapy” in oncology, particularly related to protein-drug systems characteristic of diseases as chronic myeloid leucemia (LMC) and gastrointestinal stromal tumors (GISTs) using molecular simulations methods in the framework of a collaboration with the Istituto Tumori of Milan. During the second year, the attention was pointed to the study of the c-KIT complex, often mutated in GIST, with various inhibitors in another collaboration with the M.D. Anderson hospital of Houston (TX, USA). In this framework we performed studies on primary and secondary mutations and direct energetic and structural comparison between complexes composed of c-KIT with two inhibitor drugs (imatinib and dasatinib), and the therapy response. In the last year of activity, the study of the KIT L576P mutation, present in few rare tumors, was investigated further and, together with the Istituto Tumori of Milan, we explored the causes of such decreased affinity for imatinib reported by this mutation. This study provided very interesting results, highlighting how other inhibitors (sorafenib and nilotinib) can show the same affinity problems of imatinib with kinases, being their penetrations in the binding pocket of c-KIT extremely similar. On the contrary, drugs like dasatinib and sunitinib, that bind rather differently with the receptor, seem not to be affected by the presence of the L576P mutation. In conclusion, the study of a set of several mutations on the c-KIT-imatinib complex, again in collaboration with the M.D. Anderson hospital, evidenced an optimal accordance between the results obtained in silico and the clinical evidences, demonstrating the reliability and the potentiality of molecular simulation as a powerful tool for biomedical survey. Publications on scientific journals (printed or in press) 1. E. Conca, T. Negri, A. Gronchi, E. Fumagalli, E. Tamborini, G.M. Pavan, M. Fermeglia, M.A. Pierotti, S. Pricl, S. Pilotti. Activate and resist: L576P-KIT in GIST. Molecular Cancer Therapeutics. Mol Cancer Ther 1535-7163.MCT-09-0662. Mol Cancer Ther 8(9):2491-5, 2009. 2. S.E. Woodman, J.C. Trent, K. Stemke-Hale, A.J. Lazar, S. Pricl, G.M. Pavan, M. Fermeglia, Y.N. Gopal, D. Yang, D.A. Podoloff, D. Ivan, K.B. Kim, N. Papadopoulos, P. Hwu, G.B. Mills and M.A. Davies. Activity of dasatinib against L576P KIT mutant melanoma: Molecular, cellular, and clinical correlates. Mol Cancer Ther 8(8):2079-85, 2009. 3. T. Negri, G.M. Pavan, S. Pricl, S. Lagonigro, F. Miselli, A. Greco, M. Fermeglia, M.A. Pierotti, S. Pilotti, E. Tamborini, T670X KIT mutations in GISTs: making sense of missense. J Natl Cancer Inst 2009;101:1–11. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 20 4. J.C. McAuliffe, W.L. Wang, G.M. Pavan, S. Pricl, D. Yang, S.S. Chen, A.J.F. Lazar, R.E. Pollock, J.C. Trent. Unlucky number 13? Differential effects of KIT exon 13 mutation in gastrointestinal stromal tumors. Molecular Oncology. August 2008. Vol. 2, Issue 2, Pages 161-163. 5. P. Posocco, G.M. Pavan, G. Scocchi, J.W. Handgraaf, A. Malek, M. Maly, M. Fermeglia, J.G.E.M. Fraaije, C.V. Catapano, A. Danani, S. Pricl. Base Invaders. Coupling Experiments and Multiscale Modeling of Dendrimer-Based siRNA Delivery Agents. Advances in Science and Technology. 2008, 57: 154-159. Publications/abstracts in conferences/congresses (national or international) 1. S.E. Woodman, J.C. Trent, K. Stemke-Hale, A. Lazar, S. Pricl, G.M. Pavan, N. Papadopoulos, P. Hwu, G.B. Mills, M.A. Davies. Selective Activity of Dasatinib for the Most Common KIT Mutation in Melanoma (L576P). Journal of Clinical Oncology, 2009 ASCO Annual Meeting Proceedings (Post-Meeting Edition). Vol 27, No 15S (May 20 Supplement), 2009: 9019. 2. S. Pricl, G.M. Pavan, M. Fermeglia, E. Tamborini, M.A. Pierotti, S. Pilotti. EGFR mutations and gefitinib affinity: molecular insights from in silico experiments. European Journal of Cancer Supplements, Volume 6, Issue 12, October 2008, Page 154. EORTC-NCI-AACR 2008. Geneva, 21-24 October 2008. 3. S. Pricl, E. Tamborini, M. Ferrone, G.M. Pavan, T. Negri, M.A. Pierotti, S. Pilotti. A clinical/modelling investigation of the activity of PKC412 against an imatinib resistant gastrointestinal stromal tumor (GIST) carrying a D842V mutation in PDGFRA. AACR 2007 – Los Angeles. Educational Activity Periods abroad (date and place) Classes followed (date, course, professor, type of course) Conferences, seminars, advanced courses and other didactic activities 1. 2. 3. 4. 5. 6th International Dendrimer Symposium. Stockholm, 14-18 June 2009. Trans-alp Nano 2008. Lione, 27-29 October 2008. BIO-dendrimer 2008 – Lodz, Poland, 03-05 July 2008. 1st European Conference for Clinical Nanomedicine – Basel, 18-21 May 2008. II Scuola ARS2 - Applicazioni della radiazione di sincrotrone allo studio dei materiali nanostrutturati e dei film sottili - Grignano (TS), 22-26 aprile 2007 Support educational activity and teaching Molecular Modelling class (Prof. Sabrina Pricl), module of “ab inizio Methods for Molecular Modelling”. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 21 Candidate PAOLA POSOCCO Title of the thesis: Multiscale molecular simulation of nanostructured systems Supervisor: prof. M. Fermeglia Tutors (if any): prof. S. Pricl Research Activity In recent years considerable interest and economic resources have been devoted to the nanotechnology and particularly to nanostructured materials by the European and international community. Their potential is related to the fact that these materials posses a structure at the nanometer level which confers macroscopic properties not comparable or detectable in common materials. To date, the knowledge of the properties and characteristics at the nanometric level and the resulting relations with the macroscopic performances achieved by the material are limited. Molecular simulation techniques are valuable tools that can be used not only to increase the understanding of phenomena at the molecular level, but also as a support for more efficient and sustainable design of new systems. The aim of the research was to develop novel procedures in the framework of a multiscale simulation approach to be applied to systems of industrial interest, with the ultimate goal of creating an effective tool effectively for the design and implementation of new nanostructured materials. The systems analyzed belong to different fields, ranging from polymeric nanocomposite materials, to epoxy resins, block copolymers, and gels for biomedical applications, in order to demonstrate the broad applicability of the developed methodology. As an example, the key results obtained in the case of three systems are summarized briefly: (i) block copolymers (polystyrene-poly(vinylpyridine)) loaded with metal nanoparticles of gold, (ii) cross-linked epoxy resins (based on glycidoxy propyl silane) with nanoparticles of titanium oxide, (iii) composite polymers (polyethylene oxide, nylon 6, …) in the presence of lamellar silicates (montmorillonite). (i) The morphology of the copolymer, when loaded with metallic particles functionalized with one or both polymeric building blocks in different percentages, has been predicted. In particular, the effect of concentration, degree and type of covering (enthalpic effect) and shape (entropic effect) of the nanoparticle on the morphology of the final composite was assessed, highlighting the thermodynamic parameters that can be used to control the dispersion of the metal in the polymer. (ii) A code for the simulation of the crosslinked matrix was developed, and the thermo-mechanical characteristics as a function of the degree of crosslinking achieved during the reaction has been evaluated. Accordingly, it has been possible to predict the mechanical properties of composite material as a function of volume concentration of nanofiller. (iii) A procedure has been create to calculate macroscopic properties of the nanocomposite materials (such as mechanical properties - Young‟s modulus, shear modulus, bulk modulus, Poisson's ratio – thermal properties- thermal expansion coefficient- electrical properties – electrical conductivity) depending on the concentration of clay and the quality of the dispersion starting only from molecular information of the material. According to the conceived computational recipe, no Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 22 experimental data are required as input at any scale level. In addition, we have analyzed the molecular interactions between the components of the system and assessed the impact of those on the final properties of the material, providing a tool for a better evaluation and a priori selection of each component. Publications on scientific journals (printed or in press) 1. Toth R, Voorn DJ, Handgraaf JW, Fraaije JGEM, Fermeglia M, Pricl S, Posocco P. Multiscale computer simulation studies of water-based montmorillonite/poly(ethylene oxide) nanocomposites. Macromolecules, 2009, on web (ma200901584w). 2. Scocchi G, Posocco P, Handgraaf JW, Fraaije JGEM, Fermeglia M, Pricl S. A complete multiscale modelling approach for polymer-clay nanocomposites. Chemistry - A European Journal, 15, 7586-7592, 2009. 3. Posocco P, Lisal M, Posel Z, Fermeglia M, Pricl S. A multiscale molecular simulation approach to the prediction of the morphology of self-assembled nanoparticles in diblock copolymers. Journal of Physical Chemistry B, submitted. 4. Posocco P, Fermeglia M, Pricl S. A multiscale toolbox for morphology prediction of diblock copolymers for drug delivery. Biomacromolecules, submitted. 5. Fermeglia M, Maly M, Posocco P, Pricl S. Multiscale Molecular Modeling of Hybrid Organic-Inorganic Nanocomposites of Type I and II. Advances in Science and Technology, 54, 265-269, 2008. 6. Maly M, Posocco P, Fermeglia M, Pricl S. Scripting approach in hybrid organic-inorganic condensation simulation: the GPTMS proof-of-concept. Molecular Simulation, 34, 12151236, 2008. 7. Maly M, Posocco P, Pricl S, Fermeglia M. Self-assembly of nanoparticle mixtures in diblock copolymers: multiscale molecular modeling. Industrial & Engineering Chemistry Research, 47, 5023-5038, 2008. 8. Scocchi G, Posocco P, Fermeglia M, Pricl S. Polymer-Clay Nanocomposites: A Multiscale Molecular Modeling Approach. Journal of Physical Chemistry B, 111, 2143-2151, 2007. 9. Scocchi G, Posocco P, Pricl S, Fermeglia M. To the nanoscale, and beyond! Multiscale molecular modeling of polymer-clay nanocomposites. Fluid Phase Equilibria, 261, 366-374, 2007. 10. Posocco P, Ferrone M, Fermeglia M, Pricl S. Binding at the core. Computational study of structural and ligand binding properties of naphthiridine based dendrimers. Macromolecules, 40, 2257-2266, 2007. Publications/abstracts in conferences/congresses (national or international) 1. Posocco P, Fermeglia M, Pricl S. Multiscale molecular modeling of di/triblock copolymers for Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 23 drug delivery. FOMMS, Blaine, USA, (2009). 2. Fermeglia M, Posocco P, Pricl S, Fraaije JGEM, Handgraaf JW, Scocchi G, Danani A. A complete multiscale modeling approach for nanocomposites. Eurofillers, Alessandria, Italy, (2009). 3. Fermeglia M, Posocco P, Pricl S, Fraaije JGEM, Handgraaf JW, Deglmann P, Kurkal-Siebert V, Weiss H. On the DPD Parameter Estimation From Atomistic/Quantum Mechanics Information. AIChE Annual meeting, Nashville, USA, (2009). 4. Fermeglia M, Scocchi G, Pricl S, Handgraaf JW, Fraaije JGEM, Posocco P. A Complete Multiscale Modeling Approach for Polymer-Clay Nanocomposites. AIChE Annual meeting, Nashville, USA, (2009). 5. Posocco P, Fermeglia M, Pricl S. The Long and Winding Road. Multiscale Molecular Modeling Approach to the Self-Assembly of Di/Triblock Copolymers for Drug Delivery in Aqueous Solution. AIChE Annual meeting, Nashville, USA, (2009). 6. Posocco P. Modellistica molecolare multiscala per la progettazione di materiali nanostrutturati. I giovani e la chimica in FVG, Trieste, (2009). 7. Posocco P, Handgraaf JW, Fraaije JGEM, Scocchi G, Fermeglia M, Pricl S. A multiscale approach to the self-assembly of dendrimers in solution, CECAM, Lausanne, Switzerland, (2008). 8. Fermeglia M, Pricl S, Posocco P, Mály M, Lisal M. Computer Simulation of Hybrid OrganicInorganic Nanocomposites, AICHE Annual meeting, Philadelphia, USA, (2008). 9. Pricl S, Posocco P, Mály M, Lisal M, Fermeglia M. Beyond Patterns to Mechanisms. Multiscale Molecular Simulations of Nanoparticles/block Copolymers Self-Assembled Bulk Nanocomposites, AICHE Annual meeting, Philadelphia, USA, (2008). 10. Posocco P, Scocchi G, Fermeglia M, Handgraaf JW, Fraaije JGEM, Pricl S. A Complete Multiscale Modeling Approach for Nanocomposites, AICHE Annual meeting, Philadelphia, USA, (2008). 11. Fermeglia M, Posocco P, Pricl S, Maly M. Multiscale Molecular Modeling of Hybrid Organic-Inorganic Nanocomposites of Type I and II, 12th International Conferences on “Modern Materials and Technologies” CIMTEC, Acireale, Italia, (2008). 12. Posocco P, Toth R, Voorn DJ, Handgraaf JW, Fermeglia M, Pricl S. Paving the way to new nanocomposite materials: multiscale computer simulations of PEO and exfoliated layer silicates in aqueous dispersions, 1st Transalp' Nano Conference, Lyon, France, (2008). 13. Paneni M, Posocco P, del Santo I, Causa F, Netti PA, Pricl S. “Math”-odological insights into smart nanochannels: a multiscale molecular modeling of molecular motion in confined nanospaces, 1st Transalp' Nano Conference, Lyon, France, (2008). 14. Scocchi G, Posocco P, Pricl S, Fermeglia M. To the nanoscale and beyond! Multiscale molecular modelling of polymer-clay nanocomposites, 11th International Conference on “Properties and Phase Equilibria for Product and Process Design” PPEPPD, Crete, Greece, (2007). Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 24 15. Posocco P, Scocchi G, Fermeglia M, Pricl S, Ferrari M. The nanoroad less travelled. A multiscale approach to self-assembly of dendrimers for cancer therapy, 11th International Conference on “Properties and Phase Equilibria for Product and Process Design” PPEPPD, Crete, Greece, (2007). 16. Fermeglia M, Posocco P, Maly M, Pricl S. Enthalpy/entropy effect in the self assembly of a nanoparticle complex system: a multiscale molecular modeling (M3) approach. AIChE Annual Meeting, Salt Lake City, UT, USA, (2007). 17. Pricl S, Posocco P, Fermeglia M, Scocchi G, Danani A, Handgraaf JW, Fraaije JGEM. What goes around comes around. Multiscale molecular modeling of dendrimers self-assembly, IDS:5 fifth international dendrimer symposium, Tolouse, France, (2007). 18. Cosoli P, Fermeglia M, Ferrone M, Posocco P, Pricl S, Scocchi G. New materials from multiscale modeling procedures: properties prediction and customization of polymeric nanocomposites, ICheaP-8, Ischia, Italia, (2007). Books /Chapters and sections of books 1. Pricl S, Posocco P, Scocchi G, Fermeglia M. “Polymer-clay nanocomposites”, in Handbook of Nanophysics, Klaus Sattler Editor, Taylor&Francis Publisher, 2009. Other publications 1. Scocchi G, Posocco P, Ferrone M, Fermeglia M, Pricl S, Handgraaf JW, Fraije JGEM. “Nanocompositi. Da micro a mesoscala”, Plastix, (2007), 9, 26. 1. Participation to conferences (as speaker) Posocco P, Fermeglia M, Pricl S. Multiscale molecular modeling of di/triblock copolymers for drug delivery. FOMMS, Blaine, USA, (2009). 2. Posocco P, Fermeglia M. Self-assembly of nanoparticle mixtures in diblock copolymers. 2nd PhD Workshop, Wittenberg, Germany, (2009). 3. Posocco P. Modellistica molecolare multiscala per la progettazione di materiali nanostrutturati. I giovani e la chimica in FVG, Trieste, (2009). 4. Posocco P, Handgraaf JW, Fraaije JGEM, Scocchi G, Fermeglia M, Pricl S. A multiscale approach to the self-assembly of dendrimers in solution, CECAM, Lausanne, Switzerland, (2008). 5. Posocco P, Toth R, Voorn DJ, Handgraaf JW, Fermeglia M, Pricl S. Paving the way to new nanocomposite materials: multiscale computer simulations of PEO and exfoliated layer silicates in aqueous dispersions, 1st Transalp' Nano Conference, Lyon, France, (2008). 6. Posocco P, Scocchi G, Fermeglia M, Pricl S, Ferrari M. The nanoroad less travelled. A multiscale approach to self-assembly of dendrimers for cancer therapy, 11th International Conference on “Properties and Phase Equilibria for Product and Process Design” PPEPPD, Crete, Greece, (2007). Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 25 Educational Activity Periods abroad (date and place) Classes followed (date, course, professor, type of course) Conferences, seminars, advanced courses and other didactic activities 1. 2. 3. 4. 5. 6. 7. 8. 2nd PhD Workshop, 11-13 September 2009, Wittenberg, (Germany). “How to write (and manage) a research project”, 16 October 2009, Trieste. “Chimica-fisica delle intefasi in sistemi nanostrutturati”, 15 May 2009, Trieste. Seminario VPN e Portale Scuola Nanotecnologie, 20 March 2009, Trieste. “Modeling reactions at the nanoparticle scale”, 8 May 2009, Trieste. “Culgi Advanced Course”, 8-10 April 2008, Leiden (Olanda). II Scuola ARS2 - Applicazioni della radiazione di sincrotrone allo studio dei materiali nanostrutturati e dei film sottili - 22-26 April 2007, Grignano (TS) XXVII Convegno-scuola AIM 2007- Materiali polimerici ibridi e nanostrutturati- 30 April- 4 May 2007, Gargnano (BS). Support educational activity and teaching Dissipative Particle Dynamics methodology, course of Molecular Simulation (prof. Pricl), theory and exercises. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 26 Candidate: ANDREA TRAVAN Title of the thesis: “Nanocomposite systems based on metal nanoparticles and polysaccharides for biomedical applications” Supervisor: Prof. Sergio Paoletti Tutor: Dott. Ivan Donati Research Activity The Ph.D research project refers to the development of nanocomposite systems for biomedical applications and is included in the framework of the European Project called “Newbone”; in particular, the final goal is to realize coatings for orthopedic prosthesis endowed with antimicrobial properties. Nanocomposite systems based on natural polysaccharides that stabilize metal nanoparticles (silver and gold) in colloidal solutions and as three-dimensional hydrogels are been studied, as antimicrobial agents. During the first and second year of the Ph.D we have set up the protocols for the preparation of the colloidal solutions and of the hydrogels containing the metal nanoparticles on the basis of physical-chemical and biological characterizations. Moreover we have studied and defined a particular chemical mechanism of silver ions reduction carried out by a lactose modified chitosan; the optical properties of the so-formed metallic nanoparticles obtained via this mechanism were tested by means of Raman spectroscopy, thus detecting the possibility to have considerable enhancements of the signal due to the SERS effect (Surface Enhanced Raman Spectroscopy). Thanks to the antibacterial properties of silver, the nanocomposite gels display potent bactericidal activity without showing cytotoxic effects towards eucariotic cells, as verified by both in vitro and in vivo tests. This result is particularly important in relation to the state of the art in this research field. Since the core material of the prosthesis is realized in methacrylic materials, during the third year of Ph.D we have devised a technique for coating of substrates based on its activation followed by deposition of the bioactive nanocomposite due to introduction of negative charges on the substrate surface, the coating is grafted by means of electrostatic interactions with the polysaccharide chains. Biological in vitro tests have demonstrated that the antimicrobial activity persists together with the lack of cytotoxicity, determining the choice of this coating for the final in vivo test as a conclusion of the European project. The main characterization techniques employed were UV-Vis and Raman spectroscopy, TEM, SEM and AFM microscopy, Confocal Fluorescence Microscopy, Mechanical bending tests, ICP-MS as well as other cellular and microbiological techniques. The results obtained during this Ph.D have been published on scientific journals, books, abstracts, posters and proceedings of International Congresses; based on theses results two Italian Patents were filed and the PCT extension is being processed. Publications on scientific journals (printed or in press) Polyol Synthesis of Silver Nanoparticles: Mechanism of Reduction by Alditol Bearing Polysaccharides (Ivan Donati, Andrea Travan, Chiara Pelillo, Anna Coslovi, Alois Bonifacio,Valter Sergo, Sergio Paoletti). Biomacromolecules, 2009, 10 (2), 210-213 Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 27 Non-Cytotoxic Silver Nanoparticle – Polysaccharide Nanocomposites with Antimicrobial Activity (Andrea Travan, Chiara Pelillo, Ivan Donati, Eleonora Marsich, Monica Benincasa, Tommaso Scarpa, Sabrina Semeraro, Gianluca Turco, Renato Gennaro, Sergio Paoletti). Biomacromolecules 2009, 10, 1429–1435 Surface Modification and Polysaccharide Deposition on BISGMA/TEGDMA Thermosets (Andrea Travan, Ivan Donati, Eleonora Marsich, Francesca Bellomo, Satish Achanta, Sabrina Semeraro, Tommaso Scarpa, Mila Toppazzini, Vittorio Spreafico, and Sergio Paoletti). Biomacromolecules 2010. (DOI: 10.1021/bm9011419) Silver-Polysaccharide Nanocomposite Antimicrobial Coatings for Methacrylic Thermosets (Andrea Travan, Eleonora Marsich, Ivan Donati, Monica Benincasa, Marta Giazzon, Laura Felisari, Sergio Paoletti. Submitted to European Cells and Materials Journal (2010) Characterization of silver nanoparticles for biomedical applications by means of quantitative analysis of TEM micrographs (Francesco Brun, Andrea Travan, Agostino Accardo, Sergio Paoletti). Biomedical Sciences Instrumentation 2010 (In press). Publications/abstracts in conferences/congresses (national or international) Silver Nanoparticles for Antimicrobial Applications (World Biomaterials Congress Amsterdam 2008, abstract and poster) Polysaccharide – Based Silver Nanoparticles Systems (World Biomaterials Congress Amsterdam 2008, abstract and poster) Characterization of Composite Polysaccharide-Based Scaffolds (World Biomaterials Congress Amsterdam 2008, abstract and poster) Silver Nanoparticle – Polysaccharide Nanocomposites with Antimicrobial Activity (European Materials Research Society – EMRS - Fall Meeting, Warsaw 2008, abstract and poster) Silver Nanoparticles – Polysaccharides Based Systems (National Biotechnology Congress, Perugia 2008, abstract and poster) Non-Cytotoxic Silver Nanoparticle – Polysaccharide Nanocomposites with Antimicrobial Activity (European Polymer Congress, Graz 2009, abstract and poster ) Silver nanoparticle - Polysaccharide systems for biomaterials applications (European Polysaccharide Network of Excellence, Turku 2009, abstract and poster) Nanocomposite systems based on polysaccharides and silver nanoparticles. (Nanotechnology for the study of cellular and molecular interactions, Engineering Conference International, Barga 2009, abstract and poster) Porous Nano-Hydroxyapatite/Alginate Scaffolds for Bone Regeneration. (Nanotechnology for the study of cellular and molecular interactions, Engineering Conference International, Barga 2009, abstract and poster) Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 28 Books /Chapters and sections of books Silver nanocomposites and their biomedical applications (Andrea Travan, Eleonora Marsich, Ivan Donati, Sergio Paoletti). Chapter of the book entitled “Nanocomposites for the Life Sciences”. In press, Wiley-VCH (2010) Other publications (Patents filed) Materiali nanocompositi basati su nanoparticelle metalliche stabilizzate con polisaccaridi a struttura ramificata (Andrea Travan, Ivan Donati, Eleonora Marsich, Sergio Paoletti, Brevetto 8853 PTIT) Materiali nanocompositi formati da una matrice polisaccaridica e nanoparticelle metalliche, loro preparazione ed uso (Andrea Travan, Ivan Donati, Eleonora Marsich, Sergio Paoletti, Brevetto 8981 PTIT) Nanocomposite materials based on metallic nanoparticles stabilized with branched polysaccharides (Andrea Travan, Ivan Donati, Elonora Marsich, Sergio Paoletti). PCT Patent extension (2009) Three-dimensional nanocomposite materials consisting of a polysaccharidic matrix and metallic nanoparticles, preparation and use thereof (Andrea Travan, Ivan Donati, Elonora Marsich, Sergio Paoletti). PCT Patent extension (2009) Participation to conferences (as speaker) Silver Nanoparticle – Polysaccharide Nanocomposites with Antimicrobial Activity CIRMIB Biomaterials School. Nanomedicine: Imaging, Drug Release, Regenerative Medicine (Ischia 2007) Nanocomposite systems based on polysaccharides and silver nanoparticles. (Nanotechnology for the study of cellular and molecular interactions, Engineering Conference International, Barga, 2009) Silver nanocomposites for biomaterials applications. (Trondheim-Trieste Bilateral Workshop on Biopolymers, 2009) Non-Cytotoxic Silver Nanoparticle – Polysaccharide Nanocomposites with Antimicrobial Activity (European Polymer Congress, Graz 2009) Educational Activity Periods abroad (date and place) 22 march – 22 may (2009), Centre Suisse d' Electronique et Microtechnique (CSEM), Neuchatel, Switzerland. Classes followed (date, course, professor, type of course) 56 hours, Introduction to Biochemistry, march-june 2007, Prof. Ivan Donati (corso di laurea in Biotecnologie) Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 29 48 hours, Organic Chemoistry, october 07-february 08, Prof. Fabio Benedetti (corso di laurea in Biotecnologie) Conferences, seminars, advanced courses and other didactic activities Antibacterial Materials Congress (London 2007) Ceramic, cells and tissues: Nanotechnology for the functional repair and regenerative medicine (Faenza 2007) Scuola ARS2: Applicazione della radiazione di sincrotrone allo studio dei materiali nanostrutturati e dei film sottili (Trieste 2007) Confined and composite soft matter on the nanoscale (M. Saboungi, 11/04/08) Scanning Probe Microscopies (SPMs), Agilent workshop al TASC (11 June 2008) Applications of near field Raman spectroscopy (G. Picardi-22 Maggio 2008) Nanochallenge and Polymerchallenge (4 Luglio 2008) Modern Trends in Nanobiology and Nanomedicine (Workshop, 13-14 october) Image Analysis and Biomechanical Modelling: From Biomolecules to Bioactive Biomaterials (Trieste 1st-2nd September 2008) Mastering interfaces in composite and nanostructured materials: advances in processing and characterization methods (COST Training School, May 4-8 2009, Thun, Switzerland 2009) Fracture physics of biopolymer gels (Prof. Tristan Baumberger, Institut des NanoSciences de Paris, France) (20 ottobre 2009) Seminar on how to write and manage a research project (School of Nantochnology, Trieste ottobre 2009) Support educational activity and teaching Co-tutor of a Master Thesis in Medical Biotechnologies (A. Di Luca: “Nanocomposite systems based on polysaccharides and metal nanoparticles for biomedical applications”) and of two Diploma Thesis in Biotechnologies (M. Ricciarelli: “Nanocomposite systems based on gold nanoparticles and polysaccharides for biomedical applications”, E. Minighin : “Idrogels and nanocomposite coatings based on polysaccharides and metal nanoparticles for biomedical applications”). Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 30 Candidate ANDREA UMERI Title of the thesis: Stress state and crystallographic analysis in relation to the ageing process in submicron composite Zirconia - Alumina Supervisor: Prof. Valter Sergo Tutors (if any): Research Activity The focus of research concerns the analysis of composites Alumina - Zirconia in relation to the phenomenon of aging of zirconium, in light of the renewed interest of this material in dental field. The zirconia was mentioned by several articles of literature in dentistry as a main material for the construction of dentures, but these articles do not deal in sufficient depth the issue of ageing and its consequences. In the first phase of the research work were analyzed several samples, having undergone a natural aging in the atmosphere of about 10 years, differentiated by size of ceramic powders and the initial volumetric rate of aluminum. In the second phase was analyzed a second set of samples made with the aim of verifying the actual aging of the composite through an artificial aging process that is followed by a third set of samples which vary in the relative amounts of alumina and zirconia. In both cases it was monitored the development in time of phase transformation by Raman spectroscopy. Through the simultaneous use of AFM and NSOM has developed a method for selective identification of each grain in order to Raman measurements at the nanoscale in single point. (In collaboration with the Dental Clinic and stomatology Ospedale Maggiore in Trieste) Publications on scientific journals (printed or in press) Journal of Materials Science, “Raman investigation of the ageing of Ni-BaTiO3 multilayer ceramic capacitors”, A.Umeri, T.A. Kuku, N.Scuor and V.Sergo, Volume 43, Issue 3, P.922-926,2008-02-01, DOI - 10.1007/s10853-007-2215-4 Publications/abstracts in conferences/congresses (national or international) POSTER - “Nanostructured Zirconia in dental applications: new problems for an old material” – A.Umeri, A. Bonifacio and V. Sergo – National Nanomedicine Conference – 28,29 November 2008 - Genova Books /Chapters and sections of books Other publications Participation to conferences (as speaker) Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 31 Educational Activity Periods abroad (date and place) Classes followed (date, course, professor, type of course) Conferences, seminars, advanced courses and other didactic activities Advanced Course – “6th National course of concrete technology” – 83 hours of lessons, Engineering Faculty of University of Bergamo. Workshop: “Smart Energy systems and fuel cells: on path to a sustainable future” – Mechanical engineering department of University of Trieste Scientific Congress: Young researchers and Chemistry in Friuli Venezia Giulia – University di Trieste Seminar: Prof. Fermeglia “VPN – Virtual Private Networking” – Univ. of Trieste Seminar: Prof. Fermeglia, Prof. Sergo “How to write and manage a research project” – Univ. of Trieste Seminar: Prof. Phillip R. Westmoreland, Dept. of Chemical Engineering, University of Massachusetts Amherst : “Modeling reactions at the nanoparticle scale” Seminar: dott. Colombo “Chemistry and Physics of inter-phases in nanostructured systems” – Univ. Of Trieste Support educational activity and teaching Main teacher of the course: “Materials and Renewable Energy in construction” Engineering Faculty, University of Trieste, A.A. 2008/2009, 30 hours. Teacher of the course “R.E.C.A. – Risparmio Energy saving and living comfort”, University of Trieste, 2009, 10 hours. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 32 Dottorandi del 23 ciclo: Graduate Student ALBERTO ASTOLFO Title of the thesis: DEVELOPMENT OF NOVEL EXPERIMENTAL METHODS FOR CELL TRACKING USING NANOPARTICLES Supervisor: Dr. Fulvia Arfelli Tutors (if any): Dr. Rer.Nat. Ralf-Hendrik Menk Research Activity The aim of this project is to develop novel experimental methods for cell tracking using nanoparticles as contrast agent. The goal is to quantify and follow the cells during them life. The using of nanoparticles (NPs) as well as a suitable tomographic X-ray imaging setup can be a good solution of the problem above mentioned. During the past year we have done a double experiment at the SYRMEP beamline (synchrotron radiation facility) and at the TOMOLAB laboratory (microfocus X-Ray tube facility). The samples were 20 rat‟s heads ex-vivo that were injected into the brain with the same amount of gold loaded C6 cells. The rats were sacrificed at different moments in order to estimate the tumor visibility during its grow. The results‟ analysis has confirm the cells‟ visibility obtained last year. We have found some troubles doing the quantitative analysis due to some results in conflict caused by the small number of samples. We have found also another problem related by the small bone pieces created during the hole drilling before the cell injection. The instrumentation that we were using didn‟t allow us to separate the bone powder signal to the marked cells signal. This can represent a technique limitation in this kind of experiments especially if we want to count the cells. With the aim to better understand this problem, during the transfer at the synchrotron Canadian Light Source (CLS, Saskatoon, Canada) we have prepared dedicated samples containing the same kind of labeled cells and bone powder into agarose gel. At the CLS I‟ve contributed to the set up of a tomography system. We have used it to scan also the samples prepared. We have grown part of the same marked cells on a metalize cover slip in order to visualize the cells on the Scanning Electron Microscopy (SEM). During the SEM measurements at the TASC laboratories (Area di Ricerca, Basovizza) we have shown that it is possible to estimate the amount of NPs on single cell. This is a different approach respect to the mass spectroscopy approach that provides a mean gold weight of a large number of cells. On the instrumental part of my work, during the last year, we have complete the new double crystal analyzer setup for the Analyzer Based Imaging (ABI) now available at the SYRMEP beamline. This setup permits new imaging modalities based on phase contrast instead on absorption contrast, increasing the details visibility. During an experimental run dedicated, we have used the ABI to one rat ex-vivo that was injected with marked C6 cells. Again at the SYRMEP beamline, we have installed an experimental setup that permits to increase the imaging system resolution using the beam diffraction of two silicon crystals cut asymmetrically (Bragg Magnifier). During this Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 33 experiment, we have done a tomography on one of the samples prepared in Canada (the C6 cells in agarose gel) obtaining a single cell resolution (pixel size ~1 μm; PSF ~5 μm). Objectives for the following year (if applicable) Implementation of a cell counting software in IDL code (to be applied to samples with a well known number of cells); studies and estimation of the NPs clusters partition during the mitosis using SEM; new measurements of ABI (beamtime approved for the first part of 2010); tomographic measurements on ex-vivo mice using marked stem cells (beamtime approved for the first part of 2010); implementation and use of “local area tomography” algorithms to scan with high resolution only a zone of big samples; implementation and use of tomosynthesis algorithms to decrease the mean dose to the sample; magnetic resonance imaging measurements and histological studies of some already CT scanned samples to confirm what we have seen in CT (possible transfer at the Australian Synchrotron in Melbourne). Implementation and use of a system for fluorescent measurements. Publications on scientific journals (printed or in press) 1. L. Rigon, A. Astolfo, F. Arfelli, R.H. Menk, “Generalized diffraction Enhanced imaging: Application to tomography”, Eur J Radiol, Volume 68, Issue 3, Pages 3-7, 2008 2. L. Rigon, F. Arfelli, A. Astolfo, A. Bergamaschi, D. Dreossi, R. Longo, R.H. Menk, B. Schmitt, E. Vallazza, E. Castelli, “A single-photon counting “edge-on” silicon detector for synchrotron radiation mammography”, Nucl. Instr. And Meth. A, 608, S62-S65, 2009 Publications/abstracts in conferences/congresses (national or international) 1. Spatio-Temporal Radiation Biology: Transdiscipinary Advances for Biomedical Applications – Booklet of abstracts (Saint Feliu de Guixols, Spain, 16-21 May 2009), A. Astolfo, R.-H. Menk, F. Arfelli, E. Schultke, C. Hall, L. Rigon, B.H.J. Juurlink, “Long Term Cell Tracking in Small Animals Phase Using Phase Contrast Based Micro CT and Synchrotron Radiation”, P.53. Books /Chapters and sections of books Other publications Participation to conferences (as speaker) 2. Poster at “IEEE Dresden 2008 Medical Imaging Conference” (Dresden, 19-25 October 2008), “Long Term Cell Tracking in Small Animals Phase Using Phase Contrast Based Micro CT and Synchrotron Radiation”. 3. Poster at “physics@UniTS” (Trieste, 19 and 20 June 2008), “Generalized Diffraction Enhanced X-ray Imaging: Application to Tomography”. 4. Short-Talk, “Spatio-Temporal Radiation Biology: Transdiscipinary Advances for Biomedical Applications” (Saint Feliu de Guixols, Spain, 16-21 May 2009), “Long Term Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 34 Cell Tracking in Small Animals Phase Using Phase Contrast Based Micro CT and Synchrotron Radiation”. 5. Talk, Canadian Light Source (Saskatoon, Canada, 28 August 2009), “Computer Tomography @ BMIT – Present, future and resources at the Canadian Light Sources Biomedical Beamline” 6. Talk, “Joint Workshop of SFB762 & IMPRS” (Wittenberg, Germany, 10-11 September 2009), “Development of novel experimental methods for cell tracking using nanoparticles”. Educational Activity Periods abroad (date and place) o 19-25 October 2008, Dresden, Germania, IEEE Medical Imaging Conference o 16-21 May 2009, Saint Feliu de Guixols, Spain, Spatio-Temporal Radiation Biology: Transdiscipinary Advances for Biomedical Applications o 3 June-30 August 2009, Saskatoon, Canada, Canadian Light Source o 11-12 September 2009, Wittenberg, Germania, Max Plank Institute o 11-13 November 2009, Chicago, Illinois (USA), Advance Photon Source Classes followed (date, course, professor, type of course) o “Tomographic measurement with a microfocus X-ray tube”, February-March 2008, Dr. Ralf Menk, TOMOLAB at Elettra, 32 hours o “Tomographic measurement with Synchrotron Radiation”, April 2008, Dr. Fulvia Arfelli-Dr. Ralf Menk, SYRMEP at Elettra, 40 hours o “Electron Microscopy and Scanning Probe Microscopy”, June-July 2008, Dr. Cristina Africh-Dr. Laura Felisari, PhD School of Physics course, 16 hours o “Metodi statistici in fisica”, September 2008, Dr. Paolo Schiavon, PhD school of physics course, 9 hours o “Tecnologie Cellulari”, October-December 2008, Dr. Roberto Marzari, Functional Genomic course, 20 hours o “Genetica Molecolare”, October-December 2008, Dr. Paolo Edoni, Functional Genomic course, 38 hours Conferences, seminars, advanced courses and other didactic activities o “Aspetti principali della radioprotezione presso l‟INFN”, Prof. Franco Calligaris, 28 March 2008, Seminario, 2 hours o “Workshop on nanotechnologies@see”, 3 April 2008, Workshop, 7 hours o “... che Anova sior paron”, Dott. Massimo Borelli, 18 April 2008, Seminario, 2 hours o “L‟analisi della varianza con il free software R”, Dott. Massimo Borelli, 15 May 2008, Seminary, 2 hours o “physics@UniTs”, 19-20 June 2008, Meeting, 12 hours o “Image Analysis and Biomechanical Modelling”, 1-2 September 2008, Workshop, 6 hours o “Modern Trends in Nanobiology and Nanomedicine”, 13-14 October 2008, Workshop, 3 hours o “IEEE Dresden 2008 NSS-MIC-RTSD”, 19-25 October 2008, Conference, 13 hours o Congresso dei dottorandi di Nanotecnologie 2009 (14 hours) Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 35 o “La statistica basta saperla oppure bisogna saperla faRe?”, Trieste, 21-23 Gennaio 2009, Lessons, Dott. Massimo Barelli, 9 hours o “Introduction to Pore3D”, Basovizza, 23 February 2009, Talk, Dott. Francesco Brun, 1 hour o “Spatio-Temporal Radiation Biology: Transdiscipinary Advances for Biomedical Applications”, Saint Feliu de Guixols (Spain),16-21 May 2009, 29 hours o “Microbeam Radiation Theraphy (MRT) – Historical Prospective”, Saskatoon (Canada), Dr. Daniel Slatkin, 27 August 2009, 1 hours o “Joint Workshop of SFB762 & IMPRS”, Wittenberg (Germany), Workshop, 1011 September 2009, 7 hours o How to write (and manage) a research project (5 hours) o Congresso dei dottorandi di Nanotecnologie 2010 (14 hours) Support educational activity and teaching o Teaching temporary post at “Liceo Linguistico Pujati” (Sacile, PN), Math, September-October 2008, 21 hours o Teaching temporary post at “Liceo Linguistico Pujati” (Sacile, PN), Physics, September-October 2008, 4 hours o Participation as Tour Guide at the Canadian Light Source (July, 2009) Other activities o CT experiment at the SYRMEP beamline Elettra (Basovizza, TS, Italy), “Brain distribution of nanogold targeted for brain delivery”, 12-14 October 2009 o CT experiment at the Photon Source (Chicago, Illinois, USA), “In situ bubble nucleation and growth in crystal-bearing basaltic melts at 1 bar”, 11-13 November 2009. o Analyzer Based Imaging experiment at the SYRMEP beamline Elettra (Basovizza, TS, Italy) “Diffraction Enhanced Imaging of breast tissue samples with the PICASSO detector”, 7-12 December 2009. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 36 Graduate Student: Francesca Bellomo Title of the thesis: Biopolymer based scaffold for tissue engineering Supervisor: Prof.Sergio Paoletti Tutors (if any):Dott. Biasotto Matteo Research Activity The aim of my study is the development of biocomposite scaffolds for orthopedic applications, based on the combination of polysaccharides (mainly alginate, Alg) engineered with bioactive molecules and nano-hydroxyapatite (nHAp). In the first year of PhD, I have synthesized and characterized the different components of the scaffold; furthermore I have prepared the composite (Alg/Hap scaffolds) and studied their biological and structural properties. During the second year of PhD, according the results obtained from the previous cytocompatibility tests, I have performed preliminary in vivo tests. The animal model was New Zealand rabbit and the produced scaffolds were inserted into bone defects on femur. Post-operatively, five fluorochromes were administered sequentially every week. After 1 and 2 months, the rabbits were sacrificed and all the implanted bones were analyzed using µ-CT and light and confocal microscopy. We observed a high level of osteointegration of the scaffolds and ingrowth of newly deposited structured lamellar bone inside them, indicating good osteoconductive properties. To introduce bioactive molecules and antimicrobial agents, enhancing in this way the biological property of the scaffolds, we exploited chitlac as vector. Chitlac is a lactitolated-derivative of chitosan that can be modified by chemical grafting of bioactive peptides like RGD and that can be use to produce and stabilize silver nanoparticles (nAg) with antimicrobial activity. By adsorbing the chitlac on the scaffold‟s surface we spread the bio-signal inside the structure to induce a specific cell reaction. Alg/Hap scaffolds were coated with chitlac-RGD and chitlac-nAg; on those, biological and antimicrobial in vivo tests were performed. For both scaffolds we observed good cytocompatibility and, in the case of scaffold with RGD, an improved cell proliferation; moreover, the scaffold with nAg showed a high level of antimicrobial activity. Objectives for the following year (if applicable) The aims for the next year activity will be the in vivo tests on the bioactive scaffolds obtained, to investigate both their integration and antimicrobial properties. Publications on scientific journals (printed or in press) Alginate/Hydroxyapatite biocomposite for bone ingrowth: a trabecular structure with high and isotropic connectivity.Turco G, Marsich E, Bellomo F, Semeraro S, Donati I, Brun F, Grandolfo M, Accardo A, Paoletti S. Biomacromolecules. 2009 Jun 8; 10(6):1575-83 Surface modification and polysaccharide deposition on BISGMA/TEGDMA based resins. Donati I., Travan A., Marsich E., Bellomo F., Achanta S., Semeraro S., Scarpa T., Toppazzini M., Spreafico V., Paoletti S. Submitted to Biomacromolecules Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 37 Publications/abstracts in conferences/congresses (national or international) ARACTERIZATION OF COMPOSITE POLYSACCHARIDE-BASED SCAFFOLDS” Gianluca Turco, Francesca Bellomo, Eleonora Marsich, Sabrina Semeraro, Ivan Donati, Tommaso Scarpa, Andrea Travan, Francesco Brun, Agostino Accardo, Gianni Schena and Sergio Paoletti (aprile 2008, Amsterdam; 7-9 novembre 2008 Bone-tec Hannover) “POROUS NANO-HYDROXYAPATITE/ALGINATE SCAFFOLDS FOR BONE REGENERATION” Eleonora Marsich, Sabrina Semeraro, Gianluca Turco, Francesca Bellomo, Ivan Donati and Sergio Paoletti (7-9 novembre 2008 Bone-tec Hannover; Joint Workshop of SFB762 & IMPRS 10th/11thSeptember 2009 in the Leucorea at Wittenberg) “ EVALUATION OF CELLS ISOLATION AND BMPS PRESENCE ON DIFFERENT CRYOPRESERVED BONE TISSUE” Francesca Bellomo, Matteo Biasotto, Michela Faraon, Alessandro Viscioni, Maurizio Franco, Eleonora Marsich, Roberto Di Lenarda (7-9 novembre 2008 Bone-tec Hannover) “SPERIMENTAZIONE IN VIVO DI SCAFFOLD DI ALGINATO E IDROSSIAPATITE PER RIGENERAZIONE OSSEA” F. Bellomo, M. Biasotto, G.Turco, R. Di Lenarda, S. Paoletti (22° riunione nazionale “A. Castellani” dei dottorandi di ricerca in discipline biochimiche Brallo di Pregola (PV) 9 – 12 Giugno 2009; Collegio dei docenti di odontoiatria Roma 2224 aprile 2009) Participation to conferences (as speaker) Informal Workshop Scuola di Dottorato di Ricerca in Nanotecnologie and Int. Max-Planck Research School for Science and Technology of Nanostructures in Halle on July 15-16, 2009 Educational Activity Conferences, seminars, advanced courses and other didactic activities Confined and composite soft matter on the nanoscale (M. Saboungi, 11/04/08). Scanning Probe Microscopies (SPMs), Agilent workshop al TASC (11 June 2008). Modern Trends in Nanobiology and Nanomedicine (Workshop, 13-14 october). La prevenzione nei laboratori di ricerca, seminario 12 marzo 2008, Trieste. Seminario di scrittura scientifica ,7 maggio 2008 ( prof. Frederick Ruggeberg, Direttore del Department of Oral Rehabilitation del Medical College of Georgia ). Wednesday 16th april at 10.30 in the TASC seminar room, there will be held the phd students briefing: C. Blasetti, E. Sovernigo. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 38 AFM Workshop organized by SITEM / Agilent Technologies, Trieste, June 11th. Bone-tec , Hannover 2008. Image Analysis and Biomechanical Modelling: From Biomolecules to Bioactive Biomaterials (Trieste 1st-2nd September 2008). Phd Course Biotecnologie cellulari e Molecolari applicate alla medicina “Molecular Biotechnologies applied to Medicine” Santa Margherita Ligure (Genova) 20-22 February 2008. “Bilateral Workshop on Biopolymers” TRD (NTNU) - TRS (UNITS) Trieste, October 1st3rd, 2009. Workshop @ Elettra"CCD per Imaging e Spettroscopia" 28 Gennaio 2009 Elettra Sincrotrone Trieste. “Modern Trends in Nanobiology and Nanomedicine” October, Monday 13th and Tuesday 14th - Basovizza – Trieste. 22° riunione nazionale “A. Castellani” dei dottorandi di ricerca in discipline biochimiche Brallo di Pregola (PV) 9 – 12 Giugno 2009. Seminars of reology, Romano Lapasin, DICAMP-University of Trieste, 20-22 July 2009. Joint Workshop of SFB762 & IMPRS 10th/11thSeptember 2009 in the Leucoreaat Wittenberg . “How to write (and manage) a research project” 16 October 2009 –University of Trieste. “St-scCO2 sterilization by means of supercritical Carbon Dioxide” international workshop, University of Trieste, 10th February 2009. “Incontri informativi per i dottorandi” di ARABITO STEFANIA - lunedì, 22 giugno 2009, Trieste ,Italia. Support educational activity and teaching Laboratory tutor within LLC-Trieste (Life Learning Center), hands-on laboratory activities in the field of Life Sciences for secondary schools students and teachers. Teaching assignment, “Laboratory of Biochemistry II”, degree in Medical Biotechnology, School of Medicine, University of Trieste. December 2009: Secondary school teachers‟ training. Project “LLC-Trieste on the territory”, at the secondary school “N. Tron” of Schio (VI, Italy). Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 39 Graduate Student GIOVANNI BIRARDA Title of the thesis: Development of microfluidic devices for biomedical applications of Synchrotron Radiation Fourier Transform Infrared Microspectroscopy Supervisor: Prof. Alfonso Franciosi Tutors: Dott.ssa Lisa Vaccari – Dott. Luca Businaro Research Activity This PhD project focuses on the development of microfluidic devices transparent to both visible and mid-infrared (MIR) light, in order to study the biochemical response of living cells to diverse stimuli, by exploiting capabilities of FTIR microspectroscopy (μ-FTIR) with synchrotron radiation (SR). During this second year, the manufactured 2D prototypes designed, fabricated and tested during the first year of the PhD, have been used to investigate the biochemical response of leucocytes to both mechanical and /or chemical stimuli. Living cells belonging to two different cell lines (THP1 and U937) have been measured in vitro in diverse conditions: in resting state, undergoing purely mechanical deformation, subjected only to chemical activation (activating agents: fMLP -formylMethionyl - leucyl-Phenylalanine- and PMA -Phorbol-12-Myristate-13-acetate-), and combaining the two sources of stimulation. Contemporary, we further optimized the fabrication processes for producing a three- dimensional microfluidic device and the engineering of a home-made thermalized sample holder with connections for syringe pumps. The new prototype will be used during the beamtime scheduled for 14-19 December 2009 at he infrared beamline of Elettra Sincrotrone Trieste (SISSI). Primary human leukocytes (monocytes and lymphocytes) will be measured trying to validate the data collected so far using cells belonging to the same cellular phase (synchronized cells). Objectives for the following year o Move from static experiments to dynamic ones by using 3D microfluidic devices transparent both to MIR and visible. o Measure primary cells instead of immortalized ones. o Optimize algorithms for the water subtraction and for the correction of spectral artefacts due to Mie scattering phenomena in order to improve data analysis Publications on scientific journals (printed or in press) oGiovanni Birarda, Gianluca Grenci, Luca Businaro, Benedetta Marmiroli, Sabrina Pacor, Lisa Vaccari - “Fabrication of a microfluidic platform for investigating Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 40 dynamic biochemical processes in living samples by FTIR microspectroscopy – Microelectronic Engineering (in press) oGiovanni Birarda, Gianluca Grenci, Luca Businaro, Benedetta Marmiroli, Sabrina Pacor, Federica, Piccirilli, Lisa Vaccari - Infrared microspectroscopy of biochemical response of living cells in microfabricated devices” – Vibrational Spectroscopy (submitted - evaluated) 2009 Publications/abstracts in conferences/congresses (national or international) oPoster Presentation in the 5th International Conference on Advanced Vibrational Spectroscopy, Melbourne (Australia) from 12-17 July 2009 oPoster Presentation in the 2nd PhD Workshop Wittenberg 10-11 September 2009 oPoster Presentation in the 35th International Conference on Micro & Nano Engineering, Ghent (Belgium) from 28 September - 1 October 2009. oPoster Presentation in the 13th International Conference on Miniaturized Systems for Chemistry and Life Sciences (MicroTAS 2009), Jeju (South Korea) from 1-5 November 2009. oThe Proceedings of Conference on Miniaturized Systems for Chemistry and Life Sciences (MicroTAS 2009), Giovanni Birarda,Gianluca Grenci, Luca Businaro, Benedetta Marmiroli, Giuseppe Bellisola and Lisa Vaccari, Single Living Cell Biochemical Rearrangements Investigated By Infrared Microspectroscopy In Microfluidic Devices - 978-0-9798064-21/μTAS2009/$20ⓒ2009CBMS pp 338-341. Participation to conferences (as speaker) oFabrication of microfluidic platform for infrared microspectroscopy analysis of dynamic biochemical processes in living sample. NNC2009. Pavia, 21-22 September 2009 Educational Activity Conferences, seminars, advanced courses and other didactic activities o Micelles, your cells", by Michael Rappolt;11 February 2009 1 h o CDK7 and CDK9 at the interface of Cell Cycle and Transcription Regulation: from structure to function; Graziano Lolli; 4 May 2009; 1 h o Advanced Imaging and Spectromicroscopy methods for chemical and structural characterization of micro- and nano-materials; 11-15 May 2009; Dott.sa Maya Kiskinova; 15 h o Joint Workshop between the SFB762, the Nano-IMPRS and the GRADUATE SCHOOL OF NANOTECHNOLOGY; September 2009; Wittenberg; 15 h o NNC2009. Pavia, 21-22 September 2009; 12 h o 13th International Conference on Miniaturized Systems for Chemistry and Life Sciences (MicroTAS 2009), Jeju (South Korea) from 1-5 November 2009, 30 h Support educational activity and teaching: o Laboratory demonstration in clean room for students of Material Science of Padova University (Prof. Filippo Romanato), 6 h 29th of may 2009 Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 41 Graduate Student: LUCAFONTANIVE Title of the thesis: Nanoscale interaction for higher efficiency of contrast media Supervisor: Prof. Attilio Cesàro Tutor: Dr. Nicola D’Amelio Research Activity In this study we investigate the nanoscale interactions in solution of iodurated contrast media of oversaturated solutions to control and to tune the aggregation phenomenon. During this year NMR spectroscopy was mainly used. Experiments were carried out to evaluate the size and mobility of aggregates from diffusion and relaxation time. The ratio T1/T2 gives information about local and global mobility to identify the moieties involved in intermolecular interactions. Chemical shift deviations as a function of concentration confirms the molecular regions involved in interactions. Few molecules seem to be involved into a nanostructurated aggregate. Aggregations seems to involve mainly lateral chain of the ICM. To check hydrogen bonds in solution from amidic protons chemical shift deviation data were carried out as a function of temperature, but stable hydrogen bonds were not revealed. In addition, ICM solutions were studied by raman spectroscopy in function of concentration at constant temperature in university of Perugia. Changes in conformation were not revealed. However, an anomalous peak was observed at low frequencies (20 cm-1) for iomeprol, iopamidol and iopromide. This could be due to rotation around single bond between aromatic system and carbonilic groups. Objectives for the following year (if applicable) The objective is to identify all the accessible conformations in solutions by using 1H and 13C spectra of simple molecules of ioduinated contrast media; the aim is to know the percentages of atropisomers in solutiona at high concentrations to control aggregation phenomenon. Other techniques in solution (scattering Raman) and on the solid state (calorimetry) will be complementary used. The final aim is to understand and to tune the phenomenon of the atropisomerism that is responsible of nanostructurated aggregates in solutions. Publications on scientific journals D‟Amelio N, Fontanive L, Uggeri F, Suggi-Liverani F, Navarini L. NMR reinvestigation of the caffeine-chlorogenate complex in acqueous solution and in coffee brews. Food Biophys. 2009, 4, 321-330. Educational Activity Conferences, seminars, advanced courses and other didactic activities Young Researchers Oral Communication, EuroNanoMedicine 2009, Bled, Slovenia, September 28 – 30 Seminario sul Virtual Private Network (VPN), Prof. Maurizio Fermeglia, 20 Marzo Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 42 Modeling reaction at the nanoparicle scale, Prof. Phillip R. Westmoreland, Dept of Chemical Engineering, University of Massachusetts Amherst, 08 Maggio Chimica fisica delle interfasi in sistemi nano strutturati, Dr. Italo Colombo, 15 Maggio Strategie bioprotettive in sistem alimentari: il modello dei tessuti vegetali, Prof. ssa Paola Pittia, Dipartimento di Scienze degli Alimenti, Università degli studi di Teramo, 28 Maggio Strategie adattative in invertebrati estremo fili: il modello animale tardigradi, Prof.ssa Lorena Rebecchi, Dipartimento di Biologia Animale, Università di Modena e Reggio Emilia, 28 Maggio How to write (and manage) a research project, Prof. Valter Sergo, Prof. Maurizio Fermeglia, Dr. Cecilia Blasetti, 16 Ottobre SPETTROSCOPIA RAMAN: Dott. M. Paolantoni, Dipartimento di Chimica, Università di Perugia. (Settembre 2009, 6 h) SPETTROSCOPIA NMR: Dott. Nicola D‟Amelio, Bracco Imaging S.p.A. - CRB TS (Febbraio 2009, 20 h) CALORIMETRIA: Dott. F. Sussich (Febbraio 2009, 6 ore) Support educational activity and teaching Training of a polish student (S. DEJA Univ. Wroclaw) on theoretical bases of NMR spectroscopy. Area di Ricerca Science Park (July 2009, 20 h). Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 43 Graduate Student Giulio Marchesi Title of the thesis: Analysis of stability of bonded interfaces in dentistry: the role of MMps and low contraction materials. Supervisor: Prof. Lorenzo Breschi Tutors: Prof.ssa Milena Cadenaro Research Activity Despite excellent immediate and short-term bonding effectiveness of dental adhesives, the durability and stability of resin bonded interfaces on dentin created by some bonding systems remains questionable. The research activity of the present year investigated various factors involved in the failure of bonded interfaces: 1.insufficient impregnation of the dentin substrate; 2.increased permeability of hybrid layer; 3.degradation of dentinal collagen fibrils due to endogenous dentin MMPs. These phenomena are influenced by the elastic modulus of the adhesive system, thus the percentage of residual ethanol on E-modulus of experimental adhesive blends was investigated. The results of this study showed that resin blends with 10% 20% residual ethanol produced a significant reduction in the E-modulus after 24h water storage. Another experimental protocol investigated bond strength and stability of the adhesive interface of different self adhesive cements used to lute fiber posts within intraradicular dentin after storage in artificial saliva for 1 year. The value of the different self adhesive cements never exceeded 10 MPa of bond strength and degradation of the adhesive interface between dentin and cements was investigated. Since previous studies demonstrated a protective role of chlorexidine in inhibiting the bond degradation induced by MMPs, an experiment was carried out to test the influence of 2% digluconate chlorexidine as additional primer during the luting procedure with self adhesive on fiber posts. The results have shown no differences between experimental groups and control groups at 6 months. For the final result we are looking forward to investigate the 1yr specimens currently ongoing. Objectives for the following year (if applicable) A research protocol an experiment to evaluate the release of chlorexidine from dentin bonding systems after mechanical cycling will be performated. Resin disks with known composition of monomer (at increasing hydrophilicity) containing chlorhexidine in different concentrations were polymerized, and analyzed it with spectroscopy after cyclic loading. Since the peak of release of CHX is overlapped by the peak of methacrylate resin we are currently looking for a new method to investigate the content of the eluates (HPLC) . Publications on scientific journals (printed or in press) Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 44 Cadenaro M, Marchesi G, Antoniolli F, Davidson CL, De Stefano Dorigo E, Breschi L. “Flowability of composites is no guarantee for contraction stress reduction.” Dental Materials 2009;25(5):649-54. Mazzoni A, Marchesi G, Cadenaro M, Mazzotti G, Di Lenarda R, Ferrari M, Breschi M. “Push-out stress for fiber posts luted using different adhesive strategies.” European Journal Oral Science 2009;117(4):447-453. Cadenaro M, Pashley DH, Marchesi G, Carrihlo M, Antoniolli F, Mazzoni A, Tay FR, Di Lenarda R, Breschi L. “Influence of chlorexidine on the degree of conversion and Emodulus of experimental adhesive blends”. Dental Materials 2009;25(5):1269-74. Marchesi G, Breschi L, Antoniolli F, De Stefano Dorigo E, Ferracane J, Cadenaro M. “Contraction stress of composite materials with different polymerization reactions assayed by low-and high-compliance systems. Dental Materials submitted. Publications/abstracts in conferences/congresses (national or international) Marchesi G, Cadenaro M, Antoniolli F, Di Lenarda R, Pashley DH, Breschi L. “Influenza della clorexidina sul grado di conversione e sul modulo elastico in adesivi sperimentali.” Acts of XIII national meeting SIDOC-Rome 19-21/2/2009. Marchesi G, Breschi L, Antoniolli F, De Stefano Dorigo E, Cadenaro M. “Stress da polimerizzazione di una resina a base siloranica.”Acts of national meeting Docenti di Odontoiatria e di chirurgia Maxillofacciale, Roma 22-24/4/2009. Marchesi G, Cadenaro M, Breschi L, Antoniolli F, Tay FR, Di Lenarda R, Pashley DH. “Influence of chlorexidine on the E-modulus of experimental resins.” J Dent Res 88 (spec Iss A). Annual meeting of The International Association for Dental Research. Miami FL USA. Marchesi G, Cadenaro M, Di Lenarda R, Breschi. Bond strenght of Post Luted with different Self-adhesive Resin Cements. Annual meeting of the Accademy Dental Materials. Portland Oregon USA 29-31/10/2009. Other publications Breschi L, Cadenaro M, Mazzoni A, Navarra CO, Marchesi G, Di Lenarda R, De Stefano Dorigo E. “La durata del legame adesivo:la nuova sfida dell‟ odontoiatria resteurativa.” Dentista Moderno 2009;4:41-54. Marchesi G. Analysis of aging and stability of bonded interface in dentistry. Poster 2° Workshop of the SFB 762-Wittenberg, Germany 10-11/09/2009. Educational Activity Periods abroad (date and place) Meeting research Department of Oral Biology, School of Dentistry Medical College of Georgia, Augusta Georgia, USA 30-31/4/2009. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 45 Conferences, seminars, advanced courses and other didactic activities National meeting of Sidoc Roma 2009 19-21/2/ 2009. Annual meeting IADR Miami Usa 1-4 aprile 2009. Guided tissue remineralization prevents invitro degradation of resin-dentin bonds Tay Fr. , Recents advences in dental monomero and polymerization processes. Spencer P, Ferracane J.L. ; Tem interfacial characterization of an adhesive-free composite to enamel dentin. Van Meerbeek B. Training course “ Odontoiatria dell‟ età evolutiva” Trieste 16-17/1/2009 20-21/1/2009 2223/5/2009. Seminar of ARPE for VII° PQ Trieste 16/09/2009. Seminar “How to write a research project” Trieste 16/10/2009. Support educational activity and teaching “Traumatology in pedodontic” course of Pedodontics Prof.Cadenaro IV° year Corso di Laurea Specialistica in Odontoiatria e Protesi Dentaria, University of Trieste. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 46 Graduate Student ANTONIO RAMPINO Title of the thesis: Polysaccharide based nanoparticles for drug delivery Supervisor: Prof. Cesàro Attilio Tutors (if any): Dr. Borgogna Massimiliano, Dr. Bellich Barbara Research Activity During my PhD period the purpose is to develop and characterize biodegradable polymeric nanoparticles as drug carriers as well as to promote the rational and optimal design and development of novel carrier systems. More specifically, at the end of my project likely I will be able to design original nanocarriers and to have fully characterized the systems in order to tailor specific properties. This includes the tuning the molecular interactions in the polymer assemblies at nanoscale level. During my second year, the production of chitosan carriers based on ionotropic nano-hydrogels formation induced by tri-(poly)-phosphate (TPP) has been optimized. We focused our attention on several aspects, such as physical-chemical properties, yield, storage, production automatization, etc. To optimize chitosan properties and solve pharmaceutical-technological problems we used two different classes of molecularly engineered chitosan derivatives: a trimethylated chitosan and glycosil-based derivatives. In order to investigate drug loading capacity different model drugs has been used: OVA, BSA, Human Insulin, Bovine Insulin. We investigated the association of Chitosan carriers with other biopolymers: Alginate and different Pectins. Two different methods have been used: nanoparticle coating and polyelectrolyte complexation. Finally, a collaboration has been started with the University of Innsbruck for the mucoadhesivity study and with the University of Bremen for the a deep investigation of the dimensional properties of our polymers as a function of the chemical derivatization. Objectives for the following year (if applicable) The aims of my third PhD year are: To introduce different engineered chitosan derivatives To optimize nanocarrier coating using different biopolymers: alginate and pectin To investigate nanoparticle formation using the polyelectrolyte complexation To focus our attention on human insulin encapsulation and characterization of loaded carriers (drug release, protection effect, etc.) To extend the investigation about drug loading using different types of model peptide/protein drugs In vivo ed ex vivo studies Characterization of produced systems ( nanometric resolution spectroscopies, physicochemical properties, ect.) Publications on scientific journals (printed or in press) Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 47 Publications/abstracts in conferences/congresses (national or international) EUCHIS 2009, 9th International Conference of the European Chitin Society, Venice, Italy, 2326 May 2009 Participation to conferences (as speaker) Young Researchers Oral Communication, EuroNanoMedicine 2009, Bled, Slovenia, 28-30 September 2009 Educational Activity Periods abroad (date and place) NBP Tour 2009, presso Materials and Science Group dell‟ Istitut Quimic de Sarrià (IQS), Barcellona, Spagna, 29/06 – 03/07 Classes followed (date, course, professor, type of course) Conferences, seminars, advanced courses and other didactic activities Seminario sul Virtual Private Network (VPN), Prof. M. Fermeglia, 20/03 Modeling reaction at the nanoparicle scale, Prof. P. R. Westmoreland, Dept of Chemical Engineering, University of Massachusetts Amherst, 08/05 Chimica fisica delle interfasi in sistemi nano strutturati, Dr. I. Colombo Strategie bioprotettive in sistem alimentari: il modello dei tessuti vegetali, Prof. ssa P. Pittia, Dipartimento di Scienze degli Alimenti, Università degli studi di Teramo, 28/05 Strategie adattative in invertebrati estremofili: il modello animale tardigradi, Prof.ssa L. Rebecchi, Dipartimento di Biologia Animale, Università di Modena e Reggio Emilia, 28/05 How to write (and manage) a research project, Prof. V. Sergo, Prof. M. Fermeglia, Dr. C. Blasetti, 16/10 Fracture physics of biopolymer gels, Prof. T. Baumberger, Institut des NanoSciences de Paris, France, 20/10 Corso di Reologia, Prof. R. Lapasin, DICAMP, Università di Trieste, 07/2009, Corso Avanzato di Calorimetria, Dott.ssa F. Sussich (6 h) Support educational activity and teaching Trainig of a Polish visiting student (Mateusz Gosecki, University of Lodz, Poland) on drug delivery, ionotropic nano-hydrogels formation and polymer characterization. 06/2009 (20 h) Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 48 Graduate Student XENJA SANTARELLI Title of the thesis: Correlation between structure and reactivity for nanostructured catalysts Supervisor: prof. Renzo Rosei Tutors (if any): Research Activity The aim of this thesis is to highlight correlations between the activity of nanostructured catalysts and their structural and compositional characteristics. Catalytic properties in metallic alloys are often related to those of their components in a nonintuitive way.Several catalyst parameters (not only the geometrical ones) seem to modulate reactivity. Determining if and how these effects compete or act together is the objective. Preliminary DFT calculations on several bimetallic alloys, made by members of our group, suggest what are the best candidates as catalysts for selected reactions (WGS, PROX). After a check of real samples‟ activity, their careful structural characterization is required. I dedicated the first two years of my studies how to learning how to analyse data collected with EXAFS spectroscopy and TEM, and now I‟m involved with the MCX beamline (Elettra - powder diffraction) in characterizing nanostructured catalyst samples produced in the framework of an international collaboration. This beamline is equipped with an oven to bring the samples to 1200C, to observe structural changes related to temperature variations. The last months we have been occupied in tweaking and interfacing it with the data analysis system (Labview). Both the oven and the data acquisition system are currently operating. During a recently concluded experimental session we have analyzed catalysts samples that have been already subjected to Electron Microscopy, to identify structural variations that can appear in inert atmosphere as a consequence of the annealing process. The data analysis will be concluded in a short time. Objectives for the following year (if applicable) Several problems that arose during measurements highlighted modifications that must be implemented in the oven and in the samples. Most of them are related to the labor intensive alignment phase. Moreover, the first results seem to suggest that it‟s necessary to complement the XRD technique with EXAFS. Concerning the samples, it may be necessary to change the sample support (alumina) to a new one that doesn‟t obscure NC‟s signal. In the next months it will be possible to make new measurements at the MCX beamline with the oven and a reactor to test the samples while a PROX reaction goes on. The possibility to make RT measurements with the high resolution diffractomenter will also be evaluated. Other publications “Dependence of the fractional anisotropy in cervical spine from the number of diffusion gradients, repeated acquisition and voxel size”, Santarelli, X., Garbin, G., Ukmar, M., Longo, R.; Magnetic Resonance Imaging (in press) Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 49 Educational Activity Classes followed (date, course, professor, type of course) 50h - laboratory, partially spent at the MCX beamline and partially dedicated on learning data analysis software (Origin, FIT2D) Conferences, seminars, advanced courses and other didactic activities 13-15.1.09: 13.5h (Congress of the School) 20.3.09: 1h seminar (prof. Fermeglia, VPN e Portale) 8.5.09: 1h seminar (prof. Phillip R. Westmoreland, Modeling reactions at the nanoparticle scale) 30.6.09: 3h corso (Arabito Stefania, Incontro informativi per i dottorandi di area scientifica) 24.6.09: 2h (Loredana Casalis, Trasporto elettronico nei SAM; Applicazioni in campo biologico) 26.6.09: 2h (Alberto Morgante, Determinazione di strutture di SAM di alcantioli su superfici di Au. Tecniche strutturali) 29.06.09: 2h (Alberto Morgante, Film autoassemblati di aminoacidi su superfici metalliche. Determinazione delle stato chimico e del tipo di legame con tecniche spettroscopiche di fotoemissione ed assorbimento di raggi X) 01.07.09: 2h (Lucia Pasquato, Nanoparticelle, colloidi. Metodologie di sintesi di nanoparticelle protette da un monostrato organico. Tecniche di caratterizzazione. Packing del monostrato). 03.07.09: 2h (Lucia Pasquato, Metodi di sintesi di nanoparticelle funzionalizzate. Monostrati misti. Nanoparticelle monovalenti e divalenti). 16.10.09: 5h Seminar (Blasetti-Sergo-Fermeglia, How to write and manage a research project) 7-18.09.09: 50 h X School of Synchrotron Radiation: fundamentals, methods and applications (Duino-Trieste) 26.11.09: 1h CENMAT presentation Support educational activity and teaching Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 50 Graduate Student ENRICO SOVERNIGO Title of the thesis: Influence of nanostructure on the electronic properties of heterojunctions in photovoltaic cells. Supervisor: Prof. Alberto Morgante Tutors (if any): Dott. Massimo Tormen Research Activity Photovoltaic solar cells based on organic materials show an high absorption of light and conversion to electric charges, however, thay have scarce properties of transport the photo-generated charges. Thus, the study of innovative conctacts‟ geometries has been developed to better explicate the great potential of this kind of cells. In particular we want to realize a layout in which the ligth and current path are orthogonal to each other. For this purpose, in this year the research activity has been pointed to the project and assembling of a suitable high vacuum system for the evaporation of both metals and organics at variable incidence angles. Moreover, this system has to be coupled to a glove box in inert atmosphere in order to perform more processes avoiding contaminations and degradations od materials. In the meantime, the X-ray lithographic technique has been studied at the synchrotron beamline LILit1 getting, by writing a computational code for the optics simulation, to the comprehension of this high resolution exposition system. This technique will be used to fabricate substrates for the cells mentioned above. In former studies, light trapping devices based on microlenses were developed. Thus, a deposition protocol for transparent conductive electrodes has been optimized in order to enhance the applications of this system. In conclusion, we succeded in appling for a beamtime on ALOISA 2 beamline in order to carry on some more experiment on charge transfer in organic systems for photovoltaic. Objectives for the following year (if applicable) o Fabrication of photovoltaic cells with a nano-series interconnection; o Charge transfer experiments in organic compounds for photovoltaics; o Electronic characterization system for organic semiconductors (Tutor for a master student). Other publications Poster at the Joint Workshop of PhD students, 10-11 september 2009, Wittemberg Lutherstadt, Germany. Participation to conferences (as speaker) 1 2 LILit Laboratorio Interdisciplinare di Litografia presso Sincrotrone Elettra, Trieste. ALOISA linea di luce multifunzionale per la scienza delle superfici presso Sincrotrone Elettra, Trieste. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 51 Phd Briefing TASC “Design and realisation of a thermal evaporation system for organic solar cells with special geometry” 23 july 2009, Trieste. Educational Activity Periods abroad (date and place) Classes followed (date, course, professor, type of course) 1-7 july 2009 Synthesis methods for colloidal nanoparticles, L. Pasquato, PhD Nanotechnology. Conferences, seminars, advanced courses and other didactic activities o o o o o o o o o o o o o Seminar H. Pakdast Technical University of Denmark, 26 January 2009, Trieste. Seminar A. Tredicucci, 31 March 2009, Trieste. Seminar I. Colombo “Chimica fisica delle interfasi in sistemi nanostrutturati”, 15 May 2009, Trieste. Seminar Prof. P. R. Westmoreland University of Massachusetts Amherst, 8 May 2009, Trieste. Seminar Chris Armstrong “Photovoltaic Measurements: Testing the Electrical Properties of Today´s Solar Cells” 27 May 2009. Seminar D. Sammito "Dispositivi Elettroluminescenti in Silicon Rich Oxide Drogato con Erbio", 18 June 2009, Trieste. International PhD summer school on Organic Photovoltaics ISOPHOS09, 13-15 July 2009, Valencia, Spagna. Seminar E. D‟Este, “High spatial resolution BDNF delivery by means of laser tweezers to stimulate hypocampal neurons signalling” 23 July 2009, Trieste. Joint Workshop of PhD students, 10-11 September 2009, Wittemberg Lutherstadt, Germany. Seminar G. Kladink "Ultra fast charge transport in nanotubular alpha-MnO2 self assembly studied by X-ray resonant photoemission" 17 September 2009, Trieste. 24th European Photovoltaic Solar Energy Conference, 21-25 September 2009, Hamburg, Germany. Seminar How to write (and manage) a research project, 16 october 2009, Trieste. Seminar V. Lanzilotto:"Thin organic films and their charge transfer properties: an outlook on single molecule devices.", 16 October 2009, Trieste. Support educational activity and teaching Tutor for a master thesis on Material Science: “Preparazione, caratterizzazione ed ottimizzazione di film sottili di ossido di indio-stagno per celle fotovoltaiche”, Fabio Morpurgo, Università di Padova. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 52 Dottorandi del 24 ciclo: • Graduate Student MATTEO CARGNELLO – email [email protected] Laboratorio di lavoro: lab. 439-523 Dip. Sc. Chimiche, Edificio C11 Title of the thesis: Rare-earths oxides-based nanostructures as heterogeneous catalysts Supervisor: Prof. Paolo Fornasiero Tutors (if any): Dr. Tiziano Montini Research Activity The research activity mainly consisted in the development of an approach to obtain stable materials for heterogeneous catalytic reactions. The methodology is based on the encapsulation of preformed metal nanoparticles inside porous oxides in order to limit the sintering of the metal phase under reaction conditions and therefore to avoid the deactivation of the catalysts. We initially focused our attention to Au, Pd and Cu embedded inside ceria (CeO2). 1) Au has been encapsulated inside ceria through a supramolecular approach which addresses the preferential precipitation of Ce(OH)x around pre-formed Au nanoparticles. The materials obtained showed very good activities for the PReferential OXidation of CO in the presence of excess H2 (PROX) and remarkable stability after simulated aging treatments. Moreover, the developed catalysts showed better activities than those obtained with Au/CeO2 materials prepared through optimized literature methods. The characterization with complimentary techniques such as X-ray Absorption Spectroscopy, Scanning-Transmission Electron Microscopy and chemisorption confirmed the formation of small Au nanoparticles protected by a layer of porous oxide. 2) Pd@CeO2-type systems has been realized by self-assembly in solution of the components (thiolate-protected Pd nanoparticles and Ce alkoxides). The obtained core-shell structures have been adequately functionalized to make them dispersible in organic solvents; the structures have been characterized and successfully used as flexible precursors in the preparation of active catalysts for the Water-Gas Shift-Reaction (WGSR). 3) Cu@CeO2-type catalysts have been prepared using water-in-oil microemulsions. Cu nanoparticles have been prepared inside the water droplets of the microemulsion and then a cerium alkoxide has been hydrolyzed to give the final Cu@CeO2 structures. Despite the low Cu loading (2.5 wt. %), the materials resulted very active for both PROX and WGSR. The stability of the catalysts is very promising, with no loss of activity under PROX condition even after aging at 550 °C for 12 hours (harsh conditions used to simulate an accelerate aging). The results are encouraging as they highlight the possibility to use the embedding approach for the obtainment of highly active and stable catalysts for different reactions and with different metalmetal oxide combinations. Objectives for the following year (if applicable) Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 53 The main objectives are the extension of the embedding approach to other metals and metal oxides combinations and the deep characterization of the materials already prepared. Publications on scientific journals (printed or in press) 1) V. Gombac, L. Sordelli, T. Montini, J. J. Delgado, A. Adamski, G. Adami, M. Cargnello, S. Bernal and P. Fornasiero, “CuOx-TiO2 Photocatalysts for H2 Production from Ethanol and Glycerol Solutions.”, The Journal of Physical Chemistry A, in press, doi:10.1021/jp907242q. 2) L. De Rogatis, M. Cargnello, V. Gombac, B. Lorenzut, T. Montini and P. Fornasiero, “Embedded phases: a way to active and stable catalysts.”, ChemSusChem, in press. 3) M. Cargnello, T. Montini, S. Polizzi, N. L. Wieder, R. J. Gorte, M. Graziani and P. Fornasiero, “Novel embedded Pd@CeO2 catalysts: a way to active and stable catalysts.”, Dalton Transactions, in press. Other publications 1) M. Cargnello, N. L. Wieder, T. Montini, R. J. Gorte and P. Fornasiero, “Synthesis of dispersible Pd@CeO2 core-shell nanostructures by self-assembly”, Journal of the American Chemical Society, submitted. Participation to conferences (as speaker) - “Metal-doped TiO2 for hydrogen production”, V. Gombac, T. Montini, M. Cargnello, M. Graziani and P. Fornasiero, Slovenian Conference on Materials and Technologies for Sustainable Growth, oral presentation, University of Nova Gorica, Ajdovscina, Slovenia, 12th May 2009 - Informal workshop Scuola di Dottorato di Ricerca in Nanotecnologie and Int. Max-Planck Research School for Science and Technology of Nanostructures, oral presentation “Rare-earths oxides-based nanostructures as heterogeneous catalysts”, Max Planck Institute of Microstructure Physics, Halle, 15th-16th July 2009 - “I giovani e la chimica in Friuli-Venezia Giulia”, oral presentation “Self-assembled materials based on metallic nanoparticles for heterogeneous catalysis”, Department of Chemistry, University of Trieste, 24th September 2009 - “Active and stable Au catalysts for H2 purification”, T. Montini, M. Cargnello, C. Gentilini, L. Pasquato, P. Fornasiero, S. Mehraeen, N. D. Browning, E. Fonda, GOLD 2009, 5th international conference on gold technology and applications, Heidelberg (Germany), poster presentation, 25th30th July 2009 - 2nd PhD workshop, Martin-Luther Universitat Halle-Wittenberg, Wittenberg, Germany, poster presentation “Active and stable Au catalysts for H2 purification”, 10th-11th September 2009 Participation to conferences (as co-author) - “Photocatalytic H2 production over optimized CuOx-TiO2 nanocomposites.”, V. Gombac, T. Montini, L. Sordelli, M. Cargnello, M. Graziani, P. Fornasiero, Summer School in catalysis 2009, Porto Carras, Greece, May 2009 (poster presentation by V. Gombac) - “Design of active and stable catalysts for H2 purification.”, T. Montini, M. Cargnello, C. Gentilini, L. Pasquato, P. Fornasiero, S. Mehraeen, N. D. Browning, E. Fonda, E-MRS 2009 Spring Meeting, Strasbourg, June 2009 (oral presentation by T. Montini) Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 54 - “Photocatalytic H2 production over optimized CuOx-TiO2 nanocomposites.”, P. Fornasiero, V. Gombac, T. Montini, L. Sordelli, M. Cargnello, M. Graziani, VII Convegno Nazionale Consorzio Scienza e Tecnologia dei Materiali, Tirrenia, Italy, June 2009 (oral presentation by P. Fornasiero) Educational Activity Periods abroad (date and place) - Research center ICCOM-CNR Florence, Sesto Fiorentino, AFM experiments, 1-7 February 2009 - Sinchrotron Soleil, Gif-sur-Yvette, Paris, EXAFS experiments, 19-23 February 2009 - Indian Institute of Technology, Chennai, 31 March – 5 April 2009 Classes followed (date, course, professor, type of course) - “Tecniche di caratterizzazione con luce di sincrotrone”, Prof. G. Vlaic, corso di laurea magistrale in chimica, 40 hours - “Proprietà fisiche dei materiali”, Prof. A. Franciosi, corso di laurea magistrale in chimica, 40 hours - Course “Molecular self-assembling and nanostructures”, Dr. L. Casalis, Prof. A. Morgante, Prof. L. Pasquato, 8 hours - Course “Advanced Microscopy”, Dr. L. Felisari, Dr. C. Africh, 14 hours - Course “Photoemission Spectroscopies”, Prof. A. Baraldi, 11 hours Conferences, seminars, advanced courses and other didactic activities - Annual meeting PhD School in Nanotechnology, 13-15 January 2009, total 20 hours - “Information meetings for doctoral students”, 30 June 2009, 3 hours - “Seminar on writing (and managing) a research project”, 16th October 2009, 4 hours - Annual meeting PhD School in Chemical and Pharmaceutical Sciences and Technologies, 21-23 January 2009, total 10 hours - 1st International Conference on Nanustructured Materials, Kottayam, Kerala (India), 6-8 April 2009 - Conference “Modeling reactions at the nanoparticle scale”, Prof. P. Westmoreland, 8 May 2009 - Conference “Chimica fisica delle interfasi in sistemi nanostrutturati”, Dr. I. Colombo, 15 May 2009 - Conference “Supramolecular Chemistry of Naphthalenediimides”, Dr. G. Dan Pantos, 8 June 2009 - Conference “New chemistry of dithiolenes: from biomimetic models to sensor”, Prof. Partha Basu, 13 July 2009 - Conference “NMR Techniques for Investigating the Supramolecular Structure in Solution”, Prof. Alceo Macchioni, 17 September 2009 - 3rd year PhD students presentations, 26 November 2009 Support educational activity and teaching Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 55 Graduate Student: LUCA COZZARINI Title of the thesis: “Nanostructured materials for photovoltaic applications” Supervisor: Prof. Valter Sergo Tutor: Prof. Vanni Lughi Research Activity Overall project objective This PhD research project is part of a wider project, which aims at developing a high efficiency, nanostructured multiphase material for photovoltaic applications, characterized by an electronic intermediate band (IB) located within the semiconductor bandgap. This kind of material has shown to be feasible by enclosing semiconducor nanocrystals (NCs) into a wider bandgap semiconductor (host material). This research project aims at realizing this architecture through self-assembly and densification of heterophasic NCs (“coreshell”), synthesized by potentially low-cost, environmental friendly colloidal chemistry approaches. Activities performed during first year The first year research activity focused initially on laboratory training and on reviewing the available literature . Therefore, an optimal semiconductors system was chosen in terms of costs, environmental remarks and optical properties (i.e. bandgap and relative position of valence bands). Among metal chalcogenides, Cadmium Selenide or Telluride (CdSe or CdTe) NCs embedded into a Zinc Selenide, Telluride or Sulfide (ZnSe, ZnTe or ZnS) matrix were evaluated as composite systems. Hence, with respect to practical and technological limitations, the CdSe and ZnSe NCs synthesis techniques were improved, selecting favorable precursors/solvent/surfactants, to obtain NCs of the chosen size (and therefore desired optical properties). Monophasic NCs, ranging from 2 to 6 nanometers diameter, were successfully obtained. Afterwards, novel CdSe-ZnSe and CdSe-ZnS heterophasic NCs (“core-shell”) synthesis techniques were developed, obtaining controlled size , good monodispersed CdSe cores, with an overgrown ZnX (X=Se,S) shell layer with tunable thickness. NCs solutions have been characterized through absorbance and photoluminescence spectroscopy, during and after the synthesis; some films, selfassembled from NCs dispersions, have been optically characterized through photoluminescence spectroscopy, and morphologically through Wide Angle X-ray Spectroscopy (WAXS). Finally, TEM and HRTEM images were acquired, in order to evaluate NCs size. Objectives for the following year o Improving NC deposition techniques on conductive substrates o Scouting and improving densification procedures to obtain a completely inorganic film, with required nanoscopic scale architecture and desired optical properties Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 56 Educational Activity Classes followed, 1st year (substituted by personal study): Books: - S. Adachi, “Properties of group-IV, III-V and II-VI semiconductors”, ISBN 0-470-09032- M. Winterer, “Nano-crystalline Ceramics. Synthesis and Structure”, ISBN 3-540-43433-X Reviews: - C.B. Murray et al., “Synthesis and characterization of monodisperse nanocrystals and close packed nanocrystal assemblies”, Annu. Rev. Mater.Sci. 30 (2000), 545-610 S. Kumar, G.D. Scholes, “Colloidal nanocrystal solar cells”, Microchim. Acta 160 (2008), 315-325 - A.J. Nozik, “Quantum dot solar cells”, Physica E 14 (2000), 115-120 - J. Park et al., “Synthesis of monodisperse spherical nanocrystals”, Angew. Chem. Int. ed. 46 (2007), 4630-4660 - Laboratory hours, 1st year o About 1000 hours of work at DMRN3 labs. o 20 hours of WAXS e SAXS spectroscopy at ELETTRA SAXS beamline 4 Conferences and seminars organized by Nanotechnology graduate school M. Fermeglia, “Utilizzo del VPN e presentazione del portale della scuola di Nanotecnologie”, Università degli Studi di Trieste, 20.03.2009 o “Incontro formativo per i dottorandi”, Università degli Studi di Trieste, 30.06.2008 o C. Blasetti, V. Sergo, M. Fermeglia, “How to write (and manage) a research project”, Università degli Studi di Trieste, 16.10.2009 o “Activity presentation of the III year phd students and CENMAT presentation”, Università degli Studi di Trieste, 26.11.2008 Conferences, seminars, advanced courses and other didactic activities o M. Fermeglia, G. Fraziano, F. Russo, V. Prodi, “Energie rinnovabili: una sfida e una opportunità per la ricerca e le imprese europee”, Università degli Studi di Trieste, 28.05.2009 o V. Lughi (DMRN), “Approcci chimici alla fabbricazione di materiali fotovoltaici nanostrutturati”, Università degli Studi di Trieste, 24.09.2009 o P. Posocco (DICAMP5), “Modellistica molecolare multiscala per la progettazione di materiali nano strutturati”, Università degli Studi di Trieste, 24.09.2009 o A. Jarosik (Max Plank Institut6), “Percolation of oxide networks in composite electrolytes”, DMRN, 12.10.2009 3 Dipartimento dei Materiali e delle Risorse Naturali, Università degli Studi di Trieste, via Valerio 6A, I-34127 Trieste, Italy SAXS beamline, Sincrotrone Trieste, Strada Statale 14, km 163,5 AREA Science Park, I-34149 Basovizza, Trieste, Italy 5 Dip. di Ingegneria Chimica, dell‟Ambiente e delle Materie Prime, Univ. degli Studi di Trieste, Piazzale Europa 1, I-34127 Trieste, Italy 6 Max Plank Institut für Festkörperforschung, Heisenbergstraße 1, D-70569 Stuttgart, Germany 4 Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 57 Scheda del dottorando Elisa D’Este, [email protected], [email protected] Titolo della tesi: : BIO-SAMPLE ENVIRONMENT MANIPULATION USING ADVANCED MICROSCOPY TECHNIQUES Supervisore: prof. Alberto Morgante, dott. Dan Cojoc Tutori (eventuali): dott. Enrico Tongiorgi Research activity Neurotrophins are a family of proteins that induce the survival, development and function of neurons. Brain-derived Neurotrophic factor (BDNF) is a member of this family and is able to induce different cellular responses according to the site of stimulation of neurons (McAllister, Neuron 1995). During this year I developed a system that allows a high spatial resolution delivery of this protein. This system is based on silica beads (1.5um) manipulated with optical tweezers and places on the dendrites of hippocampal neurons. I demonstrated that BDNF is still biologically active when covalently attached to the beads analyzing C-Fos translocation into the nucleus (Finkbeiner, Neuron 1997) and calcium levels (Berninger, NeuroReport 1993). We saw that BDNF-coated beads induce C-Fos translocation while control beads coated with Bovine Serum Albumin (BSA) do not. Moreover, using Optical Tweezers, I stimulated neurons with a BSA-bead, I recorded calcium signal for 10 minutes and then I placed the second bead on another dendrite. This second bead could be a second BSA-bead (control experiments) or a BDNF-bead. Signal was then recorded for 50min. Stimulation of pyramidal neurons with BDNF-beads induced an increase in calcium levels both in the somas and in the stimulated dendrites and this signal is much higher then the one obtained with BSA beads. In this year I developed a new tool for local stimulation of neurons that allows a researcher to have the experiment and the control on the same cell (really usefull for electrophysiologists). This technique can be of interest also in the field of molecular neurobiology in order to analyze the effect of molecules on different part of a same cell. Goals for the next year o Setting of sperimental conditions to visualize mRNA and Endoplasmic Reticulum movements in vivo using fluorescence microscopy o Development of new vectors that prevent mechanical stimulation of cells o Building of a an optical tweezers setup coupled to a UV microdissection setup o Building of a multi-trapping setup Pubblicationms “The evolutionary conserved gene C16orf35 encodes a nucleo-cytoplasmic protein that interacts with p73.” Lunardi A, Chiacchiera F, D'Este E, Carotti M, Dal Ferro M, Di Minin G, Del Sal G, Collavin L. Biochem Biophys Res Commun. 2009 Oct 16;388(2):428-33. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 58 Pubblications/abstracts in conferences) o ORAL:“Local BDNF delivery by means of laser tweezers to stimulate hippocampal neurons signalling” Elisa D‟Este, Gabriele Baj, Paolo Beuzer, Enrico Ferrari, Federica Tavano, Enrico Tongiorgi, Dan Cojoc; ICTP-Introduction to Optofluidics o ORAL: “High spatial resolution BDNF delivery by means of laser tweezers to stimulate hippocampal neurons signalling”; Elisa D‟Este, Gabriele Baj, Paolo Beuzer, Enrico Ferrari, Federica Tavano, Enrico Tongiorgi, Dan Cojoc; EBSA 2009 o ORAL: “High Resolution Drug Delivery by Optical Tweezers Microscopy” Elisa D‟Este, Gabriele Baj, Paolo Beuzer, Enrico Ferrari, Federica Tavano, Enrico Tongiorgi, Dan Cojoc; Super and High Resolution Imaging 2009 o POSTER: “Optical Tweezers as means to stimulate hippocampal neurons with BDNF coated beads”; Elisa D‟Este, Gabriele Baj, Paolo Beuzer, Enrico Ferrari, Federica Tavano, Enrico Tongiorgi, Dan Cojoc; Nanobioviews-2nd international symposium on Optical Tweezers in life sciences; Award best poster Optical Tweezers Educational activity Ore di lezione seguite I anno (corso, data/periodo, docente, tipo di corso di laurea) o Neuroscienze; aprile-maggio 2009; prof. Leanza; CDLM in Biotecnologie mediche 20 ore o Advanced Imaging and Spectromicroscopy methods for chemical and structural characterization of micro- and nano-materials; 11-15 maggio 2009; Dott.sa Maya Kiskinova; 15 ore o Neuronal Calcium signaling; novembre 2009; dott.sa Giulietta Pinato; CdLM in Neuroscienze; 4 ore o Ottica e Microscopia avanzata; gennaio-luglio; Dan Cojoc; 25 ore o Lettura libri: 5 ore “Mechanics of Motor Proteins and the Cytoskeleton”; Howard o Lettura review: 15 ore A practical guide to Optical trapping; Shaevitz; Angels and demons: neurotrophic factors and epilepsy; Simonato et al.; Trends in Pharmacological Sciences 2006 Activity-dependent expression of BDNF in dendrites: Facts and open questions; Tongiorgi; Neuroscience research 2008 Neurotrophin-regulated signaling pathways; Reichardt; Phil. Trans. R. Soc 2006 Signaling by death receptors in the nervous system; Haase et al.; Curr. Opon in Neurobiology 2008 Role of the BDNF at glutamatergic synapses; Carvalho et al.; Brit. J. Pharmacology 2008 Molecular mechanisms of dendritic spine development and maintenance; Sata et al.; Acta Neurobiol Exp 2008 Development and regulation of dendritic spine synapses; Calabrese; Physiology 2006 RNA trafficking and local protein synthesis in dendrites: an overview; Martin and Zukin; J. of Neuroscience 2006 Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 59 From Synapse to Nucleus:Calcium-dependent Gene Transcription in the control of Synapse Development and Funcion; Greer and Greenberg; Neuron 2008 Calcium and synaptic plasticity; Cavazzini et al.; Cell Calcium 2005 Calcium Signaling in dendrites and spines: pratical and functional considerations; Higley and Sabatini; Neuron 2008 Multiple Roles of the p75 Neurotrophin Receptor in Nervous System; Chen et al.; J. of Int. Med. Research 2009 Ore di laboratorio svolte I anno (corso, data/periodo, docente, tipo di corso di laurea) La gran parte del lavoro (> 60 ore) è stata svolta presso il laboratorio di neurobiologia del dott. Enrico Tongiorgi (dipartimento di biologia) e nel laboratorio di ottica presso il CNRINFM-LN TASC sotto la supervisione del dott. Dan Cojoc. Congressi, seminari ed incontri organizzati dalla scuola o Congresso della scuola in nanotecnologie; gennaio 2009; 9 ore o Seminario VPN; 20 marzo 2009; 2 ore o Seminario Modeling reactions at the nanoparticle scale; Prof. Phillip R. Westmoreland Dept; 8 maggio 2009; 2 ore o Seminario presentazione CENMAT e dottorandi III anno; 26 novembre 2009; 4 ore Corsi avanzati seguiti – seminari – altre attività didattiche passive o Congresso dei biotecnologi italiani; 6-7 marzo 2009; 15 ore o Corso sicurezza Laser; Elettra 25 marzo 2009; 4 ore o Workshop “AFM per campioni biologici”; 5 maggio 2009; Bologna, 6 ore, o Workshop “Orion Plus – The Ultimate Resolution”; 28 maggio 2009; Milano; 5 ore o School Introduction to optofluidics; ICTP 1-5giugno 2009; Trieste; 40 ore circa o Corso teorico/pratico intensive di microscopia a scansione elettronica; Trieste; 18 giugno 2009; 6 ore o EBSA 2009 European Biophysic congress; 11-15 luglio 2009; Genova; 30 ore o Joint Workshop between the SFB762, the Nano-IMPRS and the Scuola di Dottorato di Ricerca in Nanotecnologie; settembre 2009; Wittenberg; 15 ore circa o Super and High Resolution Imaging 2009; 30 settembre-2ottobre 2009; Lipica (Slovenia); 20 ore o NanoBioViews: 2nd International symposium on Optical Tweezers in life sciences; 14-15 ottobre 2009; Berlino (Germania); 16 ore Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 60 Graduate Student: CATERINA ELIA [email protected] Title of the thesis: Molecular Interaction on Nanoscale in Cancer Therapy Supervisor: Prof. Tullio Giraldi Tutors (if any): Dr. Giuseppe Toffoli Activity This project aims to analyze the molecular interactions on nanoscale for combination therapy in cancer patient to optimize therapy. Part of the first period was spent in research and systematic evaluation of all relevant literature. After it was conducted a bibliographic research on PubMed, and clinical protocols have been defined. It was also planned procedures for the collection and processing of biological samples, the construction of databases and the development of analytical methods. It was examined two protocols: "First line treatment with exemestane in patients with metastatic breast cancer" and "Phase I study docetaxel, oxaliplatin, capecitabine (DOC) in untreated patients affected by gastric cancer". The latter is a phase I study to define the maximum tolerated dose (MTD) in patients with gastric cancer. It has been evaluate the procedures for analysis and validation for the exemestane and docetaxel in biological matrices using HPLC-MS/MS (high performance liquid chromatography coupled with tandem mass spectrometry). The analytical methods were validated for specificity, reproducibility, accuracy, linearity, precision, limit of detection and limit of quantification. The time of analysis for the exemestane and docetaxel was 5.0 and 3.0 minutes respectively. The limit of quantitation for exemestane was 0.19 ng/ml, while for docetaxel is equal to 0.15 ng/mL. The methods have a range of linearity of 0.19-51.2 ng/mL for the exemestane, and 0.15-1500 ng/mL for docetaxel with r2≥0998. So far, two complete pharmacokinetic for the exemestane and eleven for docetaxel have been investigated. Analysis of pharmacokinetic data showed a slight trend in the docetaxel AUC, however, at present, still limited number of patients investigated allowed us to observe significant differences. Clinical studies are still in progress. Investigation will be completed by 2010. Objectives for the following year (if applicable) x Continue with the recruitment of patients to determine and assess the MTD of Docetaxel in patients with gastric cancer and to define the toxicity profile. x Continue with the enrolment of patients with breast cancer to determine plasma levels of exemestane on the response and toxicity to treatment x Development and validation of additional analytical methods for the analysis of pharmacokinetic interaction in combination therapy used in specific treatment protocols in place at the CRO of Aviano. Publications on scientific journals (printed or in press) Corona G, Elia C, Casetta B, Diana C, Rosalen S, Bari M, Toffoli G. A liquid chromatographytandem mass spectrometry method for the simultaneous determination of exemestane and its metabolite 17-dihydroexemestane in human plasma. J Mass Spectrom. 2009 Jun. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 61 Corona G, De Lorenzo E, Elia C, Simula MP, Avellini C, Baccarani U, Lupo F, Tiribelli C, Colombatti A, Toffoli G. Differential protomi analysis of hepatocellular carcinoma. Internation Journal of Oncology 2009 (accepted for publication) Publications/abstracts in conferences/congresses (national or international) Corona G, Elia C, Casetta B and Toffoli G. Liquid Chromatography/Tandem Mass Spectrometry Method To Rapid Asses the Irinotecan Metabolic Phenotype. Mass Spec Europe 5-6 November 2009, Barcelona, Spain Educational Activity Periods abroad (date and place) Classes followed (date, course, professor, type of course) 200 hours of study and deepening of the topics covered by books and review-type paper and/or electronic form (on 031209) 1350 hours at "Experimental and Clinical Pharmacology" CRO Aviano headed by dr. Giuseppe Toffoli (on 031209) Conferences, seminars, advanced courses and other didactic activities “Congresso annuale delle presentazioni dell’attività scientifica dei dottorandi in corso” at University of Trieste on January 13, 14 and 15, 2009 from 9.00 to 18.30 “Seminario sull'uso della VPN e del Portale” at University of Trieste on March 20, 2009 at 15.00 “Modeling reactions at the nanoparticle scale” Prof. Phillip R. Westmoreland Dept of Chemical Engineering, University of Massachusetts Amherst, at University of Trieste on May 8, 2009 at 15.00 “Chimica fisica delle interfasi in sistemi nanostrutturati” Dr. Italo Colombo, at University of Trieste on May 15, 2009 at 11.00 am “Incontri informativi per i dottorandi: orientamento all’utilizzo delle risorse e dei servizi documentali forniti dal Sistema Bibliotecario di Ateneo; panoramicadelle nuove modalità di comunicazione scientifica: l’archivio istituzionale di Ateneo OpenstarTs; l’autoarchiviazione delle tesi di dottorato e cenni sull’accesso aperto alla letteratura di ricerca; procedure di conferimento al sito login miur e all’anagrafe di Ateneo (Saperi) at University of Trieste on June 30, 2009 from 9.30 am to 12.30 pm “How to write (and manage) a research project” at University of Trieste on October 16, 2009 from 14.00 to 19.00 Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 62 “Tumori in HIV in era HAART - IX riunione nazionale” at CRO Aviano on January 16, 2009 from 8.30 to 17.30 “HIGHLIGHTS IN ONCOLOGY. Recenti acquisizioni in oncologia. CRO Aviano” at Convention Hall - Pordenone Fiere on February 11, 2009 from 8.00 to 16.45 “Beyond UHPLC Seminar Series. The Universal Solution for fast LC” at the Hotel Minerva Pordenone on March 05, 2009 from 9.00 am to 13.00 pm “CRO INCONTRA IMPRESA. Tech Transfer e ricerca oncologica” at CRO Aviano on April 24, 2009 from 9.00 to 13.30 “Seminari in Oncologia al CRO di Aviano” at CRO Aviano on May 28 and June 4-11-18, 2009 from 16.00 to 19.00 “La donazione di sangue, cellule staminali, cordone ombelicale: un’opportunità e una risorsa” at CRO Aviano on October 03, 2009 from 08.20 to 15.30 “Utilizzo delle cellule staminali ematopoietiche in pediatria: indicazioni attuali e prospettive future” at MIB School of Management - Trieste on June 30, 2009 from 09.00 to 16.00 “English language course at the Shenker Institute of Pordenone”: January to July 2009, 20 hours of lessons with final certificate “BLSD - Corso teorico pratico di Basic Life Sup port and Defibrillation” at CRO Aviano on April 15, 2009 from 8.45 am to 18.00 pm “REFERENCE MANAGER: uno strumento straordinario per ottimizzare la gestione delle bibliografie” at CRO Aviano on May 19 and 26, 2009 from 14.00 to 17.30 “Course Hamilton Microlab Star (HMS)” Training at Experimental and Clinical Pharmacology CRO Aviano on September 29-30, 2009 Support educational activity and teaching Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 63 Graduate Student: DANIEL ERA Title of the thesis: Nanotechnological application in pharmacogenetic research Supervisor: Prof. T. Giraldi Tutors: Dr G. Toffoli Research Activity The primary objective of the research project is to evaluate the possible application of innovative nanotechnology and methodologies in clinical practice of community medicine. The project is aimed to evaluate the feasibility of the translation of pharmacogenetics approaches from clinical trials, necessarily conducted on fewer samples, to current clinical practice of community medicine. Detailed analysis of the literature indicates that pharmacogenetics of warfarin is relevant for a more appropriate use of this drug. Warfarin is a widely used oral anticoagulant drug but its use has problems due to individual variability in response, with the need to adapt dose for each patient. Such individual variability is due to the presence of Single Nucleotide Polymorphisms (SNPs) in genes encoding the enzymes involved in its metabolic inactivation (CYP2C9), and its biological target, vitamin K epoxide reductase (VKOR), with resistance (persistence of risk of thromboembolic phenomena) or limited response to treatment (bleeding). The objective of the research project even involve the validation of algorithms of prediction of warfarin dose based on pharmacogenetic variables (polymorphisms of CYP2C9 and VKORC1). The pharmacoeconomic aspects will be also considers in this study. From this evaluation may derive any indication of the possibility of develop advanced nanotechnology devices, also suitable for use in clinical practice and community medicine. The first year of PhD was dedicated to the development of the project, through extensive analysis of the literature, writing the research protocol in collaboration with the clinicians, and the identification of different methodological and technological approaches. The identified molecular genetic techniques are Polymerase Chain Reaction (PCR), followed by analysis of polymorphisms using technologies such as Pyrosequencing or TaqMan method. The project was then submitted and approved by Ethical Committee of the Azienda per i Servizi Sanitari di Trieste n.1 (ASS1), because the study covers patients recruited by the Centro Cardiovascolare and Distretto 1 of ASS1. These structures have currently begun the enrolment of the patients and the organization of the clinical records in order to create a database. In the final part of the first year it is also started the collection of biological samples (blood or oral mucosal cells), obtained after written informed consent from each patients recruited, for the analysis of polymorphisms. Objectives for the following year Over the next two years, the doctoral project will develop along the following main points: Patients enrollment and implementation of the database with the data of their medical records; collection of biological samples; DNA extracting and genptyping; statistical analysis of the data; pharmacoeconomic analysis of the results; writing a conclusion and final report. Publications/abstracts in conferences/congresses (national or international) Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 64 o Role of genetic polymorphism 5-HTTLPR of serotonin transporter in psychological response to diagnosis of breast cancer. XI national congress of Italian Society of Psycho-Oncology (SIPO). October, 1-3, 2009, Senigallia (An) (POSTER); o Genetics interaction between citalopram antidepressant activity and MAO-A VNTR polymorphism in paliative care of cancer. 34° national congress of Italian Society of Pharmacology (SIF). October, 14-17, 2009, Rimini (POSTER). Educational Activity Classes followed (date, course, professor, type of course) o In agreement with the supervisor and as provided by the school, the classes have been replaced by the reading of numerous reviews and original papers on pharmacogenetics. In addition, during the first year was made an extensive study on the statistical analysis of data through books, manuals and use of dedicated programs (SPSS, systat, R). o Laboratory of Pharmacogenetics, Department of Life Sciences, section of Pharmacology. Dr. G. Schillani. Conferences, seminars, advanced courses and other didactic activities o Congress of the “PhD school in Nanotechnology”. January 2009; o Congress “Highlights in oncology. Recenti acquisizioni in oncologia”. February 11 2009, Aviano (Pn); o III Meeting-Workshop “Nuove Prospettive in Chimica Farmaceutica”. February 13-14 2009, Castelvecchio Pascoli (Lu); o Prof. Maurizio Fermeglia “Uso del VPN per l‟accesso remoto”. March 20 2009, Trieste; o Dr A. Bardelli “Cancer mutations and targeted therapies”. May 6 2009, Trieste; o Prof. PR Westmoreland, Dept. of Chemical Engineering, University of Massachusetts Amherst, “Modeling reactions at the nanoparticle scale”. May 8 2009, Trieste; o Dr I. Colombo “Chimica Fisica delle interfasi in sistemi nanostrutturati”. May 15 2009, Trieste; o Incontri informativi per i dottorandi organizzato dalla Sezione Ricerca e Dottorati in collaborazione con il Sistema Bibliotecario di Ateneo. June 29 2009, Trieste. o 34° National Congress of the Italian Society of Pharmacology “Il valore del farmaco per la tutela della salute”. October 14-17 2009, Rimini; o Corso introduttivo alla farmacoepidemiologia, ASS1-ISS, November 19-21 2009, Trieste. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 65 Graduate Student: Raffaella Fior Title of the thesis: “Ionic channel behavior: development of a novel, non destructive method for mechanical and electrical analysis of a single cell” Supervisor: prof. O. Sbaizero Tutors (if any): Research Activity The main goal of this doctoral activity is the design and the realization of an experimental technique able to perform electrical and mechanical analysis of single living cells. In particular our research will be focused on ion channel activity correlated to mechanical properties. The background idea is to integrate micro-fabrication techniques (micro electro mechanical devices, MEMS) and an atomic force microscope (AFM). During the first year, we focused our research on the design and optimization of commercial MEMS. We used these devices to analyze single cells, in particular we evaluated the morphological modifications comparing the ratio between area and perimeter with the number and the type of stimuli (linear, cyclic, amplitude and velocity of stretch). We also used shape factor to estimate the healthy degree of each stimulated cell. However, commercial MEMS are non-transparent and therefore every analysis must be performed with reflective microscopy. To overcome this problem, I worked (and I am still working) in the nearby CNR-TASC laboratories and a transparent MEMS is under realization. We designed the masks that we will use during fabrication, we modelled with finite elements analysis each constitutive element, finally we chose the production techniques (deposition techniques and etching) and selected the best materials. Thin films, using Plasma Enhanced Chemical Vapour Deposition (PECVD), have been already deposited. Each composition has been tested focusing on transparency, refractive index, impurities, deposition rate and etching rate. Objectives for the following year (if applicable) Transparent MEMS 1. realization of a prototype 2. optical and mechanical characterization Commercial MEMS PolyMUMPs 1. surface treatment to prevent cell adhesion in the measurement area 2. local functionalization of the platforms 3. single cell stress-strain evaluation AFM analysis on fixed and living cells 1. cells over a conductive surface Participation to conferences (as speaker) “Mechanical and Electrical Analysis of a Single Cell” - HIM 2009 (Highlights in Microtechnology) – Neuchatel, Switzerland 2-5 July 2009 Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 66 Educational Activity Conferences, seminars, advanced courses and other didactic activities Courses 1. 11-15 May 2009 “Advanced Imaging and Spectromicroscopy for Chemical and Structural Characterization of Micro and Nano Materials” Maya Kiskinova Head of Microscopy projects Synchrotron Trieste 15hours School 1. 23rd August – 12th September 2009 “ESONN'2009 European School On Nanosciences & Nanotechnologies” Grenoble, France Poster presentations 1. “Development of tools for biologic applications” R. Fior, S. Maggiolino, B. Codan, E. Merola, S. Rizzi and O. Sbaizero - R&D - University of Trieste 22nd May 2009 2. "Mechanical Analysis of Fibroblast Cell Line Using MEMS Technology” R. Fior, S. Maggiolino and O. Sbaizero - ECI conference “Nanotechnology for the Study of Cellular and Molecular Interactions” - Barga (LU) 14-18 June 2009 Poster award: best poster honourable mention 3. “Micro Electro Mechanical Systems for single cell analysis: design, production and characterization” R. Fior, S. Maggiolino and O. Sbaizero - Euromat 2009 European Congress and Exhibition on Advanced Materials and Processes - Glasgow, UK 7-10 September 2009 4. “Realization of a new MEMS device to mechanically stimulate a single cell: evaluation of the morphological modification.” R. Fior, S. Maggiolino and O. Sbaizero ESONN'2009 European School On Nanosciences & Nanotechnologies - Grenoble, France 23 August – 12 September 2009 Seminars 1. “Percolation of oxide networks in composite electrolytes” A. Jarosik - International Max Planck Research School for Advanced Materials Stuttgart Germania @ DMRN Università di Trieste 12th October 2009 2. "Structure Effect on Interfaces" by Francesco Stellacci - Department of Material Science and Engineering, Massachusetts Institute of Technology @ELETTRA building Basovizza TS 12th October 2009 3. “Focused on the Fibroblast: friend or foe? Bystander or therapeutic target” C. Long MD - University of Colorado Health Sciences Center, Chief Cardiology Section Denver Health Medical Center @polo cardiologico di Cattinara Trieste 4th December 2009 Support educational activity and teaching -3 hours metallurgy seminar: starting materials for steel production, blast furnace, cast irons, ferrous and non ferrous materials, metals designation, stainless steel. -2 hours biomaterials seminar: cellular culture techniques -100 hours biomaterials laboratory following 5 working groups: 1. bio compatibility analysis of 4 materials (UNI EN ISO 10993-5); 2. evaluation of cellular migration over a polymeric stressed material; 3. set-up of a cellular manipulation system: pico-spritzer; 4. preparation of polyacrylamide gel with different composition and different adhesion proteins (polilysin, fibronectin, collagen IV) to evaluate cellular adhesion; 5. glass photolithography of a dental biocompatible polymer. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 67 Graduate Student: Valeria Lanzilotto Title of the thesis: Self-assembling and charge transfer properties of thin organic films Supervisor: Prof. Alberto Morgante Tutors (if any): Research Activity During the first year of my PhD I had the opportunity to address different research topics mainly focused on the study of both geometrical assembling and electronic properties of organic-inorganic interfaces. In parallel I have investigated more traditional systems such as organic thin film on metal or semiconductor substrates, and I began the study of systems such as the most innovative devices built from individual molecules. This allowed the use of different experimental techniques: spectroscopy (XPS, NEXAFS, ResPES), diffraction (HASPES, PED, LEED) and microscopy (STM) for the traditional systems, while conductivity measurements (STM break-junction method) for the study of the electronic properties of single molecule devices. So far the most significant results were achieved in the analysis of the ordering properties of C60 and pentacene thin films on TiO2 (in its semiconductor phase). Information concerning the electronic properties and possible charge transfer are being finalized. As part of research conducted in the field of single molecule electronics, numerous experiments have been conducted in order to deepen the study of junctions Au/benzenediamine/Au in different conditions (UHV and low temperature) than those reported in the literature (in air and room temperature). Objectives for the following year (if applicable) The plain is to investigate on the missing information on the electronic properties of the aforementioned systems (C60 and pentacene/TiO2); to this end a period of measurements (beamtime) on the ALOISA/HASPES beamline has already been approved and allocated. Futhermore the next step on the study of the single molecules conduction properties is to move forward with the support of spectroscopic informations that can be obtained from the same thin organic films on gold (in this case too we take advantage of the aforementioned beamtime). Publications on scientific journals (printed or in press) Publications/abstracts in conferences/congresses (national or international) “Charge transfer properties of thin organic films : an outlook on single molecule devices”, 2nd PhD Workshop of the SFB 762 in conjunction with the International Max Planck Resarch School for Science and Technology of Nanostructures, Wittenberg, Germany, 10-11/09/2009 “One of the main goals of nanotechnology is the miniaturization of electronic devices through the exploitation of unique properties of matter at the nanoscale. At present, many efforts have been made to develop electronic devices in which a molecule between two electrodes plays the role of an Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 68 active conducting element. Although reliable and reproducible experiments have been reported, a comprehensive conceptual understanding of electron transport in molecular system is lacking. In this work, the main results obtained by means of a home-made STM break junction set up will be presented. In the STM break junction technique an Au scanning microscope tip is repeatedly crashed in and moved out of an Au surface in the presence of the molecule. As the Au point contact is streched and finally broken, a molecule can be trapped between the tip and the substrate. It is then possible to apply a bias to the electrodes and measure the current passing through the molecule. The electron tunnelling through the molecular junction is affected by the coupling between the discrete energy levels in the molecule and the continuum states of the electrodes. To understand this coupling, the single molecule conductance measurements will be discussed with the support of the spectroscopic investigations of the same thin organic films on gold. In particular, by means of Resonant Photoemission Spectroscopy it has been possible to disentangle molecular orbitals and determine the ones involved in the charge transfer at the surface.” Participation to conferences (as speaker) “Charge transfer properties of thin organic films : an outlook on single molecule devices”, 2nd PhD Workshop of the SFB 762 in conjunction with the International Max Planck Resarch School for Science and Technology of Nanostructures, Wittenberg, Germany, 10-11/09/2009 Educational Activity Periods abroad (date and place) 25/10/09-21/12/09 Instituto de Ciencia de Materiales (Universidad Autónoma de Madrid) Classes followed (date, course, professor, type of course) 12/01/09-06/03/09 (48 ore), Spettroscopia atomica e molecolare, Prof. Alfonso Baldereschi, Corso di laurea specialistica in Fisica (Curriculum: Fisica della Materia) 02/03/09-29/05/09 (48 ore), Elementi di ottica quantistica, Prof. Fulvio Parmigiani, Corso di laurea in Fisica 11-15/05/09 (12 ore), Advanced Imaging and Spectromicroscopy methods for chemical and structural characterization of micro- and nano-materials, Maya Kiskinova, Didattica XXIV Scuola di Dottorato in Fisica Conferences, seminars, advanced courses and other didactic activities 09/01/09 "First-principles studies of single-molecule junction conductance: Links, length, and switching" Jeffrey B. Neaton, Molecular Foundry, LBNL, Berkeley, USA 13-15/01/09 Congresso Scuola nanotecnologie Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 69 13/03/09 PhD briefing @ TASC - "Templated Growth and Properties of Iron Nanowires: Anisotropic Electron States of the quasi 1D Copper Substrate, and morphological and magnetic properties of the iron adsorbate" Carlos Eduardo Viol Borbosa - "Organic molecules at metal surfaces: the role of functional groups" Martina dell‟Angela 20/03/09 Seminario VPN e Portale 08/04/09 Scuola di nanotecnologie: esame finale aprile 2009 30/06/09 Incontri Informativi Dottorandi 17/09/09 PhD briefing @ TASC - "Ultra fast charge transport in nanotubular alpha-MnO2 self assembly studied by X-ray resonant photoemission", Gregor Kladink 12/10/09 "On the effect of Nanostructure on Interfacial Energy", Francesco Stellaci, Department of Material Science and Engineering, Massachusetts Institute of Technology 16/10/09 PhD briefing @ TASC - "Design, realization and characterization of a novel device: a transparent MEMS for mechanical single cell analysis", Raffaella Fior 01/12/09 "Surface Chirality Manifestation through the Surface Stress", Maria Blanco Rey, Department of Chemistry, University of Cambridge Support educational activity and teaching 22-27/04/09 Partecipazione all‟esperimento "Chemical state and structural characterisation of adsorbed dipeptides" at ELETTRA Synchrotron lab in Trieste, Italy, “ALOISA/HASPES” beamline 16/10/09 PhD briefing @ TASC - "Thin organic films and their charge transfer properties: an outlook on single molecule devices", Valeria Lanzilotto Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 70 Graduate Student: IMMACOLATA LUISI Title of the thesis: Identification of novel protein scaffolds for binding of small molecules Supervisor: Prof. Roberto Marzari (University of Trieste) Tutor: Prof. Daniele Sblattero (University of Eastern Piedmont) Research Activity In the literature, there are well known protein structures, named scaffold, used and modified for the construction of variants able to recognize and bind small molecules. These scaffolds differ in terms of structures stability, tolerance to multiple substitutions, ease of expression and subsequent applications. Protein scaffolds are divided according to the architecture of their bones into three groups: scaffolds formed by -helix, scaffolds formed mainly by -sheets and small scaffolds with few secondary structures or irregular architecture of -helices and -sheets. Among the alpha-helices scaffolds there are the coiled-coil domains: these are composed by two right-handed alpha helices which dimerize. A research group has synthesized ex-novo a scaffold structure named E/K coiled coil. In my PhD project this E / K coiled-coil scaffold has been considered to isolate new molecular interactors on the basis of some characteristics that have been already described. The E / K coiledcoil scaffold consists of two distinct peptides, formed by a single heptad repeated five times. The sequence of the heptad for the E peptide is E-V-S-A-L-E-K while for the K peptide is K-V-S-A-LK-E (positions g-a-b-c-d-e-f). We decided to make the some changes to the basic structure of the scaffold E/K in order to create a pocket that can bind various types of small molecules. Mutations were made to both peptides E and K, in central heptads and leaving the other four heptads as wild type. The strategy adopted was a random mutagenesis in which all amino acids were mutated in the all positions of heptads considered. This randomization was obtained using a random design of primers and subsequent cycles of PCR. A library of 2 * 108 single chain fragments E random / K random was created. The quality of the library obtained was verified by PCR while the diversity was validated by sequencing the clones. The sequence shown a good variability of each central random heptad in all clones analyzed. The library has been selected with phage-display technique on a range of analytes of our interest for the identification of novel protein scaffolds that are able to bind these small molecules. Objectives for the following year (if applicable) For the future we will carry out a biochemical characterization of the clones selected against the analytes chosen. In particular we will study the affinity, the stability, the folding, the constants of association / dissociation, the chemical and physical characteristics (such as circular dichroism spectra) and the three-dimensional structure of interacting partners for future applications in the field biosensor as a new molecular scaffold. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 71 Educational Activity Classes followed (date, course, professor, type of course) 11-15 May 2009: Course: “Advanced Imaging and Spectromicroscopy methods for chimical and structural caracterization of micro and nanomaterials” Prof. Maya Kiskinova, Elettra Trieste, course for phd student by nanotechnology school (15 hours) 18 June - 6 Julye2009: Course: “Molecular self-assembling and nanostructures” Prof. L. Pasquato, A. Morgante e L. Casalis, course for phd student by nanotechnology school (16 hours) 5-30 October 2009: Course: “Cellular Neurobiology” Prof. Enrico Tongiorgi, University of Trieste, course of master degree in Neuroscience (24 hours) 5-30 October 2009: Course: “Techniques in cellular neurobiology” Dott. Gabriele Baj, University of Trieste, course of master degree in Neuroscience (24 hours) 27 October 2009: Exercise Laboratory at the Department of Chemical Sciences for measurements of CD spectrum (10 hours) Conferences, seminars, advanced courses and other didactic activities 13-15 January 2009: Presentation of phd students of nanotechnology school 20 March 2009: “Use of the basic tools for activity of the school VPN (Virtual Private Network )” Prof. M. Fermeglia 8 April 2009: Final exams of phd students of nanotechnology school 8 May 2009: “Modeling reactionsat the nanoparticle scale” Prof. Philip R. Westmoreland 15 May 2009: “Veneto-nanotech project” Dott.ssa Talarico; “Chemical physics of interphases in nanostructure systems” Prof. Italo Colombo 16 October 2009: “Seminar on writing and managing of research project” Prof. M. Fermeglia, Prof. V. Sergo e Dott.ssa Cecilia Blasetti 26 November 2009: “Activity presentation of the III year phd students and CENMAT presentation” Support educational activity and teaching Tutors activities in the laboratory of cell biology for a bachelor's degree student in the field of molecular biology for a total period of three months which includes the learning of key laboratory techniques such as preparing solutions and culture media for bacterial growth, preparation of glycerolates, preparation of chemical competent cells, bacterial transformation, plasmid DNA extraction, PCR (Polymerase Chain Reaction), agarose gel electrophoresis, preparation of acrylamide gels and Western blotting. Support in the writing of the three years thesis. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 72 Graduate Student: Monica Marini Title of the thesis: Implementation of simple logics in bioinorganic hybrid nanosensors Supervisor: Giuseppe Firrao Tutors (if any): Research Activity In this year I carried out the preliminary work for the development of the biosensing layer of a novel hybrid nanosensor comprising a nanopore and complex nucleic acid structure. For this purpose two methods were applied for the construction of an effective sensitive layer: the Hybridization Chain Reaction to obtain DNA long polymers labelled with fluorescent (FITC) or Electrochemiluminescent (Ruthenium) moieties, and the new approach of two dimensional DNA origami. The first approach resulted highly reproducible in vitro under controlled temperature, and the visualization of the polymers was very simple (both in the case of modified and not modified polymers) by gel electrophoresis, by epifluorescence microscopy or ECL detection. The implementation of the DNA origami approach required an extensive preliminary design phase, that was performed by dedicated software packages (SARSE v.1.38/DNA origami package v.1.10, NanoEngineer-1 ™ v.1.1.1 and caDNAno v.0.2 .3). These programmes were evaluated for their advantages and disadvantages, and I managed to obtain a reliable final model only with the use of the software caDNAno. The designed structure consists of 218 oligonucleotides for each strand of M13mp18 present in solution and I am currently proceeding with the in vitro validation of the computer model. In the same time the mechanism of switching of the DNA origami was investigated. This change of conformation is based on the hybridization events occurring between a single stranded DNA (linked to the sensitive layer) and a target molecule of diagnostic interest. In the case of the detection of molecules of biological interest such as mycotoxins, the protocol has been finalized to the development of a DNA aptamer specific for Zearalenone, adjusting a previous reported SELEX protocol. The didactic activities of this year included university courses at the universities of Trieste and Udine, workshops organized by the Graduate School in nanotechnology and others, advanced courses followed at ELETTRA and a summer school at the University of Karlsruhe. Objectives for the following year (if applicable) 1. 2. 3. 4. In vitro validation of the expected DNA origami structure obtained from computer modeling by caDNAno. Preliminary visualization of the origami by gel electrophoroesis and TEM; In vitro development of the ZEA specific DNA aptamer after its chemical modification and the development of affinity agarose-based columns with DADPA branches; Study of the switching mechanism working only with the hybridization between two single stranded DNA. Preliminary study on the introduction of Boolean logic for the selective switching of the biosensing layers. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 73 Educational Activity Classes followed (date, course, professor, type of course) Course: ELETTRA Maj 2009 (14 hours). Maja Kiskinova: “Advanced Imaging and spectromicroscopy methods for chemical and structural characterization of micro- and nano-materials”. Course: University of Trieste June 2009 (4 hours). Alberto Morgante, Loredana Casalis, Lucia Pasquato: “Molecular self-assembling and nanostructures”. Course: ELETTRA June – July 2009 (16 hours). Cristina Afric, Laura Felisari: “Advanced microscopy: Scanning and Transmission Electron Microscopy, Scanning Probe Microscopy”. Course: University of Udine, First level degree in Mechanical Engineering, October 2009 January 2010 (60 hours). Di Giusto Sandro: “Fondamenti di informatica”. Study of the Systematic Evolution of Ligands by EXponential enrichment and non-SELEX techniques for aptamer development. Study of the chemical modification of mycotoxins (Zearalenone) and its ligation to substrates as paramagnetics beads and agarose-based resin in presence of DiAminoDiPropyl Amine. Study of the DNA-based origami techniques for 3D and 2D structures. Application of the related softwares as SARSE v.1.38/DNA origami package v.1.10, NanoEngineer-1™ v.1.1.1 e caDNAno v.0.2.3 Conferences, seminars, advanced courses and other didactic activities Activities organized by the School PhD students activities presentation (20 hours): 13th - 15th January 2009. Seminar: April 2009 (1 hour) University of Trieste “Nanochallenge and Polymerchallenge”. th Seminar: 15 May 2009 (1.5 hours) University of Trieste. Dr. Italo Colombo “Chimica fisica delle interfasi in sistemi nanostrutturati”. th Seminar: 30 June 2009 (3 hours) University of Trieste. “Information meeting for doctoral students”. th Seminar: 16 October 2009 (5.5 hours) University of Trieste. “Writing (and managing) a research project”. Other seminars th Seminar: 4 February 2009 (2 hours). Natural Science Museum of Udine. Ian Tatterstall: “Charles Darwin and human evolution” th Seminar: 11 June 2009 (4 hours). Area Science Park. KeyToNature Technology Transfer Day: “L'identificazione rapida di organismi: dalla ricerca alle applicazioni industriali”. th Seminar : 11 June 2009 (2 hours). University of Udine. Prof. Robert S. Marks: “Biosensor systems in detecting patient exposure to pathogens and monitoring water toxicity: how combining biology, physics and chemistry helps gain in sensitivity and time.” th th Summer School: 7 - 11 September 2009 (26 hours). Universitat Karlsruhe (TH), DFG-Centrum fur Functionelle Nanostrukturen. Bad Herenhalb, Germany: “CFN Summer School on NanoBiology”. Support educational activity and teaching Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 74 Dottorato: Elisa Migliorini Titolo della tesi: The effect of nanotopography on cell differentiation: an alternative way to guide embryonic stem cells into neurons. Supervisore: Marco Lazzarino Tutori (eventuali): Elisabetta Ruaro Research Activity Description of the research activity and the main results obtained: The aim of my Phd project is to develop nanopatterned substrates which can stimulate, control and direct the Embryonic Stem (ES) Cells differentiation into neurons. My activity is divided in 3 technological different fields : 1- micro and nano fabrication to obtain nanopatterned substrates, 2-Embryonic Stem Cells colture and differentiation into neurons, 3development of imaging techniques and methodologies for cell analysis in physiological conditions with nanometrical resolution . I fabricate several PDMS substrates for cells colture using Soft Lithography. These substrates have simple 2D geometry (lines, pillars, circle) , periodicity between 180 nm and 800 nm and depth between 100-500 nm. PDMS replica obtained were analyzed using Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM) on air and in liquid. I differentiate Embryonic Stem cells into neurons using a stromal cell-derived inducing activity (SDIA) protocol. Neuronal precursors were plated on glass coverslips and on glass coverslips coated with PDMS because a first important result was the significant increase of cells vitality observed on PDMS substrates. Moreover preliminary results show that the yield of differentiation increase on nanopillars 250 nm wide and 200-400 nm deep. To observe the cell-substrate interaction with micrometrical resolution I developed an imaging methodology using AFM (in liquid). Neurons after 24 hours of differentiation were fixed and then imaged with AFM in liquid. An important goal reached this year was to find the ideal condition to perform AFM live imaging of neurons on flat glass. Neuronal growth cones movements were observed for a couple of hours and their growth and retraction were imaged. That result might be a perfect tool to study cell-substrate interaction at nanometrical level. Objectives for the following year (if applicable) 1- Fabrication of different patterns, with different aspect ratio, varying their period, depth and mechanical properties. Fabrication of disordered patterns with the same dimension of the previous ones. The patterns which induce a cellular response will be transfer on a Silicon Nitride substrate. 2- Increase the yield of differentiation and the reproducibility of ES-derived neuronal colture. Verify with a bigger statistical analysis the effect of the nanopatterned substrate (PDMS pillars with a period of 250 nm) on the neuronal differentiation using immunofluorescence essay and fluorescence Microscope. Gene expression analysis of ES-derived neurons grown on nanopatterns. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 75 3- AFM on a bigger number of neuronal growth cones on nanopatterns in liquid after fixation, to analyze the effect of the pattern on the GC‟s morphology. AFM of live neurons pleated on PDMS flat and patterned to observe the interaction between neurons and substrates. AFM to study adhesion forces, in particular, relatively to a single focal point. Pubblicazioni su riviste scientifiche (pubblicate oppure in stampa), Migliorini E., Ban J., Di Foggia V., Ruaro ME., Torre V., Pozzato A., Grenci G., Tormen M, Lazzarino M. Effect of nanopatterned substrates on growth cones activity. Eur Biophys .J. 2009 Oct, (suppl 1) S89 Kondra S, Laishram J., J. Ban J.,Migliorini E., Di Foggia V., Lazzarino M., Torre V., Ruaro M.E. Integration of Confocal and Atomic Force Microscopy. Journal of Neuroscience methods. 2009 Feb 15;177(1):94-107. Epub 2008 Oct 18. Laishram J., Kondra S., Avossa D., Migliorini E., Lazzarino M., Torre V. A morphological analysis of growth cones of DRG neurons combining Atomic Force and Confocal Microscopy. Journal of Structural Biology. 2009 Sept. Partecipazione a congressi (come relatore) “AFM live imaging of neuronal growth cones reveals a new nanometrical morphology”. SLONANO 2009, 19-21 October Lubjana, Slovenia. Oral presentation “AFM live imaging to analyze neuronal differentiation on nanopatterns” First Interim meeting Nanoscale project. 23 Sept. 2009, Paris France. Oral presentation. “AFM live imaging of ES-derived neurons and growth cones retraction at the nanoscale”. European Biophysics Congress EBSA: 11-15 July 2009. Genoa – Italy. Poster presentation Attività formativa Esami sostenuti, ore di lezione e di laboratorio seguite (data, corso, docente, tipo di corso di laurea) Corsi Data Num. ore Docente Tipo do corso Structural biology 02/09 24 Silvia Onesti SISSA (biofisica) Advanced Imaging 04/09 Spectromicroscopy 15 Maya Kiskinova S.di Dott.Nanotecnologie Optofluoidic School 06/09 40 Dan Cojoc ICTP summer school SEM 04/09 4 Laura Felisari TASC lectures Laboratorio Data Num. ore Tutors Attività svolta CNR-TASC Dal 01-09 >60 M. Lazzarino G. Grenci Nano-micro fabbricazione CBM Dal 01-09 >60 M.Lazzarino AFM prof. Dal 01-09 >60 Elisabetta Ruaro Jelena Ban Colture di cellule staminali embrionali SISSA (lab. Vincent Torre) Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 76 Congressi, seminari, corsi avanzati e altre attività didattiche passive Congressi Data Ore Organizzatore EBSA Genova 2009 11-15/07/09 35 Alberto Diaspro meeting 23/09/2009 Project 8 Vincent Torre write (and 16/10/2009 a research 4 Maurizio Fermeglia 20 Dragan Mihailović, J. Stefan Institute First interim Nanoscale (Parigi) How to manage) project Slonano (Lubiana) 19-21/10/09 Seminari Data Relatore High-resolution scanning X-ray diffraction 22/01/2009 microscopy Dr. Pierre Thibault X-ray microscopy:dealing with real-life 22/01/2009 complexities Dr. Chris Jacobsen Neuronal plasticity Prof. Francois Anserment & Prof. Pierre Magistretti 08/04/2009 Modeling reactions at the nanoparticle 08/05/2009 scale Prof. Phillip R. Westmoreland Calcium control of gene regulation in an 15/06/2009 Dr. Giulietta Pinato in-vitro model of neuronal plasticity How is Enzymatic Activity Determined by 20/07/2009 Protein Dynamics? Dr. Kerstin Blank Inhibition of scrapie prion replication by 22/07/2009 polyelectrolyte nanogold particles & Coated Nanogold and the Brain Dr. Fernanda Sousa Dopaminet summer school (CBM) Prof. Stefano Gustincich 5-6/10/09 Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 77 Graduate Student : Seid-Hossein Pakdast Title of the thesis: Advanced MEMS Resonators for High Sensitivity Molecular Detection Supervisor: Marco Lazzarino Tutors (if any): Research Activity The goal of this project is to fabricate a mechanical mass sensor with a very high sensitivity down to a few molecules. A new geometry consisting in three-coupled microcantilevers simulated by finite element analysis method to find the different resonance frequency modes and to see any correspondence between the experiment and the simulation. In this way, we can have a good estimation of the resonance frequency before fabricating the device. The most interesting mode is the anti-symmetric one where the middle cantilever is not moving. In principle, the added mass breaks the symmetry of the three-coupled microcantilevers, which triggers the onset of nonzero vibration amplitude of the middle cantilever. The results of the simulations show clearly that placing an additional mass on one of the two outer microcantilevers will trigger the middle one to oscillate. Further, simulations on displacement amplitude show that there is always present of transversal vibration. The same geometry has been fabricated in the cleanroom at TASC by photolithography technique, reactive ion etching, and wet etching processes. Scanning electron microscopy has been used to characterize and to optimize fabrication processes. The resonance modes are generated in vacuum by a piezoelectric actuator which oscillate the entire chip or by a frequency-modulated laser in a custom built setup which is focused on individual devices. The measurements showed that laser actuation method results in narrower mode peaks since local actuation does not excite spurious modes which are instead observed by piezoelectric actuation. The setup also allows to rotate the photodetector in order to measure the oscillation of the cantilevers both along transverse and longitudinal axes. The results of the experiment show that there is angle dependence of the cantilevers in both actuation methods. Objectives for the following year (if applicable) -Fabricate a number of devices with different designs and dimensions -Optimize the fabrication process -Optimize the setup in order to measure the thermo-fluctuations of the cantilevers -The laser spot needs to be in order of 3-5µm in diameter -Simulation of the real external forces e.g. laser beam or piezoelectric in order to have an idea about the amplitude oscillations. -Test the sensitivity with on purpose added masses. Other publications 07/28-09, Abstract for Max-Planck Institute MPI, Workshop in Wittenberg from 09/10-09 to 09/11-09 Participation to conferences (as speaker) Max-Planck Institute MPI, Workshop in Wittenberg from 09/10-09 to 09/11-09 Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 78 Educational Activity Classes followed (date, course, professor, type of course) Date Course Professors / Teachers Type of course Hours 03/23-09 Biological Physics Michele Vendruscolo Biophysics 18 05/11-09 to 05/15-09 Advanced Imaging and Spectromicroscopy methods for chemical and structural characterization of micro- and nano-materials Maya Kiskinova Head of Microscopy projects Sincrotrone Overview of different spectromicroscopies 15 06/01-09 to 06/05-09 Introductions to Optofluidics J. Niemela microfluidics with MEMS 40 06/23-09 to 07/15-09 Advanced Microscopy (Electron Microscopy and Scanning Probe Microscopy) Cristina Africh and Laura Felisari Microscopes 16 06/18-09 to 07/06-09 Molecular self-assembling and nanostructures Alberto Morgante, Lucia Pasquato and Loredana Casalisv Biological, nanotechnology 16 10/05-09 to 11/13-09 Photoemission spectroscopies and spectromicroscopies Alessandro Baraldi, Andrea Goldoni and Andrea Locatelli surface science 25 Silvio Modesti Semiconductor physics 72 Total hours 202 28/09-09 to Experimental physics Laboratory 18/12-09 Conferences, seminars, advanced courses and other didactic activities o4 hours, How to write (and manage) a research project, prof. Maurizio Fermeglia, period 16/10/09 Seminars 2009 01/22/09, X-ray microscopy: dealing with real-life complexities, Chris Jacobsen 01/22/09, High-resolution scanning X-ray diffraction microscopy, Pierre Thibault 02/17/09, Cavity Quantum Electrodynamics with Single Quantum Dots, Anntonio Badolato Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 79 02/18/09, Ordered Oxides: polarized x-ray spectroscopy of digital manganite superlattices, Jerald J. Kavich 03/13/09, Templated Growth and Properties of Iron Nanowires: Anisotropic Electron States of the quasi 1D Copper Substrate, and morphological and magnetic properties of the iron adsorbate, Carlos Eduardo VIOL BARBOSA 03/13/09, Organic molecules at metal surfaces: the role of functional groups in self-assembly and charge transfer, Martina Dell'angela 03/16/09, Electronic structure of transition metal and rare earth ions in complex materials by resonant core-level spectroscopies, Emanuela Carleschi 03/31/09, Engineering photonic structures for THz devices, Alessandro Tredicucci 05/08/09, Targeted Polymeric Coacervates for cancer therapy, Subhra Mandal 05/08/09, reactions at the nanoparticle scale Reactive Molecular Dynamics (RMD) Modeling, Phillip R. Westmoreland 10/22/09, SuMBD growth of oligothiophenes thin films: influence of kinetic energy on submonolayer formation and device performance, Matteo Tonezzer 02/12/09, Single graphene sheets on various substrates, Petra Rudolf Support educational activity and teaching Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 80 Graduate Student: GIACOMO SCIUTO Title of the thesis: Innovative LTHS elements design based on nanotechnologies Supervisor: Roberto Muscia Tutors (if any): Research Activity In the first phase of the first year of activity the technical background on PCM has been provided through a detailed literature review. Later, some Matlab numerical models have been developed (using Enthalpy method) for modelling the phase change (liquid/solid and vice versa) and the models have been tested on 1-D and 2-D geometries. Two kinds of discretizations have been used: Finite Differences Method and Finite Volume Method. A cylindrical heat exchanger that involves PCM has been projected and an improvement of thermal performances has been noticed by using a macro-doped mixture called CENG-PCM. With the aim of making the latent heat exchanger more suitable for commercial uses and more modular, a new topologic solution has been investigated: the panel model. The “energetic” design has been done for the unity of the system (the panel). It has been noticed that, the path of the water pipe has a very important role in the efficiency of the device and the topological CFD optimization has started (now running). In the last phase of the year activity, the effect of nano-doping in PCM (paraffin wax) has been investigated. Carbon Nano Tubes (Single Walled, diameter 1.3nm) has been selected as good doping material and a DSC analysis has been brought to highlight the alteration of latent heat: several mixtures have been tested (e.g. 0.1%-0.2%-0.5%...till 2%) and alteration (till 7%) on the latent heat have been noticed, in agreement with results of Shadab et al. in Journal of Applied Physics 103. Objectives for the following year (if applicable) In the next year: finish CFD optimization for panel latent heat exchanger (CENG-PCM); define a database of thermo-physical properties of PCMs (nano)doped design a new heat exchanger that implies nano-doped-PCM Once defined the best doped PCM, the energetic design/optimization of the prototype will be done. Publications on scientific journals (printed or in press) Waiting for a response – R.Muscia, G.Sciuto, F. Zuddas – On the usage of PCM elements within asphalt concrete to avoid ice formation on roadways. International Journal of Solar Energy Publications/abstracts in conferences/congresses (national or international) G.Sciuto, R.Muscia – Multiobjective optimization of intracoronary stents by genetic algorithm. 13th international research/expert conference, Trends in the development of machinery and associated technology, TMT 2009, Hammameth, Tunisia. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 81 R.Muscia, G.Sciuto – A method for performing quality comparisons of Rzeppa joints. 13th international research/expert conference, Trends in the development of machinery and associated technology, TMT 2009, Hammameth, Tunisia. Participation to conferences (as speaker) R.Muscia, G.Sciuto - Analisi di fattibilità concettuale di un dispositivo per la propulsione navale senza l’uso di eliche. Mathematica User Meeting, 2009, Padova Italia. Educational Activity Classes followed (date, course, professor, type of course): Advanced Spectroscopy (11-15 May): M.Kiskinova- Course by ELETTRA organized by PhD school in Nanotechnology Modellazione Molecolare (October - Dicember 2009): S. Pricl – Master Course by Chemical and Material Engineering. University of Trieste. Congressi, seminari, corsi avanzati e altre attività didattiche passive: Final Conference 2008 (January 2009 – 20 hours)– PhD School in Nanotechnology Virtual Privat Network – (1 Hour) - Fermeglia Active vibration control (March – 2 hours) – Dip. Ing. Meccanica Nanochallenge and Polymerchallenge (April – 1 hours) – Talarico E-spr Workshop (11 May– 4 hours)– Manzan Chimica Fisica delle Interfasi (15 May – 1.5 hours) – Colombo COMSOL Workshop (May– 4 hours) – Tozzo Energie rinnovabili: Europa Oggi (May – 1.5 hours) – V.Prodi et al. Visita centrale Nucleare Krsko (May – 8 hours) – Dip. Energetica Smart Energy System (June – 4 hours) – Taccani Information meeting for doctoral students (June – 3 hours) – SBA Mathematicha User Meeting (September – 8 hours) How to write (and manage) a research project (October – 5 hours) –AA.VV. Support educational activity and teaching DSC analysis on nano-doped PCM at the Pharmacy department at University of Trieste. Development of numerical code for modeling phase change (FVM,FDM), about 1 month. Article and book review, about 1.5 months. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 82 Scheda del dottorando Federica Tavano [email protected] [email protected] Titolo della tesi: Cell mobility and metastatic spreading: a study on human neoplastic cells using Optical Tweezer Supervisore: Dott.ssa Serena Bonin Tutore: Dott. Dan Cojoc, Prof. Giorgio Stanta Research activity The pourpose of this project is a systematic in vitro analysis of the mechanical properties of different human cell lines from different types of solid tumors, characterized by different metastatic potential and differentiation levels. In particular we are going to study cell membrane viscoelasticity and local adesion. A direct correlation exists between an increase in deformability and progression of the transformed phenotype from a nontumorigenic cell line into a tumorigenic, metastatic cell line. Mechanisms that generate forces for cell migration have been qualitatively described, but nowadays there are no systematic studies of quantitative viscoelastic measurements on human tumor cells. Our research will focus on the characterization of the increased cellular motility in the malignant cells during the metastatic process and on the role of biomechanics in the tumor growth. During the first year a custom optical tweezers setup, enforced with a Lateral Shearing Interferometer Microscope has been designed and realized. Optical Tweezers will be used to trap and move functionalized 1,5 μm silica beads on the top of the cell. The cell will be displaced with a nano-piezoelectric stage to induce tension/compression with controlled strain. Lateral Shearing Interferometry is a technique which permits to measure at the nanometric level phase gradients in axial direction. In this way it‟s possible to measure deformations and movements of the objects with very high precision. We will use this technique for viscoelastic measurements from the thermal fluctuations of the cell membrane. During this year part of the cell lines on which I will perform the analysis have been chosen, spread and preserved: in particular cell lines from breast cancer (SKBR, MCF-7, MDAMB 231) and colorectal adenocarcinoma (HT-29, RKO) have been selected. Experiments of bead functionalization and bead positioning have been done: first, carboxyl groups and type IV collagen functionalized beads have been tried. Then, in a second time, fibronectin and other proteins functionalized beads will be tried. Plans for the next year During the second year I will perform systematic mechanical analysis on the cell lines: an elasticity range will be determined for the analyzed cell lines, characterized by different metastatic potential and differentiation levels. The following tumor models will be analyzed: skin melanoma, breast carcinoma and colorectal adenocarcinoma. In particular, for each solid tumor model least 2 different cell lines will be used, i.e. poorly and intermediated/well differentiated cells. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 83 From the same cell lines, membrane and cytoskeletal proteins will be extracted to reveal possible significative differences at the proteomic level, in order to associate mechanical analysis results with molecular analysis. The long term objective is to define possible biomarkers of metastatic diffusion that could find applications for diagnosis and prognosis of the considered neoplastic lesions. Pubblicazioni/abstracts in conferenze/congressi (nazionali o internazionali) 1. Poster: “High spatial resolution BDNF delivery by means of laser tweezers to stimulate hippocampal neurons signalling”; Elisa D‟Este, Gabriele Baj, Paolo Beuzer, Enrico Ferrari, Federica Tavano, Enrico Tongiorgi, Dan Cojoc; EBSA 2009 Poster: “High Resolution Drug Delivery by Optical Tweezers Microscopy” Elisa D‟Este, Gabriele Baj, Paolo Beuzer, Enrico Ferrari, Federica Tavano, Enrico Tongiorgi, Dan Cojoc; Super and High Resolution Imaging 2009 Poster: “Optical Tweezers as means to stimulate hippocampal neurons with BDNF coated beads”; Elisa D‟Este, Gabriele Baj, Paolo Beuzer, Enrico Ferrari, Federica Tavano, Enrico Tongiorgi, Dan Cojoc; Nanobioviews-2nd international symposium on Optical Tweezers in life sciences Attività formativa Ore di lezione seguite I anno (corso, data/periodo, docente, tipo di corso di laurea) 1. Nanotecnologie e Nanomicroscopie Docenti: Erik Vesselli(32 ore)/ dott. L.Businaro (24 ore) Corso di Laurea Specialistica in Biotecnologie Mediche (indirizzo nanotecnologie) SSD FIS/03 2. Spettroscopie Ottiche Applicate e Analisi di Immagini Docenti: A.Bonifacio (16 ore)/ dott. A. Accardo (8 ore) Corso di Laurea Specialistica in Biotecnologie Mediche (indirizzo nanotecnologie) ING-INF/08 3. Advanced imaging and Spectromicroscopy methods for chemical and structural characterization of micro-and nanomaterials Docente: Maya Kiskikova Ph.D Sc.D (15 ore) 4. Ottica e microscopia avanzata: Docente Dan Cojoc: gennaio-luglio (25 ore) Practical work during the first year The biological part of my experimental work (choice, spreading, preservation of the cell lines….) has been done at the Molecular Histopatology Lab at the ACADEM Department of University of Trieste. Practice work regarding the design and realization of the Optical Tweezers and lateral Shearing Interferometer Microscope has been done at the Optical manipulation Lab at TASC-INFM under the supervision of Dr. Dan Cojoc. All together practical work largely covered the limit of 60 hours. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 84 Congressi, seminari ed incontri organizzati dalla scuola 1. Congresso scuola di dottorato in Nanotecnologie gennaio 2009 (9 ore) Seminario, “Modeling reactions at the nanoparticles scale” Prof. Philip R.Westmoreland.Dept. of Chemical Engineering. University of Massachuttets. Amherst; 8 maggio 2009 Seminario CENMAT e presentazione lavoro dottorandi III anno; 26 novembre 2009 (4 ore) Corsi avanzati seguiti – seminari – altre attività didattiche passive 1.Corso sicurezza laser; Elettra 25 marzo 2009; (4 ore) 2.School: Introduction to optofluidics (40 ore) 1-5 giugno 2009, ICTP 3.Workshop microscopia AFM per campioni biologici, 5 maggio 2009(6 ore) 4.Worksop: “Orion Plus-The Ultimate resolution”, Milano 28 maggio 2009(5 ore) 5.EBSA European Biophysics congress, Genova 11-15 luglio 2009(30 ore) 6.Super and High Resolution Imaging, Lipica 30 settembre-2 ottobre 2009(20 ore) 7.Nanobioviews: second International Symposium on Optical tweezers in Life Sciences,JPK Berlino,14-15 ottobre 2009(16 ore) Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 85 Graduate Student CHIARA ZANUSSO –[email protected] Title of the thesis: “Nanotechnologies and oncology: pharmacokinetics and pharmacogenomics to optimize the antitumoral therapies” Supervisor: prof. Tullio Giraldi Tutors (if any): dr. Giuseppe Toffoli Research Activity This study purpose is to characterize pharmacogenetic markers above all the neurological type involved in the response and toxicity to the pharmacologic treatment with oxaliplatin in patients with colorectal cancer. At first literature search has been done to define the genetic polymorphisms of possible prognostic/predictive significance. Polymorphisms of glutathione S-transferase (GST) has been identified, transmembrane transporters (ATP-Binding Cassette) that are responsible for the extrusion of the drug from the cell, and polymorphisms concerning DNA repair genes that codify for proteins involved in the repair of the damage exerted on nucleic acid from mutagens as alkylating drugs. 154 patients were enrolled with colorectal cancer (CCR) treated with adjuvant FOLFOX-4 from the National Cancer Institute of Aviano (CRO) and other centres of Veneto region. At first genomic DNA was extracted from peripheral blood samples and then the development of analytical methods was performed. Specifically an innovative use of nanotechnologies in gene sequencing has been implemented, such as Pyrosequencing, a technique of recent development, that allows to identify simply and quickly mutations of punctiform type (SNP). Finally statistical analysis of data was performed to evaluate the relative risk (OR) of developing colorectal cancer by means of casecontrol studies and the role of individual gene variations in making prone the patient to the development of toxic reactions after chemotherapy with oxaliplatin. Objectives for the following year (if applicable) Study of pharmacoradiogenetic variations in the toxicity and response to chemoradiotherapy in prostate cancer patients; Determine the impact of these polymorphisms in patients with prostate cancer compared with the general population in order to determine the possible role on carcinogenesis of the prostate cancer. Publications/abstracts in conferences/congresses (national or international) 1. “FARMACOGENETICA DELLA CARDIOTOSSICITÀ DA ANTRACICLINE” Chiara Zanusso and Giuseppe Toffoli, (long abstract for the conference entitled “Complicanze cardiovascolari in oncologia: ieri ed oggi. La gestione delle problematiche” at Napoli on March 25-26, 2009) 2. “NANOTECHNOLOGIES AND ONCOLOGY: PHARMACOKINETICS AND PHARMACOGENOMICS TO OPTIMIZE THE ANTITUMOR THERAPIES” Chiara Zanusso, Erika Cecchin, Paola Biason, Elena De Mattia, Franca Sartor and Giuseppe Toffoli Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 86 (Poster presented at the 2nd Phd workshop 10th/11 September 2009 at Wittenberg) (Abstract presented at the “Congresso Nazionale della Società Italiana di Chemioterapia” at Udine on October 14, 2009) Educational Activity Periods abroad (date and place) Classes followed (date, course, professor, type of course) 700 hours of study and deepening of the topics covered by books and review-type paper and / or electronic from January 1, 2009; 700 laboratory hours at the "Experimental and Clinical Pharmacology" CRO Aviano headed by dr. Giuseppe Toffoli from January 1, 2009 Conferences, seminars, advanced courses and other didactic activities “Congresso annuale delle presentazioni dell’attività scientifica dei dottorandi in corso” at University of Trieste on January 13-14-15, 2009 from 9.00 to 18.30 “Seminario sull'uso della VPN e del Portale” at University of Trieste on March 20, 2009 at 15.00. “Esame Finale 2009” at University of Trieste on April 8, 2009 at 9.00. “Modeling reactions at the nanoparticle scale” Prof. Phillip R. Westmoreland Dept of Chemical Engineering, University of Massachusetts Amherst, at University of Trieste on May 8, 2009 at 15.00. “Chimica fisica delle interfasi in sistemi nanostrutturati” Dr. Italo Colombo, at University of Trieste on May 15, 2009 at 11.00. “Incontri informativi per i dottorandi: orientamento all’utilizzo delle risorse e dei servizi documentali forniti dal Sistema Bibliotecario di Ateneo; panoramicadelle nuove modalità di comunicazione scientifica: l’archivio istituzionale di Ateneo OpenstarTs; l’autoarchiviazione delle tesi di dottorato e cenni sull’accesso aperto alla letteratura di ricerca; procedure di conferimento al sito login miur e all’anagrafe di Ateneo (Saperi) at University of Trieste on June 30, 2009 from 9.30 to 12.30. “Joint workshop 10th/11 September” at Wittenberg with a poster presentation “Nanotechnologies and oncology: pharmacokinetics and pharmacogenomics to optimize the antitumor therapies”. “How to write (and manage) a research project” at University of Trieste on October 16, 2009 from 14.00 to 19.00. Lecturers: Cecilia Blasetti (Elettra), Valter Sergo (UNITS), Maurizio Fermeglia (UNITS). Seminars (at CRO Aviano): Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 87 “Dal Focus 2009: aggiornamenti sul carcinoma mammario” on March 25, 2009 from 14.30 to 18.30. “Roles of small RNAs in genome defense” on May 7, 2009 at 11.00. “Seminari in Oncologia al C.R.O. di Aviano” on May 28 and June 4-11-18, 2009 from 16.00 to 19.00. “Matrix revolutions: Perlecan domain V as a novel cancer and stroke therapy” G. Bix - Texas A&M College of Medicine- USA on September 14, 2009 from 14.30 to 15.30. “Invasion and Metastasis in Breast Cancer” on November 23, 2009 from 14.30 to 15.30. Conferences: “Congresso Nazionale della Società Italiana di Chemioterapia”, Udine on October 14, 2009 from 9.00 to 13.00. Courses (at CRO of Aviano): “Corso di lingua inglese presso lo Shenker Institute di Pordenone”: from January to July 2009, 20 hours of lessons with final certificate. “RefWorks: creare DataBase Bibliografici personali” on May 7, 2009 from 14.00 to 18.00. “REFERENCE MANAGER: uno strumento straordinario per ottimizzare la gestione delle bibliografie” on May 19 and 26, 2009 from 14.00 to 17.30. “BLSD - Corso teorico pratico di Basic Life Support and Defibrillation” on September 22, 2009 from 8.45 to 18.00. “L'informazione scientifica in un IRCCS oncologico: formazione all'uso delle risorse informative rese disponibili dalla Biblioteca del CRO, Bibliosan” on September 29, 2009 from 9.00 to 13.15 . Support educational activity and teaching two hours of class teaching of Pharmacology Oncology of the degree course in “Biotecnologie Mediche”, University of Trieste on January 2009: “Gli inibitori della farnesiltransferasi” e “Il proteasoma: ubiquitina e Bortezomib” Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 88 4. Progetti Dottorandi del 25 ciclo: Sono inclusi in questa parte del documento i progetti scientifici dei seguenti dottorandi del 25 cilco: AMBROSINI Stefano, BIDOGGIA Silvia, CHEN Yan Xin, FRAGKOU Effrosyni, GANAU Mario, GIORGIS Valentina, LUCAFO' Marianna, MARSICH Lucia, PERONIO Angelo, SAMMITO Davide. + Dottorando STEFANO AMBROSINI Email: [email protected] Laboratorio di lavoro: IOM CNR, Laboratorio TASC Titolo della tesi: Sintesi di nanostrutture di semiconduttori e loro studio mediante luce di sincrotrone. Supervisore: dr. Silvia Rubini Attività di ricerca prevista Stato dell’arte e motivazioni I nanofili di materiali semiconduttori sono considerati nanostrutture molto promettenti per futuri sviluppi nanotecnologici nel campo della sensoristica, della conversione fotovoltaica e potrebbero trovare applicazioni nella miniaturizzazione dei dispositivi in microelettronica. In alcune di tali applicazioni si sfrutta l‟alto rapporto superficie / volume dei nanofili, mentre in altre si utilizza su scala nanometrica la loro natura di semiconduttori. L‟uso di nanofili semiconduttori per gli scopi citati necessita di una profonda conoscenza delle loro caratteristiche elettroniche e cristalline, e di un accurato controllo di esse in fase di crescita. In questo quadro di riferimento si inserisce la ricerca da svolgersi durante questo dottorato. Molti metodi sono stati proposti in letteratura per indurre la crescita di nanofili. La maggior parte di tali metodi utilizza la pre-deposizione di un catalizzatore [1](e.g, Au od altri metalli) sul substrato o processi litografici [2] per modificare il substrato in modo da creare una serie di centri di nucleazione discreti. La possibile incorporazione di atomi di catalizzatore nei nanofili o la creazione di difetti durante i processi litografici sono tuttavia potenziali problemi che abbassano la qualità globale delle nanostrutture e ne minano l‟impiego in campo tecnologico. Le proprietà dei nanofili dipendono strettamente dalla tecnica utilizzata per la loro sintesi, pertanto uno studio capillare dei processi di crescita e delle relazioni tra essi e le proprietà dei nanofili costituisce premessa fondamentale per l‟utilizzo delle nanostrutture in dispositivi. Le tecniche di caratterizzazione basate sulla luce di sincrotrone possono fornire informazioni importanti sulla struttura cristallina dei nanofili, la loro struttura elettronica, l‟incorporazione di drogante o impurezze la loro reattività superficiale anche con elevata risoluzione spaziale [3], e possono quindi dare contributi significativi alla comprensione delle proprietà delle nanostrutture e indirizzare il disegno di dispositivi innovativi. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 89 [1] V. G. Dubrovskii et al. Phys. Rev B 71, 205325 2005 [2] A. Fontcuberta i Morral, appl. Phys. Lett. 92, 063112 �2008� [3] A. Koilmakov et al, ACSNano 2, 1993 (2008). Obbiettivi da raggiungere nei tre anni oComprensione delle relazioni esistenti tra condizioni di crescita e proprietà dei nanofili. oAffinamento del controllo delle condizioni di crescita per ottenere la maggiore flessibilità possibile nelle proprietà dei nanofili. oSviluppo di prototipi di dispositivi impieganti i nanofili sintetizzati. Obbiettivi da raggiungere per il primo anno oAffinamento della tecnica di crescita senza catalizzatore e comprensione dei meccanismi di crescita coinvolti. Comprensione della dipendenza delle proprietà dei nanofili prodotti dal substrato impiegato e dalle condizioni di crescita (pressione dei materiali costituenti, temperatura di crescita) nel caso di crescita senza catalizzatore. oValutazione della possibilità di utilizzo della stessa tecnica per la crescita di nanofili di materiali diversi dal GaAs. oConoscenza approfondita delle tecniche di indagine che utilizzano la luce di sincrotrone e delle loro potenzialità per l‟analisi di nanofili semiconduttori. Progetto di ricerca Sintesi di nanofili. Dopo aver messo a punto un‟innovativa tecnica per la sintesi di nanofili di GaAs tramite epitassia da fasci molecolari (MBE) senza l‟utilizzo di catalizzatore, durante il dottorato si valuterà la possibilità di applicare questa stessa tecnica a nanofili di altro materiale. I nanofili così prodotti potranno essere confrontati con quelli cresciuti utilizzando catalizzatore metallico (Mn, Au, Fe, …). Un interesse particolare sarà rivolto alla possibilità di incorporare in maniera controllata impurezze (droganti) per modificare le proprietà elettriche delle nano strutture, e alla dipendenza del drogaggio così ottenuto dal catalizzatore utilizzato. Altro aspetto importante sarà la realizzazione di nanofili composti da regioni di materiali diversi (etero strutture), o con proprietà elettriche diverse (p.es. giunzioni p-n). Caratterizzazione dei nanofili - metodi di laboratorio. La morfologia dei nanofili sarà studiata in maniera sistematica tramite microscopia elettronica a scansione (SEM), le loro proprietà strutturali tramite microscopia elettronica in trasmissione (TEM) Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 90 grazia alla collaborazione con il dott. V. Grillo (IN –CNR, Modena) e spettroscopia Raman e microRaman, e le loro proprietà ottiche tramite spettroscopia di fotoluminescenza (PL) anche risolta spazialmente (micro-PL). Verranno realizzate misure di trasporto elettrico atte a misurare la conducibilità delle nanostrutture, drogate e non e valutare la densità di portatori di carica. Caratterizzazione dei nanofili - luce di sincrotrone. L‟attività di caratterizzazione delle nanostrutture con luce di sincrotrone comprenderà turni di misura su linee di luce che utilizzano sia tecniche di microscopia che di spettroscopia e di diffrazione. L‟interesse sarà posto sulla struttura cristallina delle nano strutture (diffrazione), l‟incorporazione e la determinazione della configurazione atomica locale di droganti o impurezze provenienti dal catalizzatore (EXAFS) , la reattività superficiale dei nanofili (fotoemissione) in relazione alle loro proprietà di trasporto in vista di possibili applicazioni come sensori. Gli esperimenti verranno realizzati in maniera più consistente a partire dal secondo anno, ed il loro programma sarà determinato nel corso del lavoro, in collaborazione con i responsabili delle linee di luce. Nel caso di misure sensibili alla superficie, le nanostrutture cresciute presso il laboratorio TASC verranno trasferite alle camere di analisi delle beamline di Elettra protette da uno strato di arsenico che, depositato nella camera di crescita, verrà rimosso termicamente prima delle misure. Questa tecnica che si è dimostrata molto efficace nell‟impedire l‟esposizione all‟aria delle nanostrutture. Attività didattica Formazione: oCorso “Applicazioni della luce di sincrotrone” tenuto dal prof. Paolucci nel curriculum di laurea magistralis di Fisica dello Stato Solido all‟università di Trieste. o“School on Synchrotron and Free-Electron-Laser Sources and their Multidisciplinary ICTP, Trieste 26-4/7-5 2010. Insegnamento: o Intervento di ore di lezione 4 presso la scuola media G. Luci di Muggia (TS) a proposito delle possibilità di impiego in campo fotovoltaico delle nanostrutture. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 91 Graduate Student: Silvia Bidoggia Email: [email protected] Laboratory: Lab. 345 Dip. Sc. Chimiche, Edificio C11 Tel. 040-5583926 Title of the thesis: Gold nanoparticles as carriers for drug delivery applications. Supervisor: Prof. Pasquato Lucia Research Activity foreseen State of the art and motivations: Recently gold nanoparticles (AuNPs) protected by organic monolayers were studied in a variety of science sectors from physics to material science, from medicine to biology.1 Gold nanoparticles have captured researchers „attention because of their peculiar properties, their high stability compared to other metal nanoparticles, solubility in organic solutions and water, easy funzionalization and also because of their biological compatibility. Numerous studies have demonstrated that they are good attractive candidates for delivery of various payloads into their targets. This payloads could be small drag molecules or large biomolecules, like proteins, DNA, RNA. These could be covalently conjugated to AuNPs via cleavable linkers, or baunded to AuNPs through weak interactions conjugation without structural modification of the drag playload. Prerequisites of drug delivery systems are the efficient release and the improvement of solubility, in vivo stability and biodistribution of these therapeutic agents. Gold nanoparticles are suitable as drag delivery systems because of their unique chemical and physical properties: -the gold core is essentially inert, non-toxic and biocompatible; -the syntheses is easy and provide monodisperse nanoparticles with core sizes ranging from 1 to 150 nm; -they have high surface-area-to-volume ratio and as a result an high density of ligands can be appended for targeting or drug-loading purposes; -they can be ready funzionalizated with a large variety of ligands that play as linkers for therapeutic agents or as labels to monitor the NPs fate or as targets for recognition. In recent years significant efforts have been devoted to the syntheses of monodisperse nanoparticles with controlled size and passivated with thiols (thiols ligands strongly bind gold due to the soft character of both Au and S). Brust and Schiffrin2 have introduced the first method for AuNPs synthesis, published in 1994, allowing a facile synthesis of thermally stable and air-stable AuNPs with reduced dispersity and controlled size. This method AuCl4- is transferred from water to toluene using tetraoctylammonium bromide as the phase-transfer reagent and reduced by NaBH4 in the presence of alkenethiols. The core size of the particles can be varied from 1.5 nm to 6 nm by varying the thiol-gold stoichiometry, the temperature and the rate of reducent addition. More recently were introduced new methodologies for the synthesis of AuNPs passivated with an organic monolayer and soluble in water.3 To enhance the functional versatility of AuNPs, mixed monolayer-protected AuNPs can be synthesized directly with proper ligands or through post synthetic functionalization. The most commonly used method for creation of mixed monolayer-protected AuNPs is through use of the Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 92 place exchange reaction first introduced by Murry.4 In this protocol, external thiols displace the existing ligands of AuNPs in an equilibrium process. Drugs linked covalently could be released by the presence of thiols (e.g. gluthatione) into the cell. 5 Rotello developed a nanoparticle-based delivery system featuring glutathione release6. The particles featured a mixed monolayer composed of cationic ligands (TTMA) and fluorogenic ligands (HSBDP). The cationic surface of the particle facilitated their penetration through cell membranes and the release was triggered by intracellular glutathione (GSH). The fluorescence of the Bodipy moiety of the HSBDP was silent when linked to the particle, but in presence of high concentrations of GSH, the Bodyp was released and that fluorescence could be detected. Using these particles the release of the drug related to the concentration of GSH into the cell could be monitorored. Non-covalent incorporation of drug into AuNPs monolayers provides an alternative delivery strategy that allows direct use of unmodified drugs. Drug encapsulation with AuNPs relies on the use of ligands that generate a hydrophobic pocket into the monolayer. Pasquato demonstrated the encapsulation of radical probes in AuNPs monolayers, using ESR spectroscopy to monitor the partition of lipophilic probes between a monolayer of AuNPs and bulk water.7 It was demonstrated also that smaller nanoparticles featuring more strongly radial monolayers favor guest encapsulation. Another important field is that of perfluorinated amphiphile compounds. They have the characteristic to be biocompatible and soluble in polar solvents. This aspects could be taken into account for applications in material science and biomedical field. In fact the use of perfluorinated amphiphilic compounds may open the way to new biomedical applications, for example in the field of antioxidant carriers or in the development of multicompartement nanoparticles with the capacity to store and release active molecules. In recent years in the laboratory in which I‟ll carry out my research activity has investigated gold nanoparticles protected by a monolayer of perfluorinated amphiphilic tiolates (HS-F8-PEG) characterized by a perfluorinated portion and a poly(ethylene glycol) unit, or a mixed monolayer composed of HS-F8-PEG and HS-C8-TEG.9 ESR experiments on this mixed monolayers suggest the formation of patches in which the hydrophobic probe interacts preferentially with the perfluorinated portions.10 These are very interesting systems and they will open the way toward the possibility to conjugated into the NPs two different active molecules with different characteristics and carry and release them into cells. 1. G. Schmid, Ed., Nanoparticles. From Theory to Application, Weinheim: Wiley-VCH, 2004. G. Schmid, Chem. Rev. 1992, 92, 1709–1727. M. C. Daniel, D. Astruc, Chem. Rev. 2004, 104, 293–346. C. M. Niemeyer, C. A. Mirkin, Eds., Nanobiotechnology,Weinheim:Wiley-VCH, 2004; (b) C. A. Mirkin, C. M. Niemeyer, Eds., Nanobiotechnology II, Weinheim: Wiley-VCH, 2007. V. Rotello, Ed., Nanoparticles. Building Blocks for Nanotechnology, New York: Kluwer Academic/Plenum, 2004. N. L. Rosi, C. A. Mirkin, Chem. Rev. 2005, 105, 1547–1562. C.-C. You, A. Chompoosor, V. M. Rotello, Nano Today 2007, 2, 34–43. G. F. Paciotti, L. Myer, D.Weinreich, D. Goia, N. Pavel, R. E. McLaughlin, L. Tamarkin, Drug Deliv. 2004, 11, 169–183. 2. M. Brust, M. Walker, D. Bethell, D. J. Schiffrin, R. Whyman, J. Chem. Soc., Chem. Commun. 1994, 801–802. 3. P. Pengo, S. Polizzi, M. Battagliarin, L. Pasquato, P. Scrimin, J. Mater. Chem. 2003, 13, 2471–2478. E. E. Foos, A.W. Snow, M. E. Twigg, M. G. Ancona, Chem. Mater. 2002, 14, 2401–2408. A. G. Kanaras, F. S. Kamounah, K. Schaumburg, C. J. Kiely, M. Brust, Chem. Commun. 2002, 2294–2295. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 93 4. M. J. Hostetler, S. J. Green, J. J. Stockes, R. W. Murray, J. Am. Chem. Soc. 1996, 118, 4212–4213; R. S. Ingram, M. J. Hostetler, R. W. Murray, J. Am. Chem. Soc. 1997, 119, 9175–9178. 5. (a) Hong, R.; Han, G.; Fernandez, J. M.; Kim, B. J.; Forbes, N. S.; Rotello, V. M. J. Am. Chem. Soc. 2006, 128, 1078–1079. (b) Paciotti, G. F.; Kingston, D. G. I.; Tamarkin, L. Drug DeVelop. Res. 2006, 67, 47–54. (c) Gibson, J. D.; Khanal, B. P.; Zubarev, E. R. J. Am. Chem. Soc. 2007, 129, 11653–11661. (d) Ghosh, P.; Han, G.; De, M.; Kim, C. K.; Rotello, V. M. AdV. Drug DeliVery ReV. 2008, 60, 1307–1315. (e) Cheng, Y.; Samia, A. C.; Meyers, J. D.; Panagopoulos, I.; Fei, B. W.; Burda, C. J. Am. Chem. Soc. 2008, 130, 10643–10647. 6. C. K. Kim, P. Ghosh, C. Pagliuca, Z.-J. Zhu, S. Menichetti, V. M. Rotello, J. Am. Chem. Soc. 2009, 131, 13601361. 7. M. Lucarini, P. Franchi, G. F. Pedulli, P. Pengo, P. Scrimin, L. Pasquato, J. Am. Chem. Soc., 2004, 126, 9326-9329. Lucarini, M.; Franchi, P.; Pedulli, G. F.; Gentilini, C.; Polizzi, S.; Pengo, P.; Scrimin, P.; Pasquato, L. J. Am. Chem. Soc. 2005, 127, 16384–16385. 9. C. Gentilini, F. Evangelista, P. Rudolf, P. Franchi, M. Lucarini, L. Pasquato, J. Am. Chem. Soc. 2008, 130, 1567815682. 10. C. Gentilini, P. Franchi, E. Mileo, S. Polizzi, M. Lucarini, L. Pasquato, Angew. Chem. Int. Ed. 2009, 47, 30603064. Objectives for the three years The main objectives of the project are: -Acquisition of the knowledges about syntheses, characterization, drug delivery applications of AuNPs. -Preparation and characterization of different kinds of AuNPs and study their application as drug delivery systems. Objectives for the first year For the first year the most important objectives are: -Bibliographic resuming and lectures to improve knowledges about self assembled monolayers. -Syntheses and characterization of AuNPs passivated with the thiol HS-fluoro-PEG. -Syntheses and characterization of mixed monolayers with fluorinated and alkylthiols. -Investigation of the binding ability of small drugs inside the monolayers of the prepared NPs. Research project -Bibliographic resuming about fluorinated nanoparticles, polymers and dendrimers focusing the attention on the methods of characterization of this kind of materials and their applications in biomedical field. -Syntheses of HS-fluoro-PEG, -Study of the syntheses of nanoparticles protected by fluorinated thiols of different size. -Characterization of this NPs with NMR and UV-Vis spectroscopy, TGA, TEM, XPS and EPR experiments. -Syntheses of mixed monolayers protected NPs and characterization also with methodologies different then EPR as STM, IR, chemical reactivity. Educational activity During the first year I‟ll carry out the following educational activity: -Lectures: Proprietà fisiche dei materiali (prof. Franciosi, 48 hours); Materiali organici (prof. Pasquato, 48 hours) -Laboratory support (Laboratorio di chimica organica I, 40 hours) Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 94 Graduate Student: Chen Yan-xin Laboratory: Department of Chemical Sciences (University of Trieste) and National Research Council (CNR) – Institute of Chemistry of OrganoMetallic Compounds (ICCOM) (Florence and associated Research Unit of the Department of Chemical Sciences - University of Trieste) Title of the Thesis: Nanostructured Titanium Dioxide Based Materials for Photocatalysis and Phototelectrocatalysis Supervisor: Prof. Paolo Fornasiero Tutors: Claudio Bianchini, Alessandro Lavacchi State of the Art and Motivations Titania NTs, are effective support materials for a variety of noble metal-based catalysts. Indeed, the physical and chemical properties of nanoscaled TiO2 (crystal structure, morphology, surface area) may increase the dispersion of active materials on the support, resulting in an high active surface area and, in turn, in an enhanced catalytic activity. In addition, cooperative effects for platinum catalysts on TiO2 nanotubes have been observed, and attributed to a change of the electronic properties of dispersed Pt. These findings well justify for the use of Pd and Pt-doped titania in photochemical devices. All the above, in conjunction with the remarkable stability of TiO2 in both acidic and alkaline solutions, suggest that TiO2 NTs may be excellent candidates as support materials for engineering metal catalyzed materials for solar production of hydrogen from aqueous solutions of renewable alcohols. The application of TiO2 NTs as a support for Pd nanoparticles for the electro-oxidation of alcohols have also been reported Figure 1: TiO2 Ordered NanoTube Array (ONTA) Alcohols are easily produced from biomasses and have an enormous potential in the context of the “green chemistry”. The possibility of their extensive use for the sustainable chemistry depends critically on the availability of efficient catalysts. In this project, we plan to use metal TiO2 NTs, to develop chemo-electro-catalytic materials for the concomitant production of hydrogen and carboxylic acids from aqueous solutions of renewable alcohols (ethanol, ethylene glycol and glycerol, mostly) and for the use in photo-activated fuel cells. This research will imply the manufacture of electrodes with improved characteristics, also in terms Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 95 of efficiency, chemical and mechanical stability. The deposition of noble and non-noble metal nanoparticles, and their mixtures thereof, onto nanostructured titania is expected to afford highly innovative, multipurpose chemo-photo-catalysts suitable for the present target. Objectives for the three years Development, fundamental and functional characterization of a variety of photocatalysts and photoelectrocatalyst for the application in photoreforming, photoelectrolysis and photoactivated fuel cells. Objective for the first year Literature analysis for the definition of the state of the art as a basic reference for benchmarking; definition of the protocols for both the fundamental and functional characterization of the materials that will be synthesized; selection trough experimental trials of the best synthetic routes for the titanium nanostructures. Research project Activity 1.1: State of the Art The state of the art for photocatalysts and photoelectrocatalysts will be critically reviewed. The obtained data will be used to select systems and synthetic strategies. Task 1.1: Literature Analysis A perusal of the existing literature will be performed. The main purposes are a clear definition of the state of the art and the extraction of the most relevant functional data on the existing systems for the benchmarking. Task 1.2: Selection of the Systems The selection of the systems to be investigated will be performed according to the data provided by the literature examination. Both the materials and the specific reaction will be selected on the basis the potential scientific and technological impact. Activity 2: Synthesis of the Titanium Nanostructures Titanium dioxide will be synthesized by both electrochemical and chemical methods for the production of both nanotube arrays and nanostructured carbon supported powders. Task 2.1: Electrochemical Methods Anodization of titanium metal substrates will be employed for the synthesis of nanotube arrays with variable nanotube diameter and length. The anodization will be followed by heat treatment in order to favour the formation of the photoactive phases. Task 2.2: Chemical Methods The chemical synthesis of titanium dioxide nanostructured powders both unsupported and carbon supported will be performed. The possibility of doping the Titania will also be explored by the adding boron, nitrogen and eventually other transition metal oxides. The carbon supported materials developed in this task will be employed as anodes for the photoactivated fuel cells. Activity 3: Catalyst Insertion Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 96 The addition of catalyst with proved activity toward the systems selected in the task 1.2 will be performed via both electrochemical and chemical approaches. This activity will provide the materials which will be tested in the activity 4. Task 3.1 Electrochemical Methods Electrodeposition techniques will be employed for adding metallic nanoparticles to the catalysts developed in the tasks 2.1 and 2.2. Deposition conditions will be varied to tailor the particle characteristic e.g. composition, structure and morphology for the best catalytic performances. Task 3.2 Chemical Methods Existing “electroless” methods will be adapted to the deposition of nanostructured metals on the materials developed in the tasks 2.1 and 2.2. Activity 4: Characterization The characterization will consist in the investigation of the catalysts basic properties (structure, morphology, composition, basic electrochemistry) and functional performances. This activity will conclude the project with a benchmarking of the produced materials with the state of the art and a summary of the main findings of the three years of work. Task 4.1: Basic Characterization The fundamental characterization will consist in the definition of the basic properties of the materials. The composition, the structure and the morphology will be investigated as well as the composition. Half cell electrochemistry of the materials designed photoelectrocatalysts will also be performed. Task 4.2: Functional Characterization The functional performances will be evaluated under the operating conditions. The selectivity, the conversion yield and the energy efficiency will be determined. A special focus will be on the time stability of the produced catalysts. Functional data will be the basis for the benchmarking which will be the object of the task 4.3. Task 4.3: Benchmarking and Conclusion The data derived from task 4.2 will be used for the benchmarking with the state of the art materials. A summary of the main research conclusions of the three years of research will be delivered at month 36. Educational Activity The educational activity of the first year will mainly consists in the examination of the existing literature on the ONTA. A special focus will be on the reading of the book “TiO 2 nanotube Arrays: Synthesis, properties and Applications” by C.A. Grimes and G.K. Mor edited by Springer in 2009. The activity will be also integrated by the seminars which will be organized by the Istituto per la Chimica dei Composti OrganoMetallici (ICCOM). Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 97 Gantt Chart M 1-3 Activity M 4-6 M 7-9 M 10- M 13- M 12 15 18 16- M 19- M 21 24 22- M 25- M 28- M 31- M 27 30 33 36 1 State of the Art Task 1.1 Literature analysis Task Selection 1.2 of the Systems Activity 2 TiO2 Nanostructure Synthesis Task 2.1 Electrochemical Methods Task 2.2 Chemical Methods Activity 3 Catalyst Insertion Task 3.1 Electrochemical Methods Task 3.2 Chemical Methods Activity 4 Characterization Task 4.1 Basic Characterization Task 4.2 Functional Characterization Task 4.3 Benchmarking and Conclusion Figure 2: Gantt Chart Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 98 34- Doctoral School in Nanotechnologies - XXV Cycle Doctoral candidate's schedule: EFFROSYNI (FENIA) FRAGKOU Email: [email protected] Laboratories: Molecular Histopathology, ACADEM Department, University Hospital of Cattinara (Trieste) / Elettra Synchrotron Light Laboratory, Centre for Biomolecular Medicine (CBM) & International Center for Genetic Engineering and Biotechnology (ICGEB), AREA Science Park (Padriciano-Basovizza, Trieste) Thesis title: Nanobiotechnologies for Dermatological Applications Supervisor: Prof. Giorgio Stanta Tutor: Dr. Serena Bonin Anticipated research activity State of the art and motivations During my PhD period, my purpose is to develop and validate new protocols, pointing to provide innovative nanotechnological applications in the fields of dermatological diagnosis, with special concern on skin melanoma. Malignant melanoma is due to an uncontrolled growth of melanocytes and is the most lethal form of skin cancer, as it can rapidly spread to the lymph system and internal organs with poor prognosis. Since surgical treatment is the golden therapy for melanoma, an early diagnosis is vital. Aim of study: This project will focus on the nanotechnological applications of tools for dermatological diagnosis. In particular in the first part of my project I will focus on the search of new biomarkers for melanoma and for multiple targets imaging I will try to apply to Archive Tissues the technique of quantum dots. A second field of interest regards the positive effects of HSPs (Heat shock proteins) on damaged dermal cells: apoptosis of altered human fibroblasts and cell recovery. Such beneficial effects could possibly apply either to UV- and chronologically-altered fibroblasts, or to pathological biostructures including melanoma cells. Materials and methods: In the first step of my project I will use tissue microarrays in order to insert on one slide multiple melanoma clinical specimens. In this first phase I will use mainly Immunohistochemistry (IHC) to test several biomarkers in a huge amount of clinical specimens. Later on I will set up the method to transfer quantum dots based imaging to archive tissues. This part will be subdivided into two steps: the set up of the method using FFPE tissues (FormalinFixed Paraffin Embedded tissues), commonly used for histological diagnosis and the second one dedicated to the actual application of the technique to the clinical specimens. Objectives to be reached in the three years Application of nanotechnological tools to the dermatological diagnosis. Objectives to be reached in the first year During the first year of my PhD project I will focus on the search of new biomarkers for skin melanoma. To reach this aim I will create a TMA (Tissue Microarray) in order to analyse a huge amount of clinical samples in one slide. Later, multiple IHC markers will be studied on this type of arrays in order to select the ones able to diagnose and prognosticate skin melanomas. The successive step will be the application of quantum dots technique to archive tissues in order to obtain multiple imaging. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 99 Graduate School of Nanotechnology, University of Trieste Graduate Student: Dr MARIO GANAU Email: [email protected] Laboratory: ELETTRA (Synchrotron Light Laboratory), Trieste; University Hospital Cattinara, Trieste; and in collaboration with the Institute of Pathophysiology, University of Ljubljana Title of thesis: Nanotechnology applications in quantitative neuroscience: proteomics assessment of astrocyte stressing and neuronal plasticity Supervisors: Prof. GIACINTO SCOLES and Dr. LOREDANA CASALIS (SISSA-ELETTRA NANO INNOVATION LAB) Proposed Tutor: Prof. ROBERT ZOREC (University of Ljubljana) Research Activity foreseen State of the art and motivations Once overlooked as merely supportive elements in the central nervous system (CNS), glial cells have come in the last decade to the centre stage of the efforts to understand the workings of the brain (P.G. Haydon, Nature 2001). Indeed, the traditional concept, built up in the 20th century, that macroglial cells, particularly astrocyte, are multifunctional housekeeping cells of neurons has largely been reconsidered: beside maintaining the optimal environment for functioning of neurons, evidence emerged that astrocytes may be involved in the regulation of synaptogenenis, in direct modulation of synaptic strength in the CNS, and they may have an important role in the regulation of brain microcirculation (E. Newman Trends Neurosci. 2003). Moreover, astrocytes play a pivotal role in pathologic conditions, by influencing neighboring cells: they are implicated in early and late stages of neurodegeneration, in reactive gliosis after brain or spinal cord injury and even in experimental brain infarction (U. Wilhelmsson et al. J Neurosci. 2004). Nowadays astrocytes are known to release chemical messengers, neurotrophins, eicosanoids and neuropeptides; they also integrate inputs and have long-range signaling systems that can lead to release of neurotransmitters at a distance and in turn affect the physiological status of neurons; nevertheless the underlying mechanism of secretion are still under debate (M. Kreft et al. Ann. N.Y. Acad. Sci. 2009). The breakthrough discoveries that showed how astrocytes are dinamic and participate in the crosstalk between glia and neurons came as a result of a series of technical advances: studies in cell cultures first and brain slice later, fluorescent indicators, patch-clamp recording, microscopy and finally quantitative imaging techniques. The current limit of knowledge advancement is related to the high sensitivity required to accurately monitor protein-protein interaction to follow changes in Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 100 cellular pathways due to different kinds of external perturbations. This need is so acute and specific that the field of protein interactions on a genome wide scale has acquired the name of Interactomics. The advent of nanotechnology held the promise to overcome these limitations with the possibility of measuring protein amounts, in samples consisting of single or few cells, down to a hundred molecules and sub-nanomolar concentrations and in nano-liter to pico-liter volumes. Therefore strong advancements in this field of neuroscience are expected and surely will come from the assessment at a nanolevel of the glial proteomics under experimental condition of stress induced by external stimuli. Objectives for the three years The main goal of this PhD thesis is to explore the astrocyte behaviour under influence of external stimuli via innovative devices and protocols based on micro/nano-fluidics. This nano-quantitative approach will eventually enable precise, high throughput and low cost measurements on large, predetermined diagnostically relevant, subsets of the proteome obtained from very small samples (down to the single cell level) with potential capability of interactomic analysis. Accordingly the objectives of the project may be highlighted as follows: acquisition of the fundamentals basis for the preparation and the study of astrocytes and their behaviour in physiologic and pathologic conditions; acquisition of the skills needed for the development of a research project; acquisition of a broad knowledge in the assessment at a nanolevel of synaptic processes and neuronal plasticity. Objectives for the first year Studying the nano-mechanical response of bio-molecular nano-structures, such as stressed astrocytes, needs as a first task the realization of a nano-chip device. Along the first year the main objectives to pursue are: introduction to nano-fluidics measurments (to be achieved by personal study and tutorials); extensive review of the current knowledge concerning astrocyte‟s exocytosis mechanisms (to be achieved by personal study and internship at the Ist. of Pathophysiology, Univ of Ljubiana). design a nano-fluidic equivalent of the Wheatstone Bridge (a standard tool for electrical resistance measurements) to further obtain a quantitative proteome analysis (work to be carried out at Sincrotrone, Trieste). Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 101 Research project: Herein is reported a standard Gantt chart for the expected tasks and milestones of the thesis. Task Start End Mos 2010 Q1 Q2 2011 Q3 Q1 Q2 2012 Q3 Q1 Q2 Design of nano-fluidc device for proteomics purposes 01/2010 04/2011 16 astrocytes behaviour 04/2010 08/2010 4 Studying principles of nano-fluidics 01/2010 12/2010 12 09/2010 08/2011 12 01/2011 12/2011 12 05/2011 12/2011 8 09/2011 06/2012 12 01/2012 08/2012 8 05/2012 12/2012 8 01/2010 12/2012 36 Studying the current state of the art on In vitro analysis of astrocytes under stressing conditions First tests of standard proteomics analysis of astrocytes in physiologic conditions Validation of the nano-fluidic device for proteomics analysis Standard proteomics analysis of astrocytes in pathologic conditions Validation tests of the nano-fluidic device for proteomic analysis of astrocytes under physiologic conditions Validation tests of the nano-fluidic device for proteomic analysis of astrocytes under pathologic conditions Editing of thesis Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 102 Q3 Graduate Student VALENTINA GIORGIS Email: [email protected] [email protected] Laboratory: ELETTRA Title of the thesis: Development, design and characterization of Metamaterials with negative refractive index Supervisor: Filippo Romanato Tutors (if any): Research Activity foreseen State of the art and motivations The neologism “metamaterial” comes from the union of the words “meta”, meaning “beyond”, and “material”: this term implies, nowadays, a structured composed material that displays properties usually not found in natural ones [1]. In 1960s Veselago (Moscow Institute of Physics and Technology) [2] first assumed an isotropic material having simultaneously negative values of electric permittivity (ε) and magnetic permeability (μ), having, so, negative refractive index (n): it is, then, possible to refer to this kind of material as Negative Refractive Index Material (NRI) or Double Negative Media. A negative refractive index implies several effects: the material exhibits negative reflection at the interface, negative Doppler shift, an obtuse angle for Čerenkov radiation and the possibility of momentum reversal. Veselago‟s idea remained pure theoretical for more than 30 years, when Smith and colleagues (University of California, San Diego) [3] designed and fabricated and artificial effectively homogeneous structure exhibiting simultaneously negative ε and μ, constituted by standard metals and dielectrics: metal thin-wires (TW) (negative-ε, positive-μ) and metal split-ring resonators (SRR) (positive-ε, negative-μ). Smith device works as a NRI material in the microwave range (GHz range). One of current researchers aim is to design a metamaterial having its operative frequency in THz range, that is to say at visible wavelength. Though SSR are easy to analyze structures, there are two main disadvantages designing and fabricating metamaterial using this geometry: it is difficult to fabricate nano-metric SSR. To face those problems in the last few years a new geometry has been introduced: a periodic porous nanostructure called fishnet [4]. A fishnet is a three layers structure: a dielectric layer (usually silicon oxide) placed between two metallic layers (gold or silver). During the three-years period of PhD fellowship my intention is to study optical metamaterials and to fabricate nano-porous fishnet using X-ray and interference lithography techniques. Bibliography 1. S. Anantha Ramakrishna, Tomasz M. Grzegorczyk. “Physics and Applications of Negative Refractive Index Materials”. CRC Press, 2009 2. V. G. Veselago. “The electrodynamics of substances with simultaneously negative values of ε and μ”. Sov. Phys. Usp., 10(4): 509–14, 1968 3. D. R. Smith et al. “Composite medium with simultaneously negative permeability and permittivity”. Phys. Rev. Lett., 84(18), 4184-4187, 2000 Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 103 P.-Y. Chen, S.-C. Wu, “A periodic porous-nanostructured left-handed material slab at optical frequences ”. DOI 10.1002/mop, 2008 4. Objectives for the three years Theoretical overview: study of metamaterials, in particular negative refractive index ones Getting acquainted with and understanding of modeling techniques Designing and nanofabrication of negative refractive index metallic metamaterials (one dimension, two dimensions, three dimensions) Optical analysis and characterization of the system Study of potential applications Obbiettivi da raggiungere per il primo anno Study of metamaterials: physical motivation of refractive index change Study of modeling techniques Gaining experience in nanofabrication techniques: EBL, X-ray lithography, electroplating, evaporation First attempts of metallic metamaterial nanofabrication and characterization Research project First year activities: Studying: the aim is to acquire a certain knowledge of physics of metamaterial. This activity will last for the whole first year at least. Design of experimental set-up: improvement of LILIT X-ray lithography beamline and its facilities. Membrane substrate fabrication to be used as X-ray mask substrate; Mask pattern design: one of the steps to use X-ray lithography technique is to design and construct X-ray masks; on this first year one of my tasks is to understand which patterns to use to fabricate metamaterials, to learn how to design them and to do it using CAD software. EBL lithography: after designing it, the pattern has to be created on the membrane. For this purpose, electron beam lithography will be performed in collaboration with LANN laboratory in Mestre. Gold film deposition: electroplating and/or evaporation will be employed; with this step, x-ray mask fabric is complete. This technique will be also used to build metamaterials after x-ray lithography. X-ray lithography: I will work at ELETTRA beam line LILIT Interference Lithography: an alternative way to fabbricate fishnet patterned metamaterials is to use interference lithography technique Characterization: after its fabrication, sample will be characterized (ellipsometry) Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 104 December November October September August July June May April March Activity February January Month Studying Beam line improvement Lilit Goniometric stage for X-ray lithography X-ray mask fabrication X-ray lithography Interference lithography Educational activity I intend to focus my attention on physics of metamaterials, physics of surface plasmons, nanofabrication techniques and synchrotron application. I will take some courses at university (“Materiali nanostrutturati” and “Applicazioni della radiazione di sincrotrone”) and integrate with study of books, articles. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 105 Graduate Student: MARIANNA LUCAFO’ mail:MARIANNA.LUCAFO’@phd.units.it Laboratory: Department of life sciences Title of the thesis: Study of carbon nanostructures as carriers for drugs for cancer chemotherapy. Supervisor: Prof. Sava Tutors:Prof. Zorzet,Dott. Pacor,Dott. Daros Research Activity foreseen State of the art and motivations The use of carbon nanostructures (NCS), such as fullerenes and nanotubes as the biomedical field is of great interest, for its possible therapeutic applications and for its use diagnostics. Potential advantages of these compounds are given by a structure which makes their internalization by the cells easy and by their large surface area and internal volume, which make them eligible as drug delivery systems for the transportation of drugs [Leshuai W. Zhang et al, 2009; Prato M. et al, 2008]. Currently, several studies are underway on nanoparticles with different size and purity, with the aim to collect an overview about their toxicological profile and to shed light on their potential side effects on biological components, cells, tissues and physiological processes [Boczkowski J. & Lanone S., 2007]. It is well known that carbon nanotubes are insoluble and have a strong tendency to aggregate and this is a constraining factor for their use in biological systems, therefore a range of strategies have been developed to overcome these problems, based on chemical modification of their surface, both through non-covalent binding of amphiphilic molecules such as polymers or lipids, or through covalent functionalization of different chemical groups [Tasis D. et al, 2006; Kostarelos K. et al, 2009]. The latter strategy, in particular, offers the possibility to bind steadily, for example, molecules with therapeutic activity, avoiding the risk of being degraded by serum enzymes or other blood components. So far in the preclinical studies performed in vivo, functionalized nanotubes have been proposed as carriers for anticancer drugs selectively conveying them just to the target cells and controlling their release [Kostarelos K. et al, 2007]. An innovative strategy that allows the specific internalization of the compound involves the binding of a target molecule to the surface of the nanotubes, such as a ligand for a receptor membrane [Shanta Dhar et al, 2008] or a variable sequence of a specific antibody. Although few works have been published, the results of the first studies in vivo appear to be encouraging for the use of carbon nanotubes: the administration of such drug delivery systems, could delay tumor growth with minimal side effects [Bhirde A. A. et al, 2009]. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 106 Leshuai W. Zhanga, Jianzhong Yang, Andrew R. Barronb, Nancy A. Monteiro-Riviere, 2009. Endocytic mechanisms and toxicity of a functionalized fullerene in human cells. Toxicology Letters, doi: 10.1016/j.toxlet.2009.08.017. Prato M., Kostarelos, K. & Bianco A., 2008. Functionalized carbon nanotubes in drug design and discovery. Acc. Chem. Res. 41, 60-68. Boczkowski J. & Lanone S., 2007. Potential uses of carbon nanotubes in the medical eld: how worried should patients be? Nanomedicine 2, 407-410. Tasis D., Tagmatarchis N., Bianco A. & Prato M., 2006. Chemistry of carbon nanotubes. Chem. Rev. 106, 1105-1136. Kostarelos K., Bianco A. and Prato M., 2009. Promises, facts and challenges for carbon nanotubes in imaging and therapeutics. Nature Nanotech. 4, 627-633. Kostarelos K., et al., 2007. Cellular uptake of functionalized carbon nanotubes is independent of functional group and cell type. Nature Nanotech. 2, 108-113. Shanta Dhar, Zhuang L., Jurgen T., Hongjie D., Stephen J. Lippard, 2008. Targeted SingleWall Carbon nanotube-mediated Pt(IV) prodrug delivery using folate as a homing device. J. Am. Chem. Soc. 130, 11467-11476. Bhirde, A. A. et al, 2009. Targeted killing of cancer cells in vivo and in vitro with EGF-directed carbon nanotube-based drug delivery. ACS Nano 3, 307-316. Objectives for the three years This project, is aimed to get data and knowledge on the mechanisms of the therapeutic activity and toxicity of carbon nano-structures, in cancer models. The purpose of the research project is to: - Study new nanostructures, prepared in collaboration with the group of Professor Prato, Department of Pharmaceutical Sciences, University of Trieste; - Define the toxicological profile of the nanotube or fullerene used as carriers for drugs, in single cells in vitro and in whole animals in vivo; - Analyze the mechanism of up-take and release of the nanostructure loaded with model anticancer drugs such as doxorubicin and cisplatin; - Validate their activity in vivo in models of target tumors. Objectives for the one year The first part of the study will focus on the therapeutic potential of the test drug loaded to the nanostructure vs the free drug and on the identification of the biological models for preliminary experiments in vitro. A number of established cell lines will be expose to different nanostructures, carrying or not a drug model, in order to select the most appropriate nanostructures in terms of interaction with the cancer cells. The objectives to be achieved for the first year are: - identify the nanostructure most suitable as carrier; Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 107 - evaluate any potential selective cytotoxicity on different tumor cell lines; characterize the sub-cellular pharmacokinetics of the selected nanostructure; Research project Outline of the main activities: -In vitro selection of the nanostructure and of the drug-associated nanostructure. The test cell lines selected for this studies are those on which adriamycin and cisplatin are mainly used in the clinical practice. Human cell lines derived from mammary carcinoma and non small cell lung cancer, including sub-lines resistant respectively to adriamycin and cisplatin will be obtained from ATCC or similar certificated structure. The dose and time of cell challenge dependence will be examined in vitro by means of conventional tests measuring cell viability and apoptosis. -In vitro analysis of cell and sub-cellular distribution. The study will be carried out using the cell line in which we showed respectively high and low response to the selected nanostructure. Conventional methods of preparation of sub-cellular fractions will be used and will allow to characterize the component(s) of the cell and of the cell compartment(s) on which the drug associated nanostructures are concentrated. The combination of the nanostructure plus cisplatin will be studied by means of atomic absorption spectroscopy where as the combination of the nanostructure with adriamycin will be studied by means of conventional fluorescent methodologies including flow cytometry. -In vivo pharmacokinetics and toxicity. The study of the in vivo pharmacokinetics of the test nanostructures will be carried on in outbred mice following conventional pharmacological procedures, e.g. intravenous administration and identification of the whole blood and plasma clearance and of the renal elimination. Host and organ toxicity will be examined considering the tipical toxicities known for the test drugs (adriamycin – cisplatin), by administering the drug-nanostructure at doses compatible with their antitumor activities. -In vivo characterization of the antitumor potential of the drug nanostructure. In vivo studies will be performed using target tumors of human origin, obtained from mammary and lung tumors. The studies will be done using the animal house facility, subject to approval from the ethical committee and using boxes for immunosuppressed animals. Educational activity For the first year, with role of co-rapporteur of some undergraduate students, I will follow them in the experimental part of their laboratory experience, and I will be working as a tutor during lessons for high school lab (LLC). Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 108 ACTIVITY FIRST YEAR SECOND YEAR THIRD YEAR Preparation of the nanostructures Preparation of drug bound nanostructures Selection of the nanostructures Test of citotoxicity of nanostrucutre-drug In vitro uptake and distribution Study of cell pathways of interaction of nanostructures Analysis of cell resistance overcoming In vivo pharmacokinetics In vivo activity on tumors In vivo toxicity Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 109 Graduate Student: Lucia Marsich Email: [email protected] Laboratory: DMRN University of Trieste Title of the thesis: “Design and synthesis of functionalized metal nanoparticles for bio-analysis with Surface-Enhanced Raman Scattering (SERS)” Supervisor: Valter Sergo Tutors: Alois Bonifacio Tentative Research plan State of the art and motivations Raman spectroscopy is a non-destructive technique that gives qualitative and quantitative information, since the spectrum is a finger print of each molecule, and the intensity of the signal is proportional to the concentration. The Raman scattering signal is typically very weak, and enhancement is required to improve the spatial resolution of the Raman scattering signal. Surface Enhanced Raman Scattering (SERS) has been successful in enhancing Raman signals using silver, gold or copper surfaces. Particles composed of such elements are specifically useful as enhancers of Raman signals, since their surface plasmons are easily excited by laser light, and generate an electric field that can be transferred to the adjacent Raman active molecules. This results in an amplification of the Raman signal. Due to its advantageous characteristics in terms of selectivity and sensitivity, SERS spectroscopy has become one of the most incisive analytical methods for chemical and biochemical detection and analysis [1]. SERS spectroscopy provides structure-specific vibrational spectra of analytes with extremely high sensitivity, and the high selectivity of the technique is ensured by enhanced detection of only species adsorbed on noble metal surfaces. Nanoparticles have found various applications in biomedical research. They are used in drug delivery, intracellular sensing, diagnosis and treatment of cancer. For example, a class of biocompatible and nontoxic gold nanoparticles for in vivo tumor targeting and surface-enhanced Raman detection has been developed [2]. Campbell and colleagues have studied the application of gold nanoshells as a surface- enhanced Raman platform for intracellular sensing in fibroblast cells by using a near-infrared Raman system [3] . Raman nanoparticle probes are used as optical labels for interrogation of physiological and pathological processes in bioassays, cells, and tissues. Furthermore, their unique emission signatures are ideal for multiplexing, i.e. simultaneous detection of different chemical species. Commonly used fluorescent dyes or quantum dots present significant limitations in multiplexing applications due to the interference from tissue autofluorescence and the overlap of emission peaks. Nanoparticle probes utilizing SERS emit unique spectral signatures with narrow peaks that are ideal for multiplexing. Raman emission is normally extremely weak compared to fluorescence, but enormous signal enhancement scan be created by adsorbing Raman-active molecules onto nanoparticles [4]. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 110 References: [1]Chourpa, Franck H. Lei, Pierre Dubois, Michel Manfait, Ganesh D. Sockalingum, “Intracellular applications of analytical SERS spectroscopy and multispectral imaging” Igor Chem.Soc.Rev., 2008, 37, 993–1000 [2]Ximei Qian, Xiang-Hong Peng, Dominic O Ansari, Qiqin Yin-Goen, Georgia Z Chen, Dong M Shin, Lily Yang, Andrew N Young, May D Wang, Shuming Nie, “In vivo tumor targeting and spectroscopic detection with surface-enhanced Raman nanoparticle tags”, Nature biotechnology volume 26, number 1, 2008 [3]Michael A. Ochsenku, Phillip R. T. Jess, Helene Stoquert, Kishan Dholakia, and Colin J. Campbell, “Nanoshells for Surface-Enhanced Raman Spectroscopy in Eukaryotic Cells: Cellular Response and Sensor Development” CS Nano, 2009, 3 (11), pp 3613–3621 [4]Lutz,Barry R. Dentinger,Claire E., Nguyen,Lienchi N., Sun,Lei; Zhang,Jingwu, Allen,April N., Chan,Selena, Knudsen,Beatrice S., “Spectral Analysis of Multiplex Raman Probe Signatures” ACS Nano, 2008, 2 (11), pp 2306–2314. Objectives for the three years Literature survey and identification of potentially suitable substrate for SERS in biological application Preparation and evaluation of the characteristics of the chosen substrates Implementation of the SERS-active substrate with biological sample (blood, cells, tissue, biological molecules) Objectives for the first year The aforementioned objectives for the three years will be limited to the problem of the detection and quantification of the protein bilirubin. Research project For each biological sample (biomolecules, cells and tissues) the following activities will be carried out: Synthesis of different kind of SERS-active substrate Characterization of the nanoparticles, in particular the size and the frequency of the surface plasmon resonance will be estimate (TEM/SEM, ultraviolet-visible spectrophotometry, Raman and SERS spectroscopy, dynamic light scattering, zeta-potential); Evaluation of the effect of the coating on nanoparticles characteristic (TEM/SEM, ultraviolet-visible spectrophotometry, Raman and SERS spectroscopy, dynamic light scattering, zeta-potential); Estimation of the enhancement of the Raman signal due to the presence of the substrate Study of the interaction between the analyte and the substrate; Measurement of the sensibility of the system (SERS spectroscopy); Trend analysis of the intensity of the spectrum as a function of the concentration of the analyte (SERS spectroscopy); Construction of calibration curves (SERS spectroscopy); Measures of biological samples and analysis of the results based on the previous experiment (SERS spectroscopy). Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 111 Educational activity Study of books and review articles about spectroscopy Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 112 Graduate Student ANGELO PERONIO Email: [email protected] Laboratory: IOM CNR, TASC laboratory – Surface Structure and Reactivity group, STM laboratory Title of the thesis: Single-molecule heterogeneous catalysis Supervisor: prof. Giovanni Comelli Tutors (if any): dr. Carlo Dri Research Activity foreseen State of the art and motivations During my PhD I will study model systems for gas-solid heterogeneous catalysis, focusing on how the single molecules of the reactants interact with the catalyst and between each other during chemical reactions. My intent is to tackle the study of these systems by means of a complementary experimental and computational approach. The word “catalysis” indicates the process where a chemical reaction is sped up or even made possible by the presence of a substance (the catalyst) that is not consumed into the reaction outcomes. Catalysis has an enormous technological impact: catalytic processes underlie the production of more than 60% of all the presently available chemicals on the market such as fuels, fertilizers and fine chemicals. Catalysts are also employed in production and purification of hydrogen for fuel cells and in the reduction of pollutants from cars and industrial plants. In gas-solid heterogeneous catalysis, the catalytic activity stems from the alteration of the chemical properties of the reactants upon adsorption on the catalyst surface. Surface science is one of the various approaches adopted for the characterization of such systems, where the latter are simplified as much as possible in order to investigate the single steps of the reaction at the atomic/molecular level, from the binding of the reactants to the catalyst, to the dynamics of the reaction itself. Among the available spectroscopic, microscopic and structural techniques, low-temperature scanning tunnel microscopy (LT-STM) allows to image, measure and control the properties of single atoms, molecules and molecular complexes on surfaces, for instance by manipulating the adsorbates on the surface [2], by identifying the chemical nature of single molecules from their vibrational spectra (STM-IETS) [3], by characterizing the processes induced by the inelastic tunnelling of electrons through the molecule (action spectroscopy) [4], measuring the local energydensity of electronic states (LDOS) by means of dI/dV spectroscopy [5]. These unique singlemolecule capabilities are crucial for instance to fully understand systems where the reactivity is due to the formation of a complex among the reactants on the surface [6], or to determine the adsorption geometries of a disordered system. The simulation of the measured properties (STM images, electronic and vibrational spectra) from the electronic structure of the surface obtained by means of density functional theory (DFT) computations is a fundamental, complementary technique to the experimental investigation. One can for instance predict how the various adsorbates will appear on the images, and in principle identify the chemical species present on the surface by comparing the theoretical and experimental images, making the STM a sub-molecular probe with chemical sensitivity. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 113 Bibliography: [1] Recognizing the Best in Innovation: Breakthrough Catalyst, R&D Magazine, September 2005, p. 20. [2] A. J. Heinrich, C. P. Lutz, J. A. Gupta, and D. M. Eigler, Molecule Cascades, Science 298, 1381 (2002). [3] B. C. Stipe, M. A. Rezaei, and W. Ho, Single-Molecule Vibrational Spectroscopy and Microscopy, Science 280, 1732 (1998) [4] Y. Sainoo, Y. Kim, T. Okawa, T. Komeda, H. Shigekawa, and M. Kawai, Excitation of Molecular Vibrational Modes with Inelastic Scanning Tunneling Microscopy Processes: Examination through Action Spectra of cis-2-Butene on Pd(110), Physical Review Letters 95, 246102 (2005) [5] R. Temirov, S. Soutbach, A. Lucian and F.S. Tautz, Free-electron-like dispersion in an organic monolayer film on a metal substrate, Nature 444, 350 (2006) [6] F. Esch, T. Greber, S. Kennou, A. Siokou, S. Ladas, and R. Imbihl, The formation of a NO-NH3 coadsorption complex on a Pt(111) surface: a NEXAFS study, Catal. Lett. 38, 165 (1996). Objectives for the three years Study of atomic- and molecular-scale properties of model systems for gas-solid heterogeneous catalysis. Objectives for first year Characterization and optimization of an LT-STM system to carry out vibrational spectroscopy on single molecules by means of inelastic electron tunnelling (STM-IETS) Design an analysis system for STM-IETS and action spectroscopy experimental data. Practice on STM-IETS measurements, beginning form systems already described in literature. Characterization of the adsorption sites of CO2 on Ni(110), a model system for catalytic hydrogenation of carbon dioxide to methanol. LT-STM characterization of NH3/Pt(111). This is both a test system to practice on action spectroscopy measurements and a first step towards the study of the NH3 + NO coadsorption complex on Pt(111). Research project STM measurements will be carried out by means of the commercial Omicron LT-STM available in the SSR-STM laboratory at TASC. The groundwork for STM-IETS measurements will start from the measurement of the noise spectral density of the instrument and the transfer function of the tunnelling current amplifier. With these information one will try to spot and remove the main sources of noise and to choose optimal parameters for IETS spectra acquisition. The data analysis system will be implemented in Igor Pro. First test measurements will be carried out on carbon monoxide adsorbed over Cu(110). CO2/Ni(110) system will be investigated by means of LT-STM microscopy. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 114 NH3/Pt(111) system will be studied with LT-STM microscopy, action spectroscopy and STMIETS. The research of the following years will start from these model systems: NH3 + NO complex over Pt(111), with STM-IETS; action spectroscopy and DFT modeling; Catalytic hydrogenation of CO2/Ni(110) to methanol with LT-STM microscopy and action spectroscopy; Adsorption and reactivity with hydrogen of carbon monoxide over Cu-Ni alloy, by means of time-resolved core-level photoemission (XPS) with synchrotron light. Educational activity Heterogeneous catalisys, module of M.Sc. programme in Chemistry at Trieste University, taught by prof. Paolo Fornsiero, 16 hours, March 2010. Spring College on Computational Nanoscience at the Abdus Salam International Centre for Theoretical Physics - Trieste, about 70 hours, may 2010. Photoemission spectroscopies and spectromicroscopies, course of PhD programme in Physics at Trieste University, taught by prof. Alessandro Baraldi, 25 hours, September-October 2010. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 115 Graduate Student: DAVIDE SAMMITO Email: [email protected] Laboratory: LILIT - TASC Title of the thesis: Design, Fabrication and Characterization of Plasmonic Nanostructures for Solar Cells Light Harvesting Enhancement Supervisor: Filippo Romanato Research Activity foreseen State of the art and motivations The research activity is called off in the area of plasmonics, a field of basic and applied research which studies and exploits the particular properties of the electromagnetic fields generated at the interface between metals and dielectrics. Light propagating in dielectrics cannot couple to surface plasmons at flat metallic interface. Nevertheless, nanostructuring metal surfaces to get gratings or realizing metal nanoparticles, it is possible to excite with ordinary light these electromagnetic modes confined to surfaces and exploit the resulting near field enhancement. During the three-year period of PhD fellowship I intend to study the plasmonic approach as a mean to increase solar cells efficiency and decrease the cost per Watt of energy produced. This is one of the targets of the European project ORION, to which most of the activities in my plan are related. Plasmonic nanostructures can offer the possibility of reducing the physical thickness of the photovoltaic absorber layers needed to convert a significant fraction on the incident photon flux in free charge carriers. There are two main approaches proposed in literature. Metallic nanoparticles can be used as subwavelength scattering elements to increase the optical path of the incoming light inside the absorber, coupling energy to waves propagating horizontally in the device [1][2]. Metallic gratings integrated in the cell structure can couple sunlight into surface plasmon polariton modes supported at the metal-absorber interface [3][4]. Conventional bulk Silicon solar cells could benefit from plasmonic nanostructures too: the absorption profile of photons with wavelengths close to the bandgap, which normally are scarcely absorbed, could be reshaped and enhanced in regions of the cell with high collection probability for the photogenerated carriers. Bibliography Pillai S., Catchpole K. R., Trupke T., Green M.A. 2007, Journal of Applied Physics, Vol. 101, p. 093105. F. J. Beck, S. Mokkapati, A. Polman, K. R. Catchpole 2009, Proceedings European Photovoltaic Solar Energy Conference, 232 – 235. Pala R., White J., Barnard E., Liu J., Brongersma M. 2009, Advanced Materials, Vol. 21, pp. 1-6. S. Collin, F. Pardo, N. Bardou, S. Averin, J.-L. Pelouard 2009, Proceedings European Photovoltaic Solar Energy Conference, 239 – 240. Objectives for the three years Numerical modelling of the electro-optical behaviour of bulk and thin film Silicon solar cells, both single- and multi-junction type, integrating plasmonic nanostructures. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 116 Designing of one or more layouts of bulk or thin film solar cells and their relative process flow in order to obtain enhancement of the efficiency by plasmonic effects. Realization and characterization of samples for some of the designed layouts. Objectives for the first year Implementation of a numerical model for the electro-optical simulation of crystalline Silicon bulk solar cells integrating plasmonic crystals. Implementation of a numerical model for the electro-optical simulation of amorphous Silicon thin film solar cells integrating plasmonic gratings. Development of lithographic processes and fabrication of prototypes of plasmonic gratings to be integrated in solar cells. Development of a goniometric stage for the positioning of samples for X-ray lithography. Upgrading and testing of the setup for electro-optical characterization of solar cells at TASC laboratory. Electro-optical characterization of bulk solar cells integrating plasmonic gratings. Research project The activities to be carried out can be divided into three work packages: 1) design and modellization; 2) nanofabrication; 3) characterization. The designing step includes the definition of possible configurations to integrate plasmonic nanostructures in solar cells and the study of the properties of the electromagnetic field generated by the interaction of sunlight with plasmonic gratings. One of the objectives is to realize an electrooptical model of solar cells to evaluate the effect of the integrated nanostructures in cell performance and to optimize the geometrical and material parameters of the nanostructures. Initially the behaviour of conventional solar cells, single junction bulk crystalline Silicon cells, will be simulated. Subsequently thin film cells will be analyzed, for which a higher enhancement of the performance is expected due to the optical trapping mechanism generated by surface plasmons. Then solar cells with more complex structures, such as multiple junctions cells, will be studied. The nanofabrication step has an essential role in the project. The requirements for the lithographic processes are the capability of realizing structures with feature size of the order of few hundred nanometers, to obtain gratings which interact with visible and near infrared light, and the compatibility with industrial mass production processes. It will be necessary to develop additive (thin film deposition) and subtractive (dry etching) processes to define the structure of the cells and of the plasmonic gratings. X-Ray lithography will be used to realize test structures and masters for nanoimprinting lithography. Initially the gratings will be integrated in bulk crystalline Silicon solar cells provided by partners of the ORION project. Then applications on suitable thin film cells will be analyzed. The solar cells with the integrated plasmonic nanostructures will be object of morphological (SEM) and electro-optical characterization (e.g. I-V curve, quantum efficiency measurements, reflectance). In case new materials will be tested as absorbers for solar cells, structural and electronic properties, such as minority carrier lifetime and charge transport properties, could be investigated by synchrotron radiation experiments. In the next page the Gantt diagram for first year activities is reported. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 117 Educational activity 1 1.1 December November October August July June May April March Activity February WP January Month September With the aim to improve the skills in modellization, I intend to use the hours of educational activity broadening my studies in the physics of inorganic semiconductor opto-electronic devices. Design and Modelling Optical model of plasmonic gratings 1.2 Electro-optical model single junction c-Si cell 1.3 Electro-optical model single junction a-Si cell 2 Nanofabrication 2.1 Development of a RIE process for pattern transfer into substrate 2.2 Fabrication of test plasmonic gratings 2.3 Development of processes for the integration of gratings in bulk cells 2.4 Goniometric stage per X-ray lithography 3 Characterization 3.1 Upgrade of the setup for cell electro-optical characterization 3.2 Electro-optical characterization of bulk cells 3.3 Optical characterization of test gratings Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 118 5.Pubblicazioni dei dottorandi. Venogono di seguito riportate le pubblicazioni dei dottorandi desunte dalla schede riportate al punto precedente: Pubblicazioni su riviste scientifiche (pubblicate o accettate per la pubblicazione) 1. Barinov, A., Malcioǧlu, O.B., Fabris, S., Sun, T., Gregoratti, L., Dalmiglio, M., Kiskinova, M. Initial stages of oxidation on graphitic surfaces: Photoemission study and density functional theory calculations, 2009, Journal of Physical Chemistry C 113 (21), pp. 9009-9013 2. Bozzini, B., Dalmiglio, M., De Gaudenzi, G.P., D'Urzo, L., Gregoratti, L. An investigation of the corrosion of WC-Co cermets in CN--containing aqueous solutions. Part II: Synchrotron-based high lateral-resolution XPS study, 2009, Corrosion Science 51 (8), pp. 1675-1678 3. M. Dalmiglio, M. Amati, L. Gregoratti, T. O. Menteş, M. A. Niño, L. Felisari and M. Kiskinova, Catalytic activity of PtRh particles, submitted to Journal of Physical Chemistry, 2010 4. P. Lacovig, M. Pozzo, D. Alfè, P. Vilmercati, A. Baraldi, S. Lizzit, Growth of DomeShaped Carbon Nanoislands on Ir(111): The Intermediate between Carbidic Clusters and Quasi-Free-Standing Graphene, Phys. Rev. Lett. 103, 166101 (2009) 5. E. Golfetto, A. Baraldi, M. Pozzo, D. Alfè, A. Sala, P. Lacovig, E. Vesselli, S. Lizzit, G. Comelli, R. Rosei, Determining the chemical reactivity trends of Pd/Ru(0001) pseudomorphic overlayers: core level shift measurements and DFT calculations, J. Phys. Chem. C, in press DOI: 10.1021/jp908568v, 2010 6. T. Montini, A. Speghini, L. De Rogatis, B. Lorenzut, M. Bettinelli, M. Graziani and P. Fornasiero, “The identification of the structural phases of CexZr1-xO2 by Eu(III) luminescence studies.”, Journal of the American Chemical Society 131 (2009), 1315513160 7. S. Specchia, L. D. Vella, B. Lorenzut, T. Montini, V. Specchia and P. Fornasiero, “Effect of the catalyst load on syngas production in SCT-CPO reactors.”, Industrial and Engineering Chemistry Research (2009), accepted for publication, doi:10.1021/ie900695j. 8. L. De Rogatis, M. Cargnello, V. Gombac, B. Lorenzut, T. Montini and P. Fornasiero, “Embedded phases: a way to active and stable catalysts”, ChemSusChem (2009), accepted for publication 9. E. Conca, T. Negri, A. Gronchi, E. Fumagalli, E. Tamborini, G.M. Pavan, M. Fermeglia, M.A. Pierotti, S. Pricl, S. Pilotti. Activate and resist: L576P-KIT in GIST. Molecular Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 119 Cancer Therapeutics. Mol Cancer Ther 1535-7163.MCT-09-0662. Mol Cancer Ther 8(9):2491-5, 2009. 10. S.E. Woodman, J.C. Trent, K. Stemke-Hale, A.J. Lazar, S. Pricl, G.M. Pavan, M. Fermeglia, Y.N. Gopal, D. Yang, D.A. Podoloff, D. Ivan, K.B. Kim, N. Papadopoulos, P. Hwu, G.B. Mills and M.A. Davies. Activity of dasatinib against L576P KIT mutant melanoma: Molecular, cellular, and clinical correlates. Mol Cancer Ther 8(8):2079-85, 2009. 11. T. Negri, G.M. Pavan, S. Pricl, S. Lagonigro, F. Miselli, A. Greco, M. Fermeglia, M.A. Pierotti, S. Pilotti, E. Tamborini, T670X KIT mutations in GISTs: making sense of missense. J Natl Cancer Inst 2009;101:1–11. 12. S.E. Woodman, J.C. Trent, K. Stemke-Hale, A. Lazar, S. Pricl, G.M. Pavan, N. Papadopoulos, P. Hwu, G.B. Mills, M.A. Davies. Selective Activity of Dasatinib for the Most Common KIT Mutation in Melanoma (L576P). Journal of Clinical Oncology, 2009 ASCO Annual Meeting Proceedings (Post-Meeting Edition). Vol 27, No 15S (May 20 Supplement), 2009: 9019. 13. Toth R, Voorn DJ, Handgraaf JW, Fraaije JGEM, Fermeglia M, Pricl S, Posocco P. Multiscale computer simulation studies of water-based montmorillonite/poly(ethylene oxide) nanocomposites. Macromolecules, 2009, on web (ma200901584w). 14. Scocchi G, Posocco P, Handgraaf JW, Fraaije JGEM, Fermeglia M, Pricl S. A complete multiscale modelling approach for polymer-clay nanocomposites. Chemistry - A European Journal, 15, 7586-7592, 2009. 15. Posocco P, Lisal M, Posel Z, Fermeglia M, Pricl S. A multiscale molecular simulation approach to the prediction of the morphology of self-assembled nanoparticles in diblock copolymers. Journal of Physical Chemistry B, submitted. 16. Posocco P, Fermeglia M, Pricl S. A multiscale toolbox for morphology prediction of diblock copolymers for drug delivery. Biomacromolecules, submitted. 17. Pricl S, Posocco P, Scocchi G, Fermeglia M. “Polymer-clay nanocomposites”, in Handbook of Nanophysics, Klaus Sattler Editor, Taylor&Francis Publisher, 2009. 18. Polyol Synthesis of Silver Nanoparticles: Mechanism of Reduction by Alditol Bearing Polysaccharides (Ivan Donati, Andrea Travan, Chiara Pelillo, Anna Coslovi, Alois Bonifacio,Valter Sergo, Sergio Paoletti). Biomacromolecules, 2009, 10 (2), 210-213 19. Non-Cytotoxic Silver Nanoparticle – Polysaccharide Nanocomposites with Antimicrobial Activity (Andrea Travan, Chiara Pelillo, Ivan Donati, Eleonora Marsich, Monica Benincasa, Tommaso Scarpa, Sabrina Semeraro, Gianluca Turco, Renato Gennaro, Sergio Paoletti). Biomacromolecules 2009, 10, 1429–1435 20. Surface Modification and Polysaccharide Deposition on BISGMA/TEGDMA Thermosets (Andrea Travan, Ivan Donati, Eleonora Marsich, Francesca Bellomo, Satish Achanta, Sabrina Semeraro, Tommaso Scarpa, Mila Toppazzini, Vittorio Spreafico, and Sergio Paoletti). Biomacromolecules 2010. (DOI: 10.1021/bm9011419) Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 120 21. Silver-Polysaccharide Nanocomposite Antimicrobial Coatings for Methacrylic Thermosets (Andrea Travan, Eleonora Marsich, Ivan Donati, Monica Benincasa, Marta Giazzon, Laura Felisari, Sergio Paoletti. Submitted to European Cells and Materials Journal (2010) 22. Characterization of silver nanoparticles for biomedical applications by means of quantitative analysis of TEM micrographs (Francesco Brun, Andrea Travan, Agostino Accardo, Sergio Paoletti). Biomedical Sciences Instrumentation 2010 (In press). 23. Silver nanocomposites and their biomedical applications (Andrea Travan, Eleonora Marsich, Ivan Donati, Sergio Paoletti). Chapter of the book entitled “Nanocomposites for the Life Sciences”. In press, Wiley-VCH (2010) 24. Journal of Materials Science, “Raman investigation of the ageing of Ni-BaTiO3 multilayer ceramic capacitors”, A.Umeri, T.A. Kuku, N.Scuor and V.Sergo, Volume 43, Issue 3, P.922-926,2008-02-01, DOI - 10.1007/s10853-007-2215-4, 2010 25. L. Rigon, F. Arfelli, A. Astolfo, A. Bergamaschi, D. Dreossi, R. Longo, R.H. Menk, B. Schmitt, E. Vallazza, E. Castelli, “A single-photon counting “edge-on” silicon detector for synchrotron radiation mammography”, Nucl. Instr. And Meth. A, 608, S62-S65, 2009 26. Alginate/Hydroxyapatite biocomposite for bone ingrowth: a trabecular structure with high and isotropic connectivity.Turco G, Marsich E, Bellomo F, Semeraro S, Donati I, Brun F, Grandolfo M, Accardo A, Paoletti S. Biomacromolecules. 2009 Jun 8; 10(6):1575-83 27. Surface modification and polysaccharide deposition on BISGMA/TEGDMA based resins. Donati I., Travan A., Marsich E., Bellomo F., Achanta S., Semeraro S., Scarpa T., Toppazzini M., Spreafico V., Paoletti S. Submitted to Biomacromolecules, 2010 28. Giovanni Birarda, Gianluca Grenci, Luca Businaro, Benedetta Marmiroli, Sabrina Pacor, Lisa Vaccari - “Fabrication of a microfluidic platform for investigating dynamic biochemical processes in living samples by FTIR microspectroscopy – Microelectronic Engineering (in press), 2010 29. Giovanni Birarda, Gianluca Grenci, Luca Businaro, Benedetta Marmiroli, Sabrina Pacor, Federica, Piccirilli, Lisa Vaccari - Infrared microspectroscopy of biochemical response of living cells in microfabricated devices” – Vibrational Spectroscopy (submitted evaluated) 2009 30. D‟Amelio N, Fontanive L, Uggeri F, Suggi-Liverani F, Navarini L. NMR reinvestigation of the caffeine-chlorogenate complex in acqueous solution and in coffee brews. Food Biophys. 2009, 4, 321-330. 31. Cadenaro M, Marchesi G, Antoniolli F, Davidson CL, De Stefano Dorigo E, Breschi L. “Flowability of composites is no guarantee for contraction stress reduction.” Dental Materials 2009;25(5):649-54. 32. Mazzoni A, Marchesi G, Cadenaro M, Mazzotti G, Di Lenarda R, Ferrari M, Breschi M. “Push-out stress for fiber posts luted using different adhesive strategies.” European Journal Oral Science 2009;117(4):447-453. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 121 33. Cadenaro M, Pashley DH, Marchesi G, Carrihlo M, Antoniolli F, Mazzoni A, Tay FR, Di Lenarda R, Breschi L. “Influence of chlorexidine on the degree of conversion and Emodulus of experimental adhesive blends”. Dental Materials 2009;25(5):1269-74. 34. Marchesi G, Breschi L, Antoniolli F, De Stefano Dorigo E, Ferracane J, Cadenaro M. “Contraction stress of composite materials with different polymerization reactions assayed by low-and high-compliance systems. Dental Materials submitted, 2010. 35. Breschi L, Cadenaro M, Mazzoni A, Navarra CO, Marchesi G, Di Lenarda R, De Stefano Dorigo E. “La durata del legame adesivo:la nuova sfida dell‟ odontoiatria resteurativa.” Dentista Moderno 2009;4:41-54. 36. “Dependence of the fractional anisotropy in cervical spine from the number of diffusion gradients, repeated acquisition and voxel size”, Santarelli, X., Garbin, G., Ukmar, M., Longo, R.; Magnetic Resonance Imaging (in press), 2010 37. 1) V. Gombac, L. Sordelli, T. Montini, J. J. Delgado, A. Adamski, G. Adami, M. Cargnello, S. Bernal and P. Fornasiero, “CuOx-TiO2 Photocatalysts for H2 Production from Ethanol and Glycerol Solutions.”, The Journal of Physical Chemistry A, in press, doi:10.1021/jp907242q, 2010. 38. 2) L. De Rogatis, M. Cargnello, V. Gombac, B. Lorenzut, T. Montini and P. Fornasiero, “Embedded phases: a way to active and stable catalysts.”, ChemSusChem, in press, 2010. 39. 3) M. Cargnello, T. Montini, S. Polizzi, N. L. Wieder, R. J. Gorte, M. Graziani and P. Fornasiero, “Novel embedded Pd@CeO2 catalysts: a way to active and stable catalysts.”, Dalton Transactions, in press, 2010. 40. 1) M. Cargnello, N. L. Wieder, T. Montini, R. J. Gorte and P. Fornasiero, “Synthesis of dispersible Pd@CeO2 core-shell nanostructures by self-assembly”, Journal of the American Chemical Society, submitted. 41. “The evolutionary conserved gene C16orf35 encodes a nucleo-cytoplasmic protein that interacts with p73.” Lunardi A, Chiacchiera F, D'Este E, Carotti M, Dal Ferro M, Di Minin G, Del Sal G, Collavin L. Biochem Biophys Res Commun. 2009 Oct 16;388(2):428-33. 42. Corona G, Elia C, Casetta B, Diana C, Rosalen S, Bari M, Toffoli G. A liquid chromatography-tandem mass spectrometry method for the simultaneous determination of exemestane and its metabolite 17-dihydroexemestane in human plasma. J Mass Spectrom. 2009 Jun. 43. Corona G, De Lorenzo E, Elia C, Simula MP, Avellini C, Baccarani U, Lupo F, Tiribelli C, Colombatti A, Toffoli G. Differential protomi analysis of hepatocellular carcinoma. Internation Journal of Oncology 2009 (accepted for publication) 44. Migliorini E., Ban J., Di Foggia V., Ruaro ME., Torre V., Pozzato A., Grenci G., Tormen M, Lazzarino M. Effect of nanopatterned substrates on growth cones activity. Eur Biophys .J. 2009 Oct, (suppl 1) S89 Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 122 45. Kondra S, Laishram J., J. Ban J.,Migliorini E., Di Foggia V., Lazzarino M., Torre V., Ruaro M.E. Integration of Confocal and Atomic Force Microscopy. Journal of Neuroscience methods. 2009 Feb 15;177(1):94-107. Epub 2008 Oct 18. 46. Laishram J., Kondra S., Avossa D., Migliorini E., Lazzarino M., Torre V. A morphological analysis of growth cones of DRG neurons combining Atomic Force and Confocal Microscopy. Journal of Structural Biology. 2009 Sept. 47. R.Muscia, G.Sciuto, F. Zuddas – On the usage of PCM elements within asphalt concrete to avoid ice formation on roadways. International Journal of Solar Energy, submitted 2010. Pubblicazioni/abstracts in conferenze/congressi (nazionali o internazionali) 48. POSTER - P. Lacovig, M. Pozzo, D. Alfè, P. Vilmercati, A. Baraldi, and S. Lizzit, Graphene Growth on Ir(111): A Fast XPS Study - CINF-DTU Summer School on “Reactivity of nanoparticles for more efficient and sustainable energy production”, Sandbjerg Gods (Denmark), 2009 49. POSTER – P. Lacovig, A. Baraldi, S. Lizzit, Chemical reactivity of nanoclusters deposited on solid surfaces: new time-domain and enhanced surface-sensitivity of photoelectron spectroscopy - Joint Workshop of SFB762 & IMPRS on “Magnetic properties of oxidic and multiferroic systems”, Wittenberg (Germany), 2009 50. Posocco P, Fermeglia M, Pricl S. Multiscale molecular modeling of di/triblock copolymers for drug delivery. FOMMS, Blaine, USA, (2009). 51. Fermeglia M, Posocco P, Pricl S, Fraaije JGEM, Handgraaf JW, Scocchi G, Danani A. A complete multiscale modeling approach for nanocomposites. Eurofillers, Alessandria, Italy, (2009). 52. Fermeglia M, Posocco P, Pricl S, Fraaije JGEM, Handgraaf JW, Deglmann P, KurkalSiebert V, Weiss H. On the DPD Parameter Estimation From Atomistic/Quantum Mechanics Information. AIChE Annual meeting, Nashville, USA, (2009). 53. Fermeglia M, Scocchi G, Pricl S, Handgraaf JW, Fraaije JGEM, Posocco P. A Complete Multiscale Modeling Approach for Polymer-Clay Nanocomposites. AIChE Annual meeting, Nashville, USA, (2009). 54. Posocco P, Fermeglia M, Pricl S. The Long and Winding Road. Multiscale Molecular Modeling Approach to the Self-Assembly of Di/Triblock Copolymers for Drug Delivery in Aqueous Solution. AIChE Annual meeting, Nashville, USA, (2009). 55. Posocco P. Modellistica molecolare multiscala per la progettazione di materiali nanostrutturati. I giovani e la chimica in FVG, Trieste, (2009). 56. G.M. Pavan, P. Posocco, M. Fermeglia, G. Scocchi, A. Malek, M.Maly, A. Danani, C. Catapano, S. Pricl. Nanocarriers in delivery of small interfering RNA theurapetics. 9th International Conference on Chemical and Process Engineering. Rome, 10-13 May 2009. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 123 57. POSTER - “Nanostructured Zirconia in dental applications: new problems for an old material” – A.Umeri, A. Bonifacio and V. Sergo – National Nanomedicine Conference – 28,29 November 2008 - Genova 58. Spatio-Temporal Radiation Biology: Transdiscipinary Advances for Biomedical Applications – Booklet of abstracts (Saint Feliu de Guixols, Spain, 16-21 May 2009), A. Astolfo, R.-H. Menk, F. Arfelli, E. Schultke, C. Hall, L. Rigon, B.H.J. Juurlink, “Long Term Cell Tracking in Small Animals Phase Using Phase Contrast Based Micro CT and Synchrotron Radiation”, P.53. 59. “POROUS NANO-HYDROXYAPATITE/ALGINATE SCAFFOLDS FOR BONE REGENERATION” Eleonora Marsich, Sabrina Semeraro, Gianluca Turco, Francesca Bellomo, Ivan Donati and Sergio Paoletti (7-9 novembre 2008 Bone-tec Hannover; Joint Workshop of SFB762 & IMPRS 10th/11thSeptember 2009 in the Leucorea at Wittenberg) 60. “SPERIMENTAZIONE IN VIVO DI SCAFFOLD DI ALGINATO E IDROSSIAPATITE PER RIGENERAZIONE OSSEA” F. Bellomo, M. Biasotto, G.Turco, R. Di Lenarda, S. Paoletti (22° riunione nazionale “A. Castellani” dei dottorandi di ricerca in discipline biochimiche Brallo di Pregola (PV) 9 – 12 Giugno 2009; Collegio dei docenti di odontoiatria Roma 22-24 aprile 2009) 61. The Proceedings of Conference on Miniaturized Systems for Chemistry and Life Sciences (MicroTAS 2009), Giovanni Birarda,Gianluca Grenci, Luca Businaro, Benedetta Marmiroli, Giuseppe Bellisola and Lisa Vaccari, Single Living Cell Biochemical Rearrangements Investigated By Infrared Microspectroscopy In Microfluidic Devices - 978-0-9798064-2-1/μTAS2009/$20ⓒ2009CBMS pp 338-341. 62. Marchesi G, Cadenaro M, Antoniolli F, Di Lenarda R, Pashley DH, Breschi L. “Influenza della clorexidina sul grado di conversione e sul modulo elastico in adesivi sperimentali.” Acts of XIII national meeting SIDOC-Rome 19-21/2/2009. 63. Marchesi G, Breschi L, Antoniolli F, De Stefano Dorigo E, Cadenaro M. “Stress da polimerizzazione di una resina a base siloranica.”Acts of national meeting Docenti di Odontoiatria e di chirurgia Maxillofacciale, Roma 22-24/4/2009. 64. Marchesi G, Cadenaro M, Breschi L, Antoniolli F, Tay FR, Di Lenarda R, Pashley DH. “Influence of chlorexidine on the E-modulus of experimental resins.” J Dent Res 88 (spec Iss A). Annual meeting of The International Association for Dental Research. Miami FL USA. 65. Marchesi G, Cadenaro M, Di Lenarda R, Breschi. Bond strenght of Post Luted with different Self-adhesive Resin Cements. Annual meeting of the Accademy Dental Materials. Portland Oregon USA 29-31/10/2009 66. Marchesi G. Analysis of aging and stability of bonded interface in dentistry. Poster 2° Workshop of the SFB 762-Wittenberg, Germany 10-11/09/2009. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 124 67. ORAL:“Local BDNF delivery by means of laser tweezers to stimulate hippocampal neurons signalling” Elisa D‟Este, Gabriele Baj, Paolo Beuzer, Enrico Ferrari, Federica Tavano, Enrico Tongiorgi, Dan Cojoc; ICTP-Introduction to Optofluidics 68. ORAL: “High spatial resolution BDNF delivery by means of laser tweezers to stimulate hippocampal neurons signalling”; Elisa D‟Este, Gabriele Baj, Paolo Beuzer, Enrico Ferrari, Federica Tavano, Enrico Tongiorgi, Dan Cojoc; EBSA 2009 69. ORAL: “High Resolution Drug Delivery by Optical Tweezers Microscopy” Elisa D‟Este, Gabriele Baj, Paolo Beuzer, Enrico Ferrari, Federica Tavano, Enrico Tongiorgi, Dan Cojoc; Super and High Resolution Imaging 2009 70. POSTER: “Optical Tweezers as means to stimulate hippocampal neurons with BDNF coated beads”; Elisa D‟Este, Gabriele Baj, Paolo Beuzer, Enrico Ferrari, Federica Tavano, Enrico Tongiorgi, Dan Cojoc; Nanobioviews-2nd international symposium on Optical Tweezers in life sciences; Award best poster Optical Tweezers 71. Corona G, Elia C, Casetta B and Toffoli G. Liquid Chromatography/Tandem Mass Spectrometry Method To Rapid Asses the Irinotecan Metabolic Phenotype. Mass Spec Europe 5-6 November 2009, Barcelona, Spain 72. G.Sciuto, R.Muscia – Multiobjective optimization of intracoronary stents by genetic algorithm. 13th international research/expert conference, Trends in the development of machinery and associated technology, TMT 2009, Hammameth, Tunisia. 73. R.Muscia, G.Sciuto – A method for performing quality comparisons of Rzeppa joints. 13th international research/expert conference, Trends in the development of machinery and associated technology, TMT 2009, Hammameth, Tunisia. 74. 1. Poster: “High spatial resolution BDNF delivery by means of laser tweezers to stimulate hippocampal neurons signalling”; Elisa D‟Este, Gabriele Baj, Paolo Beuzer, Enrico Ferrari, Federica Tavano, Enrico Tongiorgi, Dan Cojoc; EBSA 2009 75. Poster: “High Resolution Drug Delivery by Optical Tweezers Microscopy” Elisa D‟Este, Gabriele Baj, Paolo Beuzer, Enrico Ferrari, Federica Tavano, Enrico Tongiorgi, Dan Cojoc; Super and High Resolution Imaging 2009 76. Poster: “Optical Tweezers as means to stimulate hippocampal neurons with BDNF coated beads”; Elisa D‟Este, Gabriele Baj, Paolo Beuzer, Enrico Ferrari, Federica Tavano, Enrico Tongiorgi, Dan Cojoc; Nanobioviews-2nd international symposium on Optical Tweezers in life sciences 77. “FARMACOGENETICA DELLA CARDIOTOSSICITÀ DA ANTRACICLINE”, Chiara Zanusso and Giuseppe Toffoli, La gestione delle problematiche” at Napoli on March 25-26, 2009. 78. “NANOTECHNOLOGIES AND ONCOLOGY: PHARMACOKINETICS AND PHARMACOGENOMICS TO OPTIMIZE THE ANTITUMOR THERAPIES”, Chiara Zanusso, Erika Cecchin, Paola Biason, Elena De Mattia, Franca Sartor and Giuseppe Toffoli, 2nd Phd workshop 10th/11 September 2009, Wittenberg. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 125 Brevetti 79. Italian Patent FI2007A0000179 “Catalizzatori per la produzione di gas di sintesi da reforming di idrocarburi o alcoli comprendenti un supporto in ZnO e loro uso” ; Inventors: Paolo BERT, Stefano CATANORCHI, Paolo FORNASIERO, Mauro GRAZIANI, Barbara LORENZUT, Hamish MILLER, Tiziano MONTINI, Marina RAGNOLI, Adriana SCAFFIDI, Alessandro TAMPUCCI. 80. Materiali nanocompositi basati su nanoparticelle metalliche stabilizzate con polisaccaridi a struttura ramificata (Andrea Travan, Ivan Donati, Eleonora Marsich, Sergio Paoletti, Brevetto 8853 PTIT) 81. Materiali nanocompositi formati da una matrice polisaccaridica e nanoparticelle metalliche, loro preparazione ed uso (Andrea Travan, Ivan Donati, Eleonora Marsich, Sergio Paoletti, Brevetto 8981 PTIT) 82. Nanocomposite materials based on metallic nanoparticles stabilized with branched polysaccharides (Andrea Travan, Ivan Donati, Elonora Marsich, Sergio Paoletti). PCT Patent extension (2009) 83. Three-dimensional nanocomposite materials consisting of a polysaccharidic matrix and metallic nanoparticles, preparation and use thereof (Andrea Travan, Ivan Donati, Elonora Marsich, Sergio Paoletti). PCT Patent extension (2009) Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 126 6. Giudizi della commissione d’esame finale 2009 La commissione composta dai Professori Dragan Mihailovic, Istituto Josef Stefan, Ljubljana (SLO), Kostas Karatasos, Università di Thessaloniki, Dipartimento di Ingegneria Chimica (G) e Tullio Giraldi, Università di Trieste (membro interno), hanno sentito i candidati e stilato i seguenti giudizi: Matteo Maria DALMIGLIO Il candidato ha presentato il suo lavoro di tesi che ha ha avuto come obiettivo quello di studiare la reattività e le proprietà di ossidazione di cluster di catalizzatori supportati da ossidi o da nanotubi di carbonio, mediante tecniche diverse, tra cui la spettro-microscopia a scansione in fotoemissione (SPEM). La commissione ha apprezzato il livello scientifico del lavoro svolto ed ha individuato una potenzialità per applicazioni. Il candidato ha dimostrato di possedere una notevole conoscenza della materia in studio, affrontando la discussione con competenza nelle tecniche proprie del lavoro di tesi. Il candidato ha risposto compiutamente ed in modo chiaro alle domande dei Commissari. Approvata la relazione, la Commissione propone che al candidato VENGA conferito il titolo di Dottore di Ricerca. Paolo LACOVIG Il candidato ha illustrato il suo lavoro di tesi che è consistita sia dello sviluppo di strumentazione innovativa per la misura di spettri di fotoemissione e per lo studio della struttura elettronica, della morfologia e le proprietà chimiche di sistemi a bassa dimensionalità. La risoluzione temporale raggiunta dal nuovo analizzatore ha consentito poi di studiare dei processi dinamici fino ad ora inaccessibili, in particolare la crescita ad alta temperatura del grafene su diversi metalli di transizione e la reattività chimica di nano-aggregati atomici. La commissione ha apprezzato il lavoro innovativo e di frontiera affronatato dal candidato che ha dimostrato di possedere una ottima conoscenza della materia in studio, presentando con competenza e con completezza il suo lavoro di tesi, rispondendo puntualmente e compiutatamente alle domande della Commissione. Approvata la relazione, la Commissione propone che alla candidata VENGA conferito il titolo di Dottore di Ricerca. Barbara LORENZUT La candidata ha illustrato il suo lavoro di tesi che ha riguardato lo sviluppo e la caratterizzazione di sistemi catalitici per la produzione dell‟idrogeno. In particolare sono stati studiati catalizzatori per il Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 127 reforming di metanolo ed etanolo a base di metalli di transizione e per la produzione di idrogeno attraverso la reazione di cracking dell‟ammoniaca e lo steam reforming del glicerolo su catalizzatori a base di platino. La commissione ha apprezzato il livello scientifico del lavoro svolto e la applicabilità diretta su temi industriali. La candidata ha dimostrato di possedere una notevole conoscenza della materia in studio, affrontando la discussione con competenza nelle tecniche proprie del lavoro di tesi e rispondendo compiutamente ed in modo chiaro alle domande dei Commissari. Approvata la relazione, la Commissione propone che alla candidata VENGA conferito il titolo di Dottore di Ricerca. Giovanni Maria PAVAN Il candidato ha presentato il suo lavoro di tesi che ha riguardato la terapia mirata in oncologia, con particolare riguardo a sistemi farmaco/oncogene caratteristici di patologie come la leucemia mieloide cronica e il tumore gastrointestinale stromale, attraverso l‟impiego di metodi di simulazione molecolare. Lo studio ha evidenziando come inibitori interagiscono con i siti di binding. Confronti con dati sperimentali hanno evidenziato un‟ottima corrispondenza tra i dati ottenuti in silico e le evidenze cliniche, dimostrando l‟affidabilità e le potenzialità della simulazione come strumento d‟indagine biomedica. La commissione ha apprezzato il livello scientifico del lavoro svolto e la applicabilità diretta su problematiche di interpretazione di dati preclinici e clinici. Il candidato ha dimostrato di possedere una notevole conoscenza della materia in studio, affrontando la discussione con competenza nelle tecniche proprie del lavoro di tesi e rispondendo compiutamente ed in modo adeguato alle domande dei Commissari. Approvata la relazione, la Commissione propone che al candidato VENGA conferito il titolo di Dottore di Ricerca. Paola POSOCCO La candidata ha illustrato il suo lavoro di tesi che ha avuto come argomento principale lo sviluppo di procedure multiscala per la simulazione di materiali nanostrutturati di inteesse industriale. compositi polimero – silicati. I sistemi analizzati appartengono a settori diversi tra loro, si va dai materiali nanocompositi lamellari, alle resine epossidiche, ai copolimeri a blocchi, ai gel per uso biomedico. In tutti i casi è stato riscontrato un buon accordo tra le evidenze sperimetnali ed i dati simualti. La commissione ha apprezzato la completezza e il livello scientifico elevato del lavoro svolto. La candidata ha dimostrato di possedere una ottima conoscenza della materia in studio, presentando Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 128 con competenza e con completezza il suo lavoro di tesi, rispondendo puntualmente alle domande della Commissione. Approvata la relazione, la Commissione propone che alla candidata VENGA conferito il titolo di Dottore di Ricerca. Andrea TRAVAN Il candidato ha presentato il suo lavoro di tesi relativo allo sviluppo di sistemi nanocompositi per applicazioni biomediche con scopo ultimo di realizzare un rivestimento per protesi ortopediche dotato di proprietà antimicrobiche. Come agenti antimicrobici sono stati studiati sistemi nanocompositi a base di polisaccaridi di origine naturale che stabilizzano nanoparticelle metalliche in soluzione colloidale ed in matrici solide tridimensionali (gel). Nanocompositi sono stati sviluppati e caratterizzati nel lavoro di tesi. La commissione ha apprezzato l‟interdisciplinarietà della ricerca che ha utilizzato molte delle risorse scientifiche della scuola. Il candidato ha dimostrato di possedere una ottima conoscenza della materia in studio, presentando con molta competenza e con completezza il suo lavoro di tesi, rispondendo puntualmente alle domande della Commissione Approvata la relazione, la Commissione propone che al candidato VENGA conferito il titolo di Dottore di Ricerca. Andrea UMERI Il candidato ha presentato il suo lavoro di tesi che ha avuto come argomento principale l‟analisi di compositi Allumina Zirconia in relazione al fenomeno di aging della Zirconia, alla luce del rinnovato interesse di questo materiale in campo dentistico. Campioni che hanno subito invecchiamento naturale ed artificiale sono stati anlizzati a diverse concentrazioni tramite spettroscopia Raman and AFM. La commissione ha apprezzato il livello scientifico del lavoro svolto e la applicabilità diretta su temi di interesse pratico. Il candidato ha dimostrato di possedere una notevole conoscenza della materia in studio, affrontando la discussione con competenza nelle tecniche proprie del lavoro di tesi e rispondendo compiutamente ed in modo chiaro alle domande dei Commissari. Approvata la relazione, la Commissione propone che al candidato VENGA conferito il titolo di Dottore di Ricerca. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 129 7.Elenco dei componenti del collegio docenti Componente Ente Dipartimento SSD BARALDI Alessandro BONIN Serena UNITS Department of Physics - DF UNITS BRESCHI Lorenzo CADENARO Milena CASALIS Loredana CESARO Attilio UNITS Department of Anesthesia, Surgery, MED/34 RU Pathological Anatomy, Dermatology, Pathology and Molecular Sciences Clinical operative Unit of Odontoiatry MED/28 PA and Stomatologic - UCOOS Clinical operative Unit of Odontoiatry MED/28 PA and Stomatologic - UCOOS Not assigned RIC COJOC Dan INFM-TASC UNITS Elettra Synchrotron Spa UNITS Department of Life Sciences - DLS COMELLI UNITS Giovanni CONTIN Alfredo UNITS DA ROS Tatiana UNITS DANANI Andrea University School Italian Swiss DE STEFANO UNITS DORIGO Elettra DE VANNA UNITS Maurizio DE VITA Alessandro DI FABRIZIO Enzo DI LENARDA Roberto FASSINA Ambrogio FERMEGLIA Maurizio FIRRAO Giuseppe FLORIAN Fiorella UNITS FIS/03 Qualifica RU CHIM/04 PO Not assigned Department of Physics - DF FIS/03 PO Department of Electronics, ING/IND PA Electrotecnics and Informatics - DEEI Department of Pharmaceutical CHIM/08 RU Sciences - DSF Not assigned RIC Clinical operative Unit of Odontoiatry and Stomatologic - UCOOS Department of Medical, Technological and Traslational Sciences - DMTTS Department of Materials and Natural Resources - DMNR Not assigned MED/28 PO MED/25 PA PO Clinical operative Unit of Odontoiatry MED/28 PO and Stomatologic - UCOOS Not assigned MED/08 PO Exclusive Member Member PO Director UNIUD Department of Materials and Natural INGResources - DMNR IND/24 Not assigned AGR/12 PA Member UNITS Department of Life Sciences - DLS RU Exclusive Member UNITS UNIPD UNITS Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 BIO/06 PA Exclusive Member Exclusive Member Member non academic Exclusive Member Member non academic Exclusive Member Exclusive Member Exclusive Member Member foreing University Exclusive Member Exclusive Member Exclusive Member Member UNICZ INGIND/22 FIS/07 Ruolo Collegio Exclusive Member Exclusive Member 130 Componente Ente Dipartimento SSD Qualifica FORNASIERO UNITS Paolo GAMINI Amelia UNITS Department of Chemical Sciences DSCH Department of Life Sciences - DLS CHIM/03 PA GIRALDI Tullio UNITS Department of Life Sciences - DLS BIO/14 GRAZIANI Mauro LAZZARINO Marco LUGHI Vanni UNITS Department of Chemical Sciences DSCH Not assigned CHIM/03 PO UNITS INGIND/22 INGINF/01 BIO/06 RIC MARSI Stefano Department of Materials and Natural Resources - DMNR Department of Electronics, Electrotecnics and Informatics - DEEI Department of Life Sciences - DLS Department of Materials and Natural INGResources - DMNR IND/22 Department of Physics - DF FIS/01 PO Department of Mechanical Engineering - DIME Not assigned PA UNITS MARZARI UNITS Roberto MERIANI Sergio UNITS MORGANTE UNITS Alberto MUSCIA Roberto UNITS ONESTI Silvia Elettra Synchrotron Spa PAOLETTI Sergio UNITS Department of Life Sciences - DLS PASQUATO UNITS Department of Chemical Sciences Lucia DSCH PRATI Ubaldo Fund. Tommaso Not assigned Campanella PRICL Sabrina UNITS Department of Materials and Natural Resources - DMNR RAVALICO UNITS Department of Anesthesia, Surgery, Giuseppe Pathological Anatomy, Dermatology, Pathology and Molecular Sciences ROITTI Sergio UNITS Department of Materials and Natural Resources - DMNR ROSEI Renzo UNITS Department of Physics - DF RUBINI Silvia INFM-TASC SBAIZERO Orfeo UNITS SCHMID Chiara UNITS SERGO Valter UNITS CHIM/04 RU RIC Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 RU PO PA RIC BIO/19 PO CHIM/06 PA P.Osp INGPA IND/24 MED/30 PO INGIND/22 FIS/03 Not assigned Department of Materials and Natural Resources - DMNR Department of Materials and Natural Resources - DMNR Department of Materials and Natural PO PA PO RIC INGIND/22 INGIND/22 ING- PO PA PO Ruolo Collegio Exclusive Member Exclusive Member Exclusive Member Exclusive Member Member non academic Exclusive Member Exclusive Member Exclusive Member Exclusive Member Vice Director Exclusive Member Member non academic Member Exclusive Member Member non academic Exclusive Member Exclusive Member Exclusive Member Exclusive Member Member non academic Exclusive Member Exclusive Member Exclusive 131 Componente Ente SSD Qualifica CRO Aviano Resources - DMNR IND/22 Department of Anesthesia, Surgery, MED/08 PA Pathological Anatomy, Dermatology, Pathology and Molecular Sciences Not assigned P.Osp UNIVE Not assigned STANTA Giorgio UNITS TOFFOLI Giuseppe UGO Paolo Dipartimento Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 CHIM/01 PA Ruolo Collegio Member Member Member non academic Exclusive Member 132 8. Pubblicazioni rappresentative del collegio docenti Estratto della produzione scientifica del collegio dal 2004 al 2009 del personale dipendente dall’Università. N Docente 1 BARALDI Alessandro 2 BARALDI Alessandro 3 BARALDI Alessandro 4 BARALDI Alessandro 5 BARALDI Alessandro 6 BARALDI Alessandro 7 BARALDI Alessandro 8 BARALDI Alessandro 9 BARALDI Alessandro 10 BARALDI Alessandro 11 BARALDI Alessandro Pubblicazione BARALDI A. (2008). Structure and chemical reactivity of transition metal surfaces as probed by synchrotron radiation core-level photoelectron spectroscopy. JOURNAL OF PHYSICS. CONDENSED MATTER, vol. 20; p. 93001, ISSN: 0953-8984 BARALDI A., BIANCHETTIN L, VESSELLI E, DE GIRONCOLI S, LIZZIT S, PETACCIA L, ZAMPIERI G, COMELLI G, ROSEI R (2007). Highly under-coordinated atoms at Rh surfaces: interplay of strain and coordination effects on core level shift. NEW JOURNAL OF PHYSICS, vol. 9; p. 143, ISSN: 1367-2630 BARALDI A., GIACOMELLO D, RUMIZ L, MORETUZZO M, LIZZIT S, BUATIER DE MONGEOT F, PAOLUCCI G, COMELLI G, ROSEI R, NIEUWENHUYS B.E, VALBUSA U. AND KISINOVA M (2005). Unexpected behavior of the surface composition of PtRh alloys during chemical reactio. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 127; p. 5671, ISSN: 0002-7863 BARALDI A., LIZZIT S, BONDINO F, COMELLI G, ROSEI R, SBRACCIA C, BONINI N, BARONI S, MIKKELSEN A, ANDERSN J.N (2005). Thermal stability of the Rh(110) missing-row reconstruction: combination of real-time corelevel spectroscopy and ab initio modeling. PHYSICAL REVIEW. B, CONDENSED MATTER AND MATERIALS PHYSICS, vol. 72; p. 75417, ISSN: 1098-0121 BARALDI A., LIZZIT S, COMELLIG, KISKINOVA M, ROSEI R, HONKALA K. AND NORSKOV J.K (2004). A spectroscopic link between surface structure and local chemical reactivity. PHYSICAL REVIEW LETTERS, vol. 93; p. 46101, ISSN: 0031-9007 BARALDI A., VESSELLI E, BIANCHETTIN L, COMELLI G, LIZZIT S, PETACCIA L, DE GIRONCOLI S, LOCATELLI A, MENTES T.O, ABALLE L, WEISSENRIEDER J, ANDERSEN J.N (2007). The (1x1) ? hexagonal structural transition on Pt(100) studied by highenergy resolution core level photoemission. THE JOURNAL OF CHEMICAL PHYSICS, vol. 127; p. 164702, ISSN: 0021-9606 BIANCHETTIN L, BARALDI A., DE GIRONCOLI S, LIZZIT S, PETACCIA L, VESSELLI E, COMELLI G, ROSEI R (2006). Geometric and electronic structure of the N/Rh(100) system by core-level photoelectron spectroscopy: Experiment and Theory. PHYSICAL REVIEW. B, CONDENSED MATTER AND MATERIALS PHYSICS, vol. 74; p. 45430, ISSN: 1098-0121 BIANCHETTIN L, BARALDI A., VESSELLI E, DE GIRONCOLI S, LIZZIT S, PETACCIA L, COMELLI G, ROSEI R (2007). Experimental and theoretical Surface Core Level Shift study of the S-Rh(100) local environment. JOURNAL OF PHYSICAL CHEMISTRY. C, NANOMATERIALS AND INTERFACES, vol. 111; p. 4003, ISSN: 1932-7447 BUATIER DE MONGEOT F, TOMA A, MOLLE A, LIZZIT S, PETACCIA L, BARALDI A. (2007). Self-organised synthesis of Rh nanostructures with tunable chemical reactivity. NANOSCALE RESEARCH LETTERS, vol. 2; p. 251, ISSN: 1931-7573 DING X, DE ROGATIS L, VESSELLI E, BARALDI A., COMELLI G, ROSEI R, SAVIO L, VATTUONE L, ROCCA M, ANCILOTTO F, BALDERESCHI A. AND PERESSI M (2007). Interaction of carbon dioxide with Ni(110): a combined experimental and theoretical study. PHYSICAL REVIEW. B, CONDENSED MATTER AND MATERIALS PHYSICS, vol. 76; p. 195425, ISSN: 1098-0121 E. VESSELLI, L. BIANCHETTIN, BARALDI A., A. SALA, G. COMELLI, L. PETACCIA, S. LIZZIT, S. DE GIRONCOLI (2008). The Ni3Al(111) surface structure: experiment and theory. JOURNAL OF PHYSICS. CONDENSED MATTER, vol. 20; p. 195223, ISSN: 0953-8984 Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 133 12 BARALDI Alessandro 13 BARALDI Alessandro 14 BARALDI Alessandro 15 BARALDI Alessandro 16 BARALDI Alessandro 17 BARALDI Alessandro 18 BARALDI Alessandro 19 BARALDI Alessandro 20 BARALDI Alessandro 21 BARALDI Alessandro 22 BARALDI Alessandro 23 BARALDI Alessandro 24 BARALDI Alessandro 25 BARALDI Alessandro E. VESSELLI, L. DE ROGATIS, X. DING, BARALDI A., L. SAVIO, L. VATTUONE, M. ROCCA, P. FORNASIERO, M. PERESSI, A. BALDERESCHI, R. ROSEI AND G. COMELLI (2008). Carbon Dioxide hydrogenation on Ni(110). JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 130; p. 11417, ISSN: 0002-7863 E. VESSELLI, M. CAMPANIELLO, BARALDI A., L. BIANCHETTIN, C. AFRICH, F. ESCH, S. LIZZIT, G. COMELLI (2008). A surface core level shift study of hydrogen-induced ordered structures on Rh(110). JOURNAL OF PHYSICAL CHEMISTRY. C, NANOMATERIALS AND INTERFACES, vol. 112; p. 14475, ISSN: 1932-7447 F. BUATIER DE MONGEOT, A. TOMA, A. MOLLE, S. LIZZIT, L. PETACCIA, BARALDI A. (2006). Carbon monoxide dissociation on Rh nanopyramids. PHYSICAL REVIEW LETTERS, vol. 97; p. 56103, ISSN: 0031-9007 HOFMANN PH, ZAMPIERI G, PETACCIA L. LIZZIT S, BARALDI A. (2005). Comment on "Momentum-dependent energy losses in core level photoemission spectra of poorly conducting metals. PHYSICAL REVIEW LETTERS, vol. 94; p. 209703, ISSN: 0031-9007 L. BIANCHETTIN, BARALDI A., S. DE GIRONCOLI, E. VESSELLI, S. LIZZIT, G. COMELLI AND R. ROSEI (2009). SURFACE CORE LEVEL SHIFT: HIGH SENSITIVE PROBE TO OXYGEN-INDUCED RECONSTRUCTION OF RH(100). JOURNAL OF PHYSICAL CHEMISTRY. C, NANOMATERIALS AND INTERFACES, vol. 113; p. 13192-13198, ISSN: 1932-7447, doi: 10.1021/jp901223d L. BIANCHETTIN, BARALDI A., S. DE GIRONCOLI, E. VESSELLI, S. LIZZIT, L. PETACCIA, G. COMELLI, R. ROSEI (2008). Core level shifts of under-coordinated Pt atoms. THE JOURNAL OF CHEMICAL PHYSICS, vol. 128; p. 114706, ISSN: 0021-9606 L. DE ROGATIS, E. VESSELLI, BARALDI A., M.F. CASULA, T. MONTINI, G. COMELLI, M. GRAZIANI AND P. FORNASIERO (2009). Charge redistribution at the embedded Rh-alumina interface. JOURNAL OF PHYSICAL CHEMISTRY. C, NANOMATERIALS AND INTERFACES, vol. 113; p. 18069-18074, ISSN: 1932-7447 M. BIANCHI, D. CASSESE, A. CAVALLIN, R. COMIN, F. ORLANDO, L. POSTREGNA, E. GOLFETTO, S. LIZZIT, BARALDI A. (2009). Clean and oxygen induced surface core level shift on Ir(111). NEW JOURNAL OF PHYSICS, vol. 11; p. 063002, ISSN: 13672630 P. LACOVIG, M. POZZO, D. ALFÈ, P. VILMERCATI, BARALDI A., S. LIZZIT (2009). Growth of dome-shaped carbon nanoislands on Ir(111): the intermediate between carbidic clusters and quasi free-standing graphene. PHYSICAL REVIEW LETTERS, vol. 103; p. 166101, ISSN: 0031-9007 S. LIZZIT, BARALDI A., CH. GRÜTTER, J.H. BILGRAM, PH. HOFMANN (2009). The surface phase transition and low temperature phase of ?-Ga(010) studied by SPALEED. SURFACE SCIENCE, vol. 603; p. 3222, ISSN: 0039-6028 S. LIZZIT, Y. ZHANG, K.L. KOSTOV, L. PETACCIA, BARALDI A., R. LARCIPRETE, D. MENZEL, K. REUTER (2009). Oand H- induced surface core level shifts on Ru(0001): prevalence of the additivity rule. JOURNAL OF PHYSICS. CONDENSED MATTER, vol. 21; p. 134009, ISSN: 0953-8984 SANTUCCI S. C., GOLDONI A., LARCIPRETE R., LIZZIT S., BERTOLO M., BARALDI A. (2004). Calorimetry at surfaces using high-resolution core level photoemission. PHYSICAL REVIEW LETTERS, vol. 93; p. 106105, ISSN: 0031-9007 SAVIO L, GERBI A, VATTUONE L, BARALDI A., COMELLI G, ROCCA M (2006). Monitoring super- and subsurface oxygen on Ag(210) by high energy resolution Xray photoelectron spectroscopy: Subsurface diffusion and segregation. JOURNAL OF PHYSICAL CHEMISTRY. B, CONDENSED MATTER, MATERIALS, SURFACES, INTERFACES & BIOPHYSICAL, vol. 110; p. 942, ISSN: 1520-6106 T. STAUDT, A. DESIKUSUMASTUTI, M. HAPPEL, E. VESSELLI, BARALDI A., S. GARDONIO, S. LIZZIT, F. ROHR AND J. LIBUDA (2008). Modelling NOx storage meterials: a high-resolution photoelectron spectroscopy study on the interaction Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 134 of NO2 with Al2O3/NiAl(110) and BaO/Al2O3/NiAl(110). JOURNAL OF PHYSICAL CHEMISTRY. C, NANOMATERIALS AND INTERFACES, vol. 112; p. 9835, ISSN: 19327447 26 BARALDI TAIT S.L, WANG Y, LIN N, COSTANTINI G, BARALDI A., ESCH F, LIZZIT S, PETACCIA L, Alessandro KERN K (2008). Metal-Organic coordination interactions in Fe-Teraphthalic acid networks on Cu(100). JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 130; p. 2108-2113, ISSN: 0002-7863 27 BARALDI VESSELLI E, DE ROGATIS L, BARALDI A., COMELLI G, ROSEI R, GRAZIANI M (2005). Alessandro Structural and kinetic effects on a simple catalytic reaction: oxygen reduction on Ni(110). THE JOURNAL OF CHEMICAL PHYSICS, vol. 112; p. 144710, ISSN: 00219606 28 BARALDI VESSELLI E., BARALDI A., BONDINO F., COMELLI G., PERESSI M. AND ROSEI R. Alessandro (2004). Coverage-dependent hydrogen adsorption site determination on Rh(100) by means of high-resolution core-level spectroscopy. PHYSICAL REVIEW. B, CONDENSED MATTER AND MATERIALS PHYSICS, vol. 70; p. 115404, ISSN: 10980121 29 BARALDI VESSELLI E., BARALDI A., COMELLI G., LIZZIT S. AND ROSEI R. (2004). Ethanol Alessandro decomposition: C-C cleavage selectivity on Rh(111). CHEMPHYSCHEM, vol. 5; p. 1133, ISSN: 1439-4235 30 BARALDI WEESTRATE K.J., BARALDI A., RUMIZ L., LIZZIT S., COMELLI G. AND ROSEI R. (2004). Alessandro Surface Core Level Shift study of the hydrogen interaction with Rh(111). SURFACE SCIENCE, vol. 566-568; p. 486, ISSN: 0039-6028 31 BARALDI WESTSTRATE C.J, BAKKER J.W, RIENKS E.D.L, LIZZIT S, PETACCIA L, BARALDI A., Alessandro NIEUWENYUS B.E (2005). NH3 adsorption and decomposition on Ir(110): a combined temperature programmed desorption and high resolution fast x-ray phtoelectron spectroscopy study. THE JOURNAL OF CHEMICAL PHYSICS, vol. 122; p. 184705, ISSN: 0021-9606 32 BARALDI WESTSTRATE C.J, BAKKER J.W, RIENKS E.D.L, MARTINEZ J.R, VINOD C.P, LIZZIT S, Alessandro PETACCIA L, BARALDI A., NIEUWENHUYS B.E (2005). Selective NH3 oxidation on (110) and (111) iridium surfaces. JOURNAL OF CATALYSIS, vol. 235; p. 92, ISSN: 0021-9517 33 BARALDI WESTSTRATE C.J, BAKKER J.W, RIENKS E.D.L, VINOD C.P, LIZZIT S, PETACCIA L, Alessandro BARALDI A., NIEUWENHUYS B.E (2006). Synchrotron XPS and desorption study of the NO chemistry on a stepped Pt surface. SURFACE SCIENCE, vol. 600; p. 1991, ISSN: 0039-6028 34 BARALDI WESTSTRATE C.J, BAKKER J.W, RIENKS E.D.L, VINOD C.P, LIZZIT S, PETACCIA L, Alessandro BARALDI A., NIEUWENYUS B.E (2005). The role of Oad in the decomposition of NH3 adsorbed on Ir(110): a combined TPD and high-energy resolution fast XPS study. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, vol. 7; p. 2629, ISSN: 1463-9076 35 BARALDI ZAMPIERI G, LIZZIT S, PETACCIA L, GOLDONI A, BARALDI A., BREMHOLM M, Alessandro GAYONE J.E, HOFFMANN S, HOFMANN P (2005). Photoelectron diffraction study of the 6H-SiC(0001) ? 3x ? 3 R30º reconstruction. PHYSICAL REVIEW. B, CONDENSED MATTER AND MATERIALS PHYSICS, vol. 72; p. 165327, ISSN: 10980121 36 BONIN Serena BONIN S., BRUNETTI D, BENEDETTI E, DOTTI I, GORJI N, STANTA G (2008). Molecular characterisation of breast cancer patients at high and low recurrence risk. VIRCHOWS ARCHIV, vol. 452; p. 241-250, ISSN: 0945-6317, doi: 10.1007/s00428-007-0570-9 37 BONIN Serena BONIN S., BRUNETTI D, BENEDETTI E, GORJI N, STANTA G. (2006). Expression of cyclin-dependent kinases and CDC25a phosphatase is related with recurrences and survival in women with peri- and post-menopausal breast cancer. VIRCHOWS ARCHIV, vol. 448; p. 539-544, ISSN: 0945-6317 38 BONIN Serena BONIN S., PETRERA F, ROSAI J, STANTA G (2005). DNA and RNA obtained from Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 135 39 BONIN Serena 40 BONIN Serena 41 BONIN Serena 42 BONIN Serena 43 BONIN Serena 44 BONIN Serena 45 BONIN Serena 46 BONIN Serena 47 BONIN Serena 48 BONIN Serena 49 BONIN Serena 50 BRESCHI Lorenzo 51 BRESCHI Lorenzo 52 BRESCHI Lorenzo Bouin's fixed tissues. JOURNAL OF CLINICAL PATHOLOGY, vol. 58; p. 313-316, ISSN: 0021-9746 BONIN S., PETRERA F., STANTA G. (2005). PCR AND RT-PCR ANALYSIS IN ARCHIVAL POSTMORTEM TISSUES. In: UCHS J, PODDA M. ENCYCLOPEDIA OF DIAGNOSTIC GENOMICS AND PROTEOMICS. p. 985-988, NEW YORK: MARCEL DEKKER INC MIERTUSOVA S, BONIN S., TREVISAN G AND STANTA G (2004). Mycosis fungoides is not associated with HCV virus infection. BRITISH JOURNAL OF DERMATOLOGY, vol. 115; p. 1108-1110, ISSN: 0007-0963 NARDON E, DONADA M, BONIN S., DOTTI I, STANTA G (2009). Higher random oligo concentration improves reverse transcription yield of cDNA from bioptic tissues and quantitative RT-PCR reliability. EXPERIMENTAL AND MOLECULAR PATHOLOGY, vol. 87; p. 146-151, ISSN: 0014-4800, doi: 10.1016/j.yexmp.2009.07.005 PAULUZZI P, BONIN S., GONZALEZ INCHAURRAGA MA, STANTA G, TREVISAN G (2004). DETECTION OF SPIROCHETAL DNA SIMULTANEOUSLY IN SKIN BIOPSIES, PERIPHERAL BLOOD AND URINE FROM PATIENTS WITH ERYTHEMA MIGRANS. ACTA DERMATO-VENEREOLOGICA, vol. 84; p. 106-110, ISSN: 0001-5555 SCAGGIANE B, BONIN S., CRISTIANO L, SIRACUSANO S, STANTA G, DAPAS B, GIANSANTE C, FIOTTI N AND GRASSI G (2008). Prostate Tumour-Inducing gene-1 analysis in human prostate cancer cells and tissue in relation to Mycoplasma infection. CANCER INVESTIGATION, vol. 26; p. 800-808, ISSN: 0735-7907 SIRACUSANO S, NICCOLINI B, KNEZ R, TIBERIO A, BENEDETTI E, BONIN S., CICILIATO S, PAPPAGALLO GS, BELGRANO E, STANTA G (2005). The simultaneous use of telomerase, cytokeratin 20 and CD4 for bladder cancer detection. EUROPEAN UROLOGY, vol. 47; p. 327-333, ISSN: 0302-2838 STANTA G, CESCATO A, BONIN S., BARBAZZA R (2008). BIOETHICS CONSIDERATIONS FOR MEDICAL RESEARCH IN HUMAN ARCHIVE TISSUES: THE POINT OF VIEW OF THE RESEARCHER. VIRCHOWS ARCHIV, vol. 453; p. 117- 119, ISSN: 0945-6317 STANTA G, POZZI MUCELLI S, PETRERA F, BONIN S. (2006). A novel fixative improves opportunities of nucleic acids and proteomic analysis in human archive's tissues. DIAGNOSTIC MOLECULAR PATHOLOGY, vol. 15; p. 115- 123, ISSN: 10529551 TOTHOVA SM, BONIN S., TREVISAN G, STANTA (2006). Mycosis fungoides: is it a Borrelia burgdorferi-associated disease?. BRITISH JOURNAL OF CANCER, vol. 94; p. 879-883, ISSN: 0007-0920 TREVISAN G, ORTENZIO S, BONIN S. (2005). Late Lyme disease, chronic Lyme disease and post-Lyme disease syndrome. Clinical and laboratory analysis. GIORNALE ITALIANO DI DERMATOLOGIA E VENEREOLOGIA, vol. 140; p. 417-434, ISSN: 0392-0488 TREVISAN G, PADOVAN C, SCAINI MT, CINCO M, FLORIS R, BONIN S. (2008). Anetoderma Associated with Lyme Disease: A Case Report. ACTA DERMATOVENEREOLOGICA, vol. 88; p. 536-538, ISSN: 0001-5555, doi: 10.2340/000155550513 BERTACCI A, BARONI C, BRESCHI L., VENTURI M, PRATI C (2007). The influence of smear layer in lateral channels filling. CLINICAL ORAL INVESTIGATIONS, vol. 11; p. 353-359, ISSN: 1432-6981 BRESCHI L., CADENARO M, ANTONIOLLI F, SAURO S, BIASOTTO M, PRATI C, TAY FR, DI LENARDA R (2007). Polymerization kinetics of dental adhesives cured with LED: correlation between extent of conversion and permeability. DENTAL MATERIALS, vol. 23; p. 1066-1072, ISSN: 0109-5641 BRESCHI L., CADENARO M, ANTONIOLLI F, VISINTINI E, TOLEDANO M, DI LENARDA R (2007). Extent of polymerization of dental bonding systems on bleached enamel. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 136 53 BRESCHI Lorenzo 54 BRESCHI Lorenzo 55 BRESCHI Lorenzo 56 BRESCHI Lorenzo 57 BRESCHI Lorenzo 58 BRESCHI Lorenzo 59 BRESCHI Lorenzo 60 BRESCHI Lorenzo 61 BRESCHI Lorenzo 62 BRESCHI Lorenzo 63 BRESCHI Lorenzo 64 BRESCHI Lorenzo 65 BRESCHI Lorenzo 66 BRESCHI Lorenzo 67 BRESCHI Lorenzo AMERICAN JOURNAL OF DENTISTRY, vol. 20; p. 275-280, ISSN: 0894-8275 BRESCHI L., CAMMELLI F, VISINTINI E, MAZZONI A, VITA F, CARRILHO M, CADENARO M, FOULGER S, TAY FR, PASHLEY D, DI LENARDA R (2009). Influence of chlorhexidine concentration on the durability of etch-and-rinse dentin bonds: a 12-month in vitro study. JOURNAL OF ADHESIVE DENTISTRY, vol. 11; p. 191-198, ISSN: 1461- 5185 BRESCHI L., MAZZONI A, DE STEFANO DORIGO E, FERRARI M (2009). Adhesion to intraradicular dentin: a review. JOURNAL OF ADHESION SCIENCE AND TECHNOLOGY, vol. 23; p. 1053-1083, ISSN: 0169-4243 BRESCHI L., MAZZONI A, PASHLEY DH, PASQUANTONIO G, RUGGERI A JR, SUPPA P, MAZZOTTI G, DI LENARDA R, TAY FR (2006). Electric Impulse-Assisted Application of Self-Etch Adhesives to Dentin. JOURNAL OF DENTAL RESEARCH, vol. 85; p. 1092-1096, ISSN: 0022-0345 BRESCHI L., MAZZONI A, RUGGERI A JR, CADENARO M, DI LENARDA R, DORIGO E (2008). Dental adhesion review: aging and stability of the bonded interface. DENTAL MATERIALS, vol. 24; p. 90-101, ISSN: 0109-5641 BRESCHI L., PRATI C, GOBBI P, PASHLEY DH, MAZZOTTI G, TETI G, PERDIGAO J. (2004). Immunohistochemical analysis of the collagen fibrils included inside the hybrid layer: a FEISEM study. OPERATIVE DENTISTRY, vol. 29; p. 538-546, ISSN: 0361-7734 CADENARO M, ANTONIOLLI F, SAURO S, TAY FR, DI LENARDA R, PRATI C, BIASOTTO M, CONTARDO L, BRESCHI L. CADENARO M, BIASOTTO M, SCUOR N, BRESCHI L., DAVIDSON CL, DI LENARDA R (2008). Assessment of polymerization contraction stress of three composite resins. DENTAL MATERIALS, vol. 24; p. 681-685, ISSN: 0109- 5641 CADENARO M, BRESCHI L., ANTONIOLLI A, MAZZONI A, DI LENARDA R (2006). Influence of whitening on the degree of conversion of dental adhesives on dentin. EUROPEAN JOURNAL OF ORAL SCIENCES, vol. 114; p. 257- 262, ISSN: 0909-8836 CADENARO M, BRESCHI L., ANTONIOLLI F, NAVARRA CO, MAZZONI A, TAY FR, DI LENARDA R, PASHLEY DH (2008). Degree of conversion of resin blends in relation to ethanol content and hydrophilicity. DENTAL MATERIALS, vol. 24; p. 1194-1200, ISSN: 0109-5641 CADENARO M, BRESCHI L., NUCCI C, ANTONIOLLI F, VISINTINI E, PRATI C, MATIS BA, DI LENARDA R (2008). Effect of two in-office whitening agents on enamel surface in vivo: a morphological and non contact profilometric study. OPERATIVE DENTISTRY, vol. 33; p. 127-134, ISSN: 0361-7734 CADENARO M, BRESCHI L., RUEGGEBERG FA, AGEE K, DI LENARDA R, TAY FR, PASHLEY DH (2009). Effect of adhesive hydrophilicity and curing-time on the permeability of resins bonded to water vs. ethanol-saturated acidetched dentin. DENTAL MATERIALS, vol. 25; p. 39-47, ISSN: 0109-5641 CADENARO M, BRESCHI L., RUEGGEBERG FA, SUCHKO M, GRODIN E, AGEE K, DI LENARDA R, TAY FR, PASHLEY DH (2009). Effects of residual ethanol on the rate and degree of conversion of five experimental resins. DENTAL MATERIALS, vol. 25; p. 621-628, ISSN: 0109-5641 CADENARO M, DELISE C, ANTONIOLLI F, NAVARRA OC, DI LENARDA R, BRESCHI L. (2009). Enamel and Dentin Bond Strength Following Ozone Application. JOURNAL OF ADHESIVE DENTISTRY, vol. 11; p. 287-292, ISSN: 1461- 5185 CADENARO M, MARCHESI G, ANTONIOLLI F, DAVIDSON C, DE STEFANO DORIGO E, BRESCHI L. (2009). Flowability of composites is no guarantee for contraction stress reduction. DENTAL MATERIALS, vol. 25; p. 649-654, ISSN: 0109-5641 CADENARO M, PASHLEY DH, MARCHESI G, CARRILHO M, ANTONIOLLI F, MAZZONI A, TAY FR, DI LENARDA R, BRESCHI L. (2009). Influence of chlorhexidine on the degree of conversion and E-modulus of experimental adhesive blends. DENTAL Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 137 68 BRESCHI Lorenzo 69 BRESCHI Lorenzo 70 BRESCHI Lorenzo 71 BRESCHI Lorenzo 72 BRESCHI Lorenzo 73 BRESCHI Lorenzo 74 BRESCHI Lorenzo 75 BRESCHI Lorenzo 76 BRESCHI Lorenzo 77 BRESCHI Lorenzo 78 BRESCHI Lorenzo 79 BRESCHI Lorenzo 80 BRESCHI Lorenzo 81 BRESCHI Lorenzo 82 BRESCHI MATERIALS, vol. 25; p. 1269-1274, ISSN: 0109-5641 ARRILHO MR, TAY FR, DONNELLY AD, AGEE KA, TJÄDERHANE L, MAZZONI A, BRESCHI L., FOULGER S, PASHLEY DH (2009). Host-derived loss of dentin matrix stiffness associated with solubilization of collagen. JOURNAL OF BIOMEDICAL MATERIALS RESEARCH. PART B, APPLIED BIOMATERIALS, vol. 90; p. 373-380, ISSN: 1552-4981 CARRILHO MRO, GERALDELI S, TAY FR, DE GOES M, CARVALHO RM, TJDERHANE L, REIS AF, HEBLING J, MAZZONI A, BRESCHI L., PASHLEY DH (2007). In Vivo Preservation of Hybrid Layer by Chlorhexidine. JOURNAL OF DENTAL RESEARCH, vol. 86; p. 529-533, ISSN: 0022-0345 CARVALHO CA, CANTORO A, MAZZONI A, GORACCI C, BRESCHI L., FERRARI M (2009). Effect of the ethanol application on post luting to intraradicular dentin. INTERNATIONAL ENDODONTIC JOURNAL, vol. 42; p. 129-135, ISSN: 0143-2885 CARVALHO CA, MONTICELLI F, CANTORO A, BRESCHI L., FERRARI M (2009). Pushout bond strength of fiber posts luted with unfilled resin cement. JOURNAL OF ADHESIVE DENTISTRY, vol. 11; p. 65-70, ISSN: 1461-5185 CHERSONI S, SUPPA P, BRESCHI L., TAY FR, PASHLEY DH, PRATI C. (2004). Water movement in the hybrid layer after different dentin treatments. DENTAL MATERIALS, vol. 20; p. 796-803, ISSN: 0109-5641 CHERSONI S, SUPPA P, GRANDINI S, GORACCI C, MONTICELLI F, YIU C, HUANG C, PRATI C, BRESCHI L., FERRARI M, PASHLEY DH, TAY FR (2004). In vivo and in vitro permeability of one-step self-etch adhesives. JOURNAL OF DENTAL RESEARCH, vol. 83; p. 459-464, ISSN: 0022-0345 CONTARDO L, DE LUCA M, BEVILACQUA L, BRESCHI L., DI LENARDA R (2007). Influence of calcium hydroxide debris on the quality of endodontic apical seal. MINERVA STOMATOLOGICA, vol. 56; p. 509-517, ISSN: 0026-4970 DEIMLING D, BRESCHI L., HOTH-HANNIG W, RUGGERI A, HANNIG C, NEKRASHEVYCH Y, PRATI C, HANNIG M. (2004). Electron microscopic detection of salivary alpha-amylase in the pellicle formed in situ. EUROPEAN JOURNAL OF ORAL SCIENCES, vol. 112; p. 503-509, ISSN: 0909-8836 ERHARDT ACG, OSORIO R, PROENÇA JP, AGUILERA FA, OSORIO E, BRESCHI L., TOLEDANO M (2009). Influence of multiple adhesive coatings and extended etching time on the bonding effectiveness of self-etch adhesives to dentin. OPERATIVE DENTISTRY, ISSN: 0361-7734 FALCONI M, TETI G, ZAGO M, GALANZI A, BRESCHI L., PELOTTI S, RUGGERI A, MAZZOTTI G (2009). Influence of a commercial tattoo ink on protein production in human fibroblasts. ARCHIVES OF DERMATOLOGICAL RESEARCH, vol. 301; p. 539547, ISSN: 0340-3696 FALCONI M, TETI G, ZAGO M, PELOTTI S, BRESCHI L., MAZZOTTI G (2007). Effects of HEMA on type I collagen protein in human gingival fibroblasts. CELL BIOLOGY AND TOXICOLOGY, vol. 23; p. 313-322, ISSN: 0742-2091 FALCONI M, TETI G, ZAGO M, PELOTTI S, GOBBI P, BRESCHI L., MAZZOTTI G (2007). Effect of fixative on chromatin structure and DNA detection. MICROSCOPY RESEARCH AND TECHNIQUE, vol. 70; p. 599-606, ISSN: 1059-910X FERRARI M, CARVALHO CA, GORACCI C, ANTONIOLLI F, MAZZONI A, MAZZOTTI G, CADENARO M, BRESCHI L. (2009). Influence of luting material filler content on post cementation. JOURNAL OF DENTAL RESEARCH, vol. 88; p. 951-956, ISSN: 0022-0345 FERRARI M, CONIGLIO I, MAGNI E, CAGIDIACO MC, GALLINA G, PRATI C, BRESCHI L. (2008). How can droplets formation occur in endodontically treated teeth during bonding procedures?. JOURNAL OF ADHESIVE DENTISTRY, vol. 10; p. 211218, ISSN: 1461-5185 FOSCHI F, NUCCI C, MONTEBUGNOLI L, MARCHIONNI S, BRESCHI L., MALAGNINO Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 138 Lorenzo 83 BRESCHI Lorenzo 84 BRESCHI Lorenzo 85 BRESCHI Lorenzo 86 BRESCHI Lorenzo 87 BRESCHI Lorenzo 88 BRESCHI Lorenzo 89 BRESCHI Lorenzo 90 BRESCHI Lorenzo 91 BRESCHI Lorenzo 92 BRESCHI Lorenzo 93 BRESCHI Lorenzo 94 BRESCHI Lorenzo 95 BRESCHI Lorenzo VA, PRATI C. (2004). SEM evaluation of canal wall dentine following use of Mtwo and ProTaper NiTi rotary instruments. INTERNATIONAL ENDODONTIC JOURNAL, vol. 37; p. 832-839, ISSN: 0143-2885 HIRAISHI N, BRESCHI L., PRATI C, FERRARI M, TAGAMI J, KING NM (2007). Technique sensitivity associated with air-drying of HEMA-free, single-bottle, onestep self-etch adhesives. DENTAL MATERIALS, vol. 23; p. 498-505, ISSN: 0109-5641 KOMORI PC, PASHLEY DH, TJADERHANE L, BRESCHI L., MAZZONI A, DE GOES MF, WANG L, CARRILHO MR (2009). Effect of 2% chlorhexidine digluconate on the bond strength to normal vs caries-affected dentin. OPERATIVE DENTISTRY, vol. 43; p. 157-165, ISSN: 0361-7734 MAI S, KIM YK, TOLEDANO M, BRESCHI L., LING JQ, PASHLEY DH, TAY FR (2009). Phosphoric acid esters cannot replace polyvinylphosphonic acid as phosphoprotein analogs in biomimetic remineralization of resin-bonded dentin. DENTAL MATERIALS, vol. 25; p. 1230-1239, ISSN: 0109-5641 MALACARNE-ZANON J, PASHLEY DH, AGEE KA, FOULGER S, ALVES MC, BRESCHI L., CADENARO M, GARCIA FP, CARRILHO MR (2009). Effects of ethanol addition on the water sorption/solubility and percent conversion of comonomers in model dental adhesives. DENTAL MATERIALS, vol. 25; p. 1275-1284, ISSN: 0109-5641 MAZZONI A, MANNELLO F, TAY FR, TONTI G, PAPA S, MAZZOTTI G, DI LENARDA R, PASHLEY DH, BRESCHI L. (2007). Zymographic analysis and characterization of MMP-2 and -9 isoforms in human sound dentin. JOURNAL OF DENTAL RESEARCH, vol. 86; p. 436-440, ISSN: 0022-0345 MAZZONI A, MARCHESI G, CADENARO M, MAZZOTTI G, DI LENARDA R, FERRARI M, BRESCHI L. (2009). Push-out stress for fibre posts luted using different adhesive strategies. EUROPEAN JOURNAL OF ORAL SCIENCES, vol. 117; p. 447-453, ISSN: 0909-8836 MAZZONI A, PASHLEY DH, NISHITANI Y, BRESCHI L., TJADERHANE L, TOLEDANO M, PASHLEY EL, TAY FR (2006). Reactivation of quenched endogenous proteolytic activities in phosphoric acid-etched dentine by etch-and-rinse adhesives. BIOMATERIALS, vol. 27; p. 4470-4476, ISSN: 0142-9612 MAZZONI A, PASHLEY DH, RUGGERI A JR, VITA F, FALCONI M, DI LENARDA R, BRESCHI L. (2008). Adhesion to chondroitinase ABC treated dentin. JOURNAL OF BIOMEDICAL MATERIALS RESEARCH. PART B, APPLIED BIOMATERIALS, vol. 86B; p. 228-236, ISSN: 1552-4981 MAZZONI A, PASHLEY DH, TAY FR, GOBBI P, ORSINI G, RUGGERI A JR, CARRILHO M, TJÄDERHANE L, DI LENARDA R, BRESCHI L. (2009). Immunohistochemical identification of MMP-2 and MMP-9 in human dentin: Correlative FEI SEM/TEM analysis. JOURNAL OF BIOMEDICAL MATERIALS RESEARCH. PART A, vol. 88; p. 697-703, ISSN: 1549-3296 MAZZONI A, VISINTINI E, VITA F, PASQUANTONIO G, SABOIA V, RUGGERI A JR, DORIGO E, BRESCHI L. (2009). ElectroBond improves dentin impregnation of etchand-rinse adhesives. JOURNAL OF ADHESIVE DENTISTRY, vol. 11; p. 27-33, ISSN: 1461-5185 MONTANARO L, CAMPOCCIA D, RIZZI S, DONATI ME, BRESCHI L., PRATI C, ARCIOLA CR. (2004). Evaluation of bacterial adhesion of Streptococcus mutans on dental restorative materials. BIOMATERIALS, vol. 25; p. 4457-4463, ISSN: 01429612 MONTANARO L, CERVELLATI M, CAMPOCCIA D, PRATI C, BRESCHI L., ARCIOLA CR. (2005). No genotoxicity of a new nickel-free stainless steel. INTERNATIONAL JOURNAL OF ARTIFICIAL ORGANS, vol. 28; p. 58-65, ISSN: 0391-3988 NAVARRA CO, CADENARO M, ARMSTRONG SR, JESSOP J, ANTONIOLLI F, SERGO V, DI LENARDA R, BRESCHI L. (2009). Degree of conversion of Filtek Silorane Adhesive System and Clearfil SE Bond within the hybrid and adhesive layer: An in situ Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 139 96 BRESCHI Lorenzo 97 BRESCHI Lorenzo 98 BRESCHI Lorenzo 99 BRESCHI Lorenzo 100 BRESCHI Lorenzo 101 BRESCHI Lorenzo 102 BRESCHI Lorenzo 103 BRESCHI Lorenzo 104 BRESCHI Lorenzo 105 BRESCHI Lorenzo 106 BRESCHI Lorenzo 107 BRESCHI Lorenzo 108 BRESCHI Lorenzo 109 BRESCHI Lorenzo Raman analysis. DENTAL MATERIALS, vol. 52; p. 1178-1185, ISSN: 0109-5641 NAVARRA CO, CADENARO M, CODAN B, MAZZONI A, SERGO V, DE STEFANO DORIGO E, BRESCHI L. (2009). Degree of conversion and interfacial nanoleakage expression of three one-step self-etch adhesives. EUROPEAN JOURNAL OF ORAL SCIENCES, vol. 117; p. 463-469, ISSN: 0909-8836 NISHITANI Y, YOSHIYAMA M, WADGAONKAR B, BRESCHI L., MANNELLO N, MAZZONI A, CARVALHO R, TJADERHANE L, TAY FR, PASHLEY DH (2006). Activation of gelatinolytic/collagenolytic activity in dentin by selfetching adhesives. EUROPEAN JOURNAL OF ORAL SCIENCES, vol. 114; p. 160-166, ISSN: 0909-8836 ORSINI G, RUGGERI A JR, MAZZONI A, NATO A, FALCONI M, DI LENARDA R, NANCI A, BRESCHI L. (2008). Immunohistochemical Localization of DMP1 in Human Dentin. EUROPEAN JOURNAL OF HISTOCHEMISTRY, vol. 52; p. 215-220, ISSN: 1121-760X ORSINI G, RUGGERI A JR, MAZZONI A, PAPA V, MAZZOTTI G, DI LENARDA R, BRESCHI L. (2007). Immunohistochemical identification of decorin and biglycan in human dentin: a correlative FEI-SEM/TEM study. CALCIFIED TISSUE INTERNATIONAL, vol. 81; p. 39-45, ISSN: 0171-967X ORSINI G, RUGGERI A JR, MAZZONI A, PAPA V, PICCIRILLI M, FALCONI M, DI LENARDA R, BRESCHI L. (2007). Immunohistochemical identification of type I and type III collagen and chondroitin sulphate in human predentine: a correlative FEISEM/TEM study. INTERNATIONAL ENDODONTIC JOURNAL, vol. 40; p. 669-678, ISSN: 0143-2885 PASHLEY DH, TAY FR, YIU CKY, HASHIMOTO M, BRESCHI L., ITO S. (2004). Collagen degradation by host-derived enzymes during aging. JOURNAL OF DENTAL RESEARCH, vol. 83; p. 216-221, ISSN: 0022-0345 PASQUANTONIO G, TAY FR, MAZZONI A, SUPPA P, RUGGERI A JR, FALCONI M, DI LENARDA R, BRESCHI L. (2007). Electric device improves bonds of simplified etchand-rinse adhesives. DENTAL MATERIALS, vol. 23; p. 513-518, ISSN: 0109-5641 PRATI C, CHERSONI S, ACQUAVIVA GL, BRESCHI L., SUPPA P, TAY FR, PASHLEY DH. (2005). Permeability of marginal hybrid layers in composite restorations. CLINICAL ORAL INVESTIGATIONS, vol. 9; p. 1-7, ISSN: 1432-6981 PRATI C, NUCCI C, TOLEDANO M, GARCIAGODOY F, BRESCHI L., CHERSONI S (2004). Microleakage and marginalhybrid layer formation of compomer restorations. OPERATIVE DENTISTRY, vol. 29; p. 35-41, ISSN: 0361-7734 RUGGERI A JR, MONTEBUGNOLI L, MATTEUCCI A, ZINI N, SOLIMANDO L, SERVIDIO D, SUPPA P, CADENARO M, COCCO L, BRESCHI L. (2005). Cyclosporin A specifically affects nuclear PLC?1 in immunodepressed hearth transplant patients with gingival overgrowth. JOURNAL OF DENTAL RESEARCH, vol. 84; p. 747-751, ISSN: 0022-0345 RUGGERI A JR, PRATI C, MAZZONI A, NUCCI S, DI LENARDA R, MAZZOTTI G, BRESCHI L. (2007). Immunohistochemical analysis of type I collagen and chondroitin 4/6 sulphate of root dentin. ARCHIVES OF ORAL BIOLOGY, vol. 52; p. 1-8, ISSN: 0003-9969 RUGGERI A, ORSINI G, MAZZONI A, NATO F, PAPA V, PICCIRILLI M, PUTIGNANO A, MAZZOTTI G, DE STEFANO DORIGO E, BRESCHI L. (2009). Immunohistochemical and biochemical assay of versican in human sound predentine/dentine matrix. EUROPEAN JOURNAL OF HISTOCHEMISTRY, vol. 53; p. 125-134, ISSN: 1121-760X SABOIA VPA, NATO F, MAZZONI A, ORSINI G, PUTIGNANO A, GIANNINI M, BRESCHI L. (2008). Adhesion of a twostep etch-and-rinse adhesive on collagendepleted dentin. JOURNAL OF ADHESIVE DENTISTRY, vol. 10; p. 419-422, ISSN: 1461-5185 SABOIA VPA, SILVA FCFA, NATO F, MAZZONI A, CADENARO M, MAZZOTTI G, GIANNI M, BRESCHI L. (2009). Analysis of differential ageing of the adhesive Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 140 110 BRESCHI Lorenzo 111 BRESCHI Lorenzo 112 BRESCHI Lorenzo 113 BRESCHI Lorenzo 114 BRESCHI Lorenzo 115 BRESCHI Lorenzo 116 BRESCHI Lorenzo 117 BRESCHI Lorenzo 118 BRESCHI Lorenzo 119 BRESCHI Lorenzo 120 BRESCHI Lorenzo 121 BRESCHI Lorenzo 122 BRESCHI Lorenzo interface produced by a two-step etch-and-rinse adhesive. EUROPEAN JOURNAL OF ORAL SCIENCES, vol. 117; p. 618-624, ISSN: 0909-8836 SANDRUCCI MA, NICOLIN V, BIASOTTO M, BRESCHI L., CASAGRANDE L, DI LENARDA R, GRILL V (2004). The adhesion of Flow 2002 fibroblasts to titanium implant materials is influenced by different surface topographies and is related to the immunocytochemical expression of fibronectin. JOURNAL OF APPLIED BIOMATERIALS & BIOMECHANICS, vol. 2; p. 169-176, ISSN: 1722-6899 SANDRUCCI MA, NICOLIN V, CASAGRANDE L, BIASOTTO M, BRESCHI L., DI LENARDA R, SANCILIO S, GRILL V (2005). Preconditioning of dental alloys: analysis of fibroblast proliferation and expression of fibronectin and chondroitin sulphate. JOURNAL OF MATERIALS SCIENCE, vol. 40; p. 6233-6240, ISSN: 0022-2461 SANTOS J, CARRILHO MR, TERVAHARTIALA T, SORSA T, FERRAZ C, BRESCHI L., MAZZONI A, PASHLEY DH, TJÄDERHANE L (2009). Determination of matrix metalloproteinases in human radicular dentin. JOURNAL OF ENDODONTICS, vol. 35; p. 686-689, ISSN: 0099-2399 SAURO S, WATSON TF, TAY FR, CHERSONI S, BRESCHI L., BERNARDI F, PRATI C (2006). Water uptake of bonding systems applied on root dentin surfaces: SEM and confocal microscopic study. DENTAL MATERIALS, vol. 22; p. 671-680, ISSN: 0109-5641 SAVARINO L, BRESCHI L., TEDALDI M, BALDINI N, PRATI C (2004). Ability of restorative and fluoride releasing materials to prevent marginal dentin demineralization. BIOMATERIALS, vol. 25; p. 1011-1017, ISSN: 0142-9612 SAVARINO L, GRECO M, BALDINI N, GIUNTI A, PISTONE M, MARCHIONNI S, BRESCHI L., PRATI C (2008). Evaluation of restorative materials with a new perfusion system. JOURNAL OF ADHESIVE DENTISTRY, vol. 10; p. 269-275, ISSN: 1461-5185 STACCHI C, ORSINI G, DI IORIO D, BRESCHI L., DI LENARDA R (2008). Clinical, histologic and histomorphometric analyses of regenerated bone in maxillary sinus augmentation using fresh frozen human bone allografts. JOURNAL OF PERIODONTOLOGY, vol. 79; p. 1789-1796, ISSN: 0022-3492 SUPPA P, BRESCHI L., RUGGERI A, MAZZOTTI G, PRATI C, CHERSONI S, DI LENARDA R, PASHLEY DH, TAY FR (2005). Nanoleakage within the hybrid layer: A correlative FEISEM/TEM investigation. JOURNAL OF BIOMEDICAL MATERIALS RESEARCH. PART B, APPLIED BIOMATERIALS, vol. 73; p. 7-14, ISSN: 1552-4981 SUPPA P, RUGGERI A JR, TAY FR, PRATI C, BIASOTTO M, FALCONI M, PASHLEY DH, BRESCHI L. (2006). Reduced antigenicity of type I collagen and proteoglycans in sclerotic dentin. JOURNAL OF DENTAL RESEARCH, vol. 85; p. 133-137, ISSN: 00220345 TAY FR, LOUSHINE RJ, MONTICELLI F, WELLER NR, BRESCHI L., FERRARI M, PASHLEY DH (2005). Effectiveness of resin-coated gutta-percha cones and a dualcured, hydrophilic methacrylate resin-based sealer in obturating root canals. JOURNAL OF ENDODONTICS, vol. 31; p. 659-664, ISSN: 0099-2399 TAY FR, MAZZONI A, PASHLEY DH, DAY TE, NGOH EC, BRESCHI L. (2006). Potential iatrogenic tetracycline staining of endodontically treated teeth via NaOCl/MTAD irrigation - a preliminary report. JOURNAL OF ENDODONTICS, vol. 32; p. 354-358, ISSN: 0099-2399 TETI G, MAZZOTTI G, ZAGO M, ORTOLANI M, BRESCHI L., PELOTTI S, RUGGERI A, FALCONI M (2009). HEMA down-regulates procollagen ?1 type I in human gingival fibroblasts. JOURNAL OF BIOMEDICAL MATERIALS RESEARCH. PART A, vol. 90; p. 256-262, ISSN: 1549-3296 VENTURI M, BRESCHI L. (2004). Evaluation of apical filling after warm vertical compaction using different procedures. JOURNAL OF ENDODONTICS, vol. 30; p. 436-440, ISSN: 0099-2399 Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 141 123 BRESCHI Lorenzo 124 BRESCHI Lorenzo 125 BRESCHI Lorenzo 126 BRESCHI Lorenzo 127 BRESCHI Lorenzo 128 BRESCHI Lorenzo 129 BRESCHI Lorenzo 130 CADENARO Milena 131 CADENARO Milena 132 CADENARO Milena 133 CADENARO Milena 134 CADENARO Milena 135 CADENARO Milena 136 CADENARO Milena 137 CADENARO VENTURI M, BRESCHI L. (2005). A comparison between two electronic apex locators: an in vivo investigation. INTERNATIONAL ENDODONTIC JOURNAL, vol. 38; p. 36-45, ISSN: 0143-2885 VENTURI M, BRESCHI L. (2007). A comparison between two electronic apex locators: an ex-vivo investigation. INTERNATIONAL ENDODONTIC JOURNAL, vol. 40; p. 362-373, ISSN: 0143-2885 VENTURI M, DI LENARDA R, BRESCHI L. (2006). An ex vivo comparison of three different gutta-percha cones when compacted at different temperatures: rheological considerations in relation to the filling of lateral canals. INTERNATIONAL ENDODONTIC JOURNAL, vol. 31; p. 877-881, ISSN: 0143-2885 VENTURI M, DI LENARDA R, PRATI C, BRESCHI L. (2005). An in vitro model to investigate filling of lateral canals. JOURNAL OF ENDODONTICS, vol. 31; p. 877881, ISSN: 0099-2399 VISINTINI E, MAZZONI A, VITA F, PASQUANTONIO G, CADENARO M, DI LENARDA R, BRESCHI L. (2008). Effects of thermocycling on bonds created by simplified onestep self-etch adhesives applied with ElectroBond. EUROPEAN JOURNAL OF ORAL SCIENCES, vol. 116; p. 564-570, ISSN: 0909-8836 YIU CKY, HIRAISHI N, CHERSONI S, BRESCHI L., FERRARI M, PRATI C, KING NNM, PASHLEY DH, TAY FR (2006). Single-bottle adhesives behave as permeable membranes after polymerisation. II. Differential permeability reduction with oxalate desensitiser. JOURNAL OF DENTISTRY, vol. 34; p. 106-116, ISSN: 03005712 ZAGO M, TETI G, MAZZOTTI G, RUGGERI A JR, BRESCHI L., PELOTTI S, ORTOLANI M, FALCONI M (2008). Expression of procollagen ?1 type I and tenascin proteins induced by HEMA in human pulp fibroblasts. TOXICOLOGY IN VITRO, vol. 22; p. 1153-1159, ISSN: 0887-2333 BEVILACQUA L, BIASOTTO M, CADENARO M., DI LENARDA R., DORIGO E. (2005). Reaction exothermia of 2 relining resins for temporary crowns. MINERVA STOMATOLOGICA, vol. 54; p. 35-41, ISSN: 0026-4970 BEVILACQUA L, CADENARO M., SOSSI A, BIASOTTO M, DI LENARDA R (2007). Influence of air abrasion and etching on enamel and adaptation of a dental sealant. EUROPEAN JOURNAL OF PAEDIATRIC DENTISTRY, vol. 8(1); p. 25-30, ISSN: 1591-996X BEVILACQUA L, SOSSI A, CADENARO M., DI LENARDA R (2007). Comparative evaluation of the microhardness of 4 dental sealants. 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SCHINTKE, M.STENGEL, L. COLOMBI CIACCHI, W-D.SCHNEIDER, M.SVETINA, J.V.BARTH, O. SBAIZERO, S.ROITTI, S.MERIANI, A. DE VITA (2004). Modeling nucleation and insulating properties of oxide surfaces and ultrathin films. KEY Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 152 278 DE VITA Alessandro 279 DE VITA Alessandro 280 DE VITA Alessandro 281 DI LENARDA Roberto 282 DI LENARDA Roberto 283 DI LENARDA Roberto 284 DI LENARDA Roberto 285 DI LENARDA Roberto 286 DI LENARDA Roberto 287 DI LENARDA Roberto 288 DI LENARDA Roberto 289 DI LENARDA Roberto 290 DI LENARDA Roberto 291 DI LENARDA Roberto ENGINEERING MATERIALS, vol. 264-268; p. 485, ISSN: 1013-9826 S. SCHINTKE, M.STENGEL, L. COLOMBI CIACCHI, W-D.SCHNEIDER, M.SVETINA, J.V.BARTH, O. SBAIZERO, S.ROITTI, S.MERIANI, A. DE VITA (2004). Modeling nucleation and insulating properties of oxide surfaces and ultrathin films. KEY ENGINEERING MATERIALS, vol. 264; p. 485-489, ISSN: 1013-9826 S.PISCANEC, F.ZULIANI, L.C.CIACCHI, G.LEVITA, O.SBAIZERO, A. DE VITA (2007). Density Functional-based Atomistic Modelling of Ceramic Materials and Interfaces. INTERNATIONAL JOURNAL OF MATERIALS & PRODUCT TECHNOLOGY, vol. ?; p. ?, ISSN: 0268-1900 S.PISCANEC, L.C.CIACCHI, E.VESSELLI, G.COMELLI, O.SBAIZERO, S.MERIANI, A. DE VITA (2004). Bioactivity of TiN-coated titanium implants. ACTA MATERIALIA, vol. 52; p. 1237, ISSN: 1359-6454 BEVILACQUA L, BIASOTTO M, CADENARO M, DI LENARDA R., DORIGO E. (2005). Reaction exothermia of 2 relining resins for temporary crowns. MINERVA STOMATOLOGICA, vol. 54; p. 35-41, ISSN: 0026-4970 BEVILACQUA L, CADENARO M, SOSSI A, BIASOTTO M, DI LENARDA R. (2007). Influence of air abrasion and etching on enamel and adaptation of a dental sealant. EUROPEAN JOURNAL OF PAEDIATRIC DENTISTRY, vol. 8; p. 25-30, ISSN: 1591-996X BEVILACQUA L, SOSSI A, CADENARO M, DI LENARDA R. (2007). 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Polymerization kinetics of dental adhesives cured with LED: correlation between extent of conversion and permeability. DENTAL MATERIALS, vol. 23; p. 1066-1072, ISSN: 0109-5641 BRESCHI L, CADENARO M, ANTONIOLLI F, VISINTINI E, TOLEDANO M, DI LENARDA R. (2007). Extent of polymerization of dental bonding systems on bleached enamel. AMERICAN JOURNAL OF DENTISTRY, vol. 20; p. 275-280, ISSN: 0894-8275 BRESCHI L, CAMMELLI F, VISINTINI E, MAZZONI A, VITA F, CARRILHO M, CADENARO M, FOULGER S, MAZZOTI G, TAY FR, DI LENARDA R., PASHLEY D (2009). Influence of chlorhexidine concentration on the durability of etch-andrinse dentin bonds: a 12-month in vitro study. JOURNAL OF ADHESIVE DENTISTRY, vol. 11; p. 191-198, ISSN: 1461-5185 BRESCHI L, MAZZONI A, PASHLEY DH, PASQUANTONIO G, RUGGERI A, SUPPA P, MAZZOTTI G, DI LENARDA R., TAY FR (2006). Electric-current-assisted Application of Self-etch Adhesives to Dentin. JOURNAL OF DENTAL RESEARCH, vol. 85; p. 1092-1096, ISSN: 0022-0345 BRESCHI L, MAZZONI A, RUGGERI A, CADENARO M, DI LENARDA R., DE STEFANO DORIGO E (2008). Dental adhesion review: Aging and stability of the bonded interface. DENTAL MATERIALS, vol. 24; p. 90-101, ISSN: 0109- 5641 Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 153 292 DI LENARDA Roberto 293 DI LENARDA Roberto 294 DI LENARDA Roberto 295 DI LENARDA Roberto 296 DI LENARDA Roberto 297 DI LENARDA Roberto 298 DI LENARDA Roberto 299 DI LENARDA Roberto 300 DI LENARDA Roberto 301 DI LENARDA Roberto 302 DI LENARDA Roberto 303 DI LENARDA Roberto 304 DI LENARDA Roberto 305 DI LENARDA Roberto 306 DI LENARDA Roberto 307 DI LENARDA CADENARO M, ANTONIOLLI F, SAURO S, TAY FR, DI LENARDA R., PRATI C, BIASOTTO M, CONTARDO L, BRESCHI L. (2005). Degree of conversion and permeability of dental adhesives. EUROPEAN JOURNAL OF ORAL SCIENCES, vol. 113(6); p. 525-530, ISSN: 0909-8836 CADENARO M, BIASOTTO M, CONTARDO L, CHIESA R, DI LENARDA R., DORIGO E (2006). Surface roughness of three resin restorative materials after finishing and polishing. MINERVA STOMATOLOGICA, vol. 55; p. 179-187, ISSN: 0026-4970 CADENARO M, BIASOTTO M, SCUOR N, BRESCHI L, DAVIDSON CL, DI LENARDA R. (2008). Assessment of polymerization contraction stress of three composite resins. DENTAL MATERIALS, vol. 24; p. 681-685, ISSN: 0109- 5641 CADENARO M, BRESCHI L, ANTONIOLLI A, MAZZONI A, DI LENARDA R. (2006). Influence of whitening on the degree of conversion of dental adhesives on dentin. EUROPEAN JOURNAL OF ORAL SCIENCES, vol. 114; p. 257- 262, ISSN: 0909-8836 CADENARO M, BRESCHI L, ANTONIOLLI F, NAVARRA CO, MAZZONI A, TAY FR, DI LENARDA R., PASHLEY DH (2008). Degree of conversion of resin blends in relation to ethanol content and hydrophilicity. DENTAL MATERIALS, vol. 24; p. 1194-1200, ISSN: 0109-5641 CADENARO M, BRESCHI L, ANTONIOLLI F, VISINTINI E, DORIGO E, DI LENARDA R. (2006). Effetto delle lampade LED sulla microdurezza degli adesivi smaltodentinali. GIORNALE ITALIANO DI CONSERVATIVA, ISSN: 1724-2908 CADENARO M, BRESCHI L, NUCCI C, ANTONIOLLI F, VISINTINI E, PRATI C, MATIS BA, DI LENARDA R. (2008). Effect of two in-office whitening agents on enamel surface in vivo: a morphological and non contact profilometric study. OPERATIVE DENTISTRY, vol. 33; p. 127-134, ISSN: 0361-7734 CADENARO M, BRESCHI L, RUEGGEBERG FA, AGEE K, DI LENARDA R., CARRILHO M, TAY FR, PASHLEY DH (2009). Effect of adhesive hydrophilicity and curing-time on the permeability of resins bonded to water vs. ethanolsaturated acid-etched dentin. DENTAL MATERIALS, vol. 25; p. 39-47, ISSN: 0109-5641 CADENARO M, BRESCHI L, RUEGGEBERG FA, SUCHKO M, GRODIN E, AGEE K, DI LENARDA R., TAY FR, PASHLEY DH (2009). 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Clinical and diagnostic imaging of bisphosphonate-associated osteonecrosis of the jaws. DENTOMAXILLOFACIAL RADIOLOGY, vol. 35; p. 236-243, ISSN: 0250-832X CONTARDO L, CESCHI M, CASTALDO A, DENOTTI G, DI LENARDA R. (2008). Differences in skeletal Class II diagnosis using various cephalometric analyses. JOURNAL OF CLINICAL ORTHODONTICS, vol. 42; p. 389-392, ISSN: 0022-3875 CONTARDO L, DE LUCA M, BEVILACQUA L, BRESCHI L, DI LENARDA R. (2007). Influence of calcium hydroxide debris on the quality of endodontic apical seal. MINERVA STOMATOLOGICA, vol. 56; p. 509-517, ISSN: 0026-4970 CONTARDO L, MENEGUZZI E, CADENARO M, DI LENARDA R. (2005). CLINICAL Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 154 Roberto 308 DI LENARDA Roberto 309 DI LENARDA Roberto 310 DI LENARDA Roberto 311 DI LENARDA Roberto 312 DI LENARDA Roberto 313 DI LENARDA Roberto 314 DI LENARDA Roberto 315 DI LENARDA Roberto 316 DI LENARDA Roberto 317 DI LENARDA Roberto 318 DI LENARDA Roberto 319 DI LENARDA Roberto 320 DI LENARDA EVALUATION OF ANTIBIOTIC PROPHYLAXIS BEFORE ENDODONTIC TREATMENT OF NECROTIC TEETH. MINERVA STOMATOLOGICA, vol. 54; p. 153-160, ISSN: 00264970 DE IUDICIBUS S, CASTRONOVO G, GIGANTE A, STOCCO G, DECORTI G, DI LENARDA R., BARTOLI F (2008). Role of MDR1 gene polymorphisms in gingival overgrowth induced by cyclosporine in transplant patients. JOURNAL OF PERIODONTAL RESEARCH, vol. 43; p. 665-672, ISSN: 0022-3484 DORE F, FILIPPI L, BIASOTTO M, CHIANDUSSI S, CAVALLI F, DI LENARDA R. (2009). Bone scintigraphy and SPECT/CT of bisphosphonate-induced osteonecrosis of the jaw. THE JOURNAL OF NUCLEAR MEDICINE, vol. 50; p. 30-35, ISSN: 0161-5505 MAZZONI A, MANNELLO F, TAY FR, TONTI GA, PAPA S, MAZZOTTI G, DI LENARDA R., PASHLEY DH, BRESCHI (2007). Zymographic analysis and characterization of MMP-2 and -9 forms in human sound dentin. JOURNAL OF DENTAL RESEARCH, vol. 86; p. 436-440, ISSN: 0022-0345 MAZZONI A, MARCHESI G, CADENARO M, MAZZOTTI G, DI LENARDA R., FERRARI M, BRESCHI L (2009). Push-out stress for fibre posts luted using different adhesive strategies. EUROPEAN JOURNAL OF ORAL SCIENCES, vol. 117; p. 447-453, ISSN: 0909-8836 MAZZONI A, PASHLEY DH, RUGGERI A JR, VITA F, FALCONI M, DI LENARDA R., BRESCHI L (2008). Adhesion to chondroitinase ABC treated dentin. JOURNAL OF BIOMEDICAL MATERIALS RESEARCH. PART B, APPLIED BIOMATERIALS., vol. 86B; p. 228-236, ISSN: 1552-4973 MAZZONI A, PASHLEY DH, TAY FR, GOBBI P, ORSINI G, RUGGERI A JR, CARRILHO M, TJÄDERHANE L, DI LENARDA R., BRESCHI L (2009). Immunohistochemical identification of MMP-2 and MMP-9 in human dentin: Correlative FEISEM/ TEM analysis. JOURNAL OF BIOMEDICAL MATERIALS RESEARCH. PART A, vol. 88; p. 697-703, ISSN: 1549- 3296 MAZZONI A, VISINTINI E, VITA F, PASQUANTONIO G, SABOIA VP, RUGGERI A JR, DI LENARDA R., DORIGO E, BRESCHI L (2009). ElectroBond improves immediate dentin microtensile bond strength of two etch-and-rinse adhesives. JOURNAL OF ADHESIVE DENTISTRY, vol. 11; p. 27-33, ISSN: 1461-5185 MOIMAS L, BIASOTTO M, DI LENARDA R., OLIVO A, SCHMID C (2006). Rabbit pilot study on the resorbability of three-dimensional bioactive glass fibre scaffolds. ACTA BIOMATERIALIA, vol. 2; p. 191-199, ISSN: 1742-7061 NAVARRA CO, CADENARO M, ARMSTRONG SR, JESSOP J, ANTONIOLLI F, SERGO V, DI LENARDA R., BRESCHI L (2009). Degree of conversion of Filtek Silorane Adhesive System and Clearfil SE Bond within the hybrid and adhesive layer: an in situ Raman analysis. 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Versluis "History force on coated Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 203 990 991 992 993 994 995 996 997 998 999 1000 1001 1002 microbubbles propelled by ultrasound" , Physics of Fluids (accepted July 2009). D. Cojoc, H. Amenitsch, C. Riekel, M. Rappolt, M. Burghammer, S. Santucci, G. Grenci, B. Sartori, B. Marmiroli, "X-ray microdiffraction of microsamples manipulated in fluidic environment without mechanical contact", ESRF Highlights 2008 48-49 http://www.esrf.eu/files/Highlights/HL2008.pdf .(2009) V. Garbin, G. Volpe, E. Ferrari, M. Versluis, D. Cojoc and D. Petrov, "Mie scattering distinguishes the topological charge of an optical vortex: a homage to Gustav Mie", New Journal of Physics, 11, 013046, (2009). E. Connell, A. Giniatullina, J.L.K. Him, P. Scott, E. Ferrari, A. Roseman, D. Cojoc, A.R. Brisson and B. Davletov, "Crosslinking of Phospholipid Membranes is a Conserved Property of Calcium-Sensitive, Synaptotagmins", J. Mol. Biol. 380 42 (2008). M. Mihailescu, A. Preda, D. Cojoc, E. Scarlat, L. Preda, "Diffractive patterns from a phyllotaxis type arrangement", Opt. Laser Eng. 46, 802-809, (2008). J. Garcia, V. Mico, D. Cojoc and Z. Zalevsky, "Full field of view superresolution imaging based on two static gratings and white illumination", Appl. Opt. 47(17) 3080 (2008). D. Cojoc, E. Ferrari, V. Garbin, E. Di Fabrizio, H. Amenitsch, M. Rappolt, B. Sartori, P. Laggner, M. Burghammer, C. Riekel, "Scanning x-ray microdiffraction of optically manipulated liposomes", Appl. Phys. Lett. 91 234107 (2007). D. Cojoc, E. Ferrari, F. Difato, R. Shahapure, J. Laishram, M. Righi, E. Di Fabrizio, Vincent Torre, "Properties of the force exerted by filopodia and lamellipodia and the involvement of cytoskeletal components", PLoS ONE 2(10): e1072. doi:10.1371/journal.pone.0001072 (2007). H. Amenitsch, E. Ferrari, M. Rappolt, B. Sartori, P. Laggner, V. Garbin, E. Di Fabrizio, M. Burghammer, C. Riekel, D. Cojoc "Development of optical tweezers for sample fixing in microdiffraction experiments" ESRF, Newsletter 45 26 (2007) M. Mihailescu, A. Preda, D. Cojoc, L. Preda E. Scarlat, I.M. Popescu, "Intensity redistribution in diffractive pattern due to fractal phase changes", J. Optoel. Adv. Mat. June 2007. Moradi, E. Ferrari, V. Garbin, E. Di Fabrizio, D. Cojoc, "Strength control in multiple optical traps generated by means of diffractive optical elements",.Optoelectronics and Advanced Materials - Rapid Communications 1 158 (2007). V. Garbin, D. Cojoc, E. Ferrari, E. Di Fabrizio, M. Overvelde, M. Versluis, S. van der Meer, N. de Jong, D. Lohse "Changes in microbubble dynamics near a boundary revealed by combined optical micromanipulation and high-speed imaging", Appl. Phys. Lett. 90 114103 (2007). M. Mihailescu, A. Preda, D. Cojoc, E. Scarlat, L. Preda, "Diffractive patterns correlation with shape and structure of imprint objects", J. Optoel. Adv. Mat. 9 1071 (2007). A. Alexandrescu, D. Cojoc, and E. Di Fabrizio, "Mechanism of Angular Momentum Exchange between Molecules and Laguerre-Gaussian Beams", Phys. Rev. Lett. 96 243001 (2006) Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 204 9.Criteri di valuatazione delle scuole di dottorato Si riportano di seguito i criteri di valutazione delle scuole di dottorato utilizzati dal nucleo previa approvazione degli organi accademici (questi sono i criteri adottati per la valutazione del 2008). 1. INTRODUZIONE E RIFERIMENTI LEGISLATIVI L‟attività di valutazione dei requisiti di idoneità dei corsi di dottorato di ricerca viene effettuata dal Nucleo di Valutazione (entrato in carica per il triennio 2006-2009 con DR 102/07 del 23/01/07 e riconfermato per il triennio 2009-2012 con D.R. 1817/09) in adempimento al disposto di cui al primo comma dell'art.3 del D.M. 30 aprile 1999, n. 224.I riferimenti legislativi sono i seguenti: D.M. 30 aprile 1999 n. 224 “Regolamento in materia di Dottorato di ricerca”, art.3 comma 2; Circolare M.I.U.R (Dipartimento per l‟Università, l‟Alta Formazione Artistica, Musicale e Coreutica e per la Ricerca Scientifica e Tecnologica – Direzione Generale per l‟Università Ufficio IX) prot. 323, dd. 21/02/2006; Regolamento in materia di Dottorato di Ricerca dell‟Università degli Studi di Trieste (D.R. n. 908/AG dd. 08/10/99, ultima modifica D.R. n. 1867/2006 dd. 30/10/06); Regolamento Generale per le Scuole di Dottorato dell‟Università di Trieste (D.R. n.1188/2006 dd. 14/7/06). I requisiti di idoneità, in base ai quali sarà condotta la valutazione dei Corsi di Dottorato, sono quelli previsti dal D.M. 224/99: a) la presenza nel collegio dei docenti di un congruo numero di professori e ricercatori dell'area scientifica di riferimento del corso; b) la disponibilità di adeguate risorse finanziarie e di specifiche strutture operative e scientifiche per il corso e per l‟attività di studio e di ricerca dei dottorandi; c) la previsione di un coordinatore responsabile dell‟organizzazione del corso, di un collegio di docenti e di tutori in numero proporzionato ai dottorandi e con documentata produzione scientifica nell‟ultimo quinquennio nell‟area di riferimento del corso; d) la possibilità di collaborazione con soggetti pubblici o privati, italiani o stranieri, che consenta ai dottorandi lo svolgimento di esperienze in un contesto di attività lavorative; e) la previsione di percorsi formativi orientati all'esercizio di attività di ricerca di alta qualificazione presso università, enti pubblici o soggetti privati; f) l‟attivazione di sistemi di valutazione relativi alla permanenza dei requisiti di cui al presente comma, alla rispondenza del corso agli obiettivi formativi di cui all‟articolo 4, anche in relazione agli sbocchi professionali, al livello di formazione dei dottorandi; e il requisito aggiuntivo previsto dal regolamento di Ateneo: la presenza nel Collegio dei docenti (…) di almeno dieci docenti di ruolo presenti in maniera esclusiva in quel Collegio. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 205 Il MIUR (circolare Prot.323, dd. 21/2/2006), “al fine di consentire l‟adozione di criteri omogenei di valutazione da parte dei Nuclei e di disporre di informazioni in grado di permettere un‟analisi comparativa dello stato dei dottorati nelle diverse sedi e nei diversi ambiti disciplinari”, ha inviato ai Nuclei di Valutazione uno schema di valutazione, proposto dal Comitato Nazionale per la Valutazione del Sistema Universitario, da utilizzare per la verifica dei requisiti di idoneità dei dottorati di ricerca di ciascuna sede. Tale schema, confermato anche dalla circolare MIUR n.124 del 2/2/2007, consiste in un questionario di domande che vanno a definire i requisiti del D.M. 224/99 in modo puntuale e operativo, individuando alcuni aspetti che i Nuclei devono analizzare per le loro valutazioni. I Nuclei sono, quindi, chiamati dal Ministero a formulare un giudizio motivato e ad esprimere una valutazione di merito su ciascun dottorato per ciascuno degli aspetti individuati. Per quanto riguarda le Scuole di Dottorato, in base all‟art.2, comma 8 del relativo regolamento, oltre ai requisiti già individuati dal D.M. 224/99, è necessario verificare la sussistenza dei seguenti ulteriori requisiti: g) l‟esistenza di un progetto formativo e di ricerca che illustri dettagliatamente gli obiettivi scientifico-formativi relativamente a tematiche sufficientemente ampie e, ove possibile, a carattere interdisciplinare; h) l‟inserimento dei percorsi formativi all‟interno di documentate iniziative di collaborazione internazionale anche attraverso il coinvolgimento di una qualificata docenza internazionale i) la documentata esistenza di iniziative rivolte ad attirare finanziamenti da parte di Enti pubblici e privati finalizzati all‟erogazione di borse di studio e di contributi di funzionamento; j) la documentata esistenza di iniziative rivolte alla pubblicizzazione verso l’esterno sia delle modalità di selezione e accesso sia delle attività scientifico-didattiche, allo scopo di ottimizzare l‟attrattività della Scuola, con particolare attenzione per i potenziali candidati stranieri. Inoltre, in base all‟art.4.2, è previsto tra gli organi della Scuola un Consiglio Scientifico costituito da almeno 5 componenti. Infine, ai sensi dell‟art.5 “1. La Scuola di Dottorato può articolarsi in indirizzi. L’articolazione in indirizzi, che deve essere giustificata sulla base di adeguate motivazioni scientifico-culturali e che deve riferirsi ad un programma formativo relativo a un ambito disciplinare sufficientemente ampio (…). 2. Un indirizzo può essere attivato soltanto qualora: (…) b. sussista nel Collegio la presenza di almeno quattro docenti non soprannumerari afferenti ai settori scientifico-disciplinari caratterizzanti l’indirizzo in modo esclusivo; c. siano assegnate all’indirizzo almeno due borse.” 2. PROCEDURA DI VALUTAZIONE 2.1 Presentazione delle domande e tempistica della valutazione Le domande di attivazione di Scuole di Dottorato e di Istituzione/Rinnovo di Corsi di Dottorato di Ricerca sono state presentate tramite una nuova procedura elettronica realizzata a cura dalla Divisione ISI denominata ADO, nel periodo dal 22 febbraio 2010 al 22 marzo 2010. Per facilitare il lavoro di compilazione, sono state inserite all’ interno della Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 206 procedura ADO, a cura dell’ Ufficio Studi per la Valutazione tutte le domande di istituzione/rinnovo presentate in forma cartacea per il XXV ciclo (2009). All’inizio della scheda di proposta, sono stati comunicati i criteri che il Nucleo avrebbe utilizzato in sede di valutazione: “ - Produzione scientifica del Collegio Docenti come elemento fondamentale per qualificare le proposte di Dottorato di Ricerca (3° requisito DM.224/99). Il Nucleo potrà utilizzare a tale scopo le informazioni presenti nella banca dati SAPERI, ma desidera che ciascun componente del collegio docenti, in una logica di autovalutazione, indichi sulla propria scheda (allegato1) esclusivamente le 3 pubblicazioni che ritiene più significative degli ultimi 5 anni nell’area di riferimento del dottorato; - congruo numero di docenti dell’Ateneo coinvolti nel collegio (1° requisito DM.224/99); - rapporto del dottorato con il mondo del lavoro, valutato in termini di profilo professionale che si intende formare nonché di monitoraggio dell’inserimento lavorativo di coloro che hanno conseguito il titolo e di verifica della relazione tra gli obiettivi formativi e le specifiche posizioni lavorative (4° requisito DM.224/99); - attrattività del dottorato e della sede nell’ultimo ciclo attivo (rapporto candidati presenti/posti con borsa banditi; rapporto iscritti dottorato provenienti da altri atenei/iscritti totali); - livello di soddisfazione dei dottorandi (informazione ricavata dal questionario inviato agli iscritti ai corsi di dottorato nel novembre 2008); - produzione scientifica dei dottorandi ed iniziative esistenti di pubblicizzazione e referaggio delle tesi di dottorato; - adeguata formulazione delle tematiche scientifiche e degli obiettivi formativi, coerentemente con le risorse disponibili (collegio docenti, progetti di ricerca attivi, strutture di ricerca, risorse finanziarie finalizzate al funzionamento del dottorato); - sintesi nell’esposizione del progetto formativo e accuratezza delle informazioni fornite per la valutazione; - qualità del sito web dedicato al dottorato di ricerca, considerando che “il sito web del dottorato deve essere uno strumento di comunicazione rivolto principalmente ai potenziali studenti (e come va indicato nel bando) e deve contenere tutte le informazioni necessarie all’orientamento dello studente”; - internazionalizzazione, ovvero esistenza di convenzioni con atenei stranieri, attività didattiche in lingua inglese, ecc. - per le scuole di nuova istituzione o che chiedono il rinnovo ai sensi dell’art.3 del regolamento, esistenza di un progetto formativo e di ricerca che illustri dettagliatamente gli obiettivi scientifico formativi relativamente a tematiche sufficientemente ampie e, ove possibile, a carattere interdisciplinare (art.2, comma 9, lett. g del regolamento). Infine, limitatamente alle Scuole di Dottorato che chiedono il rinnovo ai sensi dell’art.3 del Regolamento per le Scuole di dottorato dell'Università degli Studi di Trieste, il Nucleo dovrà disporre anche di una relazione del Direttore che dia conto delle attività effettivamente svolte nei tre cicli precedenti, della produttività scientifica dei docenti, degli iscritti, nonché di coloro che nel frattempo abbiano conseguito il titolo, nonché della relazione del Consiglio Scientifico di cui all’art.6 comma 2 del medesimo Regolamento. Per quanto riguarda le informazioni relative a iscritti al corso di dottorato, studenti che hanno conseguito il titolo, pubblicazioni degli iscritti, il Nucleo provvederà a reperirle autonomamente dalle banche dati di Ateneo o sul sito del corso di dottorato che si richiede sia opportunamente aggiornato. Per quanto riguarda le informazioni necessarie per la verifica della permanenza dei requisiti per i dottorati in corso di svolgimento (ex sezione III- Rinnovo dei dottorati), queste verranno Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 207 richieste in una fase successiva con apposito questionario, in quanto i Nuclei sono in attesa di indicazioni dal MIUR su quali dati dovranno essere analizzati ai fini della valutazione ex-post”. 2.2 Criteri di valutazione 2010 (XXVI ciclo) Il Nucleo ha verificato preliminarmente che nella scheda di ogni componente del collegio fossero state indicate solamente 3 pubblicazioni degli ultimi 5 anni, scelte tra quelle ritenute più significative della produzione scientifica connessa con le tematiche del dottorato. Infatti, poiché il Nucleo ha la possibilità di visualizzare l'intera produzione scientifica dei docenti nella banca dati Saperi/CINECA, ritiene più informativo ed efficace per la valutazione che i docenti selezionino nella proposta la propria produzione di eccellenza. Il Nucleo analizzerà anche con l’ausilio di opportuni indicatori, i seguenti aspetti: − produzione scientifica del Collegio Docenti come elemento fondamentale per qualificare le proposte di Dottorato di Ricerca (3° requisito DM.224/99); − congruo numero di docenti dell’Ateneo coinvolti nel collegio (1° requisito DM.224/99); − rapporto del dottorato con il mondo del lavoro, valutato in termini di profilo professionale che si intende formare (4° requisito DM.224/99); − attrattività del dottorato e della sede nell’ultimo ciclo attivo (rapporto candidati presenti/posti con borsa banditi; rapporto iscritti dottorato provenienti da altri atenei/iscritti totali); − livello di soddisfazione dei dottorandi (informazione ricavata dal questionario inviato agli iscritti ai corsi di dottorato nel novembre 20081); − produzione scientifica dei dottorandi ed iniziative esistenti di pubblicizzazione e refe raggio delle tesi di dottorato; − adeguata formulazione delle tematiche scientifiche e degli obiettivi formativi, coerentemente con le risorse disponibili (collegio docenti, progetti di ricerca attivi, strutture di ricerca, risorse finanziarie finalizzate al funzionamento del dottorato); − accuratezza − sito delle informazioni fornite per la valutazione; web dedicato al dottorato di ricerca. Inoltre, come auspicato dal consiglio delle Strutture Scientifiche, il Nucleo ha valutato, oltre alla capacità di cofinanziamento prevista per il nuovo ciclo, il cofinanziamento effettivo ex post dell’ultimo ciclo attivo e il suo scostamento da quello inizialmente preventivato. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 208 10.Valutazione da parte del nucleo di valutazione dell’Ateneo Criterio ID Dottorato tipo_rec ord nome_dottorato nuova_istituzione anno_attivazione Dipartimento cognome _docente nome_docente Borse cofinanziate Borse richieste all'Ateneo Borse cofinanziate / Tot borse Cofinanziamento dichiarato XXIII (o ultimo ciclo attivo) Cofinanziamento consuntivo XXIII (o ultimo ciclo attivo) Valutazione cofinanzi amen to Posti ordinari Posti ordinari coperti da borsa (vincolo >= 50%) Posti ordinari coperti da borsa (vincolo >= 50%) (consuntiv o bando XXIII ciclo) N. Componenti esclusivi Collegio (vincolo >=10) Attrattività del dottorato (Presenti alla prova esame XXIII o ultimo ciclo attivo/Posti con borsa) Attrattività della sede (Iscritti altro Ateneo/Totale iscritti XXIII o ultimo ciclo attivo) Valutazione attrattività della sede Composizione Collegio docenti eProduzione Scientifica (1° e 3° requisito DM 224/99) Obiettivi formativi e progetto scientifico (1° requisito DM 224/99) Disponibilità risorse e strutture (2° requisito DM 224/99) Rapporto del dottorato con il mondo lavoro (4° requisito DM 224/99) Percorsi formativi orientati alla ricerca (5° requisito DM 224/99) Valutazione sistemi di valutazione (6° requisito DM 224/99) Valutazione sito web Soddisfazione dottorandi (punteggio 1- 5 questionario novembre 2009) Valutazione produzione scientifica dottorandi Valutazione complessi va Valutazione 1028 Scuola di dottorato senza indirzzi NANOTECNOLOGIE Rinnovo 2006 Dipartimento di Fisica Fermeglia Maurizio 5,00 5,00 0,50 0,50 0,50 POSITIVO 17 50,00% 52.94% 34 2,22 40,00% media OTTIMO POSITIVO MOLTO POSITIVO POSITIVO POSITIVO POSITIVO OTTIMO 3.05 OTTIMO A+ (OTTIMO) Il documento completo di valutazione di tutte le scuole di dottorato dell‟università di Trieste è riportato in allegato. Questo documento è utile per posizionare la scuola anche in relativo rispetto alle altre scuole e corsi di dottorati valutati con lo stesso metro. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 209 11. Giudizi dei referee esterni per dottorandi ammessi all’esame finale Di seguito sono riportati i referee esterni scelti dal collegio per ciascuno dei dottorandi: Dottorando/a Titolo tesi Supervisore/Tutore Matteo Maria Reattività e modalità di Luca Gregoratti Dalmiglio ossidazione di nanocluster Alberto Morgante supportati di catalizzatori. Paolo Lacovig Electronic morphology and Reviewer Herbert Over, University D Liebig structure, Alessandro Baraldi Svetlozar Surnev, Karlchemical Silvano Lizzit Franzens-Universitaet reactivity of nanoclusters and low-dimensional systems: fast photoemission spectroscopy studies. Graz, A Barbara Lorenzut Sviluppo di nanostrutturati produzione e dell‟idrogeno. Alessandro UNIUD, I Giovanni Maria Pavan Analisi energetica e strutturale Sabrina Pricl di sistemi organici e inorganici. Le potenzialità della modellistica molecolare. Paola Posocco Simulazione molecolare Maurizio Fermeglia Peter Cummings, multiscala di sistemi Sabrina Pricl Vanderbilt Univ, Oak nanostrutturati Ridge Nat. Lab, US catalizzatori Paolo Fornasiero per la Tiziano Montini purificazione Andrea Travan Nanocomposite systems based Sergio Paoletti on metal nanoparticles and Ivan Donati polysaccharides for biomedical Trovarelli, Ursula Röthlisberger Swiss Fed. Inst. of Techn., Lausanne, CH Martha Lilley, fisico, centro nanotech “CSEM” di Neuchatel, CH applications. Andrea Umeri Analisi dello stato tensionale e Valter Sergo cristallografico in relazione al processo di invecchiamento in compositi sub-micrometrici Zirconia – Allumina Wolfgang Oximatec, D Burger, Vedi dettaglio negli allegati. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 210 12.Presentazioni dei dottorandi al congesso del 2009 Le presentazioni PPT dei dottorandi al congresso del 2010 sono riportate negli allegati. Scuola di dottorato di ricerca in Nanotecnologie: attività 2009 211