PROGRAMME AND ABSTRACT PROGRAMME AND ABSTRACT

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INTERNATIONAL CONGRESS

“THE CENTENARY”

100th

Anniversary of the Italian Chemical Society

Padova, August 31-September 4, 2009

PROGRAMME AND ABSTRACTPROGRAMME AND ABSTRACTPROGRAMME AND ABSTRACTPROGRAMME AND ABSTRACT

by: [email protected] - [email protected]

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ACKNOWLEDGEMENTSACKNOWLEDGEMENTSACKNOWLEDGEMENTSACKNOWLEDGEMENTS

The organisers greatefully acknowledge the financial support listed below:

• Consiglio Nazionale delle Ricerche-I.T.M.

• Comune di Padova

• Università degli Studi di Padova

• Società Chimica Italiana

• C.N.R.-Dipartimento di Progettazione Molecolare

• Consorzio di Ricerca Lagunare (CORILA)

• International Year of Astronomy

• Miteni

• Reckitt Benckiser

• Lundbeck

• Zambon

• FIS

• Glaxo Smith Kline

• Unione Italiana Vini

• Istituto Grappa Veneta

• Oleificio Gabro S.r.l.

• Dipartimento di Chimica, Università della Calabria

• Ministero Beni e Attività Culturali

• Telerete Nordest srl

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Honour Committee

• Presidents of S.C.I.: Gianfranco Pregaglia (1978-1980); Cesare Cardani (1984-1986); Gianfranco Scorrano (1990-1992); Ivano Bertini (1993-1995); Bruno Scrosati (1996-1998); Domenico Spinelli (1999-2001); Giovanni Natile (2002-2004); Luigi Campanella (2008-2010).

• Rectors of Italian Universities: Mario Pasquali (Pisa); Ezio Pelizzetti (Torino); Antonino Recca (Catania).

Scientific and Organizing Committee

• Marino Basato; Renato Bozio; Armando Gennaro; Michele Maggini; Franco Magno; Antonio Marigo; Giorgio Moro; Paolo Maria Scrimin; Eugenio Tondello; Marina Brustolon; Nicola Cardellicchio; Paolo Cescon; Adriana Chilin; Giovani Sindona; Gianfranco Scorrano (chairman).

Local Committee

• Alessandro Bagno, Marcella Bonchio, Tommaso Carofiglio, Mauro Carraro, Giulia Licini,

Michele Maggini, Fabrizio Mancin, Ester Marotta, Enzo Menna, Cristina Paradisi, Leonard

Prins, Federico Rastrelli, Giacomo Saielli, Andrea Sartorel, Paolo Scrimin, Cristiano Zonta

Secretary

M. Elvira Piaia Istituto Tecnologia delle Membrane – Sede Operativa di Padova Dipartimento di Scienze Chimiche Via Marzolo 1 – 35131 – Padova Phone: +39 049 8275253 Fax: +39 049 8275300 E-mail: [email protected]

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WELCOME ADDRESSWELCOME ADDRESSWELCOME ADDRESSWELCOME ADDRESS

Dear Colleagues and Friends,

In the year 2009 we are celebrating the 100th anniversary of the Italian Chemical Society, the scientific association to which about 5000 chemists subscribe; they operate in Italy within Universities, Scientific Research Councils, Schools, Industries. In this same year we are also celebrating the 100th anniversary of the definition of pH, quantity also known to the laymen, and the 25th anniversary of the “Chemistry Games” a competition among high school students which, born in Padova, is now held nationwide with about 30000 students participating to the national finals.

To celebrate these recurrences, chemists organize from August 31 to September 4 an International Congress “The Centenary” where to discuss problems of general interest (job opportunities for young people after the University degree, the chemical industrial settlements in Veneto, the pollution in the Venetian Lagoon) and other issues more specifically connected with chemistry (pH in wine and oil, chemistry and cultural heritage, the Chemistry Games, etc.). The Congress will take place in the “Centro Culturale Altinate-San Gaetano”, in Via Altinate in Padova.

Gianfranco Scorrano Chairman

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CONTENTSCONTENTSCONTENTSCONTENTS

General Information → → → → 6

- Scientific Programme → → → → 7

Abstracts → → → → 10

- List of Plenary Lectures → → → → 11

- List of Invited Lectures → → → → 12

- List of Posters → → → → 16 -

- Abstract Plenary Lectures→ → → → 20

- Abstract Invited Lectures → → → → 32

- Abstract Posters → → → → 70 -

Appendices

- Author Index → → → → 114

- List of Participants → → → → 115

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GENERAL INFORMATIONGENERAL INFORMATIONGENERAL INFORMATIONGENERAL INFORMATION

Symposium venue The meeting will be held at the “Centro Culturale Altinate-San Gaetano” Via Altinate 71, Padova.

Symposium Office The symposium office is located in the “Centro Culturale Altinate-San Gaetano”, in Via Altinate 71 in Padova. A map of the city is available at: http://www.chimica.unipd.it/the-centenary/howto.htm - see Google Michelin Guide The registration desk will be open from: 08,30 to 12,30 and from 15,30 to 17,30 from Monday to Friday In emergency you may call: 328 2149226

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SCIENTIFIC PROGRAMMESCIENTIFIC PROGRAMMESCIENTIFIC PROGRAMMESCIENTIFIC PROGRAMME

MONDAY AUGUST 31

08,30-09,30 REGISTRATION 09.30-10,00 INTRODUCTION: SINDACO, DIRETTORE CNR, DIRETTORE DIP., RETTORE, PRESIDENTE SCI, SCORRANO 10,00-10,15 PAOLO CESCON - UNIVERSITÀ CÀ FOSCARI VENEZIA, PRESIDENTE DEL CORILA"LE PROBLEMATICHE CHIMICO-AMBIENTALI DEL SISTEMA LAGUNARE VENEZIANO" 10,15-10,45 PIER PAOLO CAMPOSTRINI – DIRETTORE DEL CORILA "IL COORDINAMENTO SCIENTIFICO DELLE RICERCHE IN LAGUNA" 10,45-11,15 FABIANA CORAMI - IDPA-CNR VENEZIA "RISANAMENTO DEI SEDIMENTI CONTAMINATI DELLA LAGUNA DI VENEZIA" 11,15-11.45 GABRIELE CAPODAGLIO - UNIVERSITÀ CÀ FOSCARI VENEZIA "SPECIAZIONE CHIMICA DI METALLI NELLE ACQUE DELLA LAGUNA DI VENEZIA" 11.45-12.15 MENEGHINI MEDAL: MAURIZIO RANCAN - UNIVERSITA’ DI PADOVA, “POLINUCLEAR CHROMIUM CHAINS: SYNTHESIS AND MAGNETIC PROPERTIES 14,30-14,50 LUCA SPADONI, RECKITT BENCKISER ITALIA SPA "LOW TEMPERATURE LAUNDRY WASHING, A BETTER CHEMISTRY FOR THE ENVIRONMENT & THE CONSUMER" 14.50-15,10 MARIANO STIVANELLO, GIULIO VOLPE, LUNDBECK “NEW LIFE FOR MATURE PRODUCTS: APPLICATION OF PAT AND QUALITY BY DESIGN ON API MANUFACTURING” 15,10-15.30 ANDREA MISSIO, MITENI SPA "PROCESS DEVELOPMENT AND ELECTROCHEMICAL FLUORINATION: IS A RATIONAL APPROACH POSSIBLE?” 15,30-15,50 LIVIUS COTARCA*, PAOLO MARAGNI E MASSIMO VERZINI ZAMBON ADVANCED FINE CHEMICALS, LONIGO (VI), ITALY "HYDROLYTIC KINETIC RESOLUTION (HKR) IN AN EFFICIENT PROCESS FOR A COMPLEX ACTIVE PHARMACEUTICAL INGREDIENT" 15,50-16,10 A. CASTELLIN*, S. FOGAL, G. ARVOTTI, M. GALVAGNI, E. BERGANTINO – FABBRICA ITALIANA SINTETICI ENANTIOSELECTIVE HYROLYSIS FOR A MOXIFLOXACIN BINDING BLOCK PREPARATION 16,30-18,00 INDUSTRY FAIR: INCONTRO TRA INDUSTRIA E DOTTORANDI E LAUREANDI CHIMICI 18,00-19,00 ETTORE NOVELLINO, UNIVERSITA’ DI NAPOLI: “L’INVENZIONE DELLA SALUTE”

TUESDAY SEPTEMBER 1 90,00-09.40 JENS DUUS, CARLSBERG LABORATORY,DENMARK "100 YEARS OF RESEARCH AT CARLSBERG LABORATORY; FROM PH TO HIGH FIELD NMR SPECTROSCOPY" 09,40-10,20 A.P.DE SILVA, QUEEN'S UNIVERSITY OF BELFAST "THE ROLE OF PH IN CONCEPT-BUILDING FOR MOLECULAR SENSING AND COMPUTING".

10,20-10.40 COFFEE BREAK 10.40-11.20 VALERIA CONTE UNIVERSITY OF ROME TOR VERGATA "EFFICIENT TREATMENT OF IRON GALL INKED PAPERS" WORKSHOP “VINO E GRAPPA”

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11,20-12,00 GIUSEPPE VERSINI (UNIONE ITALIANA VINI) “PARAMETRI ISOTOPICI DELLA GRAPPA INFLUENZATI DALL’ORIGINE E VARIABILI COMPOSITIVE LEGATE AL MIGLIORAMENTO TECNOLOGICO” 12,00-12.30 VINCENZO GERBI, UNIVERSITÀ DI TORINO - "APPLICAZIONI TECNOLOGICHE DELLA CHIMICA DEI POLIFENOLI PER LA PRODUZIONE DI ALCUNI VINI TIPICI" 12,30-13,00 BRUNO FEDRIZZI, UNIVERSITÀ DI PADOVA "I COMPOSTI SOLFORATI NELLE UVE E NEI VINI: PRESENZE, PRECURSORI E TECNICHE ANALITICHE MIRATE" 15,00-15,20 RICCARDO FLAMINI, CENTRO RICERCHE VITIENOLOGICHE DI CONEGLIANO "TECNICHE STRUMENTALI AVANZATE NEGLI STUDI COMPOSITIVI DELL'UVA E DEI VINI"

WORKSHOP “CHEMISTRY AND BIOCHEMISTRY OF OLIVE OIL” 15.20-15.50 GIOVANNI SINDONA, UNIVERSITA’ DELLA CALABRIA, ARCAVACATA DI RENDE " MASS SPECTROMETRY. AN ORPHAN METHODOLOGY FOR OLIVE OIL QUALITY AND SAFETY" 15,50-16,20 ELENA MARTINI, UNIVERSITÀ DI BRESCIA ANTI-INFLAMMATORY EFFECT OF OLEOPENTADIAL ON PRIMARY HUMAN VASCULAR ENDOTHELIAL CELLS 16,40-17,10 ANTONIO PROCOPIO, UNIVERSITA’ DI CATANZARO "THE ORGANIC CHEMISTRY OF OLIVE NUTRACEUTICALS" 18,00-19,00 ROSANGELA MARCHELLI, UNIVERSITA’ DI PARMA - "I SEGRETI MOLECOLARI DELLA GASTRONOMIA"

WEDNESDAY SEPTEMBER 2 09,00-09,40 IVANO BERTINI, UNIVERSITA’ DI FIRENZE - "METALS IN SYSTEMS BIOLOGY", 09,40-10,20 GALILEIAN LECTURE: PIERO RAFANELLI - " CHEMISTRY OF THE UNIVERSE"

10,20-10,50 COFFEE BREAK 10,50-11,30 GALILEIAN LECTURE: PIERLUIGI LUISI, UNIVERSITA’ ROMA III "FROM THE ORIGIN OF LIFE TO COGNITION” 11,30-12,00 VITO CAPRIATI, “REACTION CONTROL BY NON-COVALENT INTERACTIONS: THE INFLUENCE OF AGGREGATION AND SOLVATION ON THE STRUCTURE-REACTIVITY RELATIONSHIP OF LITHIUM OXYGEN CARBENOIDS 12,00-12,30 ANNA LLANES-PALLÀS, “NANOSTRUCTURING OF ORGANIC MATERIALS TEMPLATED BY HYDROGEN BONDING” 15,00-15,15 LAURA BARTALI “SYNTHESIS OF PEPTIDOMIMETICS AND THEIR APPLICATION AS DIAGNOSTICS AND THERAPEUTICS” 15,15-15,30 MARIA GRAZIA BARTOLOZZI “SYNTHESIS AND ANTIOXIDANT ACTIVITY OF 4-THIATOCOPHEROLS” 15,30-15,45 DAVIDE BINI “SYNTHESIS AND NMR CHARACTERIZATION OF NEOPEPTIDES CONTAINING A FRUCTOSE-BASED PROLINE ANALOGUE” 15,45-16,00 FRANCESCO DE VINCENTIIS “DEVELOPMENT OF NEW DOMINO ORGANOCATALYZED SYSTEMS FOR THE SYNTHESIS OF COMPLEX CHIRAL MOLECULES” 16,00-16,15 VINCENZO FINO, “NOVEL PHOSPHORESCENT FLUORINE FUNCTIONALIZED IRIDIUM COMPLEXES” 16,15-16,30 MAURO MAZZELLA “NOVEL PALLADIUM AND COPPER BASED METALLOMESOGENS FROM TIOPHENE CONTAINING LIGANDS” 16,30-16,45 FRANCESCA ROSATO “OXAZIRIDINES FOR THE 2,3-DIHYDRO-1,2,4-OXADIAZOLES SYNTHESIS” 16,45-17,00 ANTONIO SALOMONE “ON THE CONFIGURATION STABILITY OF α-LITHIATED ARYLOXIRANES”

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17,00-17,15 STEFANO SANTORO “PhSeZnCl IN NUCLEOPHILIC VINYLIC SUBSTITUTIONS: REACTIVITY AND THEORETICAL INVESTIGATION” 17,15-18,00 ASSEMBLEA COSTITUENTE DEL GRUPPO SENIOR DELLA SCI 18,00-19,00 VINCENZO BALZANI, UNIVERSITA’. DI BOLOGNA - “ENERGIA PER L’ASTRONAVE TERRA”

20,30 SOCIAL DINNER

THURSDAY SEPTEMBER 3 08,45-09,00 SIGNATURE OF THE AGREEMENT BETWEEN THE INTERNATIONAL CENTRE FOR THE STUDY OF THE PRESERVATION AND RESTORATION OF CULTRAL ROPERTY (ICCROM, DIRECTOR GENERAL, MOUNIR BOUCHENAKI ) AND THE ITALIAN CHEMICAL SOCIETY (PRESIDENT LUIGI CAMPANELLA) 09,00-09,40 ALEX VON BOHLEN, INSTITUT ANALYTICAL SCIENCES, DORTMUND “VIOLINS – ABOUT CHEMISTRY AND PHYSICS OF SOUND " 09,40-10,20 LUIGI CAMPANELLA, UNIVERSITY "LA SAPIENZA", ROME - “THE SINDONE AGE”;

10,20- 10,50 COFFEE BREAK

10.50-11,30 PROF. PHILIPPE WALTER, CENTRE DE RECHERCHE ET DE RESTAURATION DES MUSÉES DE FRANCE, PARIS - “TUNING THE PH, THE KEY TO WET CHEMISTRY ONSET DURING ANTIQUITY”. 11,30–12,00 OSCAR CHIANTORE, UNIVERSITÀ DI TORINO "FROM BAKELITE TO (NANO)COMPOSITES: 100 YEARS OF POLYMERS IN ART". 12,00-12,30 RENZO BERTONCELLO AND MARINA R.BRUSTOLON, UNIVERSITA’ DI PADOVA - "LA CHIMICA: UN BENE CULTURALE" 15,00-15,20 MICHELA BERZIOLI, ELISA CAMPANI, ANTONELLA CASOLI, UNIVERSITÀ DI PARMA - "LE TECNICHE PITTORICHE RISCOPERTE DALLA RICERCA CHIMICA" 15,20-15,40 ROCCO MAZZEO, UNIVERSITY OF BOLOGNA - "MOLECULAR SPECTROSCOPIES FOR THE STUDY OF HERITAGE MATERIALS: FROM CONSERVATION TO AUTHENTICATION"

15,40 16,00 COFFEE BREAK

16,00-16,20 PAOLO CREMONESI, CESMAR 7 - " A CHEMICAL APPROACH TO THE CLEANING OF PAINTINGS" 16,20-16,40 LORENZO APOLLONIA, VALLE D'AOSTA 16,40-17,10 GUIDO BISCONTIN, UNIVERSITA’ DI VENEZIA "LA CHIMICA PER LA CONOSCENZA E LA CONSERVAZIONE DEI BENI CULTURALI" 17,10-17,30 MARCO TADDIA, UNIVERSITA’ DI BOLOGNA “DAL CARBONE SARDO AL PROIETTILE DI GARIBARLDI. LE ANALISI CHIMICE DI PAOLO TASSINARI” 18,00-19,00 ANTONIO SGAMELLOTTI, UNIV. DI PERUGIA - “LA SCIENZA MOLECOLARE PER L’ARTE: DAL RINASCIMENTO AL CONTEMPORANEO”

FRIDAY SEPTEMBER 4 9,00-10,00 PREMIAZIONE ORGANIZZATORI GIOCHI DELLA CHIMICA E OLIMPIADI 10,00-10,30 LUIGI ANASTASIA, UNIVERSITÀ DI MILANO "I GIOCHI DELLA CHIMICA E L'AGGIORNAMENTO DELL'INSEGNAMENTO DELLA CHIMICA". 10,30-11,00 INTERVENTO DEL RESPONSABILE UFFICIO SCOLASTICO REGIONALE DEL VENETO 11,00-12,30 PREMIAZIONE DEI GIOCHI DELLA CHIMICA DEL VENETO 2009

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ABSTRACTSABSTRACTSABSTRACTSABSTRACTS

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LIST OFLIST OFLIST OFLIST OF PLENARY LECTURESPLENARY LECTURESPLENARY LECTURESPLENARY LECTURES

PL1 L’INVENZIONE DEL FARMACO ETTORE NOVELLINO

Dipartimento di Chimica Farmaceutica e Tossicologia, Università di Napoli, Via D. Montesano, 49, 80131 Napoli – Italia E-mail: [email protected]

PL2 100 YEARS OF RESEARCH AT CARLSBERG LABORATORY; FROM pH TO HIGH FIELD NMR SPECTROSCOPY JENS DUUS Carlsberg Laboratory, Gaemle Carlsberg Vej 10 – DK-2500 Valby, Denmark E-mail: [email protected] PL3 I SEGRETI MOLECOLARI DELLA GASTRONOMIA ROSANGELA MARCHELLI Dipartimento di Chimica Organica e Industriale, Università di Parma, Via G.P. Usberti, 17, 43100 Parma – Italia E-mail: [email protected] PL4 METALS IN SYSTEMS BIOLOGY IVANO BERTINI Dipartimento di Chimica – CERM, Universita’ di Firenze, Via Sacconi, 6, 50019 Sesto Fiorentino (FI) – Italia E-mail: [email protected] PL5 CHEMISTRY OF THE UNIVERSE PIERO RAFANELLI Dipartimento di Astronomia, Università di Padova, Vicolo dell’Osservatorio, 3, 35100 Padova – Italia E-mail: [email protected] PL6 FROM THE ORIGIN OF LIFE TO COGNITION PIERLUIGI LUISI Dipartimento di Biologia, Università di Roma III, L.go S. Leonardo Murialdo, 1, 00146 Roma – Italia E-mail: [email protected] PL7 ENERGIA PER L’ASTRONAVE TERRA VINCENZO BALZANI Dipartimento di Chimica “G. Ciamician”, Università di Bologna, Via Selmi, 2, 40126 Bologna – Italia E-mail: [email protected] PL8 ABOUT CHEMISTRY AND PHYSICS OF SOUND ALEX von BOHLEN ISAS Institut Analytical Sciences – Bunsen-Kirchhoff-Str. 11 – 44139 Dortmund – Germany E-Mail: [email protected] PL9 THE SINDONE AGE LUIGI CAMPANELLA Dipartimento di Chimica, Università di Roma “La Sapienza”, P.le Aldo Moro, 5, 00185 Roma – Italia E-mail: [email protected] PL10 TUNING THE pH , THE KEY TO WET CHEMISTRY ONSET DURING ANTIQUITY PHILIPPE WALTER Centre de Recherche et de Restauration des Musées de France, 14, Quai Francois Mitterand, Paris, 75001 – France E-mail: [email protected] PL11 LA SCIENZA MOLECOLARE PER L’ARTE: DAL RINASCIMENTO AL CONTEMPORANEO ANTONIO SGAMELLOTTI Dipartimento di Chimica, Università di Perugia, Via Elce di Sotto, 8, 06123 Perugia – Italia E-mail: [email protected]

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LIST OF INVITED LECTURESLIST OF INVITED LECTURESLIST OF INVITED LECTURESLIST OF INVITED LECTURES

IL1 LE PROBLEMATICHE CHIMICO-AMBIENTALI DEL SISTEMA LAGUNARE VENEZIANO PAOLO CESCON

Università Ca’ Foscari Venezia – Presidente Corila, Dip. Scienze Ambientali, Santa Marta Dorsoduro 2137, 30121 Venezia- Italia

E-mail: [email protected] IL2 IL COORDINAMENTO SCIENTIFICO DELLE RICERCHE IN LAGUNA PIER PAOLO CAMPOSTRINI Direttore Consorzio CORILA, Palazzo Franchetti, S. Marco, 2847, 30124 Venezia - Italia E-mail: [email protected] IL3 REMEDIATION AND BIOREMEDIATION OF DREDGED POLLUTED SEDIMENTS OF THE VENICE LAGOON, ITALY AN ENVIRONMENTAL-FRIENDLY APPROACH FABIANA CORAMI IDPA-CNR Istituto per la Dinamica dei Processi Ambientali, Università “Cà Foscari” di Venezia, Santa Marta, Dorsoduro, 2137, 30123 Venezia - Italia E-mail: [email protected] IL4 SPECIAZIONE CHIMICA DI METALLI NELLE ACQUE DELLA LAGUNA DI VENEZIA GABRIELE CAPODAGLIO

Dipartimento di Scienze Ambientali, Università Ca Foscari Venezia, Santa Marta, Dorsoduro 2137, 30121 Venezia - Italia E-mail: [email protected]

IL5 LOW TEMPERATURE LAUNDRY WASHING, A BETTER CHEMISTRY LUCA SPADONI

Reckitt Benckiser Italia S.p.A. – R & D Centre, P.zza S. Nicolò 12/3, 30034 Mira (VE) - Italia E-mail: [email protected]

IL6 NEW LIFE FOR MATURE PRODUCTS: APPLICATION OF PAT AND QUALITY BY DESIGN ON API MANUFACTURING MARIANO STIVANELLO - GIULIO VOLPE Lundbeck Pharmaceuticals Italy S.p.A., Via Quarta Strada 2, 35129 Padova - Italia E-mail: [email protected] IL7 ELECTROCHEMICAL FLUORINATION: A USEFUL TECHNOLOGY MOVING TOWARDS MORE ENVIRONMENTAL-FRIENDLY PRODUCTS ANDREA MISSIO Miteni, Località Colombara, 91, 36070 Trissino (VI) - Italia E-mail: [email protected] IL8 HYDROLYTIC KINETIC RESOLUTION (HKR) IN AN EFFICIENT PROCESS FOR A COMPLEX ACTIVE PHARMACEUTICAL

INGREDIENT LIVIUS COTARCA - PAOLO MARAGNI - MASSIMO VERZINI Zambon Advanced Fine Chemicals , Via Dovaro, 2, 36045 Lonigo (VI) – Italia E-mail: [email protected]

IL9 ENANTIOSELECTIVE HYDROLYSIS FOR A MOXIFLOXACIN BINDING BLOCK PREPARATION ANDREA CASTELLIN FIS – Fabbrica Italiana Sintetici S.p.A. Viale Milano, 26, 36075 Montecchio Maggiore (VI) - Italia E-mail: [email protected] IL10 THE ROLE OF pH IN CONCEPT-BUILDING FOR MOLECULAR SENSING AND COMPUTING

A. PRASANNA de SILVA School of Chemistry and Chemical Engineering, Queen’s University – Belfast - Northern Ireland E-mail: [email protected] IL11 EFFICIENT TREATMENT OF IRON GALL INKED PAPERS VALERIA CONTE Università di Roma “Tor Vergata”, Dipartimento di Scienze e Tecnologie Chimiche -Via della Ricerca Scientifica, 00133 Roma – Italia

E-mail: [email protected]

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IL12 PARAMETRI ISOTOPICI DELLA GRAPPA INFLUENZATI DALL’ORIGINE E VARIABILI COMPOSITIVE LEGATE AL

MIGLIORAMENTO TECNOLOGICO GIUSEPPE VERSINI Consulente, Unione Italiana Vini, Verona - Italia E-mail: [email protected] IL13 APPLICAZIONI TECNOLOGICHE DELLA CHIMICA DEI POLIFENOLI PER LA PRODUZIONE DI ALCUNI VINI TIPICI VINCENZO GERBI DIVAPRA , Università di Torino, Via Leonardo da Vinci, 44, 10095 Grugliasco (TO) - Italia E-mail: [email protected] IL14 I COMPOSTI SOLFORATI NELLE UVE E NEI VINI: PRESENZE, PRECURSORI E TECNICHE ANALITICHE MIRATE BRUNO FEDRIZZI Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova - Italia E-mail: [email protected] IL15 TECNICHE STRUMENTALI AVANZATE NEGLI STUDI COMPOSITIVI DELL’UVA E DEI VINI RICCARDO FLAMINI Agricultural Research Council, Viticulture Research Center, CRA-VIT, Viale XXVII Aprile, 25, 31015, Conegliano (TV) - Italia E-mail: [email protected] IL16 MASS SPECTROMETRY. AN ORPHAN METHODOLOGY FOR OLIVE OIL QUALITY AND SAFETY GIOVANNI SINDONA Dipartimento di Chimica, Cubo 12C, Università della Calabria, Via P. Pucci, 87036 Arcavacata di Rende (CS) - Italia E-mail: [email protected] IL17 ANTI-INFLAMMATORY EFFECT OF OLEOPENTADIAL ON PRIMARY HUMAN VASCULAR ENDOTHELIAL CELLS ELENA MARTINI Sezione di Microbiologia Scuola di Medicina, Universita’ di Brescia, Brescia- Italia IL18 THE ORGANIC CHEMISTRY OF OLIVE NUTRACEUTICALS ANTONIO PROCOPIO Dipartimento Scienze Farmacobiologiche, Università “Magna Grecia” di Catanzaro, Roccelletta di Borgia (CZ), 88021, Catanzaro - Italia E-mail: [email protected] IL19 POLINUCLEAR CHROMIUM CHAINS: SYNTHESIS AND MAGNETIC PROPERTIES MARZIO RANCAN ISTM-CNR, INSTM R.U. Padova, Università degli Studi di Padova, Dipartimento di Scienze Chimiche, via Marzolo 1, 35131 Padova, Italy. E-mail: [email protected] IL20 REACTION CONTROL BY NON-COVALENT INTERACTIONS: THE INFLUENCE OF AGGREGATION AND SOLVATION ON THE STRUCTURE-REACTIVITY RELATIONSHIP OF LITHIUM OXYGEN CARBENOIDS VITO CAPRIATI Dipartimento Farmaco-Chimico C.I.N.M.P.I.S. – Università di Bari – Via E. Orabona 4, 70125 Bari - Italia E-mail: [email protected] IL21 NANOSTRUCTURING OF ORGANIC MATERIALS TEMPLATED BY HYDROGEN BONDING ANNA LLANES-PALLÀS Dipartimento di Scienze Farmaceutiche and INSTM Udr Trieste, Università degli Studi di Trieste, 34127 Trieste, Italia – Email: [email protected] IL22 SYNTHESIS OF PEPTIDOMIMETICS AND THEIR APPLICATION AS DIAGNOSTICS AND THERAPEUTICS LAURA BARTALI Dipartimento di Chimica Organica “U. Schiff, dell’Università di Firenze, Via della Lastruccia 13, 50019, Sesto Fiorentino – Italia E-mail: [email protected] IL23 SYNTHESIS AND ANTIOXIDANT ACTIVITY OF 4-THIATOCOPHEROLS MARIA GRAZIA BARTOLOZZI Dipartimento di Chimica Organica “U. Schiff, dell’Università di Firenze, Via della Lastruccia 13, 50019, Sesto Fiorentino – Italia E-mail: [email protected]

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IL24 SYNTHESIS AND NMR CHARACTERIZATION OF NEOPEPTIDES CONTAINING A FRUCTOSE-BASED PROLINE ANALOGUE DAVIDE BINI Dipartimento di Biotecnologia e Bioscienze, Università di Milano – Bicocca – P.zza della Scienza, 2 – 20126 Milano - Italia Email: [email protected] IL25 DEVELOPMENT OF NEW DOMINO ORGANOCATALYZED SYSTEMS FOR THE SYNTHESIS OF COMPLEX CHIRAL MOLECULES FRANCESCO DE VINCENTIIS Dipartimento di Chimica Organica “A. Mangini”, Facoltà di Chimica Industriale, Università di Bologna – Italia E-mail: [email protected] IL26 NOVEL PHOSPHORESCENT FLUORINE FUNCTIONALIZED IRIDIUM COMPLEXES VINCENZO FINO Dipartimento di Chimica, Facoltà di Scienze MM.FF.NN, Università di Bari – Via E. Orabona, 4, 70125 Bari - Italia E-mail: [email protected] IL27 NOVEL PALLADIUM AND COPPER BASED METALLOMESOGENS FROM TIOPHENE CONTAINING LIGANDS MAURO MAZZELLA Dipartimento di Chimica, Università di Napoli “Federico II”, Via Cintia, 80126 Napoli – Italia – E-mail: [email protected]

IL28 OXAZIRIDINES FOR THE 2,3-DIHYDRO-1,2,4-OXADIAZOLES SYNTHESIS FRANCESCA ROSATO Dipartimento di Scienze e Tecnologie Biologiche ed Ambientali, Università del Salento, Via P.le Lecce-Monteroni, 73100, Lecce – Italia E-mail: [email protected] IL29 ON THE CONFIGURATION STABILITY OF α-LITHIATED ARYLOXIRANES ANTONIO SALOMONE Dipartimento Farmaco-Chimico, Università di Bari, Via E. Orabona, 4, 70125 Bari – Italia E-mail: [email protected] IL30 PhSeZnCl IN NUCLEOPHILIC VINYLIC SUBSTITUTIONS: REACTIVITY AND THEORETICAL INVESTIGATION STEFANO SANTORO Dipartimento di Chimica e Tecnologia del Farmaco – Sezione di Chimica Organica, Università di Perugia, Via del Liceo, 1, 06123 Perugia – Italia E-mail: [email protected] IL31 FROM BAKELITE TO (NANO)COMPOSITES: 100 YEARS OF POLYMERS IN ART OSCAR CHIANTORE Dipartimento di Chimica Inorganica, fisica e dei materiali, Università di Torino, Via Pietro Giuria, 7, 10125 Torino – Italia E-mail: [email protected] IL32 LA CHIMICA: UN BENE CULTURALE RENZO BERTONCELLO – MARINA R. BRUSTOLON Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova – Italia - E-mail: [email protected] – [email protected] IL33 LE TECNICHE PITTORICHE RISCOPERTE DALLA RICERCA CHIMICA MICHELA BERZIOLI*, ELISA CAMPANI, ANTONELLA CASOLI Dipartimento di Chimica Generale e Inorganica, Chimica Analitica, Chimica Fisica, Università di Parma, V.le G.P. Usberti, 17A, 43100 Parma – Italia E-mail: [email protected] IL34 MOLECULAR SPECTROSCOPIES FOR THE STUDY OF HERITAGE MATERIALS: FROM CONSERVATION TO AUTHENTICATION ROCCO MAZZEO Dipartimento di Chimica “Giacomo Ciamician” Università di Bologna, Via F. Selmi, 2, 40126 Bologna – Italia E-mail: [email protected] IL35 A CHEMICAL APPROACH TO THE CLEANING OF PAINTINGS PAOLO CREMONESI CESMAR7-Centro per lo Studio dei Materiali per il Restauro, Via Lombardia 41/43, 35020 Saonara (PD), Italia E-mail: [email protected]

15

IL36 LA CHIMICA PER LA CONOSCENZA E LA CONSERVAZIONE DEI BENI CULTURALI GUIDO BISCONTIN Dipartimento di Scienze Ambientali, Università di Venezia, Santa Marta, Dorsoduro, 2137, 30121 Venezia- Italia E-mail: [email protected]

IL37 DAL CARBONE SARDO AL PROIETTILE DI GARIBALDI. LE ANALISI CHIMICHE DI PAOLO TASSINARI (1829-1909) MARCO TADDIA Dipartimento di Chimica “Giacomo Ciamician”, Università di Bologna, Via F. Selmi, 2, 40126 Bologna – Italia

Email: [email protected]

16

LIST OF POSTERSLIST OF POSTERSLIST OF POSTERSLIST OF POSTERS

PO1 GOLD(III)-BASED ANTICANCER AGENTS: PEPTIDE DERIVATIVES OF SULFUR DONOR LIGANDS AS IMPROVED INTRACELLULAR DRUG TRANSFER AND DELIVERY SYSTEMS SUPPORTED BY TRANSPORTER PROTEINS LUCA RONCONI, M. NEGOM KOUODOM, D. ALDINUCCI, Q.P. DOU, F. FORMAGGIO, D. FREGONA

Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova- Italia E-mail: [email protected]

PO2 NOVEL MITOCHONDRION-TARGETED QUERCETIN DERIVATIVES: SYNTHESIS, OXIDATION POTENTIALS, RADICAL- SCAVENGING PROPERTIES AND CYTOTOXICITY ANDREA MATTAREI*, LUCIA BIASIUTTO, ESTER MAROTTA, SPIRIDIONE GARBISIA, MARIO ZORATTI, CHRISTIAN DURANTE, GIANCARLO SANDONA’, ARMANDO GENANRO, CRISTINA PARADISI

Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova- Italia E-mail: [email protected]

PO3 BINDING COOPERATIVITY AND ALLOSTERISM IN FATTY ACID BINDING PROTEINS HENRIETTE MOLINARI, M. ASSFALG, M PEDO’, S. ZANZONI, C. COGLIATI Dipartimento di Biotecnologie, Strada le Grazie 15, Università di Verona, 37134 Verona – Italia E-mail: [email protected] PO4 (Zn,Cu)O PHOTOCATALYTIC MATERIAL AND ZnGa22O4:Eu

3+PHOSPHORS: TAILORING STRUCTURE-PROPERTY

RELATIONSHIPS LAURA BOVO, LIDIA ARMELAO, MARCO BETTINELLI, EUGENIO TONDELLO

Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova- Italia E-mail: [email protected] PO5 NANOZYMES FOR PHOSPHATE DIESTERS HYDROLYSIS RENATO BONOMI, FRANCESCO SELVESTREL, FABRIZIO MANCIN, UMBERTO TONELLATO AND PAOLO SCRIMIN Dipartimento di Scienze Chimiche, Università di Padova via Marzolo 1, 35131 Padova - Italia E-mail: [email protected] PO6 ENCAPSULATION OF PHOTOACTIVE MOLECULES INSIDE SINGLE WALL CARBON NANOTUBES FRANCESCA COLOMBO

*, CLAUDIA AMBROSCH-DRAXL, BARBORA BARTOVA, PASCAL BLONDEAU, JIA GAO, CECILE

HEBERT, MARIA ANTONIETTA LOI, ENZO MENNA, MATUS MILKO

Dipartimento di Scienze Chimiche, Università di Padova via Marzolo 1, 35131 Padova - Italia E-mail: [email protected]

PO7 SUPPORTED BIS(ZNII-PORPHYRIN) DITOPIC RECEPTORS FOR THE CONSTRUCTION OF OPTICAL DETECTION OF DIAMINES.

ELISA LUBIAN*, TOMMASO CAROFIGLIO. Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova - Italia. E-mail: [email protected] PO8 TARGETED SILICA NANOPARTICLES FOR DRUG DELIVERY FRANCESCO SELVESTREL ,

GAETANO GUARINO,

IRIA MARIA RIO-ECHEVARRIA,

ELENA REDDI,

FABRIZIO MANCIN

A.

Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova - Italia

E-mail: [email protected] PO9 MICROGEL STABILIZED METAL NANOCLUSTERS G. DVORAKOVA*, S. PIPERNO, L.A. GHEBER, A. BIFFIS Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova – Italia E-mail: [email protected] PO10 POLYOXOMETALATE CATALISYS IN IONIC LIQUID MEDIA SERENA BERARDI*, MARCELLA BONCHIO, MAURO CARRARO, VALERIA CONTE, ANDREA SARTOEL, GIANFRANCO SCORRANO

Istituto Tecnologia delle Membrane, Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova - Italia E-mail: [email protected] PO11 FLUOROUS-TAGGED POLYOXOMETALATES AS CATALYSTS FOR SUSTAINABLE OXIDATIONS WITH O2 AND H2O2

MARTINO GARDAN*, MAURO CARRARO, ANDREA SARTOREL, MARCELLA BONCHIO, GIANFRANCO SCORRANO Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1 35131 Pasova – Italia E-mail: [email protected]

17

PO12 ROLE OF THE STRONGLY HELICOGENIC AIB RESIDUES ON THE PROPERTIES OF THE LIPOPEPTAIBOL TRICHOGIN GA IV B. BIONDI, M. DE ZOTTI, C. PEGGION*, F. FORMAGGIO, C. TONIOLO Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova - Italia E-mail: [email protected] PO13 MODELLING THE PARTITIONING OF SOLUTES IN LIPID MEMBRANES G. PARISIO*, M. STOCCHERO, A. FERRARINI Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova - Italia E-mail: [email protected] P014 PRELIMINARY STUDIES ON STRUCTURE, MORPHOLOGY AND BIODEGRADABILITY OF POLY (€-CAPROLACTONE) BASED NANOCOMPOSITES RAMESH NEPPALLI*, VALERIO CAUSIN, CARLA MAREGA, ROBERTA SAINI, ANTONIO MARIGO

Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova - Italia E-mail: [email protected] PO15 A PEPTIDO[2]ROTAXANE MOLECULAR MACHINE

A.MORETTO, I. MENEGAZZO, M. CRISMA, S. MAMMI, C. TONIOLO Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova - Italia

E-mail: [email protected] PO16 EXPLOITING NON COVALENTG INTERACTIONS FOR THE DISCOVERY OF NEW CATALYSTS: DYNAMIC COVALENT CAPTURE APPROACH

LEONARD PRINS, MARTA DAL MOLIN*, PAOLO SCRIMIN Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova - Italia E-mail: [email protected]

P017 ROLE OF INTERMOLECULAR INTERACTIONS IN OXYGEN TRANSFER CATALYZED BY SILSESQUIOXANE TRISILANOLATE VANADIUM(V) SILVIA LOVAT*, M. MBA, C. ZONTA, G. LICINI

Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova - Italia E-mail: [email protected] PO18 STORIA DELLA STEREOCHIMICA: L’ASPARAGINA DESTROGIRA DOLCE DI ARNALDO PIUTTI ANTONIO GUARNA, LAURA COLLI Dipartimento di Chimica Organica “Ugo Schiff”, Polo Scientifico e Tecnologico, Università di Firenze - Via della Lastruccia, 13, 50019 Sesto Fiorentino (FI)- Italia E-mail: [email protected] PO19 PREPARATION AND CHARACTERIZATION OF ORGANOCLAY NANOCOMPOSITES R.MILANI*, A. ZAGGIA, G. PADOAN, A. LORENZETTI, S. SEMENZATO, A. SASSI, G. FACCHIN, M. MODESTI, L. CONTE, R. BERTANI Dipartimento dei Processi di Ingegneria Chimica, Università di Padova, Via Marzolo, 9, 35131 Padova – Italia E-mail: [email protected] PO20 USE OF PHOSPHOAZENES AS A NEW APPROACH TO VERSATILE SURFACE FUNTIONALIZATION ROBERTO MILANI*, MARIO GLERIA, ROBERTA BERTANI, ROGER DE JAEGER, AHMED MAZZAH, CHARAFEDDINE JAMA, MARTINE FRERE,LEON GENGEMBRE Dipartimento dei Processi di Ingegneria Chimica, Università di Padova, Via Marzolo, 9, 35131 Padova – Italia E-mail: [email protected] PO21 SOLUBLE AND FUNCTIONAL SINGLE-WALLED CARBON NANOTUBES MARCO DE NARDI*, FABRIZIO CORDELLA, CECILE HEBERT, MARIA ANTONIETTA LOI, ENZO MENNA

Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova - Italia E-mail: [email protected] PO22 UNIVERSAL GOLD NANOPARTICLES: SYNTHESIS, PURIFICATION, APPLICATION MATTEO GRAZIANI*, LEONARD PRINS, PAOLO SCRIMIN

Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova - Italia E-mail: [email protected]

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PO23 HYDROARYLATION OF ALKYNES CATALYSED BY PD(II) COMPLEXES: OPTIMIZATION OF THE REACTION CONDITIONS LUCA GAZZOLA*, ANDREA BIFFIS, CRISTINA TUBARO, GABRIELLA BUSCEMI, MARINO BASATO

Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova - Italia E-mail: [email protected] PO24 SPONTANEOUS SELF-ASSEMBLY OF C3-SYMMETRIC Ti(iv) AMINE TRIPHENOLATE COMPLEXES MIRIAM MBA*, MARTA PONTINI, ESZTER NAGY, GERALD BERNARDINELLI, THOMAS M. SEIDEL, E.P. KUNDIG, CRISTIANO ZONTA, GIULIA LICINI

Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova - Italia E-mail: [email protected]

PO25 ORGANIC SYNTHESIS IN MICROREACTORS TOMMASO CAROFIGLIO, ANDREA CASTELLIN, PAOLA DONNOLA*, MICHELE MAGGINI, E. ROSSI

Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova - Italia E-mail: [email protected] PO26 VANADIUM (V) POSS COMPLEXES AS OXIDATION CATALYSTS C. BINDOLI*, S. LOVAT, M: MBA, C. ZONTA AND G. LICINI Dipartimento Scienze Chimiche, Università di Padova, Via Marzolo 1, 35131, Padova - Italia E-mail: [email protected] PO27 Mo(VI) AMINE TRIPHENOLATE COMPLEXES: SYNTHESIS, STRUCTURE AND CATALYTIC ACTIVITY F. ROMANO

1, S. LOVAT, M. MBA, C. ZONTA, G. LICINI

Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova – Italia E-mail: [email protected]

PO28 Pd(0) NANOPARTICLES SUPPORTED ONTO MACROPOROUS MONOLITHS FOR CONTINUOUS FLOW CARBON-CARBON CROSS COUPLINGS IN CAPILLARY MICROREACTORS PRASENJIT MAITY, TOMMASO CAROFIGLIO, MICHELE MAGGINI

Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova – Italia E-mail: [email protected] PO29 SUPRAMOLECULAR ASSEMBLY OF THE VDE PROTEIN IN MEMBRANES AS REVEALED BY SDSL-EPR AND 4P-DEER E. SALVADORI

A*, M. DI VALENTIN, G. SAGA, T. MOROSINOTTO, D. CARBONERA


PO30 SENSITIVITY TUNING IN INTRACELLULAR Zn

2+ PROBES

L. BAÙ1*

, F. MANCIN1


PO31 SYNTHESIS OF ONCOLOGICAL DRUGS BY FLOW TECHNIQUES ANDREA CASTELLIN, TOMMASO CAROFIGLIO, MICHELE MAGGINI, EMILIANO ROSSI*

Fabbrica Italiana Sintetici F.I.S. S.p.a., Viale Milano 26, 36075 Alte di Montecchio Maggiore, Vicenza - Italy. Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova – Italia

Email: [email protected].

PO32 NUCLEIC ACID RECOGNITION BY ALANYL-NUCLEOPEPTIDES PIERO GEOTTI-BIANCHINI,

OLIVIER CHALOIN,

ALBERTO BIANCO, FERNANDO FORMAGGIO*


PO33 Deg/Gly PEPTIDES AS POTENTIAL MOLECULAR SWITCHES ALESSANDRO MORETTO*, VANESSA MARCUZZO, GEMA BALLANO, MARCO CRISMA, FERNANDO FORMAGGIO, CLAUDIO TONIOLO Istituto di Chimica Biomolecolare Sede Operativa di Padova, CNR, Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova –Italia E-mail: [email protected]

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PO34 REPLACEMENT OF Ala BY Aib IMPROVES STRUCTURATION AND BIOLOGICAL STABILITY IN THYMINE-BASED NUCLEOPEPTIDES PIERO GEOTTI-BIANCHINI,

A,B ALESSANDRO MORETTO,

A CRISTINA PEGGION,

A JULIEN BEYRATH,

B ALBERTO BIANCO,

B

FERNANDO FORMAGGIOA*

Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova – Italia E-mail: [email protected] PO35 METAL NANOCLUSTERS STABILISED BY POLYAMIDES: “BOTTOM-UP” PREPARATION AND PRELIMINARY CATALYTIC DATA M. ZECCA

A,*, I. CONCINA

A, I. DUSE

A, B. CORAIN,

A, P. CENTOMO

a

Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova – Italia E-mail :[email protected] PO36 COMPARISON OF THE INITIAL DECOMPOSITION STEPS OF HALOGENATED AND NON-HALOGENATED HYDROCARBONS IN AIR UNDER DIFFERENT PLASMA REGIMES M. SCHIORLIN

1*, E. MAROTTA

1, M. DAL MOLIN

1, M. REA

2, C. PARADISI

1

Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova – Italia E-mail: [email protected] PO37 SYNTHESIS OF CHIRAL HYBRID ORGANIC-INORGANIC POLYOXOMETALATES GLORIA MODUGNO*, MAURO CARRARO, ANDREA SARTOREL, MARCELLA BONCHIO, GIANFRANCO SCORRANO, Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova – Italia . E-mail: [email protected]

PO38 LIPID OXIDATION PRODUCTS GENERATED BY THERMAL STRESS OF CULINARY OILS AND FAT: A KINETIC STUDY BY

1H NMR

SPECTROSCOPY ALESSANDRO BAGNO, FEDERICO RASTRELLI, MARCO SALMISTRARO, ADRIANO SILVAGNI

Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131 Padova – Italia

E-mail: [email protected] PO39 THIOREDOXIN REDUCTASE AS ANTICANCER TARGET. COMPUTATIONAL AND MODEL STUDIES OF INHIBITION RICCARDO BINI,

1 GIACOMO SAIELLI,

2 FRANCESCA DI SARRA,

1* ALESSANDRO BAGNO,

1 VALENTINA GANDIN,

3

FRANCESCO TISATO4

Dipartimento di Scienze Chimiche, , Università di Padova, Via Marzolo, 1, 35131 Padova – Italia

E-mail: [email protected] PO40 PEPTIDES AS LIGANDS FOR THE SELECTIVE DELIVERY OF THE CORRESPONDING METAL-BASED ANTICANCER AGENTS MORELLE NEGOM KOUODOM*, LUCA RONCONI, DOLORES FREGONA, FERNANDO FORMAGGIO Dipartimento di Scienze Chimiche, , Università di Padova, Via Marzolo, 1, 35131 Padova – Italia E-mail: [email protected] PO41 A RAPID METHOD FOR THE INERTIZATION OF MICROFLUIDIC DEVICES SIMONE SILVESTRINI

*, TOMMASO CAROFIGLIO, MICHELE MAGGINI

Dipartimento di Scienze Chimiche, Università degli Studi di Padova, via Marzolo 1, 35131 Padova – Italia E-mail: [email protected] PO42 ISOTOPE DILUTION AND MULTIPLE REACTION MONITORING MASS SPECTROMETRY IN THE IDENTIFICATION AND ASSAY OF ROTENONE IN OLIVE OIL. FABIO MAZZOTTI, LEONARDO DI DONNA, MOHAMED ATTYA, BARTOLO GABRIELE, ALESSIA FAZIO AND GIOVANNI SINDONA Dipartimento di Chimica Università della Calabria, Via P. Pucci Cubo 12B, 87036 ARCAVATA DI RENDE (CS) – Italia PO43 STUDIES OF NOVEL TREATMENTS OF TEXTILE FIBERS WITH COLD PLASMAS AT ATMOSPHERIC PRESSURE MARCO SCAPINELLO, I. KULYK, M. STEFAN, E. MAROTTA, C. PARADISI Dipartimento di Scienze Chimiche, Università degli Studi di Padova, via Marzolo 1, 35131 Padova – Italia E-mail: [email protected]

20

PLENARY LECTURESPLENARY LECTURESPLENARY LECTURESPLENARY LECTURES

21

PL1

L’INVENZIONE DEL FARMACO

Ettore Novellino

Facoltà di Farmacia

Università degli Studi di Napoli Federico Il

La storia dei farmaci e l'evoluzione delle conoscenze sulla loro natura e le loro proprietà hanno una duplice radice nella conoscenza degli elementi minerali, vegetali ed animali del mondo in cui viviamo e in quella della struttura del nostro organismo e delle sue funzioni normali o alterate da processi morbosi.

Sin dall'antichità l'uomo, consapevole che non fosse possibile evitare la morte, e nella convinzione che i mali che affliggono l'umanità, dalle malattie del singolo alle pandemie che cronicamente colpivano la specie umana, fossero le conseguenze di misteriose forze malefiche scatenate dagli dei irati contro gli uomini, aveva ritenuto che compito della medicina fosse quello di lenire le sofferenze causate da malattie e da traumi. E per fare ciò aveva cercato di scoprire rimedi efficaci basandosi sulle sue conoscenze delle proprietà curative esercitate da sostanze minerali (lapidari), vegetali (erbari), e animali (bestiari).

Questi rimedi, che oggi suscitano in noi, reazioni che vanno dal sorriso all'orrore, hanno dominato per secoli, quando non per millenni, il quadro della prevenzione delle malattie e della lotta contro di esse. E non possiamo non meravigliarci pensando quanto pochi siano stati i farmaci che tanto a lungo hanno rappresentato l'intero armamentario del medico e quanti di essi fossero sostanzialmente inutili, avvalendosi molto spesso dell'arte degli stregoni, esperti nella magia, nell'astrologia e nell'alchimia.

La fiducia riposta dagli uomini in queste forze occulte non impedì però il parallelo sviluppo di una conoscenza del tutto empirica dell'esistenza e dell'efficacia di prodotti naturali, dotati delle proprietà di lenire le sofferenze conseguenti alle alterazioni patologiche indotte dalle malattie. L'indubbio effetto terapeutico esercitato da numerosi di questi prodotti sulle varie patologie invalidanti ne indusse l'uso anche prima che ne fosse scoperta la modalità d'azione.

Con l'avvento del metodo scientifico, la farmacopea, basata sino alla metà dell'ottocento in gran prevalenza su nozioni empiriche, andò incontro ad un formidabile sviluppo determinato dalla progressiva e sempre più approfondita conoscenza della natura chimica delle sostanze dotate di proprietà terapeutiche e del loro meccanismo d'azione. In tale periodo la farmacologia, sullo sfondo delle ricerche biologiche e mediche, si concentrò sullo studio delle proprietà chimiche dei farmaci di origine naturale, cercando correlazioni tra la loro composizione ed il loro effetto sull'organismo. Allo studio di queste si aggiunse quello del numero sempre più crescente di prodotti di sintesi, preparati in laboratori specializzati. Questi sforzi, anche se spesso viziati da incomplete conoscenze, eccessivi entusiasmi e generalizzazioni premature, erano però guidati da una forte immaginazione, che indicava la strada da seguire.

Un contributo notevole alle conoscenze nel campo venne dato anche dallo sviluppo dell'anatomia patologica, che localizzava le malattie a determinati organi, permettendo ne la diagnosi e guidando la ricerca di farmaci con azione localizzata. Il primo risultato di questo indirizzo fu la scoperta di farmaci (i cosiddetti proiettili magici) capaci di uccidere selettivamente i microrganismi rispettando i tessuti normali. Il progresso della medicina e l'applicazione del metodo statistico per valutare l'effetto delle terapie, portarono al discredito di pratiche come il salasso, fin ad allora usate estesamente.

22

PL2

100 YEARS OF RESEARCH AT CARLSBERG LABORATORY; FROM pH TO HIGH FIELD NMR SPECTROSCOPY

Jens Ø. Duus*

1Carlsberg Laboratory, Gamle Carlsberg Vej 10, DK-2500 Valby, Denmark

*Corresponding Author [email protected]

The lecture will describe the special structure and statutes of the Carlsberg Laboratory that allowed S.P.L.

Sørensen to publish the concept 100 years ago.

For Sørensen the work on pH was a necessary extension of his work on peptides and enzymes allowing him

to develop the understanding of the enzymes. This was a clear example of how he back then could combine

basic chemistry and research towards practical applications.

In the same way several professors of the Carlsberg Laboratory before and after Sørensen have contributed

to important scientific breakthrough from Johan Kjeldahl (the Kjeldahl method) over Emil Chr. Hansen (pure

culture yeast) to K.U. Linderstrøm-Lang (protein structure, stability and folding).

Today the laboratory carries out research in a wide range of fields from organic chemistry (e.g., peptides

and carbohydrates) over biochemistry to biology of yeast and barley.

The research today will be exemplified by the work on development of new NMR methods to the structure

elucidation of complex molecules such as carbohydrates. Of recent results will be described a new NMR

pulse sequence useful for assignment of small molecules and biomolecules at natural 13C abundance, the

3D H2BC. This extents the previously developed standard H2BC experiment, which correlates almost

exclusively carbon and protons two-bonds apart and solve some of the ambiguities of the HMCB

experiment. The examples used to illustrate these experiments are some of the most complex

carbohydrates assigned so far by NMR.

23

PL3 I segreti molecolari della gastronomia

Rosangela Marchelli

Dipartimento di Chimica Organica e Industriale dell’Università di Parma

Universita' di Parma, V.le G.P. Usberti, 17°, 43100, Parma


Se sono segreti, non si rivelano in un riassunto come è questo: tutt’al più si lanciano interrogativi, si suscitano riflessioni, si stimolano aspettative, in attesa che i segreti siano rivelati nella conferenza vera e propria.

Il cibo racchiude in sé una gamma di fattori sensoriali, nutrizionali dati dalle molecole che lo costituiscono, ma anche di fattori psicologici legati ai ricordi dell’infanzia o a situazioni particolarmente piacevoli.

L’aroma del pane appena sfornato, una mattina presto tornando da una festa o da una sessione di studio prima degli esami, come non ricondurlo alla reazione di Maillard con i suoi prodotti derivati dalle reazioni degli zuccheri con gli ammino acidi, ma anche a quel particolare periodo della vita?

Ma vorrei presentare un menù vero e proprio, per mostrare come tanti aspetti della gastronomia, che diamo per scontati, siano riconducibili o spiegabili con molecole organiche o reazioni chimiche o interazioni di molecole tra di loro (chimica supramolecolare).

Partendo dall’antipasto: a che cosa è dovuto il colore rosa che distingue il prosciutto di Parma dagli altri salumi, che hanno un colore rosso scuro? Perché è così tenero e dolce? Cosa accade durante la stagionatura? E’ possibile individuare molecole (marker molecolari) che indichino l’età del prosciutto?

I segreti della pasta, in particolare degli spaghetti, fatti con semola di grano duro, in cui le molecole di alcune proteine formano un reticolato (glutine) che mantiene la cottura. Sui sughi ci possiamo sbizzarrire. Ad esempio, il sugo al pomodoro con il basilico e olio di oliva extra vergine che estrae il licopene dal pomodoro e gli aromi lipofili dal basilico; aglio, olio e peperoncino rosso con gli aromi solforati dell’aglio e la capsaicina del peperoncino che conferisce il gusto piccante.

Che differenza c’è tra un lesso, un arrosto, un roast beef a livello molecolare? Il tipo di cottura determina una diversa strutturazione delle proteine,nonché della loro digeribilità. E uno stufato al vino rosso: si può fare uno stufato al vino rosso senza vino?

Si può cucinare il pesce con olio di oliva extra-vergine, che contiene sostanze amare o pungenti, che potrebbero compromettere il sapore delicato del pesce? Sì, perché durante la cottura tali molecole si idrolizzano dando luogo ad altre molecole insapori. E le salse? La maionese con le sue micelle inverse, che non si devono separare in due fasi. Ma è possibile fare la maionese anche senza uova, purchè siano presenti molecole surfattanti e la giusta quantità di goccioline d’acqua.

Una torta: è in realtà un delicato equilibrio tra aria e molecole di carboidrati, lipidi e proteine: se diamo troppa “struttura” la torta diventa dura; se diamo troppa aria si spaccherà letteralmente.

Ma parleremo anche dei formaggi, della frutta, dei suoi colori, aromi e sapori, del vino e del caffè con i suoi mille aromi identificati.

E qui mi fermo: spero di non aver detto troppo. Non aspettatevi ricette, ma solo degli indizi per condividere il piacere di conoscere cosa succede alle molecole nei cibi e un incentivo alla sperimentazione scientifica nel campo ancora misterioso della gastronomia.

24

PL4

METALS IN SYSTEMS BIOLOGY

Ivano Bertini Cerm, University of Florence, Italy

Bioinformatics based methods to predict which proteins of a given genoma are metalloproteins will be presented with emphasys on Zn, Cu, Fe. The the copper human proteome will be analyzed with respect to metal traffiking, metal homeostasis and assembly of cyt-c oxidase.

25

PL5

CHEMISTRY OF THE UNIVERSE

Piero Rafanelli, Dipartimento di Astronimia, Università di Padova


26

PL6

From the origin of life to cognition

Pier Luigi Luisi

Department of Biology, University. Roma3, Italy


The main statement of contemporary science about the origin of life on Earth, is that life originated from

the inanimate matter via a long series of spontaneous steps of increasing molecular complexity, till the

formation of the first cells (at which point Darwinian evolution set in). The major biological and

epistemological concepts characterizing the living cell will be discussed in the lecture at the light of the

theory of autopoiesis developed by Maturana and Varela. An important element here is the notion of

“cognition”, defined as the capability of interacting selectively with the environment, where this interaction

permits the constitution of a co-emergent unit of mutual dependence and origination. Cognition is seen as

a stratified concept, where the sensorium increases in sophistication by increasing the complexity of the

organism: the amoeba already possesses a primitive form of cognition, which increases in insects and

higher animals, and at the level of mankind cognition becomes intelligence, perception, and eventually

consciousness.

All this development is based on immanence, i.e., it comes from within the organization of the developing

structure, with no transcendent element coming from above. And accordingly, ethical values and even the

notion of God can be seen as self-generated values emerging from this autopoietic development. The limits

and constrains of this view, which sharply contrasts the view of creation and intelligent design, will be

discussed in the lecture.

In this scenario, even remaining within the realms of science, important questions are still open to debate,

for example whether and to what extent the origin of life on Earth is an obligatory pathway (absolute

determinism), or whether is mostly the product of contingency (once upon a time called “chance”). This

will be discussed, together with research projects in the field of synthetic biology which tackle the question

of determinism versus contingency (the “never born proteins” and the “minimal cell” project).

27

PL7

ENERGIA PER L'ASTRONAVE TERRA Vincenzo Balzani

Dipartimento di Chimica “Giacomo Ciamician”, Università di Bologna

Negli ultimi due secoli abbiamo progressivamente scoperto e utilizzato a piene mani i tesori

nascosti nelle viscere della Terra che hanno nome di "combustibili fossili". È iniziata così una

nuova era che, se da un lato ha tanto migliorato la vita di una parte (piccola) dell'umanità,

dall'altro ha causato gravi danni alla salute dell'uomo e alla integrità dell'ambiente. In particolare,

l'anidride carbonica, immessa nell'atmosfera in quantità massicce, sta causando l'innalzamento

della temperatura della Terra ("effetto serra") con conseguenze climatiche e idrogeologiche che

secondo il parere degli scienziati potrebbero essere disastrose.

Nei prossimi anni ci dovrà essere inevitabilmente, seppure gradualmente, una transizione dall'uso

dei combustibili fossili a quello di altre fonti di energia. In base alle conoscenze attuali, ci sono solo

due possibilità: l'energia nucleare e l'energia che proviene dalle fonti rinnovabili.

La scelta dell'energia nucleare sarebbe un grave errore per molti motivi: pericolosità degli

impianti, difficoltà a reperire depositi sicuri per le scorie radioattive, stretta connessione tra

nucleare "civile" e nucleare 'militare', esposizione ad atti di terrorismo, enormità degli

investimenti finanziari, necessità di uno stretto controllo militare, aumento delle disuguaglianze

tra paesi tecnologicamente avanzati e paesi poveri.

E' quindi necessaria un'azione forte e decisa per sviluppare l'uso delle fonti di energia rinnovabile:

idroelettrica, geotermica, eolica e, in particolare, solare. Il sole è, di fatto, una stazione di servizio

inesauribile, che fornisce energia gratuitamente, in modo abbondante e senza sostanziali

discriminazioni fra le varie nazioni della Terra. L'energia solare, quindi, non può essere motivo di

guerre fra le nazioni; essendo una forma di energia diluita, non può essere usata per scopi bellici e

non può essere obiettivo di atti terroristici; a differenza dell'energia nucleare, non lascia

indesiderabili eredità alle future generazioni; infine il suo uso, non richiedendo tecnologie

complesse, può essere facilmente esteso alle nazioni meno progredite.

Nel frattempo, per uscire gradualmente e senza grandi traumi dalla crisi energetica ed ecologica

che si affaccia al nostro orizzonte, è necessario incoraggiare il risparmio energetico. Il risparmio

energetico e l'uso delle energie rinnovabili sono la strada maestra per condurre il mondo sulla via

della pace e per lasciare in eredità ai nostri figli un pianeta più vivibile.

Bibliografia

- N. Armaroli, V.Balzani: Angew. Chem. Int Ed46, 52, 2007. - N. Armaroli, V.Balzani: Energia per l’Astronave Terra, Zanichelli 2008 (Premio Galileo 2009 per la divulgazione scientifica) - N. Armaroli, V.Balzani: La Chimica e L’Industria, novembre, 138, 2008

28

PL8

VIOLINS – ABOUT CHEMISTRY AND PHYSICS OF SOUND

Alex von Bohlen

Institute for Analytical Sciences ISAS-Dortmund

Bunsen-Kirchhoff-Str. 11

44139 Dortmund, Germany

[email protected]

Bowed stringed musical instruments, especially those of the violin family, are central part of the European culture of the last centuries. They were created after instruments designed by Andrea Amati in Cremona until the end of the 16th century. Amati’s nephew Nicola was the teacher of the founders of the most prominent violin maker dynasties of Antonio Stradivari and of Andrea Guarneri. Amati’s violin form was exported to other European countries and also modified there. However, the quality, the general appearance and the sound of the Italian masters remain unequalled. These attributes might be the main reason for the controversy of the discussion and for the efforts done in the last decades to reconstruct the lost recipes for the old varnishes and to disclose the secret of the old masters.

The limited number of materials used for the construction of these instruments, as there are wood, glue, varnish and strings suggest a special treatment of these materials to produce outstanding products. Many efforts have been done by violin makers and all others involved in making musical instruments to create attractive instruments with good sound. The use of slightly different materials treated in different manners result in regional and individual characteristic instruments. An insight into the chemistry and into physics of violins will be presented. Modern methods of instrumental analytical chemistry were used to elucidate the composition and stratigraphy of varnishes, glue and wood.

Micro analyses made on such materials will give an insight into historical techniques and historical materials. Examples applying X-ray based analytical methods (like Total Reflection X-Ray Fluorescence (TXRF), Energy Dispersive X-Ray Fluorescence (ED-XRF), Scanning Electron Microscope (SEM- EDX), Proton Induced X-Ray Emission (PIXE), Synchrotron Radiation induced Micro Wavelength Dispersive X-Ray Fluorescence (SR-µWDXRF)), Infrared Spectroscopy (IR), Raman spectroscopy and Gas Chromatography Mass Spectrometry (GC-MS) will cover a variety of chemical aspects of the used materials. Modern and old materials will be compared, especially with emphasis on restoration and retouches.

Detailed results concerning Italian instruments, namely those of Stradivari will be shown.

References 1. A. von Bohlen, F. Meyer. Microanalysis of old violin varnishes by total reflection X-ray fluorescence.

Spectrochim. Acta B 52 (1997) 1053-1056. 2. H. Staat, L. Seifert, A. von Bohlen. Detection of casting material on historical violins by infrared

spectroscopy and total reflection X-ray fluorescence spectrometry. Anal Lett 33 (2000) 953-962. 3. A. von Bohlen. Quantitative analysis of minor and trace elements in historical varnishes by total

reflection X-ray fluorescence. Anal Letters 37 (2004) 491 – 498. 4. A. von Bohlen, S. Röhrs, J. Salomon. Spatial resolved element analysis of historical violin varnishes

using µPIXE. Anal. Bioanal. Chem. 387 (2007) 781-790. 5. J.-P. Echard, B. Lavédrine. Review on the characterisation of ancient stringed musical instruments

varnishes and implementation of an analytical strategy. J. Cult. Heritage 9 (2008) 420-429.

29

PL9

THE SINDONE AGE

Luigi Campanella

Dip.to Chimica de La Sapienza, P.le Aldo Moro, 5, 00185 Roma


Da sempre il passato con i suoi misteri, i suoi segreti e le sue curiosità è stato oggetto di numerose ricerche e indagini: certo quando sono nati i biosensori legati alle soluzioni di certi problemi non sarebbe stato facile prevederne un contributo in questo settore. La datazione dei diversi materiali ritrovati ha permesso di ricostruire importanti caratteristiche dei singoli periodi e di collocarli allínterno della storia. Le prime applicazioni della chimica in questo campo hanno avuto come oggetto di ricerca materiali inorganici come, ad esempio, manufatti di ceramica e di metallo, arrivati sino a noi in quantità più abbondanti. Solo negli ultimi anni la chimica ha iniziato ad esaminare anche materiali organici, in precedenza ignorati, anche a causa delle piccole quantità di questi campioni che solo raramente vengono rinvenute nei siti archeologici. Líncidenza delle condizioni ambientali, le esigue dimensioni e la fragilità dei campioni di materiale cellulosico comportano necessariamente lúso di tecniche analitiche non distruttive che richiedano quantità di campione dellórdine del milligrammo. Al fine di pervenire alla datazione di campioni di origine cellulosica in modo non distruttivo e sufficientemente accurato è stato realizzato un opportuno biosensore preciso, selettivo, maneggevole e di costo limitato, applicato allo studio di campioni cellulosici sia di datazione già determinata che incognita. Si parte dal presupposto che tanto più un campione è antico, tanto maggiore è la quantità di CO2 fissata dai microrganismi presenti nellámbiente circostante e quindi tanto maggiore è la quantità di gruppi carbossilici presenti nel campione ai quali un enzima può legarsi chimicamente con il legame NH2-COOH. In presenza del substrato dellénzima, tanto più è antico il campione tanto più è elevato il segnale relativo alla reazione di catalisi enzimatica. Utilizzando come enzima la glucosio ossidasi e come substrato il glucosio, il segnale è determinato dal consumo di ossigeno (ossidazione del glucosio ad acido gluconico). In tal senso il biosensore a glucosio ossidasi utilizza come trasduttore un elettrodo amperometrico a diffusione gassosa per la determinazione dellóssigeno. Le applicazioni hanno riguardato campioni di carta, di provenienza russa, tra il XVIII ed il XX secolo, e due campioni di eguale provenienza ma di età incognita. Sono stati anche studiati campioni di cuoio provenienti dal Cremlino di Mosca, e campioni di stoffa provenienti da un quadro del XIII secolo (su questi campioni si è studiato il diverso invecchiamento secondo la posizione nella tela da cui i reperti sono stati prelevati) ed alcuni campioni di legno antico (XII - XVIII secolo) e di differente natura (ciliegio, pino, noce, ulivo, castagno). Mentre con le precedenti tecniche di analisi si raggiungono buoni risultati ma i campioni utilizzati vengono, per lo più, distrutti durante il procedimento ed inoltre molte di esse risultano laboriose e richiedono strumentazioni di una certa rilevanza, al contrario, analizzando campioni di origine organica con il biosensore a glucosio ossidasi, si evita la distruzione del reperto e si opera con un metodo assai semplice che richiede soltanto un potenziometro come strumento. A questo si deve aggiungere il vantaggio del basso costo e della possibilità di eseguire lánalisi anche "in situ". Il dispositivo a glucosio ossidasi mostra diversa sensibilità a seconda della composizione del materiale, perciò è essenziale che i campioni di riferimento per la calibrazione siano non solo dello stesso materiale, ma che abbiamo la stessa provenienza geografica di quello da valutare.

30

PL10 TUNING THE pH, THE KEY TO WET CHEMISTRY ONSET DURING ANTIQUITY

Philippe Walter

Centre de recherche et de restauration des musées de France, CNRS – UMR171 14 quai François Mitterrand, 75001 Paris, France

[email protected]

The studies of materials from the Cultural Heritage shed new lights on ancient technologies. During the lecture, I will illustrate the development of the use of wet chemistry and how the pH played a key role in the elaboration of ancient Egyptian, Greek and Roman materials. We will consider analyses and reconstitution of old recipes:

We will first focus our talk on the developments of lead-based chemistry that have been initiated in Ancient Egypt for cosmetic purposes more than four thousand years ago. The study of Egyptian makeup containers from the Louvre Museum gives a first example of development of chemical technologies far more sophisticated than we had previously supposed. These containers are made of stone (alabaster, hematite, and marble), ceramic, wood or reed and have characteristics shapes. The exceptionally good state of conservation of these artifacts has enabled quantitative crystallographic and chemical analyses to be carried out on their components. Two well-known natural lead-based compounds were identified: crushed ore of galena (PbS) and cerussite (PbCO3). In addition, the cosmetic powders contain two unexpected main

constituents: laurionite (PbOHCl) and phosgenite (Pb2Cl2CO3), which were so rare in nature that they could

only have been synthesized by wet chemistry to confer therapeutic properties to the eye make-up (1). The reconstitution in the laboratory of old recipies has shown that the formation of the lead chlorides was only possible because of a stability of the pH during the synthesis obtained by a regular replacing of water. The synthesis of lead with pigments involves also similar reactions (3).

Another example of the use of unexpected lead-based chemistry and pH control concerns hair dyeing formulas: reconstitution of their chemical processes and observation of treated hair cross-sections by high resolution TEM allowed us to highlight an early use of nanotechnology during the Greco-roman period. We found that the dye involves the formation of nanocrystals of lead sulfide in the shaft volume without damaging the mechanical properties of the hair. The alkalinity of the dyeing products plays a key role in this process. The composition and supramolecular organization of proteins can control nanocrystal growth: the lead sulfide crystals look like quantum dots synthesized recently using techniques from materials science (3).

References :

1. Ph. Walter, P. Martinetto, G. Tsoucaris, R. Bréniaux, M.A. Lefebvre, G. Richard, J. Talabot, E. Dooryhée (1999) - Making make-up in Ancient Egypt. Nature, 397, pp. 483-484.

2. E. Welcomme, P. Walter, et al. (2006). "Investigation of white pigments used as make-up during the Greco-Roman period." Applied Physics a-Materials Science & Processing 83(4): 551-556

3. Ph. Walter, E. Welcomme, Ph. Hallégot, N. J. Zaluzec, C. Deeb, J. Castaing, P. Veyssière, R. Bréniaux, J.L. Lévêque, G. Tsoucaris (2006) – Evidence for early use of nanotechnology from an ancient hair dyeing formula. Nanoletters 6/10, pp. 2215-2219.

31

PL11 MOLECULAR SCIENCES FOR ART:

FROM RENAISSANCE TO CONTEMPORARY Antonio Sgamellotti

SMAArt, CNR-ISTM and INSTM - Department of chemistry, University of Perugia [email protected]

Molecular Sciences provide a powerful tool to solve many problems in the field of cultural heritage and can

be used to suggest appropriate procedures for conservation and restoration of artworks. Recent

technological developments in microelectronics and fiber optics have led to the development of portable

scientific instrumentation to carry out non-invasive in-situ measurements. This has enabled the Perugia

Centre of Excellence SMAArt to assemble a mobile laboratory MOLAB, which is a European infrastructure in

the Eu-ARTECH project. An extensive study on the state of

conservation of Michelangelo’s David with a non-invasive approach

will be discussed. Scientific investigations offer the possibility to establish

in great detail the painting techniques of ancient masters. The

investigations of the underdrawings of the Rocks (London, National

Gallery) will be discussed and the palette of the painter il Perugino

will be presented. This Renaissance artist, besides using traditional pigments of the

sixteenth century, also experimented with metal powders, such as bismuth or bronze, or

minerals with metallic lustre, or even powders of transparent uncoloured glass, in the effort

to reach more sophisticated chromatic effects. The multi-technique approach of MOLAB has

been adopted for investigations in modern and contemporary art. Six oil paintings and five

water colours by Cezanne, all exhibited at the Courtald of London, have been

investigated. The study concerns the differences and similarities of the palette of the artist

throughout his long career. The study of Victory Boogie Woogie, Gemeentemuseum in

Den Haag) allowed for the identification of the pigments used by Mondriaan in his last

unfinished masterpiece and allowed for a consideration of the building of the

painting’s construction, revealing earlier phases of the

composition. The investigations of twenty paintings

by Burri (Fondazione Palazzo Albizzini Collezione Burri, Città di Castello, Perugia)

allowed for the characterization of the execution techniques and materials

used by the artist in the period 1948-1976. Gino de Dominicis’

monumental sculpture, Calamita Cosmica, was investigated by employing a

combination of non-invasive and micro-invasive techniques. The sculpture was found to

be comprised of a polyester core, to which five subsequent

layers of varying composition had been added. The peculiar

optical properties of lustre, a ceramic decoration, are due to

a high-density distribution of copper and silver nanoclusters within the first

layer of the glaze. It is the presence of these nanoparticles that confers to the lustre its peculiar chromatic

properties: brilliant metallic reflections, iridescence and changing effects.

32

INVITED LECTURESINVITED LECTURESINVITED LECTURESINVITED LECTURES

33

IL1

LE PROBLEMATICHE CHIMICO-AMBIENTALI DEL SISTEMA LAGUNARE VENEZIANO

Paolo Cescon, Dipartimento di Scienze Ambientali, Università di Venezia


34

IL2 IL COORDINAMENTO SCIENTIFICO DELLE RICERCHE IN LAGUNA

Pierpaolo Campostrini

CORILA

[email protected]

La laguna di Venezia è la più ampia del Mediterraneo e costituisce un esempio paradigmatico della complessità delle relazioni tra azioni dell’uomo ed evoluzione naturale. Anche la laguna di Venezia avrebbe seguito il destino di molte lagune del Nord Adriatico, documentate in età storica e oggi definitivamente scomparse, se non fosse stato per una serie lunga di azioni antropiche, iniziate già nel XV secolo.

L’età moderna, in cui si è ingigantita la potenza di tali azioni, ha visto da un lato verificarsi il limite fisico di alcune misure di adattamento (quali il rialzo delle costruzioni per compensare la crescita del livello medio marino), dall’altro l’insorgere di nuove problematiche connesse sia all’introduzione di nuovi “usi” dell’ambiente (quali ad es. l’utilizzo delle aree di gronda per porto ed industrie, l’utilizzo di fertilizzanti chimici in agricoltura), sia al radicale cambiamento di pratiche tradizionali (quali la navigazione a motore e la pesca delle vongole con mezzi meccanici).

La “crisi” determinata dall’alluvione del 1966 ha evidenziato non solo il deficit delle strutture fisiche di difesa, ma anche quello delle conoscenze, la cui crescita non era stata tale da permettere di controllare gli effetti ambientali del “boom” economico del dopoguerra. A differenza di Firenze, dove in fondo il problema della piena dell’Arno era per lo più “monodisciplinare”, a Venezia apparve subito che il tema della salvaguardia apparteneva a più discipline scientifiche. Attorno al capezzale della città “in pericolo” non era sufficiente chiamare ingegneri idraulici, ma anche scienziati chimici, biologi, fisici, a colloquio stretto con storici dell’arte e dell’architettura, nonché con esperti di economia. Diversi interventi furono esperiti a tale riguardo.

Negli anni ‘90 il MIUR, con i fondi della Legge speciale per Venezia, coordinò un ampio programma di ricerca che produsse molti dati e soprattutto la consapevolezza della necessità di considerare il “sistema lagunare veneziano” nella sua interezza ed in modo interdisciplinare. Tuttavia tale programma non riuscì a produrre quelle risposte concrete “semplificate e pronte all’uso” che in fondo il sistema politico richiedeva. Nella coda di tale progetto nasce quindi nel ’98 CORILA, su indicazione del Comitato di indirizzo e controllo per la legge speciale (“Comitatone”). Esso è struttura no-profit di diretta emanazione degli attori scientifici pubblici (Università, CNR) attivi nella salvaguardia di Venezia, ma indipendente e capace di rendere conto delle risorse assegnate. CORILA viene costituito per coordinare ciò che esiste, magari non ancora del tutto valorizzato, nelle competenze del mondo scientifico e non per duplicarle. Il mandato è di produrre risultati utilizzabili, allo stato dell’arte delle conoscenze e cercando di riempire i “buchi” conoscitivi, ancora diffusi a macchia di leopardo. Dal primo finanziamento statale, correttamente utilizzato, CORILA è cresciuto nella considerazione del mondo scientifico come strumento capace di integrazione scientifica multidisciplinare in diversi settori ambientali ed oggi è parte attiva, talora con funzioni di leader, in diversi progetti internazionali. CORILA tuttavia è primariamente impegnato nell’azione di sviluppo delle conoscenze lagunari, come dimostrano alcuni esempi qui presentati.

35

IL3

REMEDIATION AND BIOREMEDIATION OF DREDGED POLLUTED SEDIMENTS OF THE VENICE LAGOON, ITALY: AN ENVIRONMENTAL-FRIENDLY APPROACH

F. Corami1*, W. R. L. Cairns1, E. Zanotto2, C. Rigo1, M. Vecchiato1, , R. Piazza1,3, M. Citron2 and P. Cescon1,3

1: CNR-IDPA, Istituto per la Dinamica dei Processi Ambientali,; 2: Autorità Portuale di Venezia, 3: Dip.

Scienze Ambientali, Università degli Studi Ca’ Foscari.

*e-mail: [email protected]

Contamination in waters and sediments of coastal areas and harbours is due to a wide range of organic (POPs, such as

PCBs, PAHs, etc.) and inorganic pollutants (trace elements, such as chromium (Cr), lead (Pb), mercury (Hg), etc.). In

these areas sediments may be a significant sink and/or source of those pollutants. Taking into account the need to

dredge sediments in order to keep channels of navigation open, remediation and environmental recovery are key

topics in harbour areas. Nowadays, the management of dredged sediments is essential for the growth of the port of

Venice, due to increasing sea traffic and to increasing foreign trades. In view of the dredging of many millions of cubic

meters of sediments according to the Piano di Recupero Morfologico (Regione Veneto, Magistrato alle Acque e ufficio

del Commissario Delegato per l'Emergenza Socio Economico Ambientale relativa ai Canali Portuali di Grande

Navigazione della Laguna di Venezia), the main goal of this project is to assess a novel washing procedure for dredged

sediments, which will be environment friendly and suitable for the variety of organic and inorganic pollutants, by

exploiting the surface-active and complexing properties of natural organic substances commercially available. In the

Venice Lagoon, sediments are classified according the Protocollo Venezia. In relation to the total concentration of

trace metals and the concentration of organic pollutants, sediments are classified as A, B, C and above C; the

sediments C and above C are the most polluted, while the sediments A are the less polluted. In the first phase of the

study, dredged sediments from the industrial area of the Venice lagoon were characterised for the concentration of

organic pollutants (such as PCBs, PAHs) and for the total concentrations of several trace elements (As, Cd, Cr, Cu, Hg,

Ni, Pb, Zn, etc.). Furthermore, we used a modified sequential extraction procedure in order to evaluate the

concentration of the trace elements in the chemical fractions: the exchangeable, the carbonate bound, the Fe and Mn

oxides bound, the sulphur and organic matter bound, the residual bound. The first two fractions are considered the

most mobile and thus the most bioavailable and those, which may exert toxic effects on biota. The RSD% for total

trace metal concentration of the elements studied was ≤10%. The different fractions of the geo-speciation are

reported as a percentage, to highlight the different weight they have. In the second phase of this study, the washing

process was assessed; different parameters were considered (such as pH, concentration of the washing solution,

sediments/volume of the washing solution ratio, length of washing, etc.). All the batch experiments were run in

duplicate, to test the homogeneity and the repeatability of the procedure. The RSD% of all the batch experiments run

was ≤ 10%; After the washing, the concentration of the total PCBs was averagely decreased by 57%, while the

concentration of the total PAHs was decreased by 40%; as for the trace elements, the average decrease was 30%, but

it was higher for some elements, such as Cd, Cu. Bioremediation experiments were run on sediments washed as

described above. The bacteria were isolated from the autochthonous microbial community of the sediments of the

Venice Lagoon and then bioaugmented, before being inoculated. Experiments were run in duplicate and in

microcosms, each with its own control. PCBs and PAHs show a decrease, which was not as great as that observed in

the washing batches. The trace metals concentrations vary within the measurement error; thus, a decrease might not

be observed. However, these results are very promising, due to the holistic approach for different classes of pollutants

and for the synergy of different techniques used. Moreover, this study underlines the importance of speciation, since,

according to the most recent frameworks on risk assessment, it is essential to know the bioavailability and

bioaccessibility of pollutants in order to plan the most suitable remediation project.

36

IL4

METAL CHEMICAL SPECIATION IN THE WATER OF THE LAGOON OF VENICE. Gabriele Capodaglio

Dipartimento di Scienze Ambientali, Università Ca’ Foscari, Venezia

The Lagoon of Venice is the largest Italian Lagoon; in the last century it have considerably reduced the environmental quality because chemical contamination deriving principally from industrial and agricultural activities as well from the increased population. One important class of contaminants was trace metals deriving from the industrial activity. On the other hand there is the evidence that trace elements behaviour and their environmental effects is strongly affected by their chemical form. Tests carried out on Lagoon sediments showed that their toxicity was not correlated to the total content of pollutants but was dependent on their speciation; this confirming that the environmental impact of trace metals on marine environment need to differentiate the forms in which are present. An important role on metal speciation in natural waters is played by dissolved and colloidal organic matter. Investigations were carried out to assess the effect of dissolved organic matter on the composition of colloidal and particulate matter at the interface between the Silone channel and the Lagoon. As normally observed in estuarine areas they found a release of Cd and Zn from particulate with the increase of salinity, in particular, they emphasized an increase of colloidal organic matter corresponding to the highest salinity gradient. Although these results highlight the fundamental role played by the organic matter in the transport and the ultimate fate of trace metals, we can not distinguish the contribution of salinity and organic compounds to the dissolved/particulate partition.

The titration of dissolved organic ligands by anodic stripping voltammetry was used to determine the labile metal fraction, the complexing capacity and the relative conditional stability constant. The metal speciation was obtained through equilibrium calculations using the ligand concentrations and the conditional stability constants obtained by titration.

The speciation of cadmium, copper and lead was investigated in samples collected during several campaigns, from 1992 to 2003, in the central Venice Lagoon in order to highlight the trend during the last decade. The variability of the trace metal concentration and their speciation were examined as a function of season and tide cycle. The concentration in dissolved phase was related to the concentration in the particulate form to evaluate the effect of metal complexation by organic ligands on partition processes.

Significant difference were observed in temporal variability of dissolved metal concentration for the three elements between 1992 and 2003. A remarkable increase of dissolved cadmium concentration was observed in the central lagoon, it range between 0.13 nM at 1992 and 0.6 nM at the 2001-2003. The dissolved copper concentration show a high variability but we can not observe a significant increase, while the lead concentration was halved. All the studied metals presented one important organic fraction, however it was different for the three elements, the organic form of copper is always higher than 70% of the total dissolved concentration, for samples where the total dissolved metal was of few nmol/L the organic fraction was higher than 90%. The cadmium complexed by organic ligands ranged between 27 and 44% of the total, while the fraction of lead complexed by organic ligands was quite constant, about 30% of dissolved metal.

References

1. V Achterberg, E.P. and C.M.G. Van Den Berg (1997). "Chemical speciation of chromium and nickel in the western Mediterranean." Deep Sea Research Part II: Topical Studies in Oceanography 44(3-4): 693-720. 2.Corami F., G. Capodaglio, C. Turetta, M. Bragadin, N. Calace, BM. Petronio. Complexation of cadmium and copper by fluvial humic matter and effects on their toxicity. Ann. Chim. (Rome), 97 (2007) 25-37. 3. Iyer, V.N. and R. Sarin (1992). "Chemical speciation and bioavailability of lead and cadmium in an aquatic system polluted by sewage discharges." Chemical Speciation and Bioavailability 4(4): 135-142. 4. Martin, J.M., M.H. Dai and G. Cauwet (1995). "Significance of colloids in the biogeochemical cycling of organic carbon and trace metals in the Venice Lagoon (Italy)." Limnology and Oceanography 40(1): 119-131. 5. Scarponi, G., C. Turetta, G. Capodaglio, G. Toscano, C. Barbante, I. Moret and P. Cescon (1998). "Chemometric Studies in the Lagoon of Venice, Italy. 1. The Environmental Quality of Water and Sediment Matrices." Journal of Chemical Information and Computer Sciences 38(4): 552-562.

37

IL5

LOW TEMPERATURE LAUNDRY WASHING:

A BETTER CHEMISTRY FOR THE ENVIRONMENT & THE CONSUMER

J. Kielholz (Reckitt Benckiser Italia S.p.a.) , L. Spadoni* (Reckitt Benckiser Italia S.p.a.)

In the past, laundry washing was usually performed at high temperature, 60°C or 90°C. This temperature was ensuring good bleaching of stains and soils by oxidising species (perborates or percarbonates, as inorganic solid sources of hydrogen peroxide) and satisfactory cleaning results. This peroxide bleaching, though, shows a strong temperature dependence with an activation energy of 50 Kcal/mole and at low temperature its cleaning effectiveness strongly decreases, being very limited at 60°C or below. In the 80s, a change in consumer habits provoked a search for new low-temperature bleaching systems. This eventually led to the development of the so-called bleach activators, i.e., species which stoicometrically reacts in-situ

with hydrogen peroxide, generating peroxyacids, a bleaching agent more reactive than hydrogen peroxide (12 Kcal/mole activation). Lead example in this area is TAED (tetraacetylethylene diamine), which generates peracetic acid via perhydrolisis in the laundry liquor. Similarly, more hydrophobic bleach activators were developed for the US market, e.g., NOBS (nonanoyloxybenzene sulfonate) which react in in-situ with hydrogen peroxide to generate pernonanoic acid, a surface-active peroxyacid. In more recent years, the market is moving toward even more sustainable laundry cleaning solutions. The industry is leading this process through a number of market initiatives and consumer education activities, promoted by either individual companies or by the relevant industry associations (AISE). Technically, this translates into an R&D focus towards the next generation of bleach activators, to provide effective laundry cleaning at 30°C or below.

Research has been looking into metal catalysts, new hydrophobic and hydrophilic bleach activators (nitrile quats, DOBA), preformed peracids (PAP), oxaziridines and dioxiranes. The presentation will give a brief overview on these technologies.

38

IL6

.

NEW LIFE FOR MATURE PRODUCTS: APPLICATION OF PAT AND QUALITY BY DESIGN ON API

MANUFACTURING

M. Stivanello*1, G. Volpe1, E. Bolzonella1, C. De Faveri1, F. Huber1, T. Piovesana1, M. Bryder2, H. Lopez De

Diego2, M. Mealy2, J.P. Nielsen2 1Lundbeck Pharmaceuticals Italy SpA, Quarta Strada, 2- 35129-Padova, Italy and

2 H. Lundbeck A/S, OttiliaVej 7-9, CK-2500 Valby, Denmark

*[email protected]

Process Analytical Technology (PAT), according to FDA statement, is a “system for designing, analyzing, and controlling manufacturing through timely measurements (i.e., during processing) of critical quality and performance attributes of materials and processes with the goal of ensuring final product quality”. PAT is therefore consistent with current guidelines for the manufacturing of pharmaceutical products, which state that quality cannot be tested only into product, but should be built-in by design (Quality by Design approach).

Various PAT tools are nowadays available, among which statistical methods (i.e. DoE and MVA) and modern on-line process analyzers are the most used in pharmaceutical and API manufacturing companies. These tools are currently used either for general process optimization or for the development of optimized and robust crystallization processes of final active pharmaceutical ingredient (API).

In this regard, a comprehensive study of crystal form of new APIs, including identification and characterization of new polymorphs, solvates or hydrates, as well as the knowledge of critical process parameters (CPPs) affecting the final API quality, is of paramount importance in the development of new drug substances.

One ‘case study’ will be presented where on-line RAMAN spectroscopy combined with other analytical techniques were used to detect and analyze different hydrate forms of an active pharmaceutical ingredients now under clinical development in Lundbeck. This API is in fact characterized by the presence of different stable hydrates and solvates which are formed and can convert each other under different crystallization conditions. Particularly the initial goal was to obtain a pure dihydrate hydrochloride salt avoiding the formation of the hygroscopic monohydrate form or other solvates with organic solvents. After an initial ‘classical’ process development, the use of on-line RAMAN spectroscopy proved to be extremely useful in differentiating the two different mono and dihydrate forms directly in the crystallization mixture; this tool, combined with other more traditional techniques, allowed identifying the key CPPs responsible of the selective dihydrate formation during the final crystallization step and thus allowed defining a robust process that could be applied successfully on pilot plant scale

39

IL7

Process Development and ElectroChemical Fluorination:

Is a Rational Approach Possible?

Dr. Andrea Missio Miteni SpA

Loc. Colombara, 91 36070 – Trissino (VI) Italy

ElectroChemical Fluorination (ECF) has been one of the technologies most widely used for the production

of fluorinated surfactants based on chain lenghts of eight or more carbon atoms.

In its simplest formulation, the ECF process converts a fully hydrogenated substrate into its corresponding

perfluorinated derivative. The reagents are anhydrous hydrofluoric acid and electricity.

RHCOX RFCOFAHF

electricity

In recent years these products have been under scrutiny due to their environmental burden.

A number of strategies, aiming at the replacement of such molecules, have been identified.

The talk will focus on examples based on C4 and C6 chemistry, where the ECF technology can be successfully used to produce fluorocehmicals with an improved environmental footprint.

40

IL8

HYDROLYTIC KINETIC RESOLUTION (HKR) IN AN EFFICIENT PROCESS FOR A COMPLEX ACTIVE PHARMACEUTICAL INGREDIENT

Livius Cotarca*, Paolo Maragni and Massimo Verzini

ZaCh System (Zambon Advanced Fine Chemicals) spa, via Dovaro 2, 36045Lonigo (VI), Italy

*[email protected]

Hydrolytic Kinetic Resolution (HKR) has emerged in recent times as a powerful tool to synthesize both terminal epoxides and their corresponding diols in a highly enantiomerically pure form1. These building blocks have been shown to be very useful for synthesizing a wide range of bioactive compounds2. While the original procedure has proved scalable for many substrates, several issues needed to be overcome for the process to be industrially practical3.Chiral processes i.e., asymmetric syntheses, chiral separation and dynamic second order transformations are ZaCh System core technologies. When the chiral starting material is not readily commercially available the process design and development is forced to solve deracemization by introducing specific process steps, e.g., classical resolutions, liquid column separations or catalytic (dynamic) asymmetric resolutions. Since the economics of the process for future generics is a key success factor, the “chiral atom-efficiency” is a crucial point. Our success in applying this approach to design a novel process for a known API4 is an ideal example of a target-oriented application of HKR technology to exploit the full “chiral content” of the starting material. The bioactive compound which is the object of this novel application of HKR is Nebivolol hydrochloride (Nebilet®; Lobivon®; Bystolic® ) (Figure 1). This is a third generation β-blocker which is being developed as an optional treatment for essential hypertension, angina, migraine and congestive heart failure.

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(D-Nebivolol)

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(L-Nebivolol)

(2) (3)

Figure 1 – (+) and (-) enantiomers in the racemic mixture of marketed Nebivolol

ZaCh is pleased to report the successful design of an innovative and atom efficient synthetic route to

racemic Nebivolol hydrochloride (API). The approach involves a convergent synthesis to the

enantiomerically pure precursors of both (+)-Nebivolol (SRRR-configuration; D-Nebivolol), and (-)-Nebivolol

(RSSS-configuration; L-Nebivolol) starting from the corresponding chroman epoxide as a key raw material.

The result is a practical and economically viable process which permits strict control over the quality of final

API both in terms of chemical and stereoisomeric impurities.

References 1. a) M. DiMare, H. Kabir, Chiral Technologies Today - Oct 2004, p.40-43 (supplement to Chimica Oggi - Chemistry Today - Mar-Apr 2005, 23, n.2) b) M. DiMare, Innovations in Pharmaceutical Technology 2002, 02(10), 116, 118-121. 2. For a recent review, see: P. Kumar, V. Naidu, P. Gupta, Tetrahedron 2007, 63, 2745-2785. 3. a) D. E. White and E. N. Jacobsen, Tetrahedron:Asymmetry 2003,14, 3633-38; b) L. Aouni, K. E. Hemberger, S. Jasmin, H. Kabir, J. F. Larrow, I. Le-Fur, P. Morel and T. Schlama, Chapter in H. U. Blaser and E. Schmidt (Ed), Asymmetric Catalysis on Industrial Scale:

Challenges, Approaches and Solutions 2004, p. 165, Wiley-VCH, Verlag GmbH & Co, KGaA; c) J. F. Larrow, K. E. Hemberger, S. Jasmin, H. Kabir, P. Morel, Tetrahedron: Asymmetry 2003, 14(22), 3589-3592. 4. P. Maragni and L. Cotarca, Spec. Chem. Magazine, 2009, 29(1), 48-50; E. Ullucci, P. Maragni, J. Foletto (ZaCh System S.P.A.), WO2008064826A1, 2008; R. Volpicelli, P. Maragni, L. Cotarca, J. Foletto (ZaCh System S.P.A.), WO2008040528A2, 2008; R. Volpicelli, P. Maragni, L. Cotarca, J. Foletto, F. Massaccesi (ZaCh System S.P.A.), WO2008064827A2, 2008.

41

IL9

Biotransformations in Organic Synthesis

Enantioselective hydrolysis for a Moxifloxacin

binding block preparation

Fogal S.a*, Motterle R.b, Arvotti G.b, Galvagni M.b, Castellin A.b,

Bergantino E.a

aDepartment of Biology, University of Padova, Viale G. Colombo 3, 35121

Padova, Italy

bFabbrica Italiana Sintetici, Viale Milano 26, 36075

Alte di Montecchio Maggiore – Vicenza, Italy

The compound C in synthesis of Moxifloxacin represents an expensive binding block because of its

enantiomeric configuration. Enzymes became recently promising and available tools for chemical synthesis.

In particular lipases and esterases are often used to resolve racemic mixture of esters1-3.

We propose an enzymatic step in order to obtain B, precursor of C, in enatiopure form. The process

consists in preparation of racemic mixture of water- soluble A, enantioselective hydrolysis catalyzed by Cal

B and separation of product from unreact substrate. This last was used as precursor of C. The

process is going to be develop.

References

1. A. Liljeblad, J. Lindborg, A. Kanerva, J. Katajisto, L. T. Kanerva, Tetr.Lett. 2002, 43, 2471-2474. 2. M. C. Ng-Youn-Chen, A. N. Serreqi, Q. Huang, R. J. Kazlauskas, J.Org. Chem. 1994, 59, 2075-2081. 3. E. J. Toone, Bryan Jones Can. J. Chem. 1987, 65, 2722-2726.

42

IL10

THE ROLE OF pH IN CONCEPT-BUILDING FOR MOLECULAR SENSING AND COMPUTING

Gareth J. Brown,a A. Prasanna de Silva,*

a Kaoru Iwai,

b Gareth D. McClean,

a Bernadine O.F. McKinney,

a David C. Magri,

a

Seiichi Uchiyamac and Sheenagh M. Weir

a

a. School of Chemistry and Chemical Engineering, Queen’s University, Belfast, Northern Ireland

b. Department of Chemistry, Nara Women's University, Kitauoya-Nishimachi, Nara, Japan

c. Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo , Japan

([email protected])

Chemical species can serve as carriers of data for molecular information gatherers (sensors) and processors (logic gates). Protons are perfect for this application due to their relative simplicity and due to the convenience of pH measurements. In our design of such molecules, protons trigger luminescence which is an appealing signal output. Luminescence is a major channel of de-exciting excited states. Photoinduced electron transfer (PET) (at the heart of photosynthesis)1 is another such channel. The controlled competition of luminescence with PET can switch the luminescence ‘on’ or ‘off’ with protons in an easy, predictable manner (Scheme).

These sensors can monitor the pH of blood within millimeter-sized channels or the status of acidic compartments in micrometer-sized cells. Some of these even map proton distributions in nanometric spaces near membranes.2 Notably, some of these serve wider society by operating in hospital intensive care units.3

The logic gates can use protons along with other species. Logic gates allow us to perform simple computations. These form molecular-scale information processors4 which employ chemical species as inputs, light as output and wireless interfacing to human operators. These processors operate comfortably in nanometer-sized regions near membranes,5 for instance. These spaces are far too small for the tiniest silicon-based electronic devices to enter. Such molecular logic devices are continually growing in complexity. Some of these have potential as ‘lab-on-a-molecule’ systems for intelligent medical diagnostics.6

Another robust application is molecular computational identification (MCID) of nano/micrometric objects.7 This is an application which addresses a problem that does not currently have solutions from semiconductor computing technology. This application uses proton-triggered luminescence. The growth of molecular computation can also be aided by the provision of easy-to-use methods for logic gate production. Proton-triggered, self-assembled luminescent PET systems are the newest of these methods.8

References 1. Electron Transfer in Chemistry, V. Balzani; Ed.,Wiley-VCH, Weinheim, 2001 2. S. Uchiyama, K. Iwai and A.P. de Silva, Angew. Chem. Int. Ed. Engl. 47, 4667 (2008).

3. See OPTI® blood gas and electrolyte analyzers at www.optimedical.com. 4. A.P. de Silva and S. Uchiyama, Nature Nanotechnol. 2, 399 (2007).

5. S. Uchiyama, G.D. McClean, K. Iwai and A.P. de Silva, J. Am. Chem. Soc. 127, 8920 (2005).

6. D.C. Magri, G.J. Brown, G.D. McClean and A.P. de Silva, J. Am. Chem. Soc. 128, 4950 (2006).

7. A.P. de Silva, M.R. James, B.O.F. McKinney, D.A. Pears and S.M. Weir Nature Mater. 5, 787 (2006).

8. A.P. de Silva, C.J. Dobbin, T.P. Vance and B. Wannalerse Chem. Commun. 1386 (2009).

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43

IL11

Efficient treatment of Iron Gall Inked papers Valeria Conte*, Gabriele Ceres, Valentina Mirruzzo, Jana Kolar, Matija Strlič

Università di Roma "Tor Vergata", Dip. Scienze e Tecnologie Chimiche, via della Ricerca Scientifica, 00133

Roma, Italy, Morana RTD d.o.o., Oslica 1b, 1295 Ivančna Gorica, Slovenia, University College London, Centre

for Sustainable Heritage, The Bartlett School of Graduate Studies, London WC1E 6BT, U.K. corresponding

author: [email protected]

With no doubts, starting from Medieval Age up to the middle of 20th century, iron gall ink was the most used ink in

western history, therefore there are a plethora of important documents written with this ink. However iron-gall inks

are also well-known to deteriorate paper, due to corrosive action of transition metal ions and acidity contained in ink

components. Due to the extent of damage, the topic has been in the focus of several recent studies. In restoration

field, the treatments used are principally carried out in aqueous solution, and the research of new non-aqueous

methods is a goal still open. “Calcium phytate method” is considered one of the most effective aqueous stabilisation

method. It involves treatment with an aqueous solution of an antioxidant calcium ammonium phytate, followed by

the deacidification with calcium bicarbonate. Recently, use of magnesium phytate solution was proposed1, because, at

odd with “Calcium phytate” method, avoids the use of ammonia solution, thus minimizing health risks. Moreover, as

magnesium phytate is fully dissolved at the conditions of use, risks of formation of the surface deposits are minimised.

In addition to aqueous treatments, from an EU co-funded project InkCor the use of bromide antioxidants for non-

aqueous stabilisation of iron gall inks was proposed.2,3,4

Within this study, the stabilising effect of aqueous treatments

with calcium and magnesium phytate but also non-aqueous treatments involving several imidazolium based ionic

liquids as antioxidants was evaluated. In particular Two new antioxidants, 1-ethyl-3-methylimidazolium bromide

(EMIMBr) and 1-butyl-2,3-dimethyl-imidazolium bromide (BDMIMBr), together with alkali magnesium ethoxide in

ethanol, were found to play an effective stabilization of iron gall ink containing model paper. The effect of stabilisation

was superior to the previously studies antioxidants, either bromides or phytates. Furthermore adverse effects on

colour of the ink were not observed, which makes the two antioxidants potential appealing alternatives to the

currently used aqueous phytate treatments. However, more studies are needed, before they may be considered save

for use on historical documents.

Degradation rate constants of untreated paper containing iron gall ink (Untreated) and the ones stabilised using prototype non-aqueous treatments or aqueous calcium or magnesium phytate treatments. The papers were aged for 168 hrs at 80 oC and the 65% relative humidity. Non-aqueous treatment solutions contained either alkali (MgEtO), or a combination of an alkali and antioxidants tetrabutyl-ammonium bromide (TBABr), 1-benzyl-3-butyl-ammonium bromide (BBABr), 1-ethyl-3-methylimidazolium bromide (EMIMBr), 1-butyl-3-methyl-imidazolium bromide (BMIMBr), 1-butyl-2,3-dimethyl-imidazolium bromide (BDMIMBr) and 1-hexyl-3-methylimidazolium bromide (HMIMBr) or 1-hexyl-3-methylimidazolium chloride (HMIMCl).

References 1. J. Kolar, A. Možir, M. Strlič, G. de Bruin, B. Pihlar, T. Steemers, e-PS, 4, 19-24, 2007,. 2. J. Kolar, M. Strlič, M. Budnar, J. Malešič, V. S. Šelih, J. Simčič, Acta Chim. Slov., 50, 763−770, 2003. 3. J. Malešič, J.Kolar, M. Strlič, S. Polanc, e-PS, , 2, 13-18, 2005. 4. J. Kolar, M. Strlič (Eds.), Iron gall inks: on manufacture, characterisation, degradation and stabilisation, Narodna in

univerzitetna knjižnica, Ljubljana, 2006. 5. G. Ceres, V. Conte, V. Mirruzzo, Matija Strlic, J. Kolar; ChemSusChem 1, 921-926, 2008.

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44

IL12

REGIONAL ORIGIN CONTROL OF GRAPE MARC DISTILLATES (GRAPPA) BY STABLE ISOTOPES ANALYSIS OF ETHANOL AND TECHNOLOGY IMPROVEMENT VERIFICATION BY MEASURING SOME

COMPONENTS

Giuseppe Versini1*, Fabio Finato1, Bruno Fedrizzi1,2, Michela Cipriani1 and Alberto Marangon3

1. Unione Italiana Vini, Laboratorio Enologico, I-37135 Verona;

2. Università di Padova, Dipartimento di Scienze Chimiche, I-35131 Padova;

3. Laboratorio Analisi Sensoriale, Veneto Agricoltura, Istituto per la Qualità e le Tecnologie Agrarie , I-

36016 Thiene (Vicenza)

Objective origin and quality control by physico-chemical analysis are becoming even more important tools to judge typical products, which are also sensorially evaluated. ‘Origin’ includes several concepts emphasized by the EU Regulation N. 110/2008 on alcoholic beverages with relevant PDO classifications, like the strict origin from grape derivates, the ‘terroir’ effects on specific grape varieties, the traditional production technology including distillation equipments and peculiar relevant conduction methods.

A recent approach to investigate the effective origin from grape sugar and the geo-climatic influence on sugar biosynthesis is the stable isotopes analysis on the ethanol both by SNIF-2H NMR (analysis of methylic (D/HI) and methylenic (D/HII) positions), and by IRMS (Isotopic Ratio Mass Spectrometry) analysis for total 13C/12C content, according to EU Reg. N. 2676/1990 and relevant updating. Considering a possible influence of distillation techniques and grape-growing subareas on the parameters variability as evidenced in previous researches on some Italian grappas and German Kirsch renowned production areas, particular attention has been paid in Veneto on the effect of vintage, prevalent marc delivering areas to 8 distilleries and distillation methods.

Even if such factors seem to influence the variability during two vintages, the general variability for Venetian products seems to support the origin control in comparison to those from some neighbouring regions.

On the same products, some compounds causing possible off-flavours like solvent/vinegar and cut grass/green scents as ethyl acetate and acetaldehyde + acetal, have been sensorially evaluated in comparison to the analytical values to establish the highest contents admissible in a Venetian grappa. These limits are going to be introduced in the quality regulation.

Other off-flavours are often remembering rancid and/or sulfur compounds typical scents. A research has been focused on the development of a HS-SPME/GC-MS method to easily quantify some substances possibly contributing to this group of off-flavours, u.a. unsaturated aldehydes and sulfur compounds.

Among sulfur compounds, CS2, dimethyl di- (DMDS) and trisulfide (DMTS), diethyl disulfide (DEDS) and methylethyl disulfide (MEDS) are mostly linked to original mercaptans levels in marcs and therefore to the silage conditions. Methionine-derived compounds are dimethyl sulfide (DMS), 3-(methylthio)propyl acetate (MTPA), ethyl 3-(methylthio)propanoate (EMTP) and dihydro-2-methyl-3(2H)-thiophenone (DHMTP). Two other sulfur unidentified compounds have been evaluated as possible acetals. A possible ‘distillery effect’ seems to be emphasised. Some formations can be favoured by the copper catalysis and linked to the distillation methods.

Considerations about saturated and unsaturated and aromatic aldehydes have been also drawn, as so as on minor aroma compounds linked to aroma precursors depending on climate conditions and grape processing technology.

45

IL13

APPLICAZIONI TECNOLOGICHE DELLA CHIMICA DEI POLIFENOLI PER LA PRODUZIONE DI ALCUNI VINI TIPICI

Vincenzo Gerbi*, Enzo Cagnasso, Luca Rolle, Fabrizio Torchio

Dipartimento di valorizzazione e Protezione Risorse Agroforestali – Settore Microbiologia e Industrie

Agrarie, Università degli Studi di Torino, Via L. da Vinci 44, 10095 Grugliasco (TO), Italy

Corresponding author: [email protected]; Fax +39 0116708549

Riassunto

I polifenoli estratti dalle bucce e dai vinaccioli degli acini d’uva1 hanno una notevole influenza sulle proprietà sensoriali dei vini rossi, specialmente sulle caratteristiche cromatiche2,3,4, sulle sensazioni di astringenza e amaro5,6. Gli antociani, le proantocianidine ed i loro composti di combinazione e co-pigmentazione che si formano durante la vinificazione7,8, sono i principali responsabili di queste proprietà. Notevoli sono stati i progressi della chimica delle sostanze polifenoliche di interesse enologico nel corso degli ultimi decenni9,10. In particolare sono stati chiariti molti meccanismi delle reazioni coinvolte nelle profonde trasformazioni che caratterizzano la vinificazione e soprattutto l’invecchiamento del vino9. Queste conoscenze sono fondamentali da un punto di vista tecnologico per una gestione razionale del processo di vinificazione.

La conoscenza del potenziale fenolico delle uve è molto importante nella gestione del processo di macerazione e vinificazione di uve rosse11,12,13. Questo lavoro prende in considerazione i punti critici della vinificazione di uve Nebbiolo e Barbera da cui derivano rinomati e tipici vini piemontesi quali il Barolo, il Barbaresco, il Barbera d’Asti e il Barbera d’Alba. Le uve Nebbiolo sono caratterizzate da un medio contenuto di antociani, soprattutto disostituiti, più facilmente degradabili, e da un consistente tenore di tannini, estratti soprattutto dalle bucce. Invece le uve Barbera presentano un contenuto di antociani medio-alto, mentre basso è il contenuto di tannini estraibili dalla buccia. Conseguentemente i vinaccioli possono rivestire un ruolo fondamentale nella definizione della struttura tannica del vino.

In generale, a livello tecnologico, le conoscenze sulla chimica dei polifenoli risultano fondamentali per esaltare le caratteristiche varietali della materia prima e per garantire l’ottenimento di vini con un colore stabile nel tempo e con proprietà gustative equilibrate. References 1. Amrani-Joutei K., Glories Y., Mercier M. Vitis. 33: 133. 1994. 2.. Somers T.C. Vitis, 7: 303. 1968. 3 .Ribérau-Gayon P. Vitis, 12: 119. 1973. 4. Glories Y.. Conn. Vigne Vin, 18 : 195. 1984 5. Arnold R.A., Noble A.C., Singleton V.L. J. Agric. Food Chem. 28: 675. 1980. 6. Robichaud J.L., Noble A.C. J. Sci. Food Agric. 53: 343. 1990. 7. Bakker, J., Timberlake, C.F. J. Agric. Food Chem., 45: 35. 1997. 8. Benabdeljalil, C., Cheynier V., Fulcrand, H., HakikI, A., Mosaddak, M., Moutounet M. Sci. Alim., 20: 203. 2000. 9. Fulcrand H., Duenas-Paton M., Salas E., Cheynier V. Am. J. Enol. Vitic, 57: 289. 2006 10. Cheynier V., Duenas-Paton M., Salas E., Maury C., Souquet JM., Sarni-Machado P., Fulcrand H. Am. J. Enol. Vitic, 57: 298. 2006 11. Amrani-Joutei K., Glories Y. J. Int. Sci. Vigne Vin, 28, 303. 1995. 12. Gonzáles-Neves G., Charamelo D., Balado J., Barreiro L., Bochicchio A., Gatto G., Gil G., Carbonneau A., Moutounet M.. Anal. Chim. Acta, 513, 191. 2004. 13. Romero-Cascales I., Ortega-Regules A., López-Roca J.M., Fernández- Fernández J.I., and Gómez-Plaza E. Am. J. Vitiv. Enol., 56: 212. 2005.

46

IL14

SULFUR COMPOUNDS IN GRAPE AND WINE: CONTENTS, PRECUROSORS AND SUITABLE ANALYTICAL TECHNIQUES

Bruno Fedrizzi 1,2,*, Giuseppe Versini 2, Franco Magno 1

1Chemical Sciences Dept., University of Padova, via Marzolo 1, 35131 – Padova, Italy; 2Unione Italiana Vini

Soc. Coop., viale del Lavoro 8, 37135 – Verona, Italy; * [email protected]

Organosulfur compounds in wine have been studied for decades. Initially they were only recognized as strong negative contributors to wine aroma, but in the recent past they have been reassessed as fundamental to wine complexity.

These compounds can endogenously originate from 2 pathways: biological mechanisms and chemical reactions. In grape products, two groups of sulfur compounds have been found:

1. fermentative sulfur compounds (FSC) (i.e.: hydrogen sulfide, dimethyl sulfide, etc.);

2. varietal thiols (VT) (i.e.: 3-mercaptohexan-1-ol, 4-mercapto-4-methylpentan-2-one, etc.).

The many sulfur compounds present in grape derived matrices, and their extremely low content, makes their quantitation exceedingly difficult. The use of headspace (HS) approaches represents the most applied technique for studying organosulfur molecules; in particular HS-SPME and purge and trap methods have been developed.

Multicomponent analysis was applied to evaluate aging, variety and technological effects on FSC in several grape products. These researches showed the role of such parameters on the content of these molecules.

Aging and grape variety seem to deeply influence the level of sulfur compounds allowing a significant discrimination. Furthermore we firstly pointed out the effect of pre-fermentation nitrogen supplementation in defining the sulfur compounds pool in the final wine.

Lastly, we focused our attention both on developing HS procedures in quantifying VT in Italian wines and on their precursors in Australian grape juice. We defined new LC-MS/MS method and we identified a new glutathionylated precursor.

47

IL15

RECENT ANALYTICAL APPLICATIONS IN GRAPE AND WINE CHEMISTRY

Riccardo Flamini

CRA-VIT Laboratorio Chimico, Viale XXVIII aprile, 26 – 31015 Conegliano (TV), Italy

[email protected]

Viticulture and oenology play an important role for economy of many countries, and considerable efforts are devoted to improve the products quality and to match the widest approval of the market. Grape and wine are improved by selection of the best vine clones, using modern enological processes and technologies, through the study of chemical composition (aromatic compounds such as terpenols, methoxypyrazines, volatile sulfur compounds, benzenoids and nor-isoprenoids; polyphenolic compounds such as flavanols, flavonols, anthocyanins, procyanidins and tannins). On the other hand, European Community law and which of single countries are devoted to protect the consumer health and to discourage low quality products. As a consequence, legal limits on pesticides, elements and toxins are often defined and, to prevent frauds, the accordance between product characteristics and producer declarations (e.g., variety, geographic origin, vintage) is verified.

Nowadays mass spectrometry (MS) strongly interacts with the most of chemical research areas. In the case of the rich chemistry of grape and wine, the use of the different mass spectrometric techniques in the last ten years allowed considerable advancing in the knowledge providing experimental evidences for structures until few years ago only hypothesized. Some recent LC-MS, multiple MS (MSn) and MALDI-MS applications in the study of grape and wine polyphenols,1-6 contaminants,7 and proteins,8 are here presented.

References

1. Application of Electrospray Ionization Mass Spectrometry to the Study of Grape Anthocyanins. Favretto D., R. Flamini. Am. J. Enol. Vitic. 51(1), 55-64 (2000). 2. Fast Analysis of Isobaric Grape Anthocyanins By Chip-Liquid Chromatography Mass Spectrometry. Flamini R., M. De Rosso, A. Smaniotto, A. Panighel, A. Dalla Vedova, R. Seraglia, P. Traldi. Rapid Comm. Mass Spec. (2009) (in press). 3. Mass spectrometric evidence for the existence of oligomeric anthocyanins in grape skins. Vidal S., E. Meudec, V. Cheynier, G. Skouroumounis, Y. Hayasaka. J. Agric. Food Chem., 52(23), 7144–7151 (2004). 4. Changes in the detailed pigment composition of red wine during maturity and ageing. A comprehensive study. Alcade-Eon C., M.T. Escribano-Bailón, C. Santos-Buelga, J.C. Rivas-Gonzalo. Anal. Chim. Acta, 563(1–2), 238–254 (2006). 5. Fast determination of the Total Free Resveratrol Content in Wine by Direct-Exposure-Probe, Positive-Ion-Chemical-Ionization and Collisional-Induced-Dissociation Mass Spectrometry (DEP/PICI-MS/MS). Flamini R., A. Dalla Vedova. Rapid Comm. Mass Spec. 18:1925-1931 (2004). 6. Collisionally Induced Fragmentation of [M-H]- Species of Resveratrol and Piceatannol Investigated by Deuterium Labelling and Accurate Mass Measurements. Stella L., M. De Rosso, A. Panighel, A. Dalla Vedova, R. Flamini, P. Traldi. Rapid Comm. Mass Spec. 22(23), 3701–3967 (2008). 7. A new sensitive and selective method for analysis of ochratoxin A in grape and wine by direct liquid chromatography/surface activated chemical ionization-tandem mass spectrometry. Flamini R., A. Dalla Vedova, M. De Rosso, A. Panighel. Rapid Comm. Mass Spec. 21(22):3737-3742 (2007). 8. Differentiation of Vitis vinifera Varieties by MALDI-MS analysis of the Grape Seeds Proteins. Pesavento I.C., A. Bertazzo, R. Flamini, A. Dalla Vedova, M. De Rosso, R. Seraglia, P. Traldi. J. Mass Spec. 43(2), 234-241 (2008).

48

IL16

Mass Spectrometry. An Orphan Methodology for Olive Oil Quality and Safety Giovanni Sindona, Antonio De Nino, Leornardo Di Donna,

Fabio Mazzotti, Loredana Maiuolo and Antonio Tagarelli.

Dipartimento di Chimica Università della Calabria, via Bucci, cubo 12/C, Arcavacata di Rende (CS)

Hyphenated Mass spectrometric methodologies are unique in the evaluation of critical parameters related to food quality and safety, in general, and with particular regard to olive oil. The biomarkers of quality are represented, in this case, by natural microcomponents possessing pharmaceutical properties, produced by known biosynthetic pathways of the secondary metabolism of plants and referred as nutraceuticals, often undergoing degradation if exposed to enzymatic or thermal treatments. The absolute amount of secoiridoids in oil is, in fact, a function of (i) the ripening phase, (ii) the olive cultivar, (iii) the experimental procedures employed in the preparation of the oil and (iv) the final purification process. A suitable marker is represented by oleuropein (OLP), whose d-3 analogue was obtained by chemical transformation of the natural demethyloleuropein. The assay of this biomarker by isotope dilution method and LC-MS/MS has been used to assess the quality of olive oil.

1-3 Olp as any antioxidant molecule suffers by the

possibility of behaving as pro-oxidant as any good chemist would realize. Another important biomarker is represented by the dialdehyde species obtained by exposure to glucosidase and esterase of the biomarkers during oil preparation. An absolute method was recently devised to identify and quantify all the available non-steroidal anti-inflammatory drugs in extra virgin olive oil. The method is routinely applied in quality control of reliable commercial olive oil, within a joined project with Gabro-oil, funded by Calabria Region.The metabolomic approach was considered in the evaluation of the ripening phase of olives and in the determination by statistical methods of the origin of the oils thus produced. Among the different species of polluting agents, some of them are deliberately used in the cultivation protocols, even if they are banned by the national and international environmental protection agencies. The flexibility of the mass spectrometric approach is once more demonstrated by recent applications in the identification and assay of dimethoate, phthalates and rotenone contaminants, the last being used in organic production of olives! The quantitation of the latter in food and in the environment was recently reconsidered since it has been banned throughout the world and an absolute method based on a suitable labelled internal standard was devised. A proper mass spectrometric method for scientific determination of olive oil aging is under development. References

1. Quantitation of Oleuropein in Virgin Olive Oil by Ion Spray Mass Spectrometry-selected Reaction Monitoring. J. Agric. and Food Chem.

1999, 47, 4156. E. Perri, Raffaelli, G. Sindona 2. Absolute Method for the assay of Oleuropein in Olive Oils by Atmospheric Pressure Chemical Ionization tandem Mass Spectrometry.

Anal. Chem. 2005, 77, 5961. A. De Nino, L. Di Donna, F. Mazzotti, E. Muzzalupo, E. Perri, G. Sindona, A. Tagarelli. 3. Oleuropein expression in olive oils produced from drupes stoned in a spring pitting apparatus (SPIA). Food Chemistry 2008, 106, 677-684.

A. De Nino, L. Di Donna, F. Mazzotti, A. Sajjad, G. Sindona, E. Perri, A. Russo, L. De Napoli, L. Filice 4. Pro-oxidant Activity of Oleuropein Determined in Vitro by Electron Spin Resonance Spin-Trapping Methodology. J. Agr. Food Chem. 2006,

54, 7444-7449. A. Mazziotti, F. Mazzotti, M. Pantusa, L. Sportelli, G. Sindona. 5. B. Cavaliere , A. De Nino, F.Hayet, A. Lazez , B. Macchione , C. Moncef , E., Perri, E. , G. Sindona, G., A.Tagarelli, A. metabolomic

approachto the evaluation of the origin of extra virgin olive oil: a convenient statistical treatment of mass spectrometric analytical data . J. Agric. Food Chem. 2007, 55 , 1454–1462 .

6. C: Benincasa, J. Lewis, E., Perri, G. Sindona, A. Tagarelli, A. Determination of trace element in Italian virgin olive oils and their characterization according to geographical origin by statistical analysis . Anal. Chimica Acta 2007, 585 , 366–370 .

7. C. Benincasa, A. De Nino, N. Lombardo, E. Perri , G. Sindona, A. Tagarelli . Assay of aroma active components of virgin oliveoils from southern Italian regions by SPME-GC/ion trap mass spectrometry. J. Agric. Food Chem. 2003, 51 , 733–741

8. Screening of dimethoate in food by isotope dilution and electrospray ionization tandem mass spectrometry. F. Mazzotti, L. Di Donna, B. Macchione, L. Maiuolo, E. Perri and G. Sindona. Rapid Commun. Mass Spectrom. 2009; 23: 1515–1518

9. Tandem mass spectrometry in food safety assessment: The determination of phthalates in olive oil. B. Cavaliere, B. Macchione, G. Sindona, A. Tagarelli. Journal of Chromatography A, 2008, 1205, 137–143

10. High resolution electrospray and electrospray tandem mass spectra of rotenone and its isoxazoline cycloadduct, ; Cordaro, L. Di Donna,G. Grassi, L. Maioulo, F. Mazzotti, E. Perri, G. Sindona and A. Tagarelli. Eur. J. Mass Spectrm. 2004, 10, 691-697

11. High-throughput assay of rotenone in olive oil using atmospheric pressure chemical ionization tandem mass spectrometry. L. Di Donna, G. Grassi, F. Mazzotti, E. Perri and G. Sindona. J. Mass Spectrom. 2004; 39: 1437–1440

12. Assay of rotenone in river water by high-throughputtandem mass spectrometry and multiple-reaction monitoring methodology. L. Di Donna, F. Mazzotti, G. Sindona and A. Tagarelli. Rapid Commun. Mass Spectrom. 2005; 19: 1575–1577

49

IL17

Anti-inflammatory effect of Oleopentadial on primary human vascular endothelial cells

Marini Elena1, Nardi Monica2, Procopio Antonio3, Lorusso Bruno1, Fiorentini Simona1, Sindona Giovanni2,

Caruso Arnaldo1

1Section of Microbiology, University of Brescia Medical School, Brescia, Italy; 2Department of Chemistry, University of Calabria, Rende, Italy; 3Department of Chemistry, University Magna Græcia, Catanzaro, Italy.

Olive oil represents a typical lipid source of the Mediterranean diet, which consumption has been associated with a low incidence of cardiovascular diseases, a major cause of death in Western countries. These health benefits are ascribable to some polyphenolic compounds which have anti-oxidant and anti-inflammatory properties. Oleopentadial [ 2-(3, 4-hydroxyphenyl) ethyl (3S,4E)-4-formyl-3-(2-oxoethyl)hex-4-enoate] is one of the most abundant hydrophilic phenolic metabolites present in olive oil and its biomimetic synthesis has been recently achieved from natural demethyl oleuropein present in olive tissues. This provides an easy access to the molecule to perform in vitro studies and evaluate its pharmacological activity.

We investigated the effect of Oleopentadial on the expression of the inflammatory chemokine monocyte chemotactic protein (MCP)-1 by primary human vascular endothelial cells. MCP-1 is a potent inflammatory molecule both in vitro and in vivo. Much evidence exists supporting a key role for MCP-1 in the pathogenesis of atherosclerosis and other vascular diseases. We have used primary human umbilical vein endothelial cells (HUVECs) as a model to study the effects of Olepentadial during the inflammatory response of vascular endothelium triggered by cytokines and bacterial products. HUVECs were treated or not for 24 hours with Oleopentadial and then stimulated with bacterial lipopolysaccharide (LPS) or tumor necrosis factor (TNF)-α. Oleopentadial dose-dependently inhibited both LPS- and TNF-α-stimulated MCP-1 secretion. It exerted its anti-inflammatory activity at the transcriptional level, impairing the MCP-1 mRNA synthesis. Reporter gene assays with mutational MCP-1 promoter/enhancer constructs indicated the relevance of nuclear factor kB (NF-kB) and Activator protein (AP)-1 binding sites in mediating MCP-1 trascriptional inhibition. The involvement of NF-kB was finally demonstrated using a synthetic NF-kB-dependent promoter controlling luciferase synthesis.

Taken together, these data demonstrate an inhibitory effect of Oleopentadial on MCP-1 synthesis and secretion, mediated via NF-kB- and AP-1-dependent pathways. Because of the key role attributed to MCP-1 in the etiology of cardiovascular diseases, the control of MCP-1 synthesis by Oleopentadial may represent a novel pharmaceutical approach for vascular protection.

50

IL18

THE ORGANIC CHEMISTRY OF OLIVE NUTRACEUTICALS

Monica Nardi, a Antonio Procopio,*b Manuela Oliverio,b Giovanni Sindona a a Dipartimento di Chimica, Università della Calabria, ponte Bucci cubo 12/c, I-87030 Arcavacata di Rende (Cs) Italy.

b.

Dipartimento Farmaco Biologico, Università della Magna Graecia, Complesso Ninì Barbieri, I-88021 Roccelletta Di

Borgia (CZ) Italy

Epidemiological studies have shown a relationship between the Mediterranean diet and a lowered incidence of pathologies such as cardiovascular diseases, cancer, and diabetes.1 Several studies attribute these health benefits to high consumption of virgin olive oil - rich in phenols and flavonoids, as well as in other typical components of the Mediterranean diet.

OR

HO

O

O

OGlu

COOR'

R = OH: Hydroxytyrosol (1, HTyr)R = H: Tyrosol (2, Tyr)

R = OH; R' = CH3: Oleuropein (3, Ole)R = H; R' = CH3: Ligstroside4

Chart 1: Chemical structure of compounds 1-4.

The main phenolic compounds in virgin olive oil are secoiridoid derivatives of 2-(3,4-dihydroxyphenyl) ethanol (HTyr 1) and 2-(4-hydroxyphenyl) ethanol (Tyr 2) that occur either as simple phenols, or esterified with elenolic acid to form, respectively, oleuropein (Ole 3) and ligstroside aglycones (4 Chart 1).2 Many of the biological activities attributed to these, or to other natural phenolic derivatives, have anti-inflammatory component,1,3 so, various health benefits seem to overlap with those attributed to non-steroidal anti-inflammatory drugs,4 triggering a great interest in the scientific community.

Frequently, we pondered the real utility of the massive production of the so called green methodologies, and, looking for a tangible application, we decided to apply some of our protocols to the chemical manipulation of a known natural product like oleuropein with the aim to obatin natural and semi-synthetic oleuropein derivatives by means of the chemical manipulation of compound 3. Examining the molecular structure of this secoiridoid, it is quite evident that its aglycone form can be easily obtained by simple acetal hydrolysis, mimicking the natural glucosidase enzyme action. We successfully tested, and then patented, a very gentle method to realize the selective Lewis acid catalyzed oleuropein hydrolysis in water, applying one of the protocols we recently published for simple acetals.

References

1. Trichopoulou, A., Costacou, T., Bamia, C., Trichopoulos, D. N. Engl. J. Med. 2003, 348: 2599–2608; (b) Fogliano V., Sacchi R., Molecular Nutrition & Food Analysis, 2006, 50, 5; (3) Mazziotti A., Mazzotti F., Pantusa M., Sportelli L., Sindona G. J. Agric. Food

Chem. 2006, 54, 7444-7449. 2. Mateos, R.; Espartero, J. L.; Trujillo, M.; Ríos, J. J.; León-Camacho, M.; Alcudia, F.; Cert, J. Agric. Food Chem. 2001, 49, 2185-2192. 3. (a) Visioli, F.; Poli, A.; Galli, C. Med. Res. Rev. 2002, 22, 65-75, (b) Bitler, C. M.; Viale, T. M.; Damaj, B.; Crea, R. J. Nutr. 2005, 135, 1475-1479. 4. (a) Aruoma.,O. I.; Deiana, M.; Jenner, A.; Halliwell, B.; Harparkash, K.; Banni, S.; Corongiu, F. P.; Dessí, M. A.; Aeschbach, R. J. Agric. Food Chem. 1998, 46, 5181–5187; (b) de la Puerta, R.; Ruiz-Gutierrez, V.; Hoult. J. R. Biochem. Pharmacol. 1999, 57, 445–449; (c) Beauchamp, G.; Keast, R.; Morel, D.; Liu, J.; Pika, J.; Han, Q.; Lee, C.; Smith, A. B., III; Breslin, P. Nature 2005, 437, 45-46. 5. Procopio, A.; Sindona, G.; Gaspari, M.; Costa, N.; Nardi. M. PCT/IT2008/000303 titled Chemical-catalytic method for the

peracylation of oleuropein and its products of hydrolysis 6. (a) R. Dalpozzo, A. De Nino, L. Maiuolo, A Procopio, A. Tagarelli, G. Sindona, G. Bartoli J. Org. Chem. 2002, 67, 9096-9098; (b) Procopio, A.; Dalpozzo, R.; De Nino, A.; Maiuolo, L.; Russo, B.; Sindona, G. Adv. Synth. Catalysis 2004, 346, 1465-1470; (c) Bartoli, G.; Dalpozzo, R.; De Nino, A.; Maiuolo, L.; Nardi, M.; Procopio, A.; Tagarelli, A. Green Chemestry 2004, 6, 191-192.

51

IL19

POLINUCLEAR CHROMIUM CHAINS: SYNTHESIS AND MAGNETIC PROPERTIES

Marzio Rancan

ISTM-CNR, INSTM R.U. Padova, Università degli Studi di Padova, Dipartimento di Scienze Chimiche, via

Marzolo 1, 35131 Padova, Italy. E-mail: [email protected]

The discovery that individual molecules can function as magnets (Single Molecule Magnets, SMMs) fostered a new bottom-up approach to nanoscale magnetic materials and in particular to the synthesis of new polymetallic complexes.

Here, a study of the template synthesis of a new chromium finite chains family, their supramolecular assemblies, their chemistry and their magnetic properties is presented. In particular, the possibility to template both the length and the supramolecular architecture by changing the nature of only one reagent has been thoroughly investigated[1]. This strategy has led to isolate a family of molecular chains described by the general formula {[CrxFx+5(O2C(CH3)3)2x-2][NH2R2]3}n.

Due to the presence of terminal fluorides these compounds demonstrate a rich supramolecular chemistry through H-bonding interactions. By investigating the chemistry of these systems, a route to produce isolated molecular finite chain has been found. The possibility to obtain finite molecular chains is very intriguing since the magnetic properties of these compounds are not yet fully explored and investigated. Real examples of one-dimensional “spin segments” are still lacking in the literature. Furthermore, it has been demonstrated that these systems can act as cluster ligands towards other metal centres leading to new heterometallic clusters.

For some of these compounds, through magnetic measurements, EPR and inelastic neutron scattering studies the exchange coupling constants and the the single-ion anisotropy parameters of Cr (III) ion have been determined[2,3]. Moreover, these chains evidence spin excitations related to the rotation of Nèel vector and to discrete spin wave phenomena that can be rationalised in the “L&E band picture”[2].

References

1. M. Rancan, G. N. Newton, C. A. Muryn, R. G. Pritchard, G. A. Timco, L. Cronin and R. E. P. Winpenny, Chem. Commun. 2008,1560.

2. S. T. Ochsenbein, F. Tuna, M. Rancan, R. S. G. Davies, C. A. Muryn, O. Waldmann, R. Bircher, A. Sieber, G. Carver, H. Mutka, F. Fernandez-Alonso, A. Podlesnyak, L. P. Engelhardt, G. A. Timco, H. U. Gudel and R. E. P. Winpenny, Chem. Eur. J., 2008, 14, 5144.

3. M. Baker, M. Rancan, F. Tuna, G. A. Timco, E. Mcinnes and R. E. P. Winpenny, Phys. Chem. Chem. Phys., 2009 accepted.

52

IL20

REACTION CONTROL BY NON-COVALENT INTERACTIONS: THE INFLUENCE OF AGGREGATION AND SOLVATION ON THE STRUCTURE-REACTIVITY RELATIONSHIP OF LITHIUM OXYGEN

CARBENOIDS

Vito Capriati,* Saverio Florio, Filippo Maria Perna, Antonio Salomone

Università di Bari, Dipartimento Farmaco-Chimico, C.I.N.M.P.I.S.,

Via E. Orabona 4, I-70125 – Bari, Italy

*[email protected]

Organolithium compounds are amongst the most versatile reagents in all field of chemistry. Often

schematically depicted as monomeric species, lithium compounds, actually, display “hypermetallation” and

exhibit an interplay of ionic and covalent bonding. As a consequence, their solution structures tend to be

much more complicated than expected due to the formation of higher aggregates in which the metal may

be associated with more than one carbanion center. Lithium carbenoid, in particular, are species carrying a

lithium and some peculiar nucleofugal heterosubstituents at the same carbon atom (e.g., halogen OR,

NR2.). They exhibit an intriguing ambiphilic behaviour (nucleophilic and electrophilic reactivity) and are

generally recognized as useful reagents for “umpolung” of the reactivity. Due to the presence of an

heteroatom in their organic framework, which may provide additional intramolecular coordination to

lithium, their architectures in solution may differ from those of the most common symmetric types. The

knowledge of the solution structure of reactive species is crucial for the elucidation of reaction mechanisms

and the understanding of observed selectivities. In this communication, the solution structure of some

Li/oxygen carbenoids, such as the oxazolinyloxiranyllithium 1 and lithiated styrene oxide 2, will be

discussed in light of DFT calculations and multinuclear magnetic resonance investigations performed. The

factors affecting their configurational stability along with the influence of solvation and aggregation on

structure-reactivity relationship will be as well highlighted. It was very fascinating to observe how non-

covalent interactions, which are at the root of different organizational complexities are, indeed, mainly

responsible of the dichotomic reactivity exhibited by such reactive intermediates.

O

ON

Li

MeMe

Me

Me

(R)

O

ON

Li

MeMe

Me

Me

(S)

(R)-η3-1 (S)-η3-1

(S)

Li

Li

O

Ph

THF

THF

O

Ph

Li

Li

O

Ph

THF

THF

O

Ph

slow

(S)

(S)

(R)

2·(THF)2

PhLi

H

O

H

THF THF

THF

2·(THF)3

carbenoid reactivity

carbanionic reactivity

References 1. Gessner, V. H.; Däschlein, C.; Strohmann, C. Chem. Eur. J. 2009, 15, 3320–3334. 2. Boche, G.; Lohrenz, J. C. W. Chem. Rev. 2001, 101, 697–756. 3. Capriati, V.; Florio, S.; Luisi, R. Chem. Rev. 2008, 108, 1918–1942. 4. Capriati, V.; Florio, S.; Luisi, R.; Perna, F. M.; Spina, A. J. Org. Chem. 2008, 73, 9552– 9564. 5. Capriati, V.; Florio, S.; Perna, F. M.; Salomone, A.; Abbotto, A.; Amedjkouh, M.; Lill, S. O. N. Chem. Eur.

J. in press.

53

IL21

NANOSTRUCTURING OF ORGANIC MATERIALS TEMPLATED BY HYDROGEN BONDING

Anna Llanes-Pallàs, Maurizio Prato and Davide Bonifazi

Dip. di Scienze Farmaceutiche and INSTM UdR Trieste, Università degli Studi di Trieste, 34127 Trieste, Italy. Laboratory of Organic Chemistry of the Supramolecular Materials, Department of Chemistry,

University of Namur, 5000 Namur, Belgium. E-mail: [email protected]

Supramolecular multicomponent architectures supported on metallic surfaces are ultimate candidates for

the fabrication of advanced molecular-based devices. In order to exploit single-molecule devices, it is

necessary to develop systems that can form highly organized two-dimensional molecular assemblies

featuring controllable and precise structural arrangement. Towards the envisaged technological

applications, the hierarchical self-assembly of molecular modules featuring non-covalent recognition sites

reveals to be one of the most feasible approaches since it allows the simultaneous assembly of several

programmed molecules, long-range order and inherently defect-free structures. Herein we describe the

design, synthesis and supramolecular ordering of a molecular library consisting of different geometrical

molecular modules, which by establishing complementary intermolecular hydrogen-bonding interactions,

can self-assemble and generate highly ordered mono- and bi-dimensional nanostructures. As expected,

self-assembly studies conducted both in solution and on metallic surfaces confirm that the overall

formation of the systems is driven by the strong hydrogen bonding interactions established between the

complementary recognition sites and by the geometrical molecular constraints. All the described systems

provide an exceptional example for the potential of the supramolecular approach in the fabrication of

addressable molecular devices, which are hardly imaginable using established miniaturizing methods such

as the lithographic techniques.

References

1. C. Joachim, J. K. Gimzewski and A. Aviram, Nature 2000, 408, 541-548. 2. J. V. Barth, G. Costantini and K. Kern, Nature 2005, 437, 671-679. 3. D. Bonifazi, S. Mohnani and A. Llanes-Pallas, Chem. Eur. J., 2009, Accepted. 4. a) C. A. Palma, M. Bonini, A. Llanes-Pallas, T. Breiner, M. Prato, D. Bonifazi, and P. Samorì, Chem. Comm., 2008, 42, 5289-5291; b) A. Llanes-Pallas, M. Matena, T. Jung, M. Prato, M. Stöhr, and D. Bonifazi, Angew. Chem. Int. Ed., 2008, 47, 7726-7730; c) A. Llanes-Pallas, C.A. Palma, L. Piot, A. Belbakra, A. Listorti, M. Prato, P. Samorì, N. Armaroli, and D. Bonifazi, J. Am. Chem. Soc., 2009, 131, 509-520; d) L. Piot, C.A. Palma, A. Llanes-Pallas, M. Prato, Z. Szekrényes, K. Kamarás, D. Bonifazi and P. Samorì, Adv. Funct. Mater., 2009, 19, 1207-1214; e) K. Yoosaf, A. Belbakra, N. Armaroli, A. Llanes-Pallas and D. Bonifazi, Chem. Commun., 2009, 2830-2832; f) M. Matena, A. Llanes-Pallas, M. Enache, T. Jung, J. Wouters, B. Champagne, M. Stöhr and D. Bonifazi, Chem. Commun., 2009, 3525-3527.

54

IL22

SYNTHESIS OF PEPTIDOMIMETICS AND THEIR APPLICATION AS DIAGNOSTICS AND

THERAPEUTICS

Laura Bartali, Dina Scarpi, Antonio Guarna

Dipartimento di Chimica Organica “U. Schiff”, and HeteroBioLab, Polo Scientifico dell’Università di Firenze,

Via della Lastruccia 13, 50019 Sesto Fiorentino (Italy) E-mail: [email protected]

Neurotrophins are dimeric growth factor hormones that regulate development and maintenance of central and peripheral nervous systems.1 Members of this protein family include nerve growth factor (NGF), neurotrophin-3 (NT-3), brain-derived neurotrophic factor (BDNF) and neurotrophin-4/5 (NT-4/5). In particular, NGF promotes the growth and survival of sympathetic, trigeminal, dorsal root ganglia neurons and cholinergic neurons of the basal forebrain. Thus, NGF agonists or antagonists might be useful in regulating these processes.

Small peptides and peptidomimetics overcome many of drawbacks of proteins and pharmaceutical agents. Compared with proteins such as NGF, peptidomimetics are less antigenic, less subjected to proteolysis, and more able to cross blood tissues barriers. Small peptide mimetics of NGF have been produced based on sequences from the β-loops of NGF.2

The synthesis of novel molecular scaffolds should be easy and include only few steps, starting from commercially available enantiopure precursors, in both enantiomeric forms. Moreover, each step of the synthesis has to be stereochemically controlled to afford the desired stereoisomer as the final compound.

The aim of the present work is to prepare novel molecular scaffolds, deriving from (R,R)- or meso-tartaric acid and L- or D-amino acids,3 and to evaluate their in vitro and in-vivo activity as NGF agonists and/or antagonists.

References

1. Wlesmann C. et al., Nature, 1999, 401, 184-188. 2. (a) Maliartchouk S. et al., Mol. Pharm., 2001, 57, 385-391; (b) Xie Y. et al., J. Biol. Chem., 2000, 275, 29868-29874. 3. Trabocchi A. et al., Synlett., 2006, 331-354.

55

IL23

Synthesis and Antioxidant Activity of 4-Thiatocopherols

Maria Grazia Bartolozzi, Caterina Viglianisi, Stefano Menichetti* Dipartimento di Chimica Organica “U. Schiff” e Laboratorio di progettazione, sintesi e studio di eterocicli

biologicamente attivi (HeteroBioLab), Polo Scientifico-Università di Firenze, Via della Lastruccia, 13, 50019

Sesto Fiorentino. [email protected]

Several cardiovascular diseases and many different types of cancer are influenced by the free radical action. Tocopherols, lipid soluble vitamins (Vitamin E), represent one of the most important family of natural antioxidants. They stabilize cell membranes and prevent oxidative damage of the tissues. The antioxidant action of tocopherols, together with the other endogenous and exogenous defences, contribute to keep under control the concentration of free radicals in biological tissues. On the other hand, these natural derivatives are not able to intercept other non-radical reactive oxygen species (ROS) as chalcogen substituted antioxidants do (i.e. Glutathione).

Herein we report the synthesis and the antioxidant activity of 4-thiatocopherols. Our original synthetic approach is based on an inverse electron-demand hetero Diels-Alder reaction of ortho-thioquinones, used as electron-poor dienes, with 1,3-dienes acting as electron-rich dienophiles (Scheme 1).1 The reaction allowed the isolation of the benzoxathiin cycloadducts with the required structure with complete chemo- and regioselectivity.

HO

O

S+

Z

O R

HO

S

O

HO

Z

O R

HO Z

O R

HO Z

O R

HO

αααα ββββ γγγγ δδδδ

R = Phytyl; Z = CH 2 : Tocopherols R = Phytyl; Z = S : 4-Thiatocopherols

The synthesis of the ortho-thioquinone precursors and the 1,3-diene with the suitable stereochemistry, as well as the antioxidant activity evaluation of the thiatocopherols prepared will be discussed in this communication.

References

1 a) Menichetti, S.; Viglianisi, C. Tetrahedron 2003, 59, 5523-5530; b) Contini, A.; Leone, S.; Menichetti, S.; Viglianisi, C.; Trimarco, P. J. Org. Chem. 2006, 71, 5507-5514; c) Amorati, R.; Fumo, M.G.; Masetti, M.; Menichetti, S.; Pagliuca, C.; Pedulli, G.F.; Viglianisi, C., Chem. Eur. J., 2007, 13, 8223-8230.

56

IL24

SYNTHESIS AND NMR CHARACTERIZATION OF NEOPEPTIDES CONTAINING A FRUCTOSE-BASED PROLINE ANALOGUE

Davide Bini, Maria Gregori, Laura Cipolla, Cristina Airoldi, Francesco Nicotra

Dept. of Biotechnology and Biosciences, University of Milano-Bicocca, P.za della Scienza 2, 20126 Milano-

Italy, [email protected]

Unnatural amino acids have found considerable use as building blocks in medicinal, peptide and protein

chemistry.1 Stereochemically and conformationally constrained amino acid analogs that strongly favor

specific backbone conformations may be used to nucleate specific secondary structures in designed

peptides.2 In particular, β-hairpins have been shown to play a key role in vital as well as in pathological

processes. They frequently participate in protein-protein, protein-RNA, and protein-DNA recognition.

Among the natural amino acids, proline is often involved in the nucleation of reverse turn structures, and in

particular D-Pro-Xaa3 have been recently proposed for induction of β-hairpin folding. Due to these unique

structural properties, numerous mimetics and analogs of L- and D-proline have been developed and applied

in the synthesis of biologically relevant peptides, but few exemples exist of proline-based glycosyl

derivatives.4

In this context, a new D-proline analog having a spiro bicyclic structure derived from D-fructose was

synthesized by our research group;5 the spiranic junction, combined with the relative rigidity of the furan

ring should provide conformational constrains to the proline ring. Different tri and tetrapeptides including

the D-proline analogue have been synthesised and their conformation studied by NMR experiments.

1H-NMR chemical shifts of the amide protons, temperature dependence of the amide proton chemical shifts [Δδ(NH)/ΔT] and Δδ(NH) upon addition of a solvent able to compete for the formation of hydrogen bonds have been investigated. All these experimets have been used to determine if amide protons are involved in intramolecular hydrogen bonds.6

References

1. a) Chorev, M.; Goodman, M. Acc. Chem. Res., 1993, 26, 266-273; b) Gruner, S. A. W. et al. Chem. Rev., 2002, 102, 491-514.

2. a) Fisk, J.D.; Powell, D.R.; Gellman, S.H. J. Am. Chem. Soc., 2000, 122, 5443-5447; b) Descours, A. et al.

ChemBioChem, 2002, 3, 318-323. 3. Das, C.R.; Raghothama, S.R.; Balaram, P.J. Chem. Soc., Perkin Trans. 2, 1998, 120, 5812-5813. 4. Owens, N. W.; Braun, C.; Schweizer, F. J. Org. Chem. 2007, 72, 4635-4643. 5. Cipolla, L.; Redaelli, C.; Nicotra, F. Lett. Drug Discov. Design, 2005, 2, 291-293. 6. Belvisi, L. et al. Eur J Org Chem, 1999, 389.

57

IL25

DEVELOPMENT OF NEW DOMINO ORGANOCATALYZED SYSTEMS FOR THE SYNTHESIS OF

COMPLEX CHIRAL MOLECULES

Dipartimento di chimica organica “A.Mangini”

Facoltà di Chimica Industriale – Università di Bologna

Prof. Giuseppe Bartoli, Dott. Paolo Melchiorre and Francesco De Vincentiis

Nowadays, asymmetric organocatalysis is recognized as an efficient and reliable strategy for the stereoselective preparation of valuable chiral compounds. In the past decade, new synthetic strategies based on organocatalytic methods have been applied for the synthesis of chiral molecules. In our previously report we focused our attention on the synthesis of aziridines, that constitute a key structural feature of several classes of natural products and are extremely versatile building blocks that can undergo synthetically useful transformations. In the aforesaid report, we developed a novel and efficient catalytic methodology for the stereoselective preparation of chiral aziridines starting from simple α,β-unsaturated ketones, via domino reaction, exploiting a primary amine as the catalyst. The excellent results obtained induce us to extend the method to a larger class of challenging cyclic ketones. Therefore our target is the synthesis of cyclic aziridines starting from cyclic α,β-unsaturated ketones employing organocatalytic methodologies.

References “Organocatalytic Asymmetric Aziridination of Enones” F. Pesciaioli, F. De Vincentiis, P. Galzerano, G. Bencivenni, G. Bartoli, A. Mazzanti and P. Melchiorre; Angew. Chem. Int. Ed. 2008, 47, 8703-8706

R2

N

R1

A-

R2

O

R1

H2O H

NH3A-

R2

NR1

H

R3 NLg

H

R3NLg

HA

H 2O

R 2

N

R 1

A -H

N R3R2

O

R1N R 3

H A

Lg H

R2

N

R1

A -

H

R3N

Lg

R2

O

R1 R3N

Lg H2O

58

IL26

NOVEL PHOSPHORESCENT FLUORINE FUNCTIONALIZED IRIDIUM COMPLEXES Fino, V.; Ragni, R.; Farinola, G.M.; Babudri, F.; Naso, F.

Dipartimento di Chimica, Facoltà di Scienze MM. FF. NN. Università degli Studi di Bari

via E. Orabona, 4 – 70125 Bari

e-mail: [email protected]

Cyclometalated iridium(III) complexes have recently emerged as one of the most interesting classes of materials for applications in highly efficient electroluminescent devices, based on phosphorescent emission. (PHosphorescent Light Emitting Diodes, PHOLEDs).1 Proper choice and functionalization of the cyclometalating ligands enable to finely tune the emission energy of the iridium complexes.

In the frame of our studies dealing with the synthesis of novel organic and organometallic materials,2 we have recently developed protocols for the preparation of 2-phenylpyridines bearing electron-withdrawing substituents as fluorine atoms and perfluorinated oligophenyl functional groups. New homoleptic and heteroleptic iridium complexes have been obtained using these novel functionalized phenylpyridines as the cyclometalating ligands and their photophysical and electrochemical properties have been investigated.

HETEROLEPTIC COMPLEXES

N

F F

N

F

F

N

F

Ir

F

FF

F

N

F F

N

F

F

N

F

Ir

F

F

F

F

HOMOLEPTIC COMPLEXES

facial meridianal

X: F; perfluorinated oligophenylsN

X

IrL

Y

2

XX

X X

XX

Electrochemical analysis of perfluorinated oligophenyl functionalized complexes leads to expect high electron transporting ability of these materials in PHOLEDs. Photophysical characterization of the complexes bearing electron-withdrawing fluorine atoms has shown that these substituents induce a substantial blue-shift of the emission energy, in comparison with the corresponding phosphors bearing unsubstituted 2-phenylpyridine ligands. The effect of the stereochemistry on the photophysical properties of the homoleptic complexes, prepared in both facial and meridianal configurations, was also investigated and the performances of blue-emitting PHOLEDs fabricated using both the stereisomers were compared.

References [1] Adachi, C.; Baldo, M. A.; Forrest, S. R.; Thompson, M. E. Appl. Phys. Lett. 2000, 77, 904. [2] (a) Ragni, R.; Plummer, E. A.; Brunner, K.; Hofstraat, J. W.; Babudri, F.; Farinola, G. M.; Naso, F.;De Cola, L. J. Mat. Chem. 2006, 16, 1161-1170; (b) Babudri, F.; Farinola, G. M.; Naso, F.; Ragni, R. Chem. Commun.

2007, 1003-1022; (c) Ragni, R.; Orselli, E.; Kottas, G. S.; Hassan Omar, O.; Babudri, F.; Pedone, A.; Naso, F.; Farinola, G. M.; De Cola, L. Chem. Eur. J. 2009, 15, 136-148.

59

IL27

NOVEL PALLADIUM AND COPPER BASED METALLOMESOGENS FROM TIOPHENE CONTAINING LIGANDS.

U. Caruso, R. Diana, B. Panunzi, A. Roviello, M. Tingoli, A. Tuzi, M. Mazzella Department of

Chemistry, University of the studies of Naples “Federico II”, Via Cintia , 80126 Naples, Italy. Tel.

+39.081.674089 ; Fax +39.081.674090;


Heterocyclic rings as core units in mesogenic materials have been widely investigated during the past decades 1. These compounds hold in general great potential in the field of optics and electro-optics, for example in NLO applications or as active materials for OLED 2,3 In particular, thiophene based mesogens are receiving increasing attention4 as their slightly bent structures leads to a variety of desirable unique features, such as significant lateral dipole moments, low melting points, high anisotropy , low viscosity and high solubility. Mesogenic complexes, the so-called metallomesogens, derived from heterocyclic containing ligands are relatively rare5 although worth of interest. In fact, the different electronic configurations and coordination geometries of the metal ions exercize influence over the kind and the stability of the observed mesophases. In this work we prepared two thiophene based LC ligands, 1 and 2 in the figure 1:

O

O

NSR

O

R=H

R= NN

1

2

HO

figure 1:

Componds 1 and 2 display a nematic phase. As expected, the longer compound 2 shows a larger stability field of the mesophase (about 80°C) respect to compound 1. Both 1 and 2 show an increase of LC properties respect to the analogous all benzenoid structures. From these chelating molecules we synthetised four new symmetrically substituted metallomesogens as shown in figure 2:

O

O

NSR

OR=H

R= NN

1a (M=Pd), 1b (M=Cu)

OM

O

O

NS R

O

O

2a (M=Pd), 2b (M=Cu) figure 2

Complexes 1a and 1b show a nematic mesophase, with wider stability range in the case of 1a probably due to the planarity of the Pd coordination geometry. Complexes 2a and 2b show higher melting points and display decomposition before isotropization. Ligands and complexes have been characterized both thermically and spectroscopically. In particular, useful informations about ligand 2 and complex 1a were obtained by X-ray technique. References:

1. Demus D., Goodby J., Gray G. V., Spiess H.W., Vill V., Handbook of Liquid Crystals, Wiley-VCH, Weinheim, 1998, Vols.1-3

2. Centore R., Concilio S., Panunzi B., Sirigu A., Tirelli N., J. Polym. Sci., Part A, Polym. Chem. 1999, 37, 603-608

3. Ko C.W., Tao Y.T., Chem. Mater., 2001, 13, 2441-2446. 4. 4. Seed A., Chem. Soc. Rev., 2007, 36, 2046-2069 5. Liao C-T., Wang Y-J., Huang C-S., Sheu H-S., Lee G-H., Lai C. K., Tetrahedron, 2007, 63, 12437-12445.

60

IL28

OXAZIRIDINES FOR THE 2,3-DIHYDRO-1,2,4-OXADIAZOLES SYNTHESIS Luigino Troisi, Ludovico Ronzini, Francesca Rosato e Valeria Videtta

Dipartimento di Scienze e Tecnologie Biologiche ed Ambientali Università del Salento Via Prov-le Lecce-Monteroni, 73100 – Lecce

[email protected] The oxaziridines represent a class of small heterocycles characterized by the presence of one carbon, one oxygen and one nitrogen atom. The biological properties are not well known, but some studies were performed about their antifungal1 and anticancer activities. 2 In contrast, their high reactivity and stereo selectivity were investigated and oxaziridines were largely used in asymmetric organic synthesis.

The oxaziridines are the starting material for the preparation of biologically active molecules, in fact, opening the three-membered ring with specific reactions, more natural and non natural products can be synthesized.7

We have recently described the [3+2] cycloaddition reaction between a variety of terminal alkynes and oxaziridines. The novelty of this reaction lies in the oxaziridine C-O bond breaking and the synchronous attack on the triple bond. As a consequence, the cycloaddition is regioselective for the formation of isoxazolines (Scheme 1).

ON

Ar

R'+ R C CH N

O R'

Ar

Rtoluenereflux

R = alkyl or aryl groups; R' = alkyl group; Ar = aryl group Scheme 1 With these promising results as a starting point, we thought to develop a corresponding [3+2] cycloaddition between oxaziridines and nitriles to access 2,3-dihydro-1,2,4-oxadiazoles by employing the aforementioned reaction conditions. The results of our investigation will be presented in this contribution (Scheme 2)

.

ON

Ar'+ Ar C N

NN

O

Ar'

Ar

Ar' = aryl or heteroaryl group,Ar = aryl group Scheme 2

2,3-dihydro-1,2,4-oxadiazoles are a lesser-known class of heterocycles for which few syntheses and applications have been reported in the literature.11 Consequently, the development of novel approaches toward the synthesis of these compounds is of fundamental interest. Interestingly, numerous application in various medical fields have been reported12a,d about the isomeric 4,5-dihydro-1,2,4-oxadiazoles, which differ from the 2,3-dihydro-1,2,4-oxadiazoles only in the position of the ring double bond. The possibility of obtaining different 2,3-dihydro-1,2,4-oxadiazoles by changing the starting substrates make this contribution extremely interesting in the organic synthesis of potential biologically active compounds. References 1. Vu, Chi B.; Corpuz, E. G.; Merry, T. J.; Pradeepan, S. G.; Bartlett, C., J.Med.Chem., 1999, 42, 4088-4098; 2. Tyrkov, A. G.; Tyurenkov, I. N.; Timchenko, M.V.; Perfilova V.N.; Pharmaceytical Chemistry journal, 2006, 40,

(5), 8-9; 3. Davis, F. A.; Sheppard, A. C. Tetrahedron, 1989, 45, 5703–5742. 4. Aube, J. J. Chem. Soc. Rev 1997, 26, 269–277. 5. Davis, F. A.; Chen, B. C. Chem. Rev. 1992, 92, 919–934. 6. Troisi, L.; De Lorenzis, S.; Fabio, M. ; Rosato, F.; Granito, C. Tetrahedron: Asymmetry 2008, 19, 2246-2255. 7. Andersen, K. E.; Lundt, B. F.; Jorgensen, A. S.; Braestrup, C., Eur. J. Med. Chem., 1996, 31, 417-425; 8. Fabio, M.; Ronzini, L.; Troisi, L. Tetrahedron 2008, 64, 4979. 9. Troisi, L.; Fabio, M.; Rosato, F.; Videtta, V. Arkivoc in press. 10. Troisi, L.; Ronzini, L.; Rosato, F.; Videtta, V. Synlett in press. 11. Bokach, N. A.; Kukushkin, V. Yu. Russian Chemical Bullettin, International Edition, 2006, 55, 1869. 12. (a) Singh, C. P.; Hasan, H. J. Indian Council of Chemists, 2002, 19, 46. (b) Chimirri, A.; Grasso, S.; Montforte, A.-

M.; Rao, A.; Zappala, M. Farmaco, 1996, 51, 125. (c) Mnrao, M. R. G.; Karamjit, K.; Sharma, J. R.; Kalsi, P. S. Indian J. Heterocycl. Chem., 1995, 5, 151. (d) Sterne, J.; Le Guilcher, S.; Rousselet, M. Therapie, 1972, 27, 517.

61

IL29

ON THE CONFIGURATIONAL STABILITY OF αααα-LITHIATED ARYLOXIRANES

R. Altamura, V. Capriati, S. Florio, F. M. Perna, A. Salomone Dipartimento Farmaco-Chimico, Università di

Bari,

Consorzio Interuniversitario Nazionale Metodologie e Processi Innovativi di Sintesi C.I.N.M.P.I.S., via E.

Orabona 4, I-70125 Bari, Italy


Lithiated aryloxiranes constitute a useful class of chiral polar organometallic compounds of increasingly interest not only in preparative organic chemistry but also in more basic aspects of the chemistry of “lithium carbenoids”. To date, as nucleophiles, their reactivity has been exploited for the asymmetric synthesis of substituted styrene oxides, cyclopropanes, 1,2-oxazetidines, epoxy--butyrolactones, diols and triazolyl-alcohols. While the trapping reactions of lithiated styrene oxide and their halogen derivatives occur with complete retention of configuration at the benzylic carbon, optically active ortho-tolylsulfinyl- as well as trifluoromethyl-substituted lithiated styrene oxides have been proved to undergo a fast enantiomer equilibration with a rate comparable to that of their addition to electrophiles.

This evidence prompted us to begin a systematic investigation on the reactivity of variously substituted -lithiated styrene oxides in order to shed light on the mechanisms and the structural features responsible of the stereochemical outcome of their coupling reactions.

k1

k-1

O

R2

O

R2

LiLi

R1= o-, m-, p-Fconfigurationally stable

R2= o-, m-, p-CF3configurationally unstable

O

R1

Li

This communication will be mainly focused on the kinetics of racemization under way in our laboratory of

some trifluoromethyl-substituted lithiated styrene oxides and the determination of their corresponding

activation and thermodynamic parameters. The utility in asymmetric synthesis of chiral non racemic and

configurationally stable -lithiated fluoro-derivatives will be as well highlighted.

References

Capriati, V.; Florio, S.; Luisi, R.; Salomone, A.; Tocco, M. G.; Martín Castro, A. M.; García Ruano, J. L.;

Torrente, E. Tetrahedron 2009, 65, 383-388.

62

IL30

PhSeZnCl IN NUCLEOPHILIC VINYLIC SUBSTITUTIONS: REACTIVITY AND THEORETICAL INVESTIGATION

Stefano Santoro, Benedetta Battistelli, Marcello Tiecco and Claudio Santi

Dipartimento di Chimica e Tecnologia del Farmaco – Sezione di Chimica Organica, Università degli Studi di

Perugia; Via del Liceo, 1; 06123 Perugia


Among the methods for the introduction of a selenium moiety the use of selenolate anions is particularly convenient. However these species usually require troublesome “in situ” preparation and inert atmosphere. Recently we reported that treatment of commercially available PhSeCl with a stoichiometric amount of zinc powder in refluxing THF leads to the formation of the corresponding zinc selenolate (PhSeZnCl). This is a white amorphous solid which can be stored at room temperature and in the air for several days without appreciable decomposition.

The nucleophilic properties of this zinc selenolate have been proved in the opening of several epoxides, in different conditions. Interestingly the reaction showed a rate acceleration when performed in “on water” suspension in respect to the reaction conduced in THF solution or neat.

Here we report our recent results in the use of this reagent in the nucleophilic substitution on vinyl halides. Different activated and non-activated substrates have been used in this reaction and, even in this case, a rate acceleration has been observed conducing the reactions “on water”.

Finally DFT calculations have been performed on a model system in order to enlighten the reaction mechanism.

EWGX PhSeZnCl EWG

SePh

References “Organoselenium Chemistry: Modern Developments in Organic Synthesis”, in Top. Curr. Chem., Springer, Berlin, 2000, vol. 208 (Ed.: T.Wirth). Santi, S. Santoro, B. Battistelli, L. Testaferri, M. Tiecco Eur. J. Org. Chem., 2008, 5387

63

IL31

FROM BAKELITE TO (NANO)COMPOSITES: 100 YEARS OF POLYMERS IN ART

Oscar Chiantore

Department of IPM Chemistry & NIS Center of Excellence

University of Torino, Italy


Polymer materials are widely diffused in every aspect of our daily life, and their presence as constituents of works of art is more and more a common experience. Plastics and rubbers have influenced artists techniques since the beginning of their industrial applications and appearance on the markets, and also fostered new forms of artistic expressions, expanding vision and creativity to levels never reached before. Materials devised for technological or domestic applications started to be adopted by artists which were fascinated by the possibilities of obtaining new optical and constructive effects, by the modulation of space offered by the lightness and transparency of the new plastic materials, and by the easiness of shaping. Since the beginning of their discovery, these were the polymer premium characteristics who promoted their use in the art field.

After the invention of Bakelite, “the material of thousand uses”, whose mass diffusion started 100 years ago, practically every type of new polymer introduced in the market has found application in art works, either occasionally or systematically.

The introduction of polymers in art took place along two important mainstreams. The first one is that of tridimensional works (sculptures, objects and installations), where the materials are exploited for obtaining, thanks to their specific characteristics of weight and look, original spatial effects and new forms. It is in this field that the first examples of polymers used for creating artworks may be seen. After the initial trials with the the up-to-then only available semi-synthetic plastics, the range of materials to exploit extended so much that now practically any type of plastic, fiber or rubber, from vinyls to acrylics, from polyolefins to styrene polymers, polyesters and polyamides, from epoxies to polyurethanes and to silicones, to composites with glass or carbon fiber reinforcements,1 and ultimately to plastics with nanofillers reinforcement, may be found in art works.

The second way for polymers as art materials is that of modern paints.2 Compared with the traditional paint media, synthetic polymers used for paints and coatings offer many advantages like drying speed, color stability, and a broad variety of formulations for many different optical effects. The innovation was so important that when the new acrylic paints were introduced as artist colors they were labelled as “the first

new painting medium in 500 years”. Acrylics soon became, and still are, the most important synthetic binders in art field, but they are not the only one. In fact vinyls, alkyds, epoxies and polyurethanes have been also adopted by artists, with the particularity that most often the products involved in the art works were household paints instead of artists colors.

A review of polymers in art works will be presented, and it will be illustrated how the presence of such variety of new materials in the fabrication of artworks brought new conservation problems.3,4 Physical and chemical ageing processes developing within the polymeric structures may strongly impair the aspect and / or the structural integrity of works recognized to have artistic or historical importance, which should therefore be preserved and transmitted to the future in their pristine material integrity.

References

1. F. Waentig, Plastics in Art, Imhof Verlag, Petersberg, 2009 2. J. Crook, T. Learner, The Impact of Modern Paints, Tate Publishing, London, 2000 3. T. van Oosten, Y. Shashoua, F. Waentig (eds.), Plastics in Art, History, Technology, Preservation, Siegl,

Munich, 2002 4. O. Chiantore, A. Rava, Conservare l’arte contemporanea – problemi, metodi, materiali, ricerche, Electa,

Milano, 2005

64

IL32

LA CHIMICA: UN BENE CULTURALE

Renzo Bertoncello, Marina Brustolon*

Dipartimento di Scienze Chimiche – Università degli Studi di Padova

L’attività di ricerca e caratterizzazione chimica e chimico-fisica dei Beni Culturali nel Dipartimento di Scienze Chimiche dell’Università di Padova è da un lato inserita in attività diagnostiche conoscitive o di degrado che precedono e accompagnano importanti restauri, e dall’altro è tesa allo sviluppo applicativo di metodologie spettroscopiche per lo studio dei materiali dei BC. I due relatori Bertoncello e Brustolon sono impegnati rispettivamente nei due settori di attività, che d’altronde si vanno integrando in un progetto comune. Le conoscenze acquisite dopo la razionalizzazione dei fenomeni di degrado sono la base per la progettazione e la verifica - in laboratorio chimico interno - di film protettivi prevalentemente inorganici atti a proteggere e consolidare i manufatti storico-artistici dal degrado.

Nella conferenza descriveremo quindi in dettaglio da un lato alcuni degli interventi diagnostici recenti, e dall’altro alcune delle metodologie più avanzate e di maggiore interesse perché finora raramente usate nello studio dei Beni Culturali.

Per quanto concerne gli interventi diagnostici verranno brevemente descritti gli studi effettuati sulle vetrate antiche della Chiesa di SS Giovanni e Paolo in sestiere Castello a Venezia e le piastrelle di ceramica in stile liberty che coprono la grande facciata dell’Hotel Hungaria al Lido di Venezia gravemente deteriorate in seguito all’esposizione ad agenti atmosferici, biologici e antropici. Al solo intervento dell’uomo è invece dovuta la ricopertura con vari strati di intonaco di un dipinto murale (affresco) situato nell’ex convento di Santa Caterina a Padova. Grazie alle indagini chimiche è stato possibile definire lo spessore degli strati coprenti e individuarne la natura agevolando così l’intervento di restauro. L’indagine sulle figure e sui pigmenti utilizzati sta consentendo inoltre di rivalutare il ruolo del pittore esecutore altrimenti destinato all’oblio.

Per quanto concerne le metodologie, di particolare rilevanza anche per le tradizioni culturali e scientifiche del gruppo chimico di Padova sono le applicazioni delle spettroscopie ottiche e magnetiche ad alcuni materiali. Si farà una panoramica di queste applicazioni, focalizzandosi in particolare sulle applicazioni della spettroscopia EPR. Con una serie di esempi di applicazione a oggetti specifici si mostrerà come questa famiglia di spettroscopie sia uno strumento potente nello studio di carta, inchiostri, pigmenti, vetri, ceramiche.

Tra le tecniche che a Padova vengono utilizzate con grande competenza e rilevanza di risultati vi è certamente la spettroscopia Mössbauer che però soffre di un limite assai oneroso in quanto è generalmente invasiva e distruttiva e inoltre il suo utilizzo è limitato nell’ambito del laboratorio. Per superare questi limiti è stato sviluppato uno strumento portatile che ha offerto notevoli risultati e grandi soddisfazioni.

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Le tecniche pittoriche riscoperte dalla ricerca chimica Michela Berzioli*, Elisa Campani, Antonella Casoli

Dipartimento di Chimica G.I.A.F. – Università degli Studi di Parma,

V.le G.P. Usberti 17/A, 43100 Parma

[email protected]

La conoscenza dei materiali costituenti le opere pittoriche è notoriamente di grande importanza ai fini conoscitivi e conservativi. Perseguendo questo obiettivo, la ricerca chimica ha permesso negli ultimi anni di disporre di tecniche analitiche e metodologie tali da raggiungere interessanti risultati nell’ambito della conoscenza delle tecniche pittoriche.

La prima opera illustrata riguarda i dipinti murali della cupola del Duomo di Parma, affrescata tra il 1522 e il 1526 da Antonio Allegri, detto il Correggio (Correggio 1489 – Correggio 1534). Nella cupola è dipinta la scena dell'Assunzione della Vergine [1,2]. L’ occasione dello studio è stata offerta dall’ultimo intervento conservativo (condotto nei mesi di luglio ed agosto 2008) che ha permesso di effettuare sopralluoghi ravvicinati, valutare lo stato di conservazione, predisporre un protocollo di indagine, che ha previsto due fasi distinte: un primo stadio di indagini non invasive in situ, impiegando strumentazione portatile, ed un secondo momento in cui si è previsto il prelievo mirato di microframmenti di materiale pittorico. Lo scopo della campagna analitica era quello di conoscere pigmenti e leganti utilizzati dall’artista per risalire alla tecnica pittorica, identificare i materiali di restauro e i prodotti di degrado.

L’altro studio riportato è quello effettuato sulla Pala Albergotti, realizzata nel 1567 da Giorgio Vasari (Arezzo 1511 - Firenze 1574) [3]. Il dipinto si trova attualmente nella Badia delle Sante Flora e Lucilla ad Arezzo. L’opera è composta da una grande tavola che raffigura “Assunzione ed incoronazione della

Vergine”, due tavole laterali con i santi Donato e Francesco e otto tavolette poligonale con le immagini delle Sante.

La campagna analitica ha avuto come obiettivo principale l’identificazione dei materiali originali impiegati dall’artista, vale a dire i pigmenti negli strati policromi, le cariche minerali nella preparazione e i leganti organici delle diverse stesure pittoriche. In più, sono stati effettuati esami stratigrafici, al microscopio, dei frammenti di pellicola pittorica per osservare la struttura dei film di colore, lo spessore e il numero delle pennellate, la presenza di sottomodellati, di “pentimenti”, di interruzioni di lavoro e ogni altro dettaglio che potesse fornire informazioni circa le scelte tecniche e le modalità operative del pittore nell’eseguire l’opera. Accanto a ciò, sono state indagate alcune aree dell’opera che presentavano evidenti fenomeni di alterazione superficiale, colature e viraggio del tono del colore.

References:

1. A. Casoli, M. Berzioli, M. E. Darecchio, L. Medeghini, P. P. Lottici, Danilo Bersani, Rossano Bolpagni, Mario Tribaudino, Paolo Zannini, Simone Caglio, Gianluca Poldi, Diego Cauzzi Indagini scientifiche su dipinti murali del Correggio: la cupola del Duomo di Parma, Convegno internazionale di studi sul Correggio 28-29 Novembre 2008, Parma 2. D. Bersani, M. Berzioli, S. Caglio, A. Casoli, D. Cauzzi, M. E. Darecchio, P. P. Lottici, L. Medeghini, G. Poldi, P. Zannini . Il blu di smalto in affreschi: il caso del Correggio nella cupola del Duomo di Parma Aiar RIFLESSIONI E TRASPARENZE DIAGNOSI E CONSERVAZIONE DI OPERE E MANUFATTI VETROSI Ravenna, 24 -26 febbraio 2009 3. Stefano Volpin, Antonella Casoli, Elisa Campani, Michela Berzioli LE INDAGINI DI LABORATORIO SVELANO I MATERIALI E LA TECNICA PITTORICA DI GIORGIO VASARI NELLA PALA ALBERGOTTI, in AA.VV. L’INGEGNO E LA MANO. Restaurare il mai restaurato.

Il restauro della pala Albergotti di Giorgio Vasari nella Badia delle Sante Flora e Lucilla di Arezzo, Edifir Edizioni, Firenze, 2009, 83 – 90

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Molecular spectroscopies for the study of heritage materials: from conservation to

authentication

Rocco Mazzeo

Laboratorio Diagnostico di Microchimica e Microscopia (M2ADL), Università di Bologna, via Guaccimanni 42, 48100 Ravenna (Italy).

[email protected]

http://www.tecore.unibo.it/html/Lab_Microscopia/M2ADL/

The last two decades have seen a substantial increase in the application to cultural heritage of different

type of non-destructive (ND) and micro-destructive (µD) spectroscopic analytical methods.

Thanks to the increasing collaboration and understanding among conservation scientists and art historians,

archaeologists, curators and conservator-restorers many questions dealing with cultural heritage materials'

characterization (pigments and dyes), state of conservation (degradation products), ancient production

techniques (tempera and oil paintings, frescoes, etc.), evaluation and monitoring of new conservation

materials and methods and authentication studies have been answered with the use of physico-chemical

techniques among which the molecular spectroscopies are playing a crucial role. Some of the results so far

achieved will be highlighted through the presentation of case studies.

An attempt will also be made in the identification of possible future research priority issues with particular

reference to the use of spectroscopic methods for the characterization, degradation behaviour and

stratigraphic spatial location of paintings' organic components such as binding media and varnishes. This

information, in fact, is of the outmost importance to conservator-restorers in the planning of any

restoration intervention.

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A chemical approach to the cleaning of paintings

Paolo Cremonesi, Scientific coordinator of Cesmar7 – The Centre for the study of Materials for Restoration,

Padua – Italy

In the conservation of artefacts, chemistry can play an important role, aside from it obvious involvement in all analytical procedures aimed to characterizing the structure and composition of the work of art.

Chemistry, in fact, could and should shape our whole approach to the restoration intervention:

• in selecting proper materials, based on predicting how the now materials we are applying onto the artefact could interact with those already present

• in assisting our intervention, trough the monitoring of some parameters (pH, composition of materials which are being removed…)

• in monitoring the results of our intervention.

A restoration treatment is made up of several different interventions, some relying on adding materials (i.e, consolidation, filling, retouching, varnishing…) and others on removing of materials (i.e., cleaning). For both types on interventions, the above “chemical approach” is critical: when new materials are added, then the main issue is probably their compatibility with the existing materials; on the contrary, when aged materials are removed, the most relevant factor becomes selectivity: the possibility of discriminating between their physico-chemical properties and those of the materials which are to be left, as unaffected as possible, in/on the artefact.

Among all artefacts, moveable paintings are among the most complex ones: because of the prevalent organic nature of their components (supports, binders, varnishes, dyes…) and of the way these different materials are often intermixed within the composite structure (= layered-structure) of a painting.

Cleaning, in this particular time in history, has become the procedure most often performed on paintings.

Several factors contribute to rendering this procedure the most critical, with the greatest risk of damage to the artefact:

• It is a procedure based on removal of materials, therefore intrinsically irreversible;

• It is periodically performed;

• It does impact on the most easily perceived part of the painting, which also is the “essence” of the painting itself: the painted image;

• It does reflect the ethic/aesthetic sense of a particular time in history; in addition, this different influences are further mediated trough the “personal touch” of the restorer’s hands.

All these factors would require a rigorous approach to such a complex intervention. In reality, time and cost, as well as a cultural issues, have contributed to hand down to us a rather “casual” methodological approach to cleaning, that has seen some changes only in these last twenty years.

In order to minimize interactions with constituent materials, a correct “chemical approach” should take into account the following issues:

- organic solvents should be used in a polarity-based sequence, so as to determine the minimal effective polarity for swelling/dissolving materials to be removed;

- acids and alkalis should only be used in an aqueous medium, within a pH “safety range” 5-9;

- to address both the issues, integrity of the artwork and safety of the working environment, the aqueous medium should be exploited, by testing the addition of “active principles” such as surfactants and chelators;

- for both solvents and aqueous solutions, diffusion into the layers should be controlled by means of gelling agents.

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CHEMISTRY FOR THE STUDY AND THE CONSERVATION OF CULTURAL HERITAGE

Guido Biscontin

Department of Environmental Science, University of Venice, Ca’ Foscari

The function performed, both in the present and in the past, by chemistry in cultural heritage is very wide and complex. Often it is decisive to characterize and gain essential information for the knowledge of the work of art in its complexity.

This relationship traced back to some centuries ago, with the work of lots eminent chemists , who firstly operated on archaeological excavations (such as Pompei and Egypt) and synthesized pigments like ultramarine blue or Egyptian blue, and who subsequently tried to develop products for requirements not already solved. The development of polymers offered new possibilities of applications creating a new branch of research and application. But the knowledge is not only a closer examination of materials, techniques, products, etc… but also the study of their behaviour in relation with the decay and the processes which cause it. The level of decay defines some basilar choices: intervening immediately or waiting?

The investigations related to the history of a work of art can influence not only operative choices for conservation but also theoretic choices managing the philosophy of restoration. There are lots examples of this way of proceeding, where chemistry together with other disciplines involved, indicate the applicative possibilities underlining the various aspects in relation with expected answers.

Some cases, used as points of reference in the field of conservation, are described , where there is a direct relationship between chemical analysis and restoration choices (not only technical but also philosophical ). The research on products and specific techniques is in continuous development with refined and high quality experimentations. The research is now dealing with to nanomaterials and the application of biological system for specific situations. The setting up of portable systems for non destructive analysis , which is carried on even by the demand of the field of cultural heritage , is giving excellent results and it is in expansion.

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DAL CARBONE SARDO AL PROIETTILE DI GARIBALDI

LE ANALISI CHIMICHE DI PAOLO TASSINARI (1829-1909)

Marco Taddia

Dipartimento di Chimica “Giacomo Ciamician”, Università di Bologna

[email protected]

Anche ai tempi nostri, nonostante lo sviluppo della strumentazione, la semplificazione delle tecniche

operative e la crescente diffusione dei metodi automatici, giungere a stabilire con sicurezza la

composizione di un campione incognito rimane, per certi aspetti, un’arte che richiede esperienza, fiuto e un

complesso di conoscenze interdisciplinari. Lo riconoscono perfino alcuni testi didattici [1] e lo sa chi,

nell’accademia, ha mantenuto viva la curiosità e la disponibilità a risolvere problemi pratici posti

dall’industria. Come si può facilmente immaginare, circa centocinquant’anni fa, quando Paolo Tassinari

praticava la chimica analitica, l’arte era ben più complicata di oggi. Tassinari (Castel Bolognese 1829 –

Solarolo 1909) aveva la fama di analista particolarmente accurato [2] e si occupò di diverse questioni

pratiche, una delle quali, legata a Garibaldi, è passata nei libri di storia [3] ed è ricordata da studiosi della

chimica pisana [4]. In occasione del centenario della morte di Tassinari, che fu allievo di Piria e grande

amico di Cannizzaro, se n’è ricordato il contributo alla didattica (SCI 2009, Sorrento). Mancava fino ad oggi

uno sguardo meno frettoloso, ma non agiografico, alla sua attività scientifica, molto modesta ma non

disprezzabile. Di lui si ricordano alcuni articoli su riviste italiane, tre dei quali citati nella bibliografia [5-7], e

due brevi monografie contenenti relazioni sull’analisi di acque. La prima (1883) riguarda le terme di Uliveto

(con C. Marchetti) e la seconda il cosiddetto Doccione dei Bagni caldi (Bagni di Lucca), 1895. I primi lavori

sono quelli che lo portarono in cattedra a Pisa nel 1862, dopo un breve passaggio a Bologna dove insegnò

Chimica Analitica, Mineralogica e Metallurgica. Dopo la conquista della cattedra si dedicò solo alla didattica

e alla stesura di opere che ebbero notevole fortuna editoriale, come l’Avviamento alla chimica – XXX lezioni

e il Manuale di chimica-chimica inorganica. Il lavoro forse più importante è la nota relativa alla conversione

dei nitrati in ammoniaca e al loro riconoscimento analitico [6], che porta anche la firma di Pietro Piazza,

professore di chimica organica a Bologna. Negli altri si occupò dell’analisi di un combustibile fossile

scoperto in Sardegna [7] e della ricerca di tracce di fosforo in ambito tossicologico [8]. Qui verrà dato il

giusto riconoscimento agli aspetti originali dei metodi di Tassinari, senza trascurare l’episodio che lo vide

consulente dei chirurghi in occasione del ferimento del Generale in Aspromonte il 29 agosto 1862.

Bibliografia

[1] Enke C.G., The Art and Science of Chemical Analysis, Wiley, New York, 2001 [2] Anonimo (T.G.), Boll. Chim. Farm., 48, 359 (1909) [3] Paolini G., La ferita di Garibaldi ad Aspromonte, Edizioni Polistampa, Firenze, 2004, p. 56 [4] Fochi G., Le radici della chimica pisana, Tipografia Università di Pisa, 1994 [5] Tassinari P., Gazz. Med. Ital. Fed.. Toscana, 2, 1(1852) [6] Tassinari P., Piazza P., Nuovo Cimento, 2, 456 (1855) [7] Tassinari P., Nuovo Cimento, 4(1), 50 (1856)

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POSTERSPOSTERSPOSTERSPOSTERS

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GOLD(III)-BASED ANTICANCER AGENTS: PEPTIDE DERIVATIVES OF SULFUR DONOR LIGANDS AS IMPROVED INTRACELLULAR DRUG TRANSFER AND DELIVERY SYSTEMS SUPPORTED BY

TRANSPORTER PROTEINS

L. Ronconi1*, M. Negom Kouodom1, D. Aldinucci2, Q.P. Dou3, F. Formaggio1, D. Fregona1 1Department of Chemical Sciences, University of Padova, Padova 35131 (ITALY); 2Department of Molecular

Oncology and Translational Research - Division of Experimental Oncology 2, National Cancer Institute (CRO-

IRCCS), Aviano (PN) I-33081 (ITALY); 3Ann Karmanos Cancer Institute and Department of Pathology, School

of Medicine, Wayne State University, Detroit MI-48201 (USA)


Only a few Au(III) compounds are currently under evaluation for their extremely promising antitumor

properties. Recently, we have reported on some Au(III)-dithiocarbamato derivatives which have proved to

be much more cytotoxic in vitro than clinically established platinum-based drugs, and showed encouraging

results in terms of both high in vivo effectiveness and lack of nephrotoxic side-effects [1,2]. Moreover, for

the first time, we have identified the ubiquitin-proteasome system as a major in vitro and in vivo target for

these compounds [3], and we have also extended the evaluation of their interaction with mitochondria [4],

thus supporting the hypothesis of a different mechanism of action compared to cisplatin. We have now

extended our research towards new Au(III) derivatives of peptides as improved intracellular drug transfer

and delivery systems supported by transporter proteins, that mediate the cellular uptake of di-/tripeptides.

As their substrate-binding site can accommodate a wide range of different molecules, they represent

excellent targets for the delivery of pharmacologically-active compounds [5]. The rationale behind our

research was to design Au(III)-dithiocarbamato derivatives of di-/tripeptides which can be able to both

maintain the antitumor properties and the lack of nephrotoxicity of the previously reported Au(III)

analogues, together with an enhanced bioavailability through the di-/tripeptide-mediated cellular

internalization. Synthesis, chemical characterization and biological activity are discussed.

References

1. L. Ronconi, C. Marzano, P. Zanello, M. Corsini, G. Miolo, C. Maccà, A. Trevisan, D. Fregona, J. Med. Chem. 2006, 49, 1648.

2. V. Milacic, D. Fregona D, Q.P. Dou, Histol. Histopathol. 2008, 23, 101. 3. V. Milacic, D. Chen, L. Ronconi, K.R. Landis-Piwowar, D. Fregona, Q.P. Dou, Cancer Res. 2006, 66,

10478. 4. D. Saggioro, M.P. Rigobello, L. Paloschi, A. Folda, S.A. Moggach, S. Parsons, L. Ronconi, D. Fregona, A.

Bindoli, Chem. Biol. 2007, 14, 1128. 5. I. Rubio-Aliaga, H. Daniel, Trends Pharmacol. Sci. 2002, 23, 434.

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Novel mitochondrion-targeted Quercetin derivatives: synthesis, oxidation potentials, radical-scavenging properties and cytotoxicity

Andrea Mattarei,a Lucia Biasutto,a,b Ester Marotta,a Spiridione Garbisa,b

Mario Zoratti,b,c Christian Durante, a Giancarlo Sandonà,a Armando Gennaro, a Cristina Paradisia aDipartimento di Scienze Chimiche, Università di Padova, Via Marzolo 1, 35100 Padova, Italy

bDipartimento di Scienze Biomediche, Università di Padova, Viale G. Colombo 3, 35100 Padova, Italy

cIstituto di Neuroscienze, Consiglio Nazionale delle Ricerche, Viale G. Colombo 3, 35100 Padova, Italy

[email protected]

We are developing polyphenol-based mitochondria-targeted molecules capable of acting as radical

scavenging anti-oxidants or death-inducing pro-oxidants.[1] Both activities may be useful in pathological

situations (e.g. neurodegeneration and cancer, respectively). We have synthesized two derivatives of

quercetin (3,3’,4’,5,7-pentahydroxy flavone) in which the 3-OH or the 7-OH have been linked via a butyl

chain to triphenylphosphonium, a membrane-permeant cation.

If these compounds are to display the desired redox activity in vivo, the chemical modifications introduced

should not significantly alter the oxidation potential and the reactivity vs radical species of the parent

compounds. To verify this point we are using cyclic voltammetry and in vitro tests of radical scavenging

using 2,2-diphenyl-1-picrylhydrazyl (DPPH•).[2] While the oxidation potential of the 7-derivative is very close

to that of quercetin itself, the 3-substituted molecule is oxidized at approx. 0.1 V higher anodic potentials.

This difference may be ascribed to the different stabilities of oxidation products, and suggests that the

compound substituted at position 7 may be more suitable for our purposes than the one substituted in 3.

In the microM range both compounds are cytotoxic for fast-growing, but much less for slow-growing,

cultured cells. As might have been expected based on their oxidation properties, 7-O-(4-

triphenylphosphoniumbutyl)-quercetin is more effective than the 3-substituted isomer.

References:

1. Mattarei et al., A Mitochondriotropic Derivative of Quercetin: a strategy to increase the effectiveness of

polyphenols. ChemBioChem. 2008, 9, 16, 2633-2642

2. Fukumoto et al., Assessing Antioxidant and Prooxidant Activities of Phenolic Compounds. J. Agric. Food.

Chem. 2000, 48, 3597-3604

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PO3

BINDING COOPERATIVITY AND ALLOSTERISM IN FATTY ACID BINDING PROTEINS

Assfalg,M.1, D’Onofrio,M.1 Pedò,M. 1, Zanzoni,S 1, Cogliati, C.1 and Molinari, H.* 1Dipartimento di Biotecnologie, Strada le Grazie 15, Università di Verona, 37134 Verona


Lipids are vital components of many biological processes and crucial in the pathogenesis of numerous common diseases, but the specific mechanisms coupling intracellular lipids to biological targets and signalling pathways are not well understood.

Intracellular lipid chaperones known as fatty acid binding proteins (FABPs) are a group of molecules that coordinate lipid responses in cells and are strongly linked to metabolic and inflammatory pathway1. FABPs display a wide range of sequence diversity, but share a common structural fold constituted by a ten-stranded beta-barrel and a helix-loop-helix motif, creating a hydrophobic interior cavity.

Our group is focussing its research towards the elucidation of the complex binding mechanisms of FABPs2. We use primarily Nuclear Magnetic Resonance (NMR) spectroscopy to investigate both the structural and the dynamic details of protein-ligand adducts. Particularly, measurements of translational diffusion and site-specific protein mobility have highlighted functionally relevant protein regions. These data are combined with calorimetry and mass spectrometry data as well as to molecular docking approaches, perfomed both on human liver-FABP and on the corresponding protein in chicken used as a model system. The emerging picture is consistent with the occurrence of strong cooperative binding to multiple sites, originated by protein allosterism.

Furthermore, very recent results from our laboratory have raised a new hypothesis on the mechanism of action of these proteins, suggesting that they can act as molecular switches allosterically activated by lipid molecules and/or membranes in the regulation of lipid trafficking. We present NMR data concerning the interplay between lipids/lipid chaperones/membranes, both in solutions containing phospholipids vesicles and directly in living cells.

As an application, we are characterizing the interaction of FABPs with lipid-functionalized gadolinium chelates to be used as potential hepatospecific contrast agents for Magnetic Resonance Imaging3-4.

References

1. Furuhashi, M. and Hotamisligil, G. S., Nat Rev Drug Discov 7, 489-503, 2008. 2. Eliseo, T., Ragona, L., Catalano, M., Assfalg, M., Paci, M., Zetta, L., Molinari, H. and Cicero, D. O.

Biochemistry 46, 12557-67, 2007. 3. Tomaselli, S., Zanzoni, S., Ragona, L., Gianolio, E., Aime, S., Assfalg, M. and Molinari, H. J Med Chem

51, 6782-92, 2008. 4. Assfalg, M., Gianolio, E., Zanzoni, S., Tomaselli, S., Russo, V. L., Cabella, C., Ragona, L., Aime, S. and

Molinari, H. J Med Chem 50, 5257-68, 2007.

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(Zn,Cu)O PHOTOCATALYTIC MATERIAL AND ZnGa2O4 : Eu3+ PHOSPHORS: TAILORING STRUCTURE-PROPERTY RELATIONSHIPS

Laura Bovo1*, Lidia Armelao2, Marco Bettinelli3, Eugenio Tondello1 1Dipartimento Scienze Chimiche, Università di Padova,via Marzolo 1 35131 Padova, INSTM,

e-mail: [email protected] 2CNR, ISTM, INSTM, Dipartimento di Scienze Chimiche, Università di Padova,via Marzolo 1 35131 Padova

3Lab. Chimica dello Stato Solido, DB, Università di Verona, INSTM, Strada Le Grazie 15 37134 Verona

Zinc oxide, an important II-IV semiconductor with direct band gap (3.2 eV1) and large exciton binding energy (60 meV1), has become one of the most attractive materials in research due to its wide application ranging from optoelectronic2, (photo)catalysis3 and devices for optic4 or biology5 together with its peculiar properties of good stability, bio-compatibility and non-toxicity. The control over the size and morphology of nanometer micrometer-sized ZnO crystals represents a great challenge for the design of novel functional devices. Doping with selective elements (generally transition metal ions), also offers an effective method to adjust the electrical, magnetic and optical properties of zinc oxide. In terms of practical photocatalytic applications the ability to fabricate ZnO nanosystems with defined morphology and high surface-to-volume ratio under soft processing conditions is highly desirable. Our project is concerned with sol-gel and hydrothermal synthesis of undoped and Cu-doped zinc oxide nanosystems (powders or layers) to prepare novel photocatalytic materials. The systems have been characterized by complementary techniques, providing important information on their composition, structure, morphology and optical properties. Moreover, ZnO is a suitable host material for doping with luminescence centers: in this sense, lanthanide-doped ZnO nanocrystals may represent a novel class of light-emitting materials in which the optical properties of the single units are combined to enhance the performance of the resulting materials. It is also possible to tailor the doping of host ZnO with III group metals (Ga, Al or In) to improve the properties of the final materials. In this, the oxide structure is modified thus allowing a higher lanthanide doping level and, at the same time, to have an efficient energy-transfer from the matrix to the emitting centers. ZnGa2O4 is a binary compound oxide material which crystallizes in the spinel structure. It has an energy gap of about 5.0 eV, and under excitation with ultraviolet light emits blue light due to transitions via a self-activation center. In addition, ZnGa2O4 is a promising transparent conducting oxide material, particularly when transparency through violet to nearUV region is desired6,7. In this work we report the sol-gel and hydrothermal synthesis of undoped and Eu-doped ZnGa2O4 nanopowder to study the effect on emission properties as a function of different synthetic strategies. References 1. S. Sakthivel et al. Sol. Energy Mater.Sol. Cell 77 (2003) 65 2. J.C. Johnson et al. Phys. Chem. B 105 (2001) 11387 3. M.R. Hoffman et al. Chem. Rev. 95 (1995) 69 (b) O. Legrini et al. Chem Rev. 93 (1993) 671 4. N. Saito et al. Adv. Mater. 14 (2002) 418 (b) J. Liquianga et al. Solar Energy Materials & Solar Cells 90 (2006) 1773 5. A. Dorfan et al. Langmuir 22 (2006) 4890 6. Liang Xu et al. Crystal Growth & Design 7 (4) (2007) 810] 7. Masanori Hirano J. Mater. Chem. 10 (2000) 469

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ENCAPSULATION OF PHOTOACTIVE MOLECULES INSIDE SINGLE WALL CARBON NANOTUBES

Francesca Colombo1*, Claudia Ambrosch-Draxl2, Barbora Bartova3, Pascal Blondeau1, Jia Gao4, Cecile

Hebert3, Maria Antonietta Loi4, Enzo Menna1, Matus Milko3

1ITM-CNR and Dipartimento di Scienze Chimiche, Università di Padova

2Department Materials Physics, University of Leoben 3EPFL SB-CIME & IPN-LSME, Lausanne

4Zernike Institute for Advanced Materials, University of Groningen

Keywords: encapsulation, photoactive derivatives, photonic devices, functionalization, raman

New nano-hybrid systems composed of a photoactive organic semiconductor (pea) inside the carbon cage

of single wall carbon nanotube (pod) are described. Rigid molecules of different size and properties have

been employed in this study. Highly stable π-conjugated systems are indeed good candidates for photonic

and electronic devices such as organic light emitting diodes (OLED’s) and field effect transistors (FET).

Optimized purification of SWNTs through air oxidation and acid treatment, followed by a final annealing

was performed before encapsulation process. Particular attention has been then given to sample

preparation before encapsulation. High power sonication of SWNTs in toluene indeed afforded a better

dispersion giving rise to yield increase. Encapsulation of photoactive molecules has been carried out

through gas phase, but the aim of supercritical CO2 has been also considered 1. Extensive washings of the

resulting peapods were performed in order to remove all the non-encapsulated molecules as confirmed by

thermogravimetric analysis. Besides, a mixture of SWNTs and the single molecule was produced as a

control experiment in a view of comparing the influence of the guest inside and outside SWNTs. To confirm

the encapsulation of single molecules, Raman spectra were carried out at both 633 and 488 nm excitation

wavelength as well as UV/Vis/NIR spectra in DMF solution. The radial breathing mode (RBM) Raman signals

of peapod resulted up-shifted. Moreover, we can remarkably distinguish Raman signals originating from the

molecules in the spectrum of SWNT after encapsulation. Besides, new peaks appeared giving evidences of

the new state of the molecule inside the confined space of the SWNT. UV/Vis/NIR spectra in DMF solution

gave less clear indications of the peapod formation due to the strong SWNT absorption.

The resulting hybrid material was characterized by high-resolution transmission electron microscopy and

photoluminescence spectroscopy measurements showing efficient emission in the visible range. In

addition, first-principles calculations based on density functional theory were performed to evaluate the

interactions between the pea and the pod

References 1 Campestrini, S.; Corvaja, C.; De Nardi, M.; Ducati, C.; Franco, L.; Maggini, M.; Meneghetti, M.; Menna, E.; Ruaro, G.; Small 4, 350-356, 2008.

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NANOZYMES FOR PHOSPHATE DIESTERS HYDROLYSIS

Renato Bonomi*, Francesco Selvestrel, Fabrizio Mancin, Umberto Tonellato and Paolo Scrimin Università di

Padova, Dipartimento di Scienze Chimiche, via Marzolo 1, Padova, Italy


The phosphodiester bonds of DNA are tremendously resistant to hydrolysis [1]. Nevertheless, several enzymes perform this reaction in few seconds in mild conditions, achieving accelerations up to 1018-fold. Such astonishing efficiency depends on a network of multiple non-covalent interactions experienced by the substrate in the enzymes active site, which cooperate to facilitate the reaction progress.[2] The development of synthetic hydrolytic agents for phosphate diesters has been brought about on the basis of this nature’s lesson.[3] Systems of increasing complexity have been prepared and studied trough the years, starting from simple metal complexes up to multinuclear complexes bearing functional groups capable to provide further activation modes. The best among these hydrolytic agents, based on rationally designed metal complexes, have reached impressive reactivities toward RNA models and oligonucleotides, still they usually fail to induce hydrolysis of DNA models. We have recently shown as nanozymes, gold nanoparticles coated with monolayers of thiols bearing reactive groups, can provide an efficient alternative strategy for the realization of self-organized cooperative hydrolytic agents.[4] In this communication we show that 2-nm gold particles (np·Zn(II)) coated with Zn(II) complexes of a ligand containing the bis-(2-amino-pyridinyl-6-methyl)amine (BAPA) unit, are very active in promoting the hydrolysis of the DNA model bis-p-nitrophenyl phosphate. At pH 7 and 40 °C BNP is cleaved by np·Zn(II), at a 50 M concentration of metal complex units, with a rate of 3.6·10-5 s-1, which represents a 300.000-fold acceleration over the background reaction. Such acceleration is, at the best of our knowledge, at least ten times greater than those obtained by any other Zn(II) based hydrolytic agent so far reported. The source of such activity resides in the spontaneous self-organization of multimetallic reactive sites on the particles surface where cooperation of metal coordination and second sphere hydrogen bonds formation results in a dramatic increase of substrate binding affinity.

References

1. Schroeder, G. K.; Lad, C.; Wyman, P.; Williams, N. H.; Wolfenden, R. Proc. Natl. Acad. Sci. U.S.A103, 4052-4055, 2006.

2. Weston, J. Chem. Rev. 105, 2151-2174, 2005. 3. (a) Mancin, F.; Scrimin, P.; Tecilla, P.; Tonellato, U. Chem. Comm. 2540-2548, 2005; (b) Niittymaki, T.;

Lonnberg, H. Org. Biomol. Chem. 4, 15-25, 2006; (c) Mancin, F.; Tecilla, P. New J. Chem. 31, 800-817, 2007.

4. (a) Pasquato, L.; Rancan, F.; Scrimin, P.; Mancin, F.; Frigeri, C. Chem. Commun. 2253-2254, 2000; (b) Manea, F.; Houillon, F. B.; Pasquato, L.; Scrimin, P. Angew. Chem.-Int. Edit. 43, 6165-6169, 2004.

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SUPPORTED BIS(ZNII-PORPHYRIN) DITOPIC RECEPTORS FOR THE CONSTRUCTION OF OPTICAL

DETECTION OF DIAMINES. Elisa Lubian*, Tommaso Carofiglio.

Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova, Italy.

Metalloporphyrins are ideal building blocks for elaborating molecular receptors1. We have recently exploited a modular approach for the straightforward synthesis of porphyrin dyads that takes advantage of the unique temperature-dependent reactivity of cyanuric chloride toward nucleophiles2. This synthetic procedure takes advantage on the unique temperature-dependent reactivity of cyanuric chloride toward nucleophiles. Typically, the first chloride reacts rapidly at 0°C, whereas room temperature or moderate heating (depending on the nucleophile strength) promotes the second substitution. The nucleophilic displacement of the third chloride requires harsher conditions (T > 80°C for multiple hours). Interestingly, since quantitative yields are almost routine for these reactions, sequential, one-pot introduction of various substituents into a triazine ring is also possible, with a minimal recourse to purification based chromatography techniques. Thus, the procedure for preparing porphyrin dyads simply involves a sequential coupling of two identical or different amino-porphyrin building blocks (Scheme 1) thus leading to homo- (PP and MM) or hetero-substituted (PM) receptors, respectively. The third chloride atom can be reacted with an amine (i.e. piperidine) to obtain a molecular compound to be used in solution. Alternatively, the third substitution can afford a convenient route for supporting the tweezers onto various materials carrying amino-group functionalities (i.e. polymeric resins, porous glass particles, and amino-cellulose) with the purpose of developing optical chemical sensor devices (optodes). In the present poster we will describe: 1) the synthesis and characterization of cyanuric acid bridged Bis(ZnII-porphyrin) hosts, 2) the chemistries employed for supporting the porphyrin receptors onto Tentagel-amino resin beads and amino-cellulose and 3) some preliminary results about the construction of optical sensors for diamines. References

1. J.K.M. Sanders, The Porphyrin Handbook, Volume 3, Chapter 22, 347-368. 2. a) T. Carofiglio, A. Varotto, U. Tonellato. J. Org. Chem., 69, 8121-8124, 2004;

78

PO8 TARGETED SILICA NANOPARTICLES FOR DRUG DELIVERY

Francesco Selvestrel *,a,b Gaetano Guarino,a Iria Maria Rio-Echevarria,a,b Elena Reddi,b Fabrizio Mancina.

a Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova, Italy; b

Dipartimento di Biologia, Università degli Studi di Padova, Via Ugo Bassi 58/B, 35131 Padova, Italy.

Email: [email protected]

In the last decade, engineered nanoparticles have become an important class of new materials with several properties that make them very attractive for different fields. In particular, nanotechnology has been applied to diverse medical and biological applications ranging from biomarkers and molecular diagnostics to drug discovery and drug delivery. The importance of such application pushed the National Institute of Health (USA) to introduce the term “nanomedicine” to describe the nanotechnologies applied to the human diseases1. Silica nanoparticles may be useful in drug delivery, because they are easy to make, inexpensive and biocompatible2, but the functionalization of their surface after the synthesis is very difficult and often leads to scarce coverage. In this work, we describe a new one-step procedure to prepare silica nanoparticles coated with a dense PEG layer. Size control is achieved in the 10-150 nm range and the nanoparticles can be easily functionalized with suitable targeting species with the aim to improve the selectivity of the nanocarrier towards diseased tissues. Folic acid, who receptors are over expressed by cancer cell3 and amino group, which allow easy conjugation of the particles with biomolecules, are easily introduced in the particles.

Acknowledgements: this project is funded by EU Grant “Nanophoto”, 7 FWP, project 201031 1. C. Medina, M.W. Radomsky and other, British Journal of Pharmacology, 2007, 150, 552. 2. P.N. Prasad and other, J Am. Chem. Soc, 2003, 125, 7860. 3. Ren-Xi Zhuo and other, Bioconjugate Chem, 2009, 20, 481.

Figure 1: Example of silica nanoparticles targeted with folic acid and amino groups

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MICROGEL-STABILIZED METAL NANOCLUSTERS

G. Dvorakova,a* S. Piperno,b L. A. Gheber,b A. Biffis a a aDipartimento di Scienze Chimiche, Università di Padova, via Marzolo 1, I-35131 Padova, Italy. Tel. +39-

049-8275216. FAX +39-049-8275223. b Department of Biotechnology Engineering, Ben-Gurion University of the Negev, P.O.BOX 653, Beer-Sheva

84105, Israel

email: [email protected]

The term "microgel" defines unimolecular, crosslinked polymer particles possessing a size comparable to the statistical dimensions of uncrosslinked macromolecules (101 - 102 nm), which give rise to stable, low-viscosity solutions in appropriate solvents1. Current application of microgels range from more traditional (additives for coatings) to more advanced applications, including inter alia their use in drug-delivery systems, colloidal crystals, biomimetic receptors/catalysts, phase transfer catalysts, soluble supports for low molecular weight reagents, scavenging agents or (bio)catalysts. Here we report on the latest developments of our work on microgels as stabilisers for metal nanoclusters. Metal ions or complexes can be incorporated in microgels bearing chemical functionalities able to interact with the metal ion and after reduction conveniently yield metal nanoclusters. The final size of the resulting nanoparticles is influenced by the morphology of the microgel, which therefore acts as an exotemplate for the nanoclusters2. The resulting nanocomposites have found promising application as catalysts in technologically relevant reactions, such as the selective aerobic oxidation of alcohols3. Furthermore, the use of these nanomaterials in the production of composite films and fibers is currently under investigation. Very recently, we have obtained for the first time microfibers upon electrospinning4 of microgel solutions. Most notably, the process has been successfully adapted for the electrospinning of solutions of nanocluster-containing microgels. In this way, we have prepared microfibers containing Au or Ag nanoclusters, for which interesting applications can be envisaged given e.g. the catalytic potency of gold nanoclusters and the antimicrobial activity of the silver ones. References 1. W. Funke, O. Okay, B. Joos-Müller, Adv. Polym. Sci. 1998, 136, 139; b) B. R. Saunders, B. Vincent, Adv.

Colloid Interface Sci. 1999, 80, 1; c) R.H. Pelton, Adv. Colloid Interface Sci. 2000, 85(1), 1. 2. A. Biffis, N. Orlandi, B. Corain, Adv. Mater. 2003, 15, 1551; b) A. Biffis, E. Sperotto, Langmuir 2003, 19, 9548; c) L. Minati, A. Biffis, Chem. Commun. 2005, 1034; d) A. Biffis, in "Metal nanoclusters in Catalysis and

Materials Science: the Issue of Size-Control", B. Corain, G. Schmid, N. Toshima (Eds.), Elsevier, Amsterdam 2008,p.341 3. A. Biffis, L. Minati, J. Catal. 2005, 236, 405; b) A. Biffis, S. Cunial, P. Spontoni, L. Prati, J. Catal. 2007 251, 1. 4. Z.M Huang, Y.Z. Zhang, M. Kotaki, S Ramakrishna, Compos. Sci. Technol. 2003, 63, 2223; b) A. Greiner, J. H. Wendorff, Angew Chem. Int. Ed. 2007, 46, 5670.

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PO10

POLYOXOMETALATE CATALYSTS IN IONIC LIQUID MEDIA

S. Berardia*, M. Bonchioa, M. Carraroa, V. Conteb, A. Sartorela, G. Scorranoa

a ITM-CNR and Department of Chemical Sciences, University of Padova,Padova, Italy, b Dept. of Chemical Sciences and Technologies, University of Rome“Tor Vergata”, Rome, Italy.


The design of catalyst packages with better performance, in terms of yields, selectivities, recycling and use

of alternative solvents, is a priority task within sustainable catalysis. In particular, catalytic epoxidation with

hydrogen peroxide retains a major interest, because of its high “atom efficiency” and the production of H2O

as the byproduct. From the catalyst side, the hybrid polyoxotungstate [-SiW10O36(PhPO)2]4- has been found

to mediate catalytic oxygen transfer with outstanding performance and selectivity, in CH3CN, under

microwave irradiation.1 Further innovation towards environmental sustainability should also consider the

replacement of the organic solvent by alternative reaction media. In such a perspective, we studied the

combined use of [-SiW10O36(PhPO)2]4- and ionic liquids (ILs) for catalytic epoxidation with H2O2 (Scheme

1).2

Our results include: (i) the screening of different ILs to optimize catalytic efficiency and recycling, (ii) catalyst speciation and recovery in the IL environment, (iii) optimization of the process under MW irradiation and simultaneous cooling, to promote unprecedented turnover frequencies (TOF > 200 min-1), and quantitative H2O2 conversion. The MW-activated epoxidation of both internal and terminal olefins by [-SiW10O36(PhPO)2]

4- and H2O2 occurs in hydrophobic ionic liquid [bmim+][(CF3SO2)2N

-] with yields and selectivities up to >99%. The catalytic phase is recyclable up to 4 times, each of them with quantitative yields (total turnover number, TON = 500). Supported Ionic Liquid Phases (SILP), integrating tailor-made POMs decorated with IL moieties, will also be presented. References 1 Carraro, M.; Sandei, L.; Sartorel, A.; Scorrano, G.; Bonchio, M. Org. Lett. 8, 3671, 2006. 2 Berardi, S.; Bonchio, M.; Carraro, M.; Conte, V.; Sartorel, A.; Scorrano G. J. Org. Chem. 72, 8954, 2007. Acknowledgements: This work was funded by CNR, MIUR (FIRB CAMERE-RBNE03JCR5, PRIN Contract No.

2006034372), ESF COST D29 and D40 actions.

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FLUOROUS-TAGGED POLYOXOMETALATES AS CATALYSTS FOR SUSTAINABLE OXIDATIONS WITH

O2 AND H2O2

M. Gardan*, M. Carraro, A. Sartorel, M. Bonchio, G. Scorrano

University of Padova, Department of Chemistry,Via Marzolo, 1, 35131 Padova, Italy.


Polyoxometalates of W(VI) have been studied for their interesting properties as oxidation catalysts.[1], [2]. Besides their particular robustness, an appealing feature of this class of inorganic complexes is that they are easily tuneable in terms of structure, composition and counterion so that the synthesis of complexes with different physical-chemical properties is easily accessibleWe report herein, the synthesis of fluorous-tagged polyoxometalates, following two diverse strategies. Both methods have provided novel oxidation catalysts for fluorinated media. In particular:

a) a fluorophilic salt of the decatungstate polyanion has been obtained by counterion metathesis, using a fluorinated tetraalkylammonium cation [3], [4]. The photocatalytic properties of the resulting system have been exploited to performs the aerobic oxidation of benzylic hydrocarbons, including ethylbenzene and cumene. Catalyst heterogenization has been obtained by incorporation of the polyanion in perfluorinated membranes, thus providing novel hybrid materials to be employed and recycled in multi-turnover photocatalytic processes (TONs up to 6100).

b) hybrid derivatives have been obtained by the covalent functionalization of lacunary polyanion with fluorous-tagged organic domains. Oxygen transfer to olefins has been achieved in the presence of hydrogen peroxide, in perfluorinated alcohols, with yields up to 99% in 15 min.

Solution characterization (heteronuclear NMR, FT-IR and UV-Vis spectroscopy), and solid state microscopy evidence will be presented.

- blank line -

H2O

HOOH O2

Sub

SubO

hν T fluorous phase

Fluorous-tagged POMs

W

OO

W

O

O

O

References

1. M. Carraro, L. Sandei, A. Sartorel, G. Scorrano, M. Bonchio Org. Lett., 8, 3671, 2006. 2. A. Sartorel, M. Carraro, A. Bagno, G. Scorrano, M. Bonchio. Angew. Chem. Int. Ed, 46, 3255, 2007. 3. M. Carraro , M. Gardan , G. Scorrano, E. Drioli , E. Fontananova, M. Bonchio, Topics in Catalysis, 133, 2006. 4. M. Carraro, M. Gardan, G. Scorrano, E. Drioli, E. Fontananova, M. Bonchio, Chem. Commun., 4533, 2006.

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ROLE OF THE STRONGLY HELICOGENIC AIB RESIDUES ON THE PROPERTIES OF THE LIPOPEPTAIBOL TRICHOGIN GA IV

B. Biondi, M. De Zotti, C. Peggion*, F. Formaggio and C. Toniolo

ICB, Padova Unit, CNR, Department of Chemistry, University of Padova, 35131 Padova, Italy


Trichogin GA IV is a 10-mer member of the class of short lipopeptaibols that are linear, membrane-active,

peptide antibiotics of fungal origin, characterized by the presence of three strongly helicogenic Aib

residues, a fatty acyl moiety at the N-terminus, and an 1,2-aminoalcohol at the C-terminus. Trichogin GA IV

and some of its analogues exhibit a strong activity against Gram positive bacteria and methicillin-resistant

S. aureus with low hemolytic effect and a remarkable resistance to proteolytic degradation.

In this work, we prepared by SPPS and fully characterized a set of trichogin GA IV analogs where the three

Aib residues at positions 1, 4, and 8 are replaced by one or two L-Leu residues. Leu is still a helix-supporting

amino acid, but less effective than the non-coded Aib. Also, the Aib hydrophobicity is more reduced that

that of Leu. A CD, FT-IR absorption, and 2D-NMR conformational study, and membrane leakage

experiments, were carried out to investigate the role of the Aib→Leu replacements.

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PO13

MODELLING THE PARTITIONING OF SOLUTES IN LIPID MEMBRANES

G. Parisio1*, M. Stocchero2 , A. Ferrarini1

1Dipartimento di Scienze Chimiche, Università degli Studi di Padova, via Marzolo 1, 35131 Padova, Italy,

2S-IN Soluzioni Informatiche, via Salvemini 9, 36100 Vicenza, Italy


The interaction of molecular solutes and nanoparticles with lipid bilayers underlies fundamental biological processes and can be relevant for pharmaceutical and biomedical applications. Yet, the understanding of this interaction remains poor, because of the difficulty of designing suitable experiments to probe the variety of time and length-scales involved in bilayer processes, and the lack of theoretical models able to capture the peculiarity of the highly heterogeneous and organized bilayer environment. Existing models simply treat a bilayer as an oil slab in water1; we have tried to improve this description, by identifying different contributions to the solvation free energy arising from: i) electrostatic interactions, treated according to a Generalized Born formalism for a heterogeneous dielectric medium2; ii) dispersion interactions, described in a mean-field form3; iii) short range repulsions, related to the work for cavity creation, which has been evaluated according to the Scaled Particle Theory approach4, extended to the case of a heterogeneous environment; iv) lipid chain order, described according to the Surface Interaction model, originally developed for liquid crystals5. An atomistic description is adopted for the solute, in terms of atomic charges and polarizabilities, and the Connolly molecular surface6. The properties of the water/bilayer system (dielectric constant, density, chain order parameter and lateral pressure profile) are derived from Molecular Dynamics simulations. Distribution profile and average orientation across the bilayer have been calculated for solutes of different chemical nature and shape, including sterols, aminoacids, fullerenes and membrane fluorescent probes, in DPPC bilayers. Here an overview of theory and results is presented. References 1. A. Grossfield, in: Current Topics in Membranes, vol. 60, Elsevier, Amsterdam 2008 2. S. Tanizaki, M. Feig, J. Chem. Phys., 122, 124706 (2005) 3. E. Gallicchio, R. M. Levy, J. Comp. Chem., 25, 479 (2004) 4. R. A. Pierotti, Chem. Rev., 76, 717 (1976) 5. A.Ferrarini, G. J. Moro, P. L. Nordio, G. R. Luckhurst, Mol. Phys., 77, 1 (1992) 6. F. M. Richards, Annu. Rev. Biophys. Bioeng., 6, 151 (1977)

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PRELIMINARY STUDIES ON STRUCTURE, MORPHOLOGY AND BIODEGRADABILITY OF POLY (ε-CAPROLACTONE) BASED NANOCOMPOSITES

Ramesh Neppalli, Valerio Causin, Carla Marega, Roberta Saini, Antonio Marigo.

Dipartimento di Scienze Chimiche, Università di Padova,, via Marzolo 1, 35131 Padova, Italy.

Since a few years, polymer-based nanocomposites have attracted the interest of industrial and academic researchers, because they offer a valuable alternative to traditional filled polymers or blends. Reinforcing the matrix with nanometer-sized particles, instead of the traditionally used micron-sized fillers, it is possible to obtain, with a very low filler content, a significant improvement in many physical mechanical properties. Due to efforts of so many researchers, now there are many well developed techniques to prepare nanocomposites and optimize the conditions. Almost all synthetic commodities, such as polyolefins, polyamides, etc. have been investigated. Because of environmental concerns and the need for high end products for niche applications increasing attention is being posed on biodegradable materials such as starch, cellulose, poly lactides, poly caprolactone or blends of some biodegradable polymers, etc1-5. The main disadvantage of such polymers is their poor physical mechanical performance, but many properties of such materials can be improved through appropriate composite and blending formulations.

In this study biodegradable polymer polycaprolactone (PCL)/organically modified clay nanocomposites

were prepared by solvent casting method employing different amounts of organoclay and polymer

matrices with different average molecular weights. Nanocomposites having intercalated structures were

obtained. The structure of nanocomposites was characterised using wide angle X-ray diffraction (WAXD)

and small angle X-ray scattering (SAXS) methods. Biodegradation studies were carried out with respect to

time and the influence of structure on the degradation of nanocomposites were studied by WAXD.

Differential Scanning Calorimetry (DSC) was used to understand crystallization behaviour of

nanocomposites prepared. SAXS6-8 results showed that the thickness of crystalline lamellae increased in low

molecular weight polymer nanocomposites by increasing clay amount and that this effect was weakened in

the case of nanocomposites with high molecular weight polymer. Crystallization temperature was

decreased by adding clay, therefore in these systems addition of filler acted as an inhibitor of

crystallization, rather than as a nucleant, as it has been frequently reported. In all cases, biodegradation

started after four weeks and rapid change occurred after eight weeks. Biodegradation rate was reduced

with the addition of clay to polymer, coherently with the observed increase in the lamellar thickness

brought about by this filler. Biodegradation is in fact favoured by a less crystalline structure.

References:

1. M. Vert, J. Fejen, A. C. Albertsson, G. Scott, E. Chiellini, (Eds.), Biodegradable Polymers and Plastics; Royal Society of Chemistry: London; 1992.

2. S. K. Lee, D. G. Seong, J. R. Youn. Fibers Polym. 6, 289 (2005). 3. G. Jimenez, N. Ogata, H. Kawai, T. Ogihara. J. Appl. Polym. Sci. 64, 2211 (1997). 4. S. S. Ray, M. Bousmina. Progress Mater. Sci. 50, 962 (2005). 5. L. Yu. Biodegradable polymer blends and composites from renewable resources; John Wiley & Sons:

Hoboken, NJ; 2008. 6. C. Marega, A. Marigo, G. Cingano, R. Zannetti, G. Paganetto. Polymer 37, 5549 (1996). 7. C. Marega, V. Causin, A. Marigo. J. Appl. Polym. Sci. 109, 32 (2008). 8. V. Causin, C. Marega, A. Marigo. G. Ferrara. Polymer 46(23), 9533 (2005)

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A PEPTIDO[2]ROTAXANE MOLECULAR MACHINE

A. Moretto, I. Menegazzo, M. Crisma,S. Mammi and C. Toniolo

Institute of Biomolecular Chemistry, Padova Unit, CNR, Department of Chemistry, University of

Padova, 35131 Padova, Italy


Rotaxanes are mechanically interlocked molecular architectures in which a central linear molecule (axle) passes through the cavity of a macrocycle (wheel).1 Inter alia, the axle is held in place by the presence of sterically bulky stoppers at either end. Oligomeric systems, typically formed by oxyethylene or methylene repeating units, are often exploited as axles in rotaxane construction.

Peptido[2]rotaxanes, based on various –Gly–Xxx– dipeptide stations of the axle, were first reported by Leigh and coworkers2 and more recently by Onagi and Rebek.3 We are currently expanding this field by synthesizing and studying the properties of a new set of symmetrical (Fig. 1) and non-symmetrical peptido[2]rotaxanes characterized by amino acid repeating units (oligopeptide systems) in their axles.

Figure 1. Two representations of the X-ray diffraction structure of the symmetrical [Fmoc-(Aib)4-O-(CH2)2-NH]2-FUM[2]rotaxanes. Right: the carbon atoms of the macrocycles are shown in light blue and of the amino acid or peptide axle in green. The oxygen atoms are depicted in red and the nitrogen atoms in dark blue. The intramolecular C=O…H-N H-bonds are shown as black dotted lines. Left:space-filling representations (macrocycle in blue and axle in green).

In particular, in this work we describe our results on a [2]rotaxane shuttle, the largest part of the axle of which is a rigid helical peptide, planned as a track for the reversible motion of a tetramide macrocyclic wheel. Photons were used as stimuli to shift the fumaric↔maleic equilibrium. By use of NMR we were able to identify all of the stations of this novel class of peptido[2]rotaxanes and to switch the wheel from one station to the next. This is the first example of a [2]rotaxane where the wheel makes a journey to one of the stations by wrapping up around a helical peptide axle.(1) (a)

References

1. Amabilino, D. B.; Stoddart, J. F. Chem. Rev. 1995, 95, 2725. (b) Balzani, V.; Gomez-Lopez, M.; Stoddart, J. F. Acc. Chem. Res. 1998, 31, 405. (c) Kay, E. R.; Leigh, D. A. Pure Appl. Chem. 2008, 80, 17. (d) Balzani, V.; Credi, A.; Venturi, M. Chem. Soc. Rev. 2009, 38, 1542.

2. Clegg, W.; Gimenez-Saiz, C.; Leigh, D. A.; Murphy, A.; Slawin, A. M. Z.; Teat, S. J. J. Am. Chem. Soc. 1999, 121, 4124.

3. Onagi, H.; Rebek, J., Jr. Chem. Commun. 2005, 4604.

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PO16

Exploiting non covalent interactions for the discovery of new catalysts: dynamic covalent capture approach

Leonard J. Prins, Marta Dal Molin*, P. Scrimin

Department of Organic Chemistry, University of Padova, via Marzolo 1, 35100, Padova, Italy. [email protected]

Recently, we have started the development of a new approach based on dynamic covalent capture that

offers an attractive and straightforward way for the design of artificial catalysts that show the same

features of selectivity and catalytic activity typical of natural enzymes. In this approach1 the screening is

performed separately for selectivity and activity using a ‘tethering’ strategy, where a target self-selects the

best interacting component, employing dynamic covalent bonds (Figure 1). In a proof-of-principle study,2

we have shown that indeed a correlation exists between the observed amplification in a dynamic library

and the catalytic activity of the selected components3. Optimization of the system is presented, with

particular focus on structural features that can increase amplification and catalytic activity.

TSA

+ +TSA

self-selection

TSA

+ +TSA

self-selection

Figure 1: self selection of the best component of the library

References

1. Gasparini, G.; Martin, M.; Prins, L.J.; Scrimin, P. Chem. Comm. 2007, 1340-1342. 2. Gasparini, G.; Prins, L.J.; Scrimin, P. Angew Chem. Int. Ed. 2008, 47, 2475-2479. 3. Prins, L.J ; Scrimin P.; Angew. Chem. Int. Ed. , 2009, 48, 4546-4550.

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ROLE OF INTERMOLECULAR INTERACTIONS IN OXYGEN TRANSFER CATALYZED BY

SILSESQUIOXANE TRISILANOLATE VANADIUM(V)

S. Lovat1*, M. Mba1, C. Zonta1, G. Licini11Dipartimento di Scienze Chimiche, Università degli Studi di Padova,

Via Marzolo 1, 35131 Padova, Italy*Corresponding Author


Oxidation mediated by vanadium compounds has been revitalized by vanadium dependent enzymes haloperoxidases, producing an ever growing number of studies on biomimetic complexes.1 The main interest has been directed toward oxidations of sulfides, halides, and olefins.2 During the course of these studies we noticed that the presence in solution of a Lewis Base was distinctively enhancing the catalytic activity of the complex 1 (Scheme 1).3

Scheme 1. Silsesquioxane Vanadium(V) complex (1) and its reactivity in oxygen transfer processes in the presence of CHP as oxidant. The Lewis Base is able to bind to the metal in addition to the ligand, and capable to selectively modify the catalytic properties of the complex. This approach not only offers the opportunity to module the catalytic systems with a defined reactivity and selectivity profile, but also to better understand the basic principles behind metal activation in synthetic and biological systems. References 1 A.G.J. Ligtenbarg; R. Hage; B. L. Feringa. Coord. Chem. Rev. 2003, 237, 89-101. 2. M. Mba; M. Pontini; S. Lovat; C. Zonta; G. Bernardinelli; P. E. Kundig, G. Licini. Inorg. Chem. 2008, 47,8616-8618. M. Mba; C. Zonta; G. Licini. Dalton. Trans. 2009, in press. 3. S. Lovat; M. Mba; H. C. L. Abbenhuis; D. Vogt; C. Zonta; G. Licini. Inorg. Chem. 2009, 48, 4724-4728.

CO-LIGAND EFFECT REACTIVITY

CHEMOSELECTIVITY

Tol-S-Me

NH

PhPh N PhPh

O

Tol-SO-Me

NEt3ONEt3

Si O

O

OR

SiR O

OSi O

Si

SiO

OSi

OOSi

R OV

R

R

RRO

O

1, R= i-butyl

CHP, 1

CHP, 1

CHP, 1

88

PO18

STORIA DELLA STEREOCHIMICA: L’ASPARAGINA DESTROGIRA DOLCE DI ARNALDO PIUTTI

A. Guarna Antonio1, B. Colli Laura2*

1, 2 Dipartimento di Chimica Organica “Ugo Schiff”, Polo Scientifico e Tecnologico via della Lastruccia 13,

50019 Sesto Fiorentino (FI) *[email protected]

L’asparagina ordinaria è un α-aminoacido scoperto nel 1815 da Vauquelin e Robiquet nei germogli degli asparagi. E’ una molecola otticamente attiva che ruota verso sinistra il piano della luce polarizzata (D- asparagina (levogira) (R) Attività ottica [α]D −35.0±0.5°, c = 5% in 5 M HCl). Nel 1851 Pasteur osservò, nei cristalli di asparagina ordinaria, le “faccette emiedriche non sovrapponibili” notando che il cristallo ottaedrico compariva solo come “emiedria di sinistra”. Secondo Pasteur doveva esistere anche un’asparagina destrogira, non ancora scoperta, di forma simmetrica rispetto all’altra. Nel 1886 Arnaldo Piutti, mentre lavorava come aiuto di Schiff nel Laboratorio di Chimica del R. Istituto di Studi Superiori di Firenze, isolò l’asparagina destrogira. Piutti ottenne anche un’altra informazione, inattesa: questa “nuova specie di asparagina” aveva sapore dolce [1]. L’asparagina destrogira dolce di Piutti è il primo composto in cui fu osservata una corrispondenza tra l’isomeria ottica di una molecola e una risposta differenziata dei recettori umani, in questo caso il sapore.

Piutti osservò che in acqua o alcali l’asparagina ruotava a sinistra il piano della luce polarizzata mentre in soluzione acida lo ruotava a destra. Grazie alla grande quantità di vecce utilizzate, riuscì a isolare l’asparagina destrogira e a misurarne l’angolo di rotazione che risultò essere lo stesso dell’asparagina ordinaria ma di segno contrario. Nel 1915 Piutti si accorse che le due asparagine rotatorie coesistevano nei prodotti della germogliazione dei lupini, l’asparagina destrogira veniva utilizzata maggiormente dalla pianta e scompariva col progredire della germogliazione: è per questa ragione che, benché sia l’amminoacido proteinogenico, se ne può isolare solo una piccola quantità.

Nel 1886 Pasteur presentò all’Académie Française des Sciences una nota relativa al lavoro di Piutti, concernente la differenza di sapore tra i due enantiomeri dell’asparagina. Pasteur spiegò in questo modo il sapore dolce dell’asparagina destrogira: “[…] i corpi attivi che interverranno nell’impressione nervosa e che

danno un sapore dolce in un caso ed insipido nell’altro, non saranno altra cosa, secondo me, che la materia

nervosa essa stessa, materia dissimmetrica come tutte le sostanze primordiali della vita” [3]. La scoperta del sapore dolce dell’asparagina destrogira quindi è forse la prima prova dell’asimmetria della materia vivente.

Un campione originale di “asparagina destrogira dolce” di Arnaldo Piutti è conservato nella Collezione

Schiff del Dipartimento di Chimica Organica “Ugo Schiff” dell’Università di Firenze.

References

1. Piutti, A. Una nuova specie di asparagina , Gazzetta Chimica Italiana, XVI, 1886, 275 2. Piutti, A. Sintesi dell’acido aspartico. Rend. della R. Ac. Sc. Fis. e Mat. Napoli, Vol.III, Fasc. 5° 1887 3. Pasteur, L. Observations de L. Pasteur relatives à une communication de M. Piutti, sur une nouvelle espèce

d'asparagine. Académie des sciences (France), (T103) 1886, 138

89

PO19

PREPARATION AND CHARACTERIZATION OF ORGANOCLAY NANOCOMPOSITES

R. Milani*1, A. Zaggia1, G. Padoan1, A. Lorenzetti1, S. Semenzato1, A. Sassi2, G. Facchin2,

M. Modesti1, L. Conte1, R. Bertani1

Department of Chemical Processes of Engineering, University of Padova, Via F. Marzolo 9, I-35131 Padova,

Institute of Sciences and Molecular Technologies, CNR, c/o Dep. Chemical processes of Engineering, Padova

Here we report the preparation and characterization of the new diphosphonium-MMT (DP-MMT) by the intercalation of the quaternary diphosphonium salt [MeOOCCH2(Ph)2PCH2CH2P(Ph)2CH2COOMe]Br2 (DP) with the aim to use it in the preparation of polyurethane foam-nanocomposites1. DP-MMT was completely characterized by multinuclear NMR in the solid state (Figures 1 and 2). Mono- and bisphosphonium salts are already used as flame retardants for textiles and paper as well as heat stabilizers for nylon. The use of phosphonium salts as organic modifiers to layered silicates may further enhance the thermal stability and flammability properties of polyurethane nanocomposites. The presence of two phosphorus atoms in the diphosphonium molecule, together with the carbonyl moieties suitable for interactions and compatibilization with the polyurethane chain and the possibility to use smaller amounts of additives in nanocomposites, make in principle DP-MMT a promising fire retardant additive for polyurethane rigid foam (PUR)2. Foams were prepared using a two step procedure. In the first step a fixed amount of clay (5 wt% on total foam mass), which was previously dehydrated overnight at 110°C, was dispersed in a polyols mixture. In order to promote clay dispersion microwave treatments were used3,4. TEM analyses showed the presence of stacks of platelets in DP-MMT containing PUR foams. Thus, in principle, phosphonium systems can be tailored in order to optimize interaction with the aluminosilicate layer with the aim to favour the formation of stable compounds and improve thermal stability of the nanocomposite. Unprecedented MMT modified with fluorinated ammonium salts of the type [RFCH(OH)CH2NR2]

+X- (RF-MMT)have been prepared. XRD data indicate a significant increase of the basal spacing to ca. 3 nm. The influence of the presence of RF-MMT on surface and thermal properties of nanocomposites is under investigation. Preliminar results on LDPE-nanocomposites are reported.

References

1. S. Semenzato, A. Lorenzetti, M. Modesti, E. Ugel, D. Hrelja, S. Besco, R.A. Michelin, A. Sassi, G. Facchin, F. Zorzi, R. Bertani, Applied Clay Science, doi: 10.1016/j.clay.2009.01.003

2. J.Q. Wang, W.K Chow, J.Applied Polymer Science, 2005, 97, 366. 3. M. Modesti, A. Lorenzetti, S. Besco, D. Hrelja,, J. Nanoscience Nanotech., submitted. 4. M. Modesti, A. Lorenzetti, S. Besco, D. Hrelja, S. Semenzato, R. Bertani, R.A. Michelin, Polymer

Degradation and Stability, doi: 10/1016/j.polymdegradstab.2008.08.005

- 40- 30- 20- 1001020304050607080( ppm )

a)

b)

c)

d)

- 40- 30- 20- 1001020304050607080( ppm )

a)

b)

c)

d)

- 160- 140- 120- 100- 80- 60- 40

( ppm )

a)

b)

c)

- 160- 140- 120- 100- 80- 60- 40( ppm )

a)

b)

c)

Figure 1- 31P{1H} NMR spectra in the solid state of :

a) DP-Br2 ,b) DP-MMT, c) DP-MMT 250, d) PU/DP-MMT

Figure 2.- 29Si NMR spectra in the solid state of : a) Dellite-HPS, b) DP-MMT, c) DP-MMT 250

90

PO20 USE OF PHOSPHAZENES AS A NEW APPROACH TO VERSATILE SURFACE FUNCTIONALIZATION

Roberto Milani*1, Mario Gleria2, Roberta Bertani3, Roger de Jaeger4, Ahmed Mazzah4, Charafeddine Jama5,

Martine Frere6, Leon Gengembre6

1-Dipartimento di Scienze Chimiche, Università di Padova, via F.Marzolo 1, Padova, Italy; 2-Istituto di

Scienze e Tecnologie Molecolari (ISTM) del Consiglio Nazionale delle Ricerche, Sezione di Padova, Via

F.Marzolo 9, Padova, Italy; 3-Dipartimento di Processi Chimici dell’Ingegneria, Università di Padova, Via

F.Marzolo 9, Padova, Italy; 4-LASIR UMR-CNRS 8516, USTL, 59655 Villeneuve d’Ascq, France ; 5-Laboratoire

PERF LSPES UMR 8008, ENSCL, BP 90108, Villeneuve d’Ascq, France; 6-Unité de Catalyse et Chimie du

Solide, UCCS CNRS UMR 8181, USTL, Villeneuve d’Ascq, France

*Presenting author, e-mail: [email protected]

The functionalization of polymer surfaces has important scientific and technological implications. It enables the tailoring of interfacial features such as wettability, adhesion, catalytic activity and biocompatibility of materials, and preserves their bulk properties.

Chlorophosphazenes are compounds whose general formula is (NPCl2)n, ranging from cyclic oligomers to high molecular weight linear polymers. Their P-Cl functions are reactive towards a great variety of alcohols, phenols and primary or secondary amines, leading to P-OR, P-OAr, P-NHR or P-NR2 bonds, respectively1.

We functionalized the surfaces of poly(ethylene-co-vinyl alcohol) (EVOH) and of cold, low pressure plasma-treated polyethylene (HDPE) and polyamide-6 (PA6) with selected nucleophiles following the general strategy below.

The surface hydroxyls of EVOH and of Ar plasma-treated2 HDPE and PA6 were first reacted with a fraction of the P-Cl moieties of hexachlorocyclotriphosphazene and poly(dichlorophosphazene). Unreacted chlorine atoms were subsequently used in further substitution reactions with 4-hydroxyazobenzene, trifluoroethanol and heptadecafluorononanol, thus endowing the surfaces of the polymers with specific optical and wetting properties. All substitution reactions were performed by immersion of the solid substrates in appropriate solutions.

The presence of phosphazenes and of subsequently grafted nucleophiles was proved by the onset of P, N, F and new C components in XPS spectra.

Water static contact angles as high as 120° were measured on heptadecafluorononanol-derivatized samples, corresponding to surface energies as low as 6 mJ/m2, which were determined by the Owens-Wendt method.

The reversible photochromic features induced on azobenzene-modified surfaces were successfully verified by UV-Vis reflectance spectroscopy.

It should be underlined that the functionalization procedure described here can be extended in principle to a wide range of solid substrates and different derivatizing compounds, in order to tailor surface physical and chemical features in a predictable way.

References

1. M.Gleria, R. De Jaeger Eds. Phosphazenes. A Worldwide Insight, NOVA Science Publishers, Hauppauge, New York, USA (2004) 2. S. Guruvenket et al., Appl. Surf. Sci. vol. 236, p. 278 (2004)

91

PO21

SOLUBLE AND FUNCTIONAL SINGLE-WALLED CARBON NANOTUBES

Marco De Nardi 1 *, Fabrizio Cordella 2, Cecile Hébert 3, Maria Antonietta Loi 2, Enzo Menna 1 1: ITM-CNR and Dipartimento di Scienze Chimiche, Università degli Studi di Padova

2: Zernike Institute for Advanced Materials, University of Groningen

3: EPFL SB-CIME & IPN-LSME, Lausanne

Keywords: functionalization, fluorescence, solubilization

Single-walled carbon nanotube (SWCNT) derivatives have been synthesized by means of an oxidation route that leads to shortened nanotubes bearing carboxylic acid end groups (SWNCT-COOH). We first demonstrated the possibility to obtain a soluble derivative (SWNCT-PEG) by grafting poly(ethylene glycol) (PEG) chains through amidation chemistry with the PEG-NH2 amine [1]. We selected PEG for its well-known solubilizing properties and also in view of a possible beneficial effect of PEG chains in minimizing aggregation of SWCNTs. In a second step, a procedure for the simultaneous attachment PEG-NH2 and amine derivatives of aromatic fluorophore was developed [2]. Different soluble products have been obtained from 2-aminofluorene (AF), 2-aminoanthracene (AA) and 1-aminomethylnaphthalene (AN). In the case of AF, we demonstrate that the fluorophore molecule acts as optical antenna for the UV-VIS light and as electron donor towards the SWCNT. Photoinduced electron transfer in soluble co-functionalized single-wall carbon nanotubes (SWCNTs) is studied by means of time resolved spectroscopy [3]. The proposed co-functionalization procedure could be easily extended to obtain a wide range of organic derivatives of SWNTs with good solubility, thanks to PEG chains that usually do not affect the chemical-physical properties such as photophysics and electronics. References 1. A. Gambetta, C. Manzoni, E. Menna, M. Meneghetti, G. Cerullo, G. Lanzani, S. Tretiak, A. Piryatinski, A. Saxena, R. L. Martin, A. R. Bishop; Nature Phys. 2006, 2, 515. 2. M. D'Este, M. De Nardi, E. Menna; Eur. J. Org. Chem. 2006, 11, 2517. 3. F. Cordella, M. De Nardi, E. Menna, C. Hébert, M.A. Loi; Carbon 2009, 47, 1264.

92

PO22

UNIVERSAL GOLD NANOPARTICLES: SYNTHESIS, PURIFICATION, APPLICATION

Matteo Graziani*, Leonard J.Prins, Paolo Scrimin

Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Vial Marzolo 1, 35131 Padova, Italy;


Gold nanoparticles are attractive scaffolds for the preparation of multivalent, functional surfaces. Self-assembled organic monolayers are spontaneously formed upon adding functionalized thiols to metastable Au colloids.1 Previously we have shown that these nanosystems are active as multivalent metallonucleases2 and have potentiala as synthetic antigens.3 Although attractive, the preparation of these functionalized nanoparticles requires the separate synthesis of each functionalized thiol and purification of each functionalized NP.4 Currently, we are developing a synthetic protocol that allows the postfunctionalization of ‘universal’ Au NPs using quantitative chemical reactions.5 Here, we will present the progress in that direction.

S

O

O2N

O

S

O

O2N

O

S

O

O2N

O

S

O

O2N

O

Au

R-NH2

S

O

O2N

S

O

O2N

S

O

O2N

S

O

O2N

Au

N

N

N

N

R

R

R

R

Figure 1. AuNPs functionalization by amine.

Project funded European Social Fund 2009, project code 2105/35/1017/2008 References 1. F. Manea, C. Bindoli, P. Scrimin, Langmuir, 2008, 24 (8), 4120-4124. 2. F. Manea, F. B. Houillon, L. Pasquato, P. Scrimin, Angewandte Chemie-International Edition, Volume 43, Issue 45, Pages 6165-6169, 2004. 3. F. Manea, C. Bindoli, F. Mancin, P. Scrimin Advanced Materials, Volume 20, Issue 22, Pages 4348-4352, 2008. 4. M. Brust, D. J. Schiffrin, J. Chem. Soc., Chem. Commun. 1994, 801. 5. E. Boisselier, D. Astruc, Chem. Commun. 2008, 5788-5790.

93

PO23

HYDROARYLATION OF ALKYNES CATALYSED BY PD(II) COMPLEXES: OPTIMIZATION OF THE

REACTION CONDITIONS.

Luca Gazzola*, Andrea Biffis, Cristina Tubaro, Gabriella Buscemi, Marino Basato

Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo 1, I-35131 Padova (PD), Italia.


Aromatic C-H bond functionalisation reactions represent green and economical alternatives to more classical coupling reactions involving e.g. aryl halides. Recently, much attention has been focused on aromatic C-H bond activation by transition metal catalysts and numerous examples of such reactions have been reported in the literature.1

We have recently reported the use of N-heterocyclic Pd(II) complexes as catalysts in the hydroarylation of alkynes.2,3

+ R1 R2

HR1

R2

R

R

0.1% [Pd]

0.2% AgTFA

Using our procedure, the reaction can be performed at r.t. in a few hours, yielding the trans-hydroarylation product in high yields and good selectivities. This synthetic protocol requires a large amount of strong acid (TFA), thus affecting the “economy” of the process. In this contribution we wish to report our recent results on protocol optimization pointed, in particular, at the reduction of the amount of acid.

Important improvements can be achieved by substituting TFA with stronger acids (like HOTf or HBF4). It will be shown that the efficiency and selectivity of the reaction can be finely tuned by a proper choice of the acid strength and of the coordinating ability of its conjugated base.4

Recent results suggest that the quantity of the acid could be further reduced by utilizing an ionic liquid as co-solvent for the reaction. The activity of the catalytic system is deeply influenced by the coordinating ability of the ionic liquid anion, while the selectivity towards the trans-hydroarylation product is not affected by the use of different ionic liquids. Moreover, the use of ionic liquids allows catalyst recycling with a negligible loss in activity, thus improving the process cleanness.

Finally, preliminary results on the catalytic efficiency of other Pd(II) complexes with diamine ligands will be reported.

References 1 Reviews: a) F. Kakiuchi, N. Chatani, Adv. Synth. Catal. 2003, 345, 1077; b) V. Ritleng, C. Sirlin, M. Pfeffer,

Chem. Rev. 2002, 102, 1731. 2 Biffis, A.; Tubaro, C.; Buscemi, G.; Basato, M. Adv. Synth. Catal. 2008, 350, 189-196. 3 Buscemi, G.; Biffis, A.; Tubaro, C.; Basato, M. Catal. Today 2009, 140, 84-89. 4 Biffis, A.; Gazzola, L.; Gobbo, P.; Buscemi, G.; Tubaro, C.; Basato, M., Eur. J. Org. Chem., in press.

94

PO24

SPONTANEOUS SELF-ASSEMBLY OF C3-SYMMETRIC Ti(IV) AMINE TRIPHENOLATE COMPLEXES

Miriam Mba1*, Marta Pontini,1 Eszter Nagy1,

Gérald Bernardinelli,2 Thomas M. Seidel,3 E.P. Kündig,3 C. Zonta1, Giulia Licini1

1 Dip. Scienze Chimiche, Università di Padova, via Marzolo 1, 35131, Padova, Italy 2 Laboratorie de Cristallographie, Université de Genève, Switzerland

3Dep. Organic Chemistry, Université de Genève, Switzerland


Triphenol-ligands have recently attracted attention because of their ability to form thermodynamically stable complexes with a large variety of metal ions.1 These metal complexes are intrinsically chiral: upon complexation the triphenol-ligands wrap in a helical fashion around the metal centre creating two enantiomeric complexes.

Control of the helicity can be achieved through introduction of a chiral centre on only one of the benzylic positions of the ligand, affording a single diastereomeric complex.2,3Here we will show how the peripheral substituents can affect the thermodynamic and kinetic stability of the complexes and we’ll present the synthesis of new S6-symmetric μ–oxo dimers stabilized through CH- interactions between those substituents .3

Starting from a racemic mixture only the formation of the heterochiral μ–oxo complex was observed, whereas enantiomerically pure monomeric complexes are no able to form the corresponding homochiral dimer.

M. Mba acknowledge the financial support provided by the University of Padova

References

1. For a review see: Licini, G.; Mba, M.; Zonta, C. Dalton Trans. 2009, DOI: 10.1039/B822653A. 2. Axe, P.; Bull, S.D.; Davidson, M. G.; Gilfillan, C.J.; Jones, M.D.; Robinson. D.E.J.E.; turner, L.E.; Mitchell,

W.L. Org. Lett. 2007, 9, 223. 3. Bernardinelli, G.; Seidel, T. M.; Kundig, E. P.; Prins, L. J.; Kolarovic, A.; Mba, M.; Pontini, M.; Licini, G.

Dalton Trans., 2007, 1573

TiNO

OO

O

Ph

Ph

Ph

Ti NO

OO

Ph

Ph

Ph

95

PO25

ORGANIC SYNTHESES IN MICROREACTORS

Carofiglio, T. Castellin, A; Donnola, P.; Maggini, M.; Rossi, E.

ITM-CNR Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova

(PD), Italy, Fax: +39-049-827-5239


Fabbrica Italiana Sintetici F.I.S. S.p.a., Viale Milano 26, 36075 Alte di Montecchio Maggiore (VI), Italy

Miniaturized chemical reactors (microreactors, MRs) offer a number of potential benefits compared to their macroscale counterparts. The elevated surface to volume ratio features of MRs produces a highly effective reagent mixing combined with enhanced heat- and mass-transfer rates leading to improved reaction yields and/or selectivities. Also, the small size of fluidic channels reduces reagent consumption and waste production allowing safer processing of toxic or highly reactive compounds.

This poster presentation will highlight the fabrication of polymer-based micro reactors, made through a fast-prototyping technique, and some selected applications such as epoxidations and photo-oxidations with singlet oxygen.

References

4. a) Watt, P. And Hswell, S.J., Chem. Soc. Rev., 43, 23, 2005; b) Geyer, K.; Codèe, J.D.C.; Seeberger, P.; c) Chem Eur, J. 12, 8434-8442, 2006; d) B.P. Mason; K.E. Price; J.L. Steinbacher; A.R. Gogdan; D.T. McQuade; Chem Rev., 107, 2300-2318, 2007 5. Carofiglio T.; Donnola P.; Maggini M.;Rossetto M.; Rossi E.; Adv. Synth: Catal., 350, 2815-2822, 2008

96

PO26

VANADIUM (V) POSS COMPLEXES AS OXIDATION CATALYSTS

C. Bindoli*, S. Lovat, M: Mba, C. Zonta and G. Licini

Dipartimento Scienze Chimiche, Università di Padova, Italy


Vanadium(V) centres are usually strong Lewis acids, which makes them suitable for the activation of peroxidic compounds.1 Accordingly, vanadium(V) complexes have been found to act as catalysts in various oxidation reactions like epoxidations of alkenes and allylic alcohols, hydroxylations of alkanes and arenes, oxidations of primary and secondary alcohols to the corrisponding aldehydes and ketones, haloperoxidation and oxidations of sulfides.2

Starting from trialkanolamines, and triphenolamines we have recently expanded our attention to silsequioxane ligands (POSSH3). These ligands are a a class of three-dimensional oligomeric organosilica compounds that with suitable metal centers they form cage frameworks like 1.3,4

SiO

O

OR

Si

RO

O

Si

O

O

Si

Si

O

OSi

O

OSi

RO

V

R

R

R

R

O

1

In this work our preliminary results on the capability of POSSVO complexes to activate alkylperoxides for

oxygen transfer processes will be presented. In particular we will report on the epoxidation of alkenes,

oxidation of sulfide and amines, together with studies on the catalyst nature and its stability under turn

over conditions.

References

1. Crans, D. C.; Smee, J.; Gaidamauskas, E.; Yang, L. Chem. Rev. 2004, 104, 849. 2. Ligtenbarg, A. G. J.; Hage, R.; Feringa, B.L. Coord. Chem. Rev. 2003, 237, 89. 3. Carniato, F.; Boccaleri, E.; Marchese, L.; Fina, A.; Tabuani, D.; Camino, G. Eur. J. Inorg. Chem., 2007, 9,

585. 4. Lovat, S.; Mba, M.; Abbenhuis, H.C.L.; Vogt, D.; Zonta, C.; Licini, G. Inorg. Chem. 2009, 47, 8616–8618

97

PO27

Mo(VI) AMINE TRIPHENOLATE COMPLEXES: SYNTHESIS, STRUCTURE AND CATALYTIC ACTIVITY

F. Romano1, S. Lovat, M. Mba, C. Zonta, G. Licini

Dipartimento Scienze Chimiche, University of Padova, Italy

*[email protected]

Triphenolamines are highly modular tetradentate molecules that effectively coordinate to transition metals and main group elements with podand topology.1 They form chiral complexes with intrinsically well defined coordination geometries controlled by the ligand, in particular by the nature of the substituents in ortho position to the hydroxyl groups, which are able to influence their reactivity and stability. The metal complexes, especially Ti(IV) and V(V), have been found to be effective catalyst in polymerization reactions and oxygen transfer processes.2 More recently we started to explore the corresponding molybdenum (VI) complexes (Scheme 1).3

Mo

N

O O

OO

R

RR

R = H, Me, t-Bu, PhX = Cl, OMe

X

Scheme 1

These neutral octahedral complexes are obtained by reaction of triphenolamines with MoO2Cl2(DMF)2 (DMF = N,N-dimethylformamide) or MoO2(OCH2CH2OH)2. All the complexes obtained possess C1 symmetry in the solid state, meaning that the tripodal ligand wraps around the metal in a propeller-like conformation. However a Cs-average symmetry is observed in solution because of fast racemization of the complexes in the NMR time scale. In this contribution we will discuss about the synthesis, characterisation and catalytic properties in N-oxidation of these complexes. References 1. G. Licini, M. Mba, C. Zonta Dalton Trans 2009, 5265-5277. 2. M. Mba, L. J. Prins, G. Licini Org. Lett. 2007, 9 21–24. C. Zonta, E. Cazzola, M. Mba, G. Licini Adv. Synth.

Cat. 2008, 350, 2503-2506. M. Mba, M. M. Pontini, S. Lovat, C. Zonta, G. Bernardinelli, P.E. Kundig, G. Licini Inorg. Chem. 2008, 47,8616-8618. 3. A. Lehtonen, R. Sillanpää Polyhedron, 2007, 26, 5293-5300.

98

PO28

Pd(0) NANOPARTICLES SUPPORTED ONTO MACROPOROUS MONOLITHS FOR CONTINUOUS FLOW CARBON-CARBON CROSS COUPLINGS IN CAPILLARY MICROREACTORS

Prasenjit Maity1, Tommaso Carofiglio1, Michele Maggini,*,1 1Dipartimento di Scienze Chimiche, Università di Padova Via Marzolo, 135131 Padova (Italy)

phone: +39-049-8275662 fax: +39-049-8275279

* [email protected]

Macroporous polystyrene-based monoliths have been generated in situ inside silica glass capillaries (250

m internal diameter) or Teflon tubings (500 m internal diameter). These materials, in turn, have been

exploited for physically supporting Pd(0) nanoparticles and for the covalent attachment of Pd(II) carbene-

complexes. The capillary-based flow systems have been used for performing microscale organic syntheses.

In particular, it has been studied for the Suzuki cross coupling between aryl halides and aryl boronic acid

derivatives to form biaryls. Excellent results, in terms of conversion and selectivity, have been obtained

both under conventional heating and by microwave irradiation. For the latter heating procedure, a special

microreactor has been designed in order to fit into the microwave cavity. These capillary microreactors are

analogous to microchip reactors but of much low cost and are potentially amenable to large scale chemical

synthesis by numbering up the devices.

99

PO29

SUPRAMOLECULAR ASSEMBLY OF THE VDE PROTEIN IN MEMBRANES AS REVEALED BY SDSL-EPR AND 4P-DEER

E. Salvadoria *, M. Di Valentina, G. Sagab, T. Morosinottob, D. Carboneraa a Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Padova, Italy

b Dipartimento di Biologia, Università degli Studi di Padova, Padova, Italy

Generally most plants receive more sunlight than they can actually use for photosynthesis. Under these circumstances, regulation of light harvesting is necessary to balance the absorption and utilization of light energy, thereby minimizing the potential for photo-oxidative damage. Besides adjusting light absorption, algae and plants have different strategies for dissipating the excess of light energy that has already been absorbed1,2.

Absorption of sunlight that exceeds a plant's capacity for CO2 fixation results in a buildup of the thylakoid ΔpH that is generated by photosynthetic electron transport. The decrease in lumen pH in turn activates the violaxanthin de-epoxidase (VDE) an enzyme that catalyzes the de-epoxidation of violaxanthin to zeaxanthin. Zeaxanthin promotes the energy dissipation. VDE is a 43-kD nucleus-encoded protein located in thylakoid lumen. Upon acidification of the lumen, VDE associates with the thylakoid membrane where it can interact with its substrate violaxanthin1,2. Nothing is known about the protein structure when it is associated with the membrane. We hypothesize a dimer formation as a consequence of a lower pH. The dimeric form might create a hydrophobic pocket where a carotenoid molecule could be accommodate.

In this contribution we used CW and pulsed-EPR spectroscopy coupled with site-direct mutagenesis and spin labelling to probe the actual structure of VDE enzyme after reconstitution into liposomes at low pH and the extent of the interaction with the membrane.

The 4p-DEER measurements allow us to demonstrate the formation of a dimeric structure upon acidification and interaction with the membrane.

Moreover power saturations curves are exploited to determine the protein region responsible for the anchorage in the membrane.

References

1. Müller P., et al., Plant. Physiol., April 2001, Vol. 125, pp. 1558-1566

2. Morosinotto T., et al., Physiol. Plant., 119, 2003 pp. 347-354

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SENSITIVITY TUNING IN INTRACELLULAR Zn2+ PROBES

L. Baù1*, F. Mancin1 1Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova, Italy

*[email protected]

Zinc plays a major role in living organisms, both by acting as a cofactor in hundreds of proteins and by

regulating a number of signaling pathways1. Its wide concentration range, spanning several orders of

magnitude (subnanomolar to millimolar), requires multiple imaging probes with appropriate sensitivities.

This problem has been addressed so far by using several receptors with different binding constants.

In this communication we discuss a novel approach to the realization of a family of probes. In our approach,

the sensitivity is tuned independently of the binding constant, allowing for the same receptor to be used in

a family of sensors covering the whole concentration range. A FRET-based fluorescent sensor was designed,

which is made of two parts: a fluorophore and a receptor/quencher whose quenching ability is switched off

upon metal complexation. By assembling the receptor/quencher unit and the fluorescent unit in different

ratios on a multivalent scaffold, the analytical signal can be amplified or dampened in a controlled fashion.

A wide range of metal concentrations can thus be detected with only two building blocks.

References

1. Que, E. L.; Domaille, D. W.; Chang, C. J. Chem. Rev. 2008, 108, 1517.

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PO31

Synthesis of oncological drugs by flow techniques

Andrea Castellina, Tommaso Carofigliob, Michele Magginib, Emiliano Rossi*b

a Fabbrica Italiana Sintetici F.I.S. S.p.a., Viale Milano 26, 36075 Alte di Montecchio Maggiore, Vicenza, Italy. b Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova, Italy.


Micro/meso continuous flow techniques for chemical synthesis have many advantages over the traditional batch techniques in terms of precise control of reaction conditions, efficient mass and heat transfer, or possibility to work under superheating conditions. Also, chemical synthesis in flow reactors allows a fast and easy reaction scale-up and an independent control of reaction conditions. These potential advantages can be profitably used for the multistep synthesis of oncological drugs of the family of kinases inhibitors. his poster presentation will illustrate a microfluidic pathway for the early stage of the Imatinib (1) synthesis and discuss the advantages with respect to the traditional batch preparations 1.

1

References 1. A. Falchi, WO Patent 2008/059551 (F.I.S. S.p.a.).

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PO32

NUCLEIC ACID RECOGNITION BY ALANYL-NUCLEOPEPTIDES

Piero Geotti-Bianchini,a,b Olivier Chaloin,b Alberto Bianco,b Fernando Formaggioa* aDepartment of Chemical Sciences, University of Padova, via Marzolo 1, 35131 Padova, Italy;

bLaboratoire d’Immunologie et Chimie Thérapeutiques UPR 9021 CNRS, 15 Rue Réné Descartes, 67084

Strasbourg, France

Sequential nucleopeptides containing α-alanyl-nucleoamino acid residues (AlaB)1,2 at i,i+3 positions have been designed and studied. In particualr, two nucleopeptides containing four thymines or adenines in their side chains and a nucleopeptide containing five thymines have been synthesized and partially functionalized with biotine. Their ability to recognize complementary strands has been investigated by SPR measurements (by immobilization of biotinylated moieties on a sensor chip). Selective adenine-thymine recognition has been detected both among complementary nucleopeptides and between nucleopeptides and RNA or DNA nucleotides. The nucleopeptide with five thymines in its sequence displays a much stronger binding than the nucleopeptide with four thymines, suggesting cooperative nucleobase pairing. CD data on complementary DNA-nucleopeptide mixtures support the SPR findings. Given that our alanyl-nucleopeptides were shown to penetrate into cells and nuclei without cytotoxic effects,2 their abilty to selectively recognize complementary oligonucleotide strands makes them promising candidates as nucleic acid modulators.

References

1. Geotti-Bianchini, P., Crisma, M., Peggion, C., Bianco, A., Formaggio, F., Chem. Commun., 2009, 3178. 2. Geotti-Bianchini, P., Beyrath, J., Chaloin, O., Formaggio, F., Bianco, A., Org. Biomol. Chem., 2008, 6,

3661.

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PO33

Deg/Gly PEPTIDES AS POTENTIAL MOLECULAR SWITCHES

Alessandro Moretto*, Vanessa Marcuzzo, Gema Ballano, Marco Crisma, Fernando Formaggio, Claudio

Toniolo

Institute of Biomolecular Chemistry, CNR, Padova Unit, Department of Chemistry,

University of Padova, I-35131 Padova, Italy

The fully-extended (or C5) peptide conformation, with torsion angles phi = psi = 180°, is characterized by intramolecular H-bonds bridging the N-H and C=O groups belonging to the same residue. This conformation is such that the N- and C-termini reach the largest possible separation in a peptide.

In globular proteins a repeating C5 motif has so far been autheticated only in the X-ray diffraction structure of the -(Gly)4- sequence of His-tRNA-synthetase (Biochemistry 1997, 36, 3084-3094). A FGFG unprotected tetrapeptide sequence was also found to adopt the C5 structure in the crystal state (Chem. Commun. 2002, 2812-2813). In both cases Gly is involved. Unnatural amino acids, such as C-alpha-diethylglycine (Deg), are also known to promote such conformation. However, it was previously observed that Deg-containing peptides can adopt the C5 structure or switch to the 3-10-helix depending on sequence, C-terminal moiety and solvent. As this phenomenon might be exploited for the construction of peptide-based molecular devices, we synthesized and investigated the conformation of a series of peptides, up to the octamer level, characterized by Gly-Deg or Deg-Gly repeating units. We observed that Gly does not adopt the C5 structure, but at the same time it is unable to suppress completely this tendency in the Deg residues.

104

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REPLACEMENT OF Ala BY Aib IMPROVES STRUCTURATION AND BIOLOGICAL STABILITY IN THYMINE-BASED NUCLEOPEPTIDES

Piero Geotti-Bianchini,a,b Alessandro Moretto,a Cristina Peggion,a Julien Beyrath,b Alberto Bianco,b Fernando

Formaggioa* aDepartment of Chemical Sciences, University of Padova, via Marzolo 1, 35131 Padova, Italy;

bLaboratoire d’Immunologie et Chimie Thérapeutiques UPR 9021 CNRS, 15 Rue Réné Descartes, 67084

Strasbourg, France

Sequential nucleopeptides containing alanyl-thymine nucleoamino acid residues (AlaT)1,2 at i,i+3 positions have been studied in view of applications as nucleic acid modulators. Indeed, if such nucleopeptides adopt a 310-helical conformation, the resulting alignment of the nucleobases along the helical axis might favor interactions with complementary strands. Three water-soluble nucleo-heptapeptides containing two tripeptide units Xxx-AlaT-Xxx2 and a C-terminal lysine amide have been synthesized: one (A) containing four Ala residues, one (B) with three Ala and one Aib (alpha-aminoisobutyric acid) residue, and the third (C) four Aib residues. A conformational investigation on the three nucleopeptides has been performed by 2D NMR in DMSO solution and by CD in phosphate buffer. All nucleopeptides are folded in DMSO, although only the Aib-rich nucleopeptide C adopts a 310-helical structure. The same peptide appears to maintain its helical structure in aqueous solution (CD analysis), whereas only some degree of folding is observed for B and none for nucleopeptide A. Enzymatic stability tests have shown that A is rapidly degraded, B is much more resistant and the Aib-rich nucleopeptide C is stable even after 48 hours.

References

1. Geotti-Bianchini, P., Crisma, M., Peggion, C., Bianco, A., Formaggio, F., Chem. Commun., 2009, 3178. 2. Geotti-Bianchini, P., Beyrath, J., Chaloin, O., Formaggio, F., Bianco, A., Org. Biomol. Chem., 2008, 6,

3661.

105

PO35

METAL NANOCLUSTERS STABILISED BY POLYAMIDES: “BOTTOM-UP” PREPARATION AND PRELIMINARY CATALYTIC DATA

M. Zecca a,*, I. Concina a, I. Duse a, B. Corain, a, P. Centomo a

a: Dipartimento di Sceinze Chimiche, Università di Padova, Padova, Italia;

e-mail :[email protected]

Organic-inorganic nanocomposites comprising metal nanoclusters stabilised by linear polyamides (PA, commercially known as “nylon”) have been little investigated sofar. Only aramides have been reported as stabilizers for palladium nanoclusters prepared by bottom-up methods 1. Other systems rely on physical methods for their preparation, such as PVD of nanoparticles over the PA surface followed by thermal treatment above Tg, which was systematically investigated by Deki and coworkers 2. No wet (“bottom-up”) methods where nylon and the metal precursor are dissolved in a single, homogeneous liquid phase have been reported sofar. Moreover, in spite of the interest into catalysis with nanostructured metals protected by linear polymers 3, classical heterogeneous metal catalysts supported on solid nylon 4 or aramides 5 are the the only PA-based metal catalysts known to date.

With a Microwave Enhanced Polyol Process we have been able to prepare nanoparticles of Ru, Pd, Pt, and Ag stabilised by PA-6, PA-6/6 and PA-11. Very large metal aggregates (hundreds of nm) were obtained with gold. For palladium the metal nanoclusters size depends mainly on the employed PA, with observed values of 2.61, 3.54-4.15 and 6.27 for PA- 11, PA-6/6 and PA-6, respectively. The Pd/PA nanocomposite have been tested in the Heck reaction as “homeopathic” catalysts (Pd ≤ 0.1 %, mol/mol, with respect to the limiting reagent), under conventional heating conditions and we report on our preliminary results.

The catalysts are generally little active: although the coupling of 4-bromoacetophenone with n-butylacrylate is generally close to completion at 120 °C in less than 24 h (final TONs around or even higher than 103), a clear induction stage is always observed. Even under dielectric heating conditions the yields at 10 minutes (300 W) are low (1.5-13 %), in spite of the known accelerating effect of microwave, and yields as high as 94% can be achieved are achieved in 10 min (300 W) only at 190 °C. The most straightforward explanation is the low solubility of the catalysts in the employed solvent (N,N-dimethylacetamide), which prevents the contact between the molecules of the substrates and the active metal.

References

1. D. Tabuani, O. Monticelli, H. Komber, S. Russo, Macromol. Chem. Phys., 204, 1576, 2003.

2. for an example K. Sayo K, S. Deki, S. Hayashi, Eur. Phys. J. D, 9, 429, 1999.

3. A. Rocoux, J. Schulz, H. Patin,. Chem. Rev., 102, 3757, 2002.

4. S. Galvagno, A. Donato, G. Neri, R. Pietropaolo, G. Capannelli, J. Mol. Catal., 78, 227, 1993.

5. D. Tabuani, O. Monticelli, A. Chincarini, C. Bianchini, F. Vizza, S. Moneti, S. Russo, Macromol. 36, 4294, 2003.

106

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COMPARISON OF THE INITIAL DECOMPOSITION STEPS OF HALOGENATED AND NON-HALOGENATED HYDROCARBONS IN AIR UNDER DIFFERENT

PLASMA REGIMES

M. Schiorlin1*, E. Marotta1, M. Dal Molin1, M. Rea2, C. Paradisi1 1Department of Chemical Sciences and 2Department of Electrical Engineering, Università di Padova, 35131

Padova, Italy


Non-thermal plasma catalysis is being actively pursued for the abatement of volatile organic compounds (VOCs).1 In non-thermal plasmas, which are conveniently produced by electric corona discharges in a gas at atmospheric pressure, primary events of ionization, excitation and dissociation of the gas molecules (air) promote the oxidative decomposition of VOCs diluted in it. Despite some well-established technological implementations, fundamental knowledge of the underlying chemical processes is still limited: product analysis and mass balance data are scarce and the reactions and mechanisms underlying VOCs decay are far from being well understood and characterized. The mechanism of corona-induced decomposition of VOCs is strongly dependent on the power supply and reactor geometry, as these determine the features of the plasma and the type and density of its reactive species.1,2 On the other hand, different VOCs will behave differently depending on their chemical structure and reactivity. It is obviously very difficult to rationalize complex sets of data for a rigorous description of the plasma chemistry under many different conditions. However, an approach targeted to minimize the variables of the system can help to point out the specific features of different plasma regimes. To this end we built a simple wire to cylinder corona reactor which can be energized by positive and negative DC and pulsed high voltages. Previous studies carried out with this system have shown that the main initiation mechanism of hydrocarbon oxidation (both for alkanes and

aromatics) is due to ion/molecule reactions with +DC, while with −DC processes involving radical and

neutral reactive species prevail. In particular, it was concluded that in −DC the major reactive species in humid air is the OH radical.3

The present study extends the investigation to CH2Br2 and CF2Br2 to test the effects of partial and total substitution of hydrogen with halogen in the VOC reagent.

Experiments were run with +DC, −DC and +pulsed to obtain process efficiency and product data and current/voltage profiles, both in dry and humid air. Ion analysis was also performed by means of APCI-MS (Atmospheric Pressure Chemical Ionization- Mass Spectrometry). The results from this integrated research approach will be presented and discussed with regard to the process efficiency and mechanism.

References 1. E. M. Van Veldhuizen, Electrical Discharges for Environmental Purposes: Fundamentals and Applications. Nova Science Publishers: New York, 2000. 2. A. Fridman, Plasma Chemistry, Cambridge University Press: Cambridge, UK, 2008. 3. E. Marotta, A. Callea, M. Rea, C. Paradisi, Env. Sci. Technol. 41, 5862 (2007); E. Marotta, A. Callea, X. Ren, M. Rea, C. Paradisi, Plasma Process. Polym. 5, 146 (2008); E. Marotta, M. Schiorlin, M. Rea, C. Paradisi, submitted.

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SYNTHESIS OF CHIRAL HYBRID ORGANIC-INORGANIC POLYOXOMETALATES

Gloria Modugno, Mauro Carraro, Andrea Sartorel, Marcella Bonchio, Gianfranco Scorrano,

Department of Chemical Sciences - University of Padova and ITM-CNR - section of Padova, Via Marzolo, 1,

35131 Padova, Italy. E-mail [email protected]

The complementary assembly of organic moieties and inorganic domains is a powerful strategy for the development of new catalytic systems and for the synthesis of hybrid materials.1-3 The presence of organic groups is indeed a valuable tool to modulate the physico-chemical properties, morphology and performance of the resulting materials.

The covalent graphting of enantiopure organic residues on the divacant Keggin-type polyoxotungstate [γ-SiW10O36]

8- has been employed to prepare hybrid organic-inorganic molecular derivatives, following different synthetic strategies: (i) the polyanion has been functionalized with pendant chiral phosphoryl groups, yielding the compounds [(R*PO)2(γ-SiW10O36)]

4- with R= N-protected aminoalkyl groups or O-protected amino acid derivatives; (ii) the vacant polyoxometalate has been functionalized with chiral organosilanes, to obtain the compounds [(R*Si)2O(γ-SiW10O36)]

4- with R= chiral tetra alkylammonium groups (Figure 1).

The poster will report the characterization of the new chiral complexes by means of heteronuclear NMR, electrospray ionisation–mass spectrometry (ESI-MS), as well as with UV-vis and circular dichroism (CD) spectroscopies, to elucidate their structural features and the chiroptical behavior. The latter technique, in particular, has been used to reveal a chirality transfer from the organic ligand to the inorganic polyanion. Since the functionalization provides stable and tuneable catalysts for the activation of hydrogen peroxide, a preliminary reactivity study on the stereoselective oxidation of methyl p-tolyl sulfide will also be presented.

CH3CN / H2O (HCl) TBABr

[γ−−−−SiW10O36]8-

RX= (RSi)2O or (RPO)2

RSiCl3 or RPO(OH)2 (2 eqs) [RX(γ-SiW10O36)]4-

R RR R

[(RSi)2O(γ-SiW10O36)]4- [(RPO)2(γ-SiW10O36)]4-

Figure 1. Syntetic approaches for the preparation of chiral hybrid polyoxometalates.

References

1. a) Carraro, M.; Sandei, L.; Sartorel, A.; Scorrano, G.; Bonchio, M. Org.Lett. 2006, 8, 3671. b) Berardi, S.; Bonchio, M.; Carraro, M.; Conte, V.; Sartorel, A.; Scorrano G. J. Org. Chem. 2007, 72, 8954.

2. Carraro, M.; Sartorel, A.; Scorrano, G.; Maccato, C.; Dickman, M. H.; Kortz, U.; Bonchio M. Angew. Chem.

Int. Ed. 2008, 47, 7275. 3. Sartorel, A.; Carraro, M.; Bagno, A.; Scorrano, G.; Bonchio, M. Angew. Chem. Int. Ed. 2007, 46, 3255.

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Lipid oxidation products generated by thermal stress of culinary oils and fat: a kinetic study by 1H NMR spectroscopy

Alessandro Bagno, Federico Rastrelli, Marco Salmistraro, Adriano Silvagni

Dipartimento di Scienze Chimiche,Università degli Studi di Padova, via Marzolo 1, 35131Padova, Italy

e-mail [email protected]

Deep fried foods introduce in the human diet some by-products that originate from the thermal stress of lipids, and the possibility that a regular intake of such materials has a deleterious effects on health has recently attracted a considerable interest.1 The main reaction involved in the oxidative degradation of lipids is the thermally induced, radical-mediated auto-oxidation of polyunsaturated fatty acids. This reaction mainly generates conjugated hydroperoxydienes that are unstable at the standard frying temperatures (180 °C) and are degraded to a variety of by-products including aldehydes. This class of compounds, in particular, is known for its ability to exert toxicological effects in vivo because of its high reactivity with most biomolecules.2

H

O

CH3n

H

OH

O

CH3n

H

O

CH3

OH

n

In this communication, we employ enhanced-sensitivity NMR techniques to explore the kinetics of peroxides and aldehydes buildup during episodes of thermal stress on culinary oils and fat3. Furthermore, we also investigate the underlying mathematical model which describes the buildup of such primary and secondary oxidation products.

References 1. S. E. Manahan, Toxicological chemistry and biochemistry, 3rd ed., Chelsea, Michigan, Lewis Publishers

2. S. Kubow, Trends Food Sci. Technol. 1 1990, 67

3. H.-D. Belitz, W. Grosch, Food Chemistry, 2nd ed., Springer

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PO39

THIOREDOXIN REDUCTASE AS ANTICANCER TARGET. COMPUTATIONAL AND MODEL STUDIES OF

INHIBITION

Riccardo Bini,1 Giacomo Saielli,2 Francesca Di Sarra,1* Alessandro Bagno,1 Valentina Gandin,3

Francesco Tisato4 1Department of Chemical Sciences of the University of Padova, 2ITM-CNR Padova Section, 3Department of

Pharmaceutical Sciences of the University of Padova, 4ICIS-CNR


Thioredoxin reductases (TrxR) are emerging in the last years as an important class of likely drug targets for a variety of diseases. The clinically established gold-based antiarthritic drug auranofin exhibits a pronounced reactivity toward thiol and selenol groups of proteins. In particular, auranofin behaves as a potent inhibitor of mammalian thioredoxin reductases causing severe intracellular oxidative stress.

We have investigated the enzyme-inhibitor interaction at a molecular level, through the characterization of the reactions between Au(I) complexes and model compounds of increasing complexity, as achieved through a combination of experimental (NMR) and computational (relativistic DFT) methods.

Firstly, we have examined the reactivity of auranofin in CDCl3 with benzenethiol (PhSH) and benzeneselenol (PhSeH) as models of cysteine (Cys) and selenocysteine (Sec), respectively.

The generally accepted mechanism whereby Au(I) complexes inhibit TrxR involves ligand exchange by nucleophilic attack at the Sec selenium atom; a general scheme for addition of a Au(I) complex to the Cys and/or Sec residues is quite analogous to the thiolate exchange established for auranofin. The selenium center is thought to be favored over other nucleophiles present in the cell owing to its high polarizability (softness).

OAcO

AcO

AcO

S

OAc

Au

PEt3

+ R-XHO

AcOAcO

AcO

SH

OAc

+ R-X-Au-PEt3

X = S, Se

The equilibrium constant for the reaction with PhSeH and PhSH has been determined by 1H NMR for different molar ratios of the two reactants. Ligand exchange is essentially quantitative in the case of PhSeH, whereas Keq is ca. 1 in the case of PhSH. Studies on phosphine Au(I) compounds of the [X–Au–PEt3] type (X = Cl, Br, CN, SCN, diethyl dithiocarbamate (dedc), diethylxanthate (xanth) ) seem to confirm the same mechanism of interaction with model thiols and selenols.

Reactivity studies have been extended to polar solvents such as CH3OH and DMSO in order to investigate the reactions of the above mentioned drugs with Cys and Sec which are insoluble in chloroform. The course of the reactions in polar solvents is more complex than in chloroform.

Relativistic DFT calculations of the thermodynamics of the reactions, both in gas phase and in solution (by means of the COSMO model), have been used to rationalize the observed behaviour in chloroform and in the other polar solvents, and to evaluate different reaction models.

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PEPTIDES AS LIGANDS FOR THE SELECTIVE DELIVERY OF THE CORRESPONDING METAL-BASED ANTICANCER AGENTS

Morelle Negom Kouodom*, Luca Ronconi, Dolores Fregona, Fernando Formaggio

Department of Chemical Sciences, University of Padova, via Marzolo 1, 35131 Padova, Italy


The selective delivery of pharmacologically active compounds into the tumor cell represents a major issue in cancer research. The therapeutic use of cisplatin is associated with some serious clinical problems, such as severe normal tissue toxicity and resistance to the treatment1. The anticancer activity of Au(III)-dithiocarbamato derivatives has been recently investigated by Fregona and coworkers2. Those complexes turned out to be extremely promising in terms of greater in vitro and in vivo antitumor activity, lack of cross-resistance, and reduced toxic and nephrotoxic side-effects compared to cisplatin, accounting for a different mechanism of action. In fact, further biological studies identified proteasome as a major target and showed that the inhibition of the proteasomal activity is associated with both apoptotic and non-apoptotic pathways3.

To obtain compounds with superior chemotherapeutic index in terms of increased bioavailability, higher cytotoxicity, and lower side-effects than cisplatin, we extended our research to Au(III)-dithiocarbamato complexes functionalized with peptide ligands, to exploit peptide transporters PEPT1 and PEPT2. These plasma membrane proteins are present predominantly in epithelial cells of the small intestine, mammary gland, lung, choroid plexus, kidney and in other cell types. These proteins are able to transport across membranes all possible di- and tripeptides containing L-amino acid residues4. Therefore, our Au(III)-peptidedithiocarbamato complexes should be able to maintain the properties of the previously reported gold(III) analogues together with an enhanced bioavailability through the peptide-mediated cellular internalization.

We report here on the synthesis, purification and characterization of a series of Au(III)-dithiocarbamato complexes, covalently bound to oligopeptides (from di- to penta-), focusing on issues related to the design of the oligopeptide chain. We selected amino acids with different features (chiral and achiral, hydrophobic and hydrophilic, aliphatic and aromatic) in order to evaluate the influence of various factors on the biological activity of the corresponding metal-dithiocarbamato complexes. Some preliminary in vitro cytotoxicity studies towards human tumor cell lines are also reported and compared to cisplatin.

References

1- R. A. Alderden, M. D. Hall, T. W. Hambley, J. Chem. Educ., 2006, 83, 728-734. 2- L. Ronconi, D. Fregona, Dalton Trans., 2009, in press. 3- V. Milacic, D. Chen, L. Ronconi, K. R. Landis-Piwowar, D. Fregona, Q. P. Dou, Cancer Res., 2006, 66,

10478-10486. 4- I. Rubio-Aliaga, H. Daniel, Trends Pharmacol. Sci., 2002, 23, 434-440.

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A RAPID METHOD FOR THE INERTIZATION OF

MICROFLUIDIC DEVICES

Simone Silvestrini*, Tommaso Carofiglio, Michele Maggini

Dipartimento di Scienze Chimiche, Università degli Studi di Padova, via Marzolo 1, 35131 Padova

Keywords: microfluidics, inertization, fast prototyping

Thin, protective silica layers have been deposited on the inner walls of polymeric microchannels by means of sol-gel techniques. Incompatibility with alogenated solvents such as dichloromethane is one of the main drawbacks of thiolene-based microfluidic devices (MFD)[1] and we demonstrated that our protective silica layers can extend the working life of a MFD by 30 times upon exposition to the aforementioned solvent. We selected silica for its ease of preparation, tunable chemical properties and possibility of further functionalization widely reported in literature.

By mixing different silanes in the mixture used for sol-gel deposition, the chemical properties of the layer produced with our inertization procedure could indeed be exploited as a bridge. Molecules, enzymes[2] and particles[3] could be linked to the microchannel, thus exploiting the large surface to volume ratio provided by MFDs for both analytical and synthetical applications.

Non inertized MFD compared to an inertized one after flushing with CH2Cl2 for 10 minutes. The inertized MFD started leaking only after about 5 hours.

References

1. Z. T. Cygan, J. T. Cabral, K. L. Beers, E. J. Amis; Langmuir 2005, 21(8), 3629-3634

2. I. Gill; Chem. Mater. 2001, 13, 3404-3421

3. V. G. Gavalas, S. A. Law, J. C. Ball, R. Andrews, L. G. Bachas; Anal. Biochem. 2004, 247-252

112

P042 ISOTOPE DILUTION AND MULTIPLE REACTION MONITORING MASS SPECTROMETRY

IN THE IDENTIFICATION AND ASSAY OF ROTENONE IN OLIVE OIL.

Fabio Mazzotti Leonardo Di Donna, Mohamed Attya, Bartolo Gabriele, Alessia Fazio and Giovanni Sindona

Università della Calabria, 87036 ARCAVATA DI RENDE (CS)

Environmental protection agencies have recent call the attention to the extremely toxicity of rotenone ((6R, 6aS, 12aS)-1,2,6,6a,12,12a-hexahydro-2-isopropenyl-8,9-dimethoxychromenyl[3,4-bfuro[2,3-h]chromen-6-one, 1), a naturally occurring chemical with insecticidal and piscicidal properties present in the roots of several tropical and subtropical plant species belonging to genus Lonchocarpus or Derris.

This is the first report on the use of labelled rotenone (3), synthesized in our laboratories, for its quantitative assay by an absolute isotope dilution method using LC-MS/MS approach.

Rotenone was until recently used as a safe pesticide in the organic production of olives, and its solubility in a-polar organic environment, such as olive oil, is extremely high. Unless the use of this phytodrug is now prohibited its presence in the market has been extended until 2011 and its use is permitted for some crops, only.

Although different methods have been introduced for the assay of rotenone1, the quantitation of the analyte can be

best performed by APCI-MS/MS under MRM condition in positive ion mode. Two diagnostic product ions for each precursor ion are monitored in order to obtain high specificity and sensitivity. The selected transitions were m/z 395 → m/z 192 and m/z 395 → m/z 213 for 1 and m/z 398 → m/z 195, m/z 398 → m/z 213 for the labelled internal standard (3); the evaluation of the absolute quantity of 1 in the examined matrices has been performed monitoring the transition that leads to the common ion at m/z 213.

The values of LOQ and LOD, 2.0 ppb and 6.0 ppb respectively for olive oil and and 0.04 ppt and 0.11 ppt for river water, suggesting that the proposed technique is suitable for evaluating very low amounts of pesticide in different food matrices.

References 1. High resolution electrospray and electrospray tandem mass spectra of rotenone and its isoxazoline cycloadduct, ; Cordaro, L.

Di Donna,G. Grassi, L. Maioulo, F. Mazzotti, E. Perri, G. Sindona and A. Tagarelli. Eur. J. Mass Spectrm. 2004, 10, 691-697 2. High-throughput assay of rotenone in olive oil using atmospheric pressure chemical ionization tandem mass spectrometry. L.

Di Donna, G. Grassi, F. Mazzotti, E. Perri and G. Sindona. J. Mass Spectrom. 2004; 39: 1437–1440 3. Assay of rotenone in river water by high-throughput tandem mass spectrometry and multiple-reaction monitoring

methodology. L. Di Donna, F. Mazzotti, G. Sindona and A. Tagarelli. Rapid Commun. Mass Spectrom. 2005; 19: 1575–1577

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STUDIES OF NOVEL TREATMENTS OF TEXTILE FIBERS WITH COLD PLASMAS AT ATMOSPHERIC PRESSURE

M. Scapinello1,2*, I. Kulyk2, M. Stefan2, E. Marotta1, C. Paradisi1

*[email protected] 1Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova, Italy

2CIVEN (Coordinamento Interuniversitario Veneto per le Nanotecnologie) Association, Via delle Industrie 5,

30175 Venezia – Marghera, Italy

Considerable fundamental and applied interdisciplinary research is presently devoted to the design, characterization and development of new processes based on cold plasmas at atmospheric pressure. Such processes offer numerous advantages over traditional ones based on ‘wet’ chemistry. Specifically, various types of plasma treatments are being tested on natural textile fibers, notably wool [1,2] and cotton, to modify their surface chemical composition and morphology in order to improve their properties and quality. This communication reports our preliminary results in this field of research. A description will be given of the experimental set-up used, which includes a prototype plasma apparatus developed at CIVEN and various diagnostics for analysis of the plasma, of the textile (SEM, FT-IR, micro Raman), of the organic extracts (LC-ESI, LC-APCI, LC-PPI) and of the process gas (GC-FID, GC-TCD, GC-MS). An account will then be given of preliminary results obtained in plasma treatments of wool, specifically with regard to the removal of surface adherent lipids. References 1. H. Thomas. Plasma modification of wool, in Plasma Technologies for Fabrics, Woodhead Publ. Ltd, 2007, Ch. 9. 2. R. Morent, N. De Geyter, J. Verschuren, K. De Clerck, P. Kiekens, C. Leys. Non-thermal plasma treatment of textiles. Surface & Coating Technology, Vol. 202 (2008), 3427-3449.

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AUTHOR INDEXAUTHOR INDEXAUTHOR INDEXAUTHOR INDEX

BAU' Luca PO30

BALZANI Domenico PL7

BARTALI Laura IL22

BARTOLOZZI Maria Grazia IL23

BERARDI Serena PO10

BERTINI Ivano PL4

BERTONCELLO Renzo IL32

BERZIOLI Michela IL 33

BINI Davide IL24

BINDOLI Cristiano PO26

BISCONTIN Guido IL37

BONOMI Renato PO5

BOVO Laura PO4

BRUSTOLON Marina IL32

CAMPANELLA Luigi PL9

CAMPOSTRINI Pier Paolo IL2

CAPODAGLIO Gabriele IL4

CAPRIATI Vito IL20

CASTELLIN Andrea IL9

CESCON Paolo IL1

CHIANTORE Oscar IL31

COLLI Laura PO18

COLOMBO Francesca PO6

CONTE Valeria IL11

CORAMI Fabiana IL3

COTARCA Livius IL8

CREMONESI Paolo IL35

DAL MOLIN Marta PO16

DE NARDI Marco PO21

de SILVA A. Prasanna IL10

De VINCENTIIS Francesco IL25

DI SARRA Francesca PO39

DONNOLA Paola PO25

DUUS Jens PL2

DVORAKOVA Gita PO9

FEDRIZZI Bruno IL14

FINO Vincenzo IL26

FLAMINI Riccardo IL15

FORMAGGIO Fernando PO32-PO33-PO34

GARDAN Martino PO11

GAZZOLA Luca PO23

GERBI Vincenzo IL13

GRAZIANI Matteo PO22

LLANES-PALLÀS Anna IL21

LOVAT Silvia PO17

LUISI Pierluigi PL6

LUBIAN Elisa PO7

MAITY Prasenjit PO28

MARCHELLI Rosangela PL3

MARTINI Elena IL17

MATTAREI Andrea PO2

MAZZELLA Mauro IL27

MAZZEO Rocco IL34

MAZZOTTI Fabio PO42

MBA Miriam PO24

MILANI Roberto PO19-PO20

MISSIO Andrea IL7

MODUGNO Gloria PO37

MOLINARI Henriette PO3

MORETTO Alessandro PO15

NEGOM KOUODOM Morelle PO40

NEPPALLI Ramesh PO14

NOVELLINO Ettore PL1

PARISIO Giulia PO13

PEGGION Cristina PO12

PROCOPIO Antonio IL18

RAFANELLI Piero PL5

RANCAN Marzio IL19

ROMANO Francesco PO27

RONCONI Luca PO1

ROSATO Francesca IL28

ROSSI Emiliano PO31

SALOMONE Antonio IL29

SALVADORI Enrico PO29

SANTORO Stefano IL30

SCAPINELLO Marco PO43

SCHIORLIN Milko PO36

SELVESTREL Francesco PO8

SGAMELLOTTI Antonio PL11

SILVAGNI Adriano PO38

SILVESTRIN Simone PO41

SINDONA Giovanni IL16

SPADONI Luca IL5

STIVANELLO Mariano IL6

TADDIA Marco IL37

VERSINI Giuseppe IL12

VOLPE Giulio IL6

Von BOHLEN Alex PL8

WALTER Philippe PL10

ZECCA Marco PO35

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LIST OF PARTICIPANTSLIST OF PARTICIPANTSLIST OF PARTICIPANTSLIST OF PARTICIPANTS

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ALLEVI Pietro Dipartimento di Chimia, Biochimica e Biotecnologie per la Medicina Università di Milano Via Saldini, 50 20133 Milano – Italia E-mail: [email protected] ANASTASIA Luigi IRCCS Policlinico San Donato Via Morandi, 30 20097 San Donato Milanese (MI) – Italia E-mail: [email protected] ANASTASIA Mario Direttore, Dipartimento di Chimia, Biochimica e Biotecnologie per la Medicina Università di Milano Via Saldini, 50 20133 Milano – Italia E-mail: [email protected] ASCHIERI Carla Via Giovanni Alessandro Venturel 37128 Verona - Italia BAGNO Alessandro Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] BAU' Luca Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] BALZANI Vincenzo Dipartimento di Chimica Universita' di Bologna "G. Ciamician" Via Selmi, 2 40126 Bologna Italia E-mail: [email protected] BARTALI Laura Dipartimento di Chimica Organica "U. Schiff" Universita' di Firenze Via della Lastruccia 13 50019 Sesto Fiorentino (FI) Italia E-mail: [email protected] BARTOLI Giuseppe Facoltà di Chimica Industriale Università di Bologna Viale Risorgimento, 4 40126 Bologna Italia E-mail: [email protected]

BARNI Ermanno Dip. Di Chim. Generale e Chi. Org. Universita' di Torino C.so Massimo d'Azeglio, 48 10125 Torino Italia E-mail: [email protected] BARTOLOZZI Maria Grazia Dipartimento di Chimica Organica "U. Schiff" Università di Firenze Via della Lastruccia 13 50019 Sesto Fiorentino (FI) Italia E-mail: [email protected] BASATO Marino Dipartimento di Scienze Chimiche Università di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] BERARDI Serena Dipartimento di Scienze Chimiche Università di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] BERTINI Ivano Dipartimento di Chimica CERM Universita' di Firenze Via Sacconi, 6 50019 Sesto Fiorentino (FI) Italia E-mail: [email protected] BERTONCELLO Renzo Dipartimento di Scienze Chimiche Università di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] BERZIOLI Michela Dipartimento di Chimica G.I.A.F. Università di Parma Viale Usberti 17A 43100 Parma Italia E-mail: [email protected] BIANCO Armandodoriano Dipartimento di Chimica Università di Roma “La Sapienza” P.le Aldo Moro, 5 00185 Roma – Italia E-mail: [email protected] BINI Davide Dipartimento dfi Biotecnologia e Bioscienze Università di Milano -Bicocca P.zza della Scienza 2 - 20126 Milano Italia E-mail: [email protected]

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BINDOLI Cristiano Dipartimento di Scienze Chimiche Università di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] BISCONTIN Guido Dipartimento di Scienze Ambientali Universita' "Ca Foscari" Venezia Santa Marta, Dorsoduro, 2137 21137 Venezia Italia E-mail: [email protected] BONCHIO Marcella Istituto Tecnologia delle Membrane Sede Operativa di Padova C.N.R. Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] BONOMI Renato Dipartimento di Scienze Chimiche Università di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] BORTOLAMEI Nicola Dipartimento di Scienze Chimiche Università di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] BORTOLINI Olga Dipartimento di Chimica Università della Calabria Via Bucci, 12C 87036 Rende (CS) Italia E-mail: [email protected] BOUCHENAKI Mounir Direttore Generale ICCROM Via San Michele, 13 00153 Roma – Italia E-mail: [email protected]

BOVO Laura Dipartimento di Scienze Chimiche Università di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] BOZIO Renato Dipartimento di Scienze Chimiche Università di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected]

BRUSTOLON Marina Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] CAMPANELLA Luigi Dipartimento di Chimica Universita' di Roma "La Sapienza" P.le Aldo Moro, 5 00185 Roma Iralia E-mail: [email protected] CAMPOSTRINI Paolo Direttore Consorzio CORILA P.zza S. Marco, 2847 30124 Venezia Italia E-mail: [email protected] CAPODAGLIO Gabriele Dipartimento di Scienze Ambientali Universita' di Venezia "Ca Foscari" Santa Marta, Dorsoduro, 2137 30121 Venezia Italia E-mail: [email protected] CAPRIATI Vito Dip. Farmaco-Chimico Universita' di Bari Via E. Orabona, 4 70125 Bari Italia E-mail: [email protected] CAPUTO Romualdo Dip. Chimica Organica e Biochimica Universita' di Napoli Federico II Via Cintia, 4 82126 Napoli Italia E-mail: [email protected] CARASSO MOZZI Fausta Via Montegrappa, 15 31021 Mogiano (TV) – Italia E-mail: [email protected] CARDELLICCHIO Nicola Istituto per l'Ambiente Marino Costiero - IAMC Consiglio Nazionale delle Ricerche Via Roma, 3 74100 Taranto Italia E-mail: [email protected] CAROFIGLIO Tommaso Dipartimento di Scienze Chimiche Università di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] CARRARA Paolo Via Libero Benedetti, 5 35100 Padova, Italia E-mail: [email protected]

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CARRARO Mauro Dipartimento di Scienze Chimiche Università di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] CASACCIA Luciano CASOLI Antonella Dip. Di Chim. Generale ed Inorg., Chim. Analitica, Chim. Fisica Universita' di Parma Viale G.P. Usberti, 17A 43100 Parma Italia E-mail: [email protected] CASTELLIN Andrea F.I.S. Fabbrica Italiana Sintetici, Viale Milano, 26 36075 Alte di Montecchio Maggiore (VI) Italia E-mail: [email protected] CESCON Paolo Presidente Corila, Dip. Scienze Ambientali Universita' "Ca Foscari" Venezia Santa Marta, Dorsoduro, 2137 30121 Venezia Italia E-mail: [email protected] CHIACCHIO Ugo Dip. Di Scienze Chimiche Universita' di Catania V.le Andrea Doria,6 95125 Catania Italia E-mail: [email protected] CHIANTORE Oscar Dip. di Chimica Inorganica, fisica e dei materiali Universita' di Torino Via Pietro Giuria, 7 10125 Torino Italia E-mail: [email protected] CHILIN Adriana Dip. Scienze Farmaceutiche-Presidente S.C.I. Veneto Università di Padova Via Marzolo, 5 35131 Padova Italia E-mail: [email protected] CIMINALE Francesco Dipartimento di Chimica Universita' degli Studi di Bari Via Orabona, 4 70126 Bari Italia E-mail: [email protected] CIOFFI Marcella C.co Vittorio Emanuele, 347 82100 Napoli - Italia

COLOMBO Francesca Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] COLLI Laura Dipartimento di Chimica Organica "U. Schiff" Universita' di Firenze Via della Lastruccia 13 50019 Sesto Fiorentino (FI) Italia E-mail: [email protected] CONTE Valeria Dip. Di Scienze e Tecnologie Chimiche Universita' di Roma "Tor Vergata" Via della Ricerca Scientifica 00133 Roma Italia E-mail: [email protected] CORAMI Fabiana IDPA-CNR Venezia Universita' "Ca Foscari" Venezia Santa Marta, Dorsoduro, 2137 30121 Venezia Italia E-mail: [email protected] CORSARO Antonio Dip. Di Scienze Chimiche Universita' di Catania V.le Andrea Doria,6 95125 Catania Italia E-mail: [email protected] COSTANTINO Umberto Dipartimento di Chimica Universita' di Perugia Via Elce di Sotto, 8 06123 Perugia Italia E-mail: [email protected] COTARCA Livius Zambon Advanced Fine Chemicals Via Dovaro, 2 36045 Lonigo (VI) Italia E-mail: [email protected] CREMONESI Paolo CESMAR7-Centro per lo Studio di Materiali per il Restauro Via Lombardia, 41/43 35020 Padova Italia E-mail: [email protected] CRISAFULLI Fabrizio EDISES s.r.l. Via Nuova San Rocco, 62/A Parco Soleado (NA) E-mail: [email protected]

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DAL MOLIN Marta Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] DE LUCCHI Ottorino Dipartimento di Chimica Universita' "Ca Foscari" Venezia Santa Marta, Dorsoduro, 2137 30121 Venezia Italia E-mail: [email protected] DE NARDI Marco Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] DE NISCO Mauro Dip. Chimica Organica e Biochimica Universita' di Napoli Federico II Via Cintia, 4 82126 Napoli Italia de SILVA A. Prasanna School of Chemistry and Chemical Engineering Queen's University Belfast Irlanda E-mail: [email protected] DESIMONI Giovanni Dipartimento di Chimica Organica Universita' di Pavia V.le Taramelli, 10 27100 Pavia Italia E-mail: [email protected] De VINCENTIIS Francesco Dipartimento di Chimica Organica "A. Mangini" Facoltà di Chimica Industriale, Università di Bologna V.le Risorgimento, 4, Bologna Italia E-mail: [email protected] DI SARRA Francesca Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] DONNOLA Paola Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] DUUS Jens Carlsberg Laboratory, Gremle Calsberg Vej 10 - 2500 Valby Denmark E-mail: [email protected]

DVORAKOVA Gita Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] FABRIZI Olga Via Badile 23 37131 Verona – Italia E-mail: [email protected] FORMAGGIO Fernando Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] FEDRIZZI Bruno Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] FINO Vincenzo Dipartimento di Chimica Universita' di Bari Via E. Orabona, 4 70125 Bari Italia E-mail: [email protected] FLAMINI Riccardo Agricoltural Research Council, Viticulture Research Center, CRA-VIT Viale XXVII Aprile, 25 31015 Conegliano (TV) Italia E-mail: [email protected] FLORIO Saverio Dip. Farmaco-Chimico Universita' di Bari Via E. Orabona, 4 70125 Bari Italia E-mail: [email protected] GAITA Elisabetta Scuola Secondaria Superiore Via Salvo d'Acquisto, 6, 1 15100 Alessandria Italia E-mail: [email protected] GALVAGNI Marco F.I.S. Fabbrica Italiana Sintetici, Viale Milano, 26 36075 Alte di Montecchio Maggiore (VI) Italia E-mail: [email protected] GARDAN Martino Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected]

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GASPARINI Giulio Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] GASPARRINI Francesco Dip. Chimica e Tecnologie del Farmaco Universita' di Roma P.le Aldo Moro, 5 00185 Roma Italia E-mail: [email protected] GAZZOLA Luca Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] GENNARO Armando Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] GERBI Vincenzo DIVAPRA Universita' di Torino Via Leonardo da Vinci, 44 10095 Grugliasco (TO) Italia E-mail: [email protected] GIBERTINI Paolo Via Bellini, 29/31 20026 Novate (MI) – Italia E-mail: [email protected] GOBBO Marina Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] GORI Silvio Via Durante, 36 20133 Milano - Italia GRAZIANI Matteo Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] KIELHOLZ Juergen Reckitt Benckiser Italia S.p.A. R&D Centre P.zza S. Nicolò 12/3 30034 Mira (VE) –Italia E-mail: [email protected]

LAFORCE Roger F.I.S. Fabbrica Italiana Sintetici, Viale Milano, 26 36075 Alte di Montecchio Maggiore (VI) E-mail: [email protected]

LICANDRO Emanuela Dipartimento di Chimica Organica e Industriale Università di Milano Via Venezian, 21, 20133 Milano E-mail: [email protected] LICINI Giulia Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] LLANES-PALLÀS Anna Dipartimento di Scienze Farmaceutiche and INSTM UdR Universita' di Trieste 34127 Trieste Italia E-mail: [email protected] LOVAT Silvia Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] LUBIAN Elisa Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] LUISI Pierluigi Dipartimento di Biologia Universita' di Roma III L.go S. Leonardo Murialdo, 1 00146 Roma Italia E-mail: [email protected] MAGGINI Michele Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] MAGNO Franco Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected]

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MAITY Prasenjit Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] MAJORANA Stefano Dipartimento di Chimica Organica e Industriale Università di Milano Via Venezian, 21, 20133 Milano E-mail: [email protected] MANCIN Fabrizio Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] MARCHELLI Rosangela Dipartimento di Chimica Organica e Industriale Universita' di Parma V.le G.P. Usberti, 17A 43100 Parma Italia E-mail: [email protected] MARIGO Antonio Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] MARTINI Elena MAROTTA Ester Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] MATTAREI Andrea Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] MAZZELLA Mauro Dipartimento di Chimica Universita' di Napoli Federico II Via Cintia, 4 80126 Napoli Italia E-mail: [email protected] MAZZEO Pietro Dipartimento di Chimica Universita' dell'Aquila Via Vetoio, 67010 Coppito AQ Italia E-mail: [email protected]

MAZZEO Rocco Dipartimento di Chimica "Giacomo Ciamician" Università di Bologna Via F. Selmi, 2 40126 Bologna Italia E-mail: [email protected] MAZZOTTI Fabio Dipartimento di Chimica Università della Calabria Via P. Pucci Cubo 12B 87036 Arcavacata di Rende (CS) MBA Miriam Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] MELLA Massimo School of Chemistry Cardiff University Main Building, Park Place Cardiff CF 10 3 AT – United Kingdom [email protected] MENNA Enzo Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] MILANI Roberto Dipartimento di Processi Chimici Universita' di Padova Via Marzolo, 9 35131 Padova Italia E-mail: [email protected] MISSIO Andrea Miteni S.p.A. Loc. Colombara, 91 36070 Trissino (VI) Italia E-mail: [email protected] MODELLI Manuela Via Faenza, 15 - 40139 Bologna Italia E-mail: [email protected] MODUGNO Gloria Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] MOLINARI Henriette Dipartimento di Biotecnologie Università di Verona Strada le Grazie, 15 37134 Verona Italia E-mail: [email protected]

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MORETTO Alessandro Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] MUSUMARRA Giuseppe Dipartimento di Scienze Chimiche Universita' di Catania V.le Andrea Doria,6 95125 Catania Italia E-mail: [email protected] NEGOM KOUODOM Morelle Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] NEPPALLI Ramesh Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] NOTO Renato Dip. Chimica Organica Universita' di Palermo V.le delle Scienze, Parco d'Orleans, 11 90128 Palermo Italia E-mail: [email protected] NOVELLINO Ettore Dip. di Chimica Farmaceutica e Tossicologia Università di Napoli Via D. Montesacro, 49 80131 Napoli Italia E-mail: [email protected] PARADISI Cristina Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] PARISIO Giulia Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] PAVAN M. Vittoria Via D. Chiesa, 8 35100 Padova – Italia PEGGION Cristina Dipartimento di Scienze Chimiche Universita' di Padova - Via Marzolo, 1 35131 Padova Italia E-mail: [email protected]

PELIZZI Giancarlo Dip. Di Chimica Generale Universita' di Parma V.le G.P. Usberti 43100 Parma Italia E-mail: [email protected] POCAR Donato Universita' di Milano Via Venezian, 21 20133 Milano Italia E-mail: [email protected] PRATO Maurizio Dipartimento di Scienze Farmaceutiche Università degli Studi di Trieste - Italia E-mail: [email protected] PRINS Leonard Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] PROCOPIO Antonio Dip. Scienze Farmacobiologiche Università "Magna Grecia" Complesso Ninì Barbieri 88021 Roccelleta di Borgia (CZ) Italia E-mail: [email protected] RAFANELLI Piero Dipartimento di Astronomia Universita' di Padova Vicolo Osservatorio 35100 Padova Italia E-mail: [email protected] RANCAN Marzio Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] RICCI Alfredo Facoltà di Chimica Industriale Università di Bologna Viale Risorgimento, 4 40126 Bologna Italia E-mail: [email protected] ROMANO Francesco Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] ROMEO Giovanni Dipartimento Farmaco Chimico V.le SS Annunziata Messina – Italia E-mail: [email protected]

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RONCONI Luca Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] ROSATO Francesca Dipartimento di Scienze e Tecnologie Biologiche ed Ambientali Università del Salento Via Prov-le Lecce-Monteroni, 73100 Lecce Italia E-mail: [email protected] ROSSI Emiliano Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] SAIELLI Giacomo Istituto Tecnologia delle Membrane Sede Operativa di Padova C.N.R. Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] SALOMONE Antonio Dipartimento Farmaco-Chimico Universita' di Bari Via E. Orabona, 4 70125 Bari Italia E-mail: [email protected] SALVADORI Enrico Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] SANTORO Stefano Dip. di Chimica e Tecnologia del Farmaco-Chim. Org. Universita' di Perugia Via del Liceo, 1 06123 Perugia Itaalia E-mail: [email protected] SARTOREL Andrea Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] SCAPINELLO Marco Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected]

SCHIORLIN Milko Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] SCORRANO Gianfranco Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] SCRIMIN Paolo Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] SELVESTREL Francesco Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 SEMINO Nadia Istituto Istruzione Superiore "Marconi" Viale Einaudi, 6 15057 Tortona Italia E-mail: [email protected] SGAMELLOTTI Antonio Dipartimento di Chimica Universita' di Perugia Via Elce di Sotto, 8 06123 Perugia Italia E-mail: [email protected] SILVAGNI Adriano Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 - 35131 Padova Italia E-mail: [email protected] SILVESTRINI Simone Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] SINDONA Giovanni Dipartimento di Chimica Università della Calabria Via P. Pucci, Cubo 12C, 87036 Arcavacata di Rende (CS) Italia E-mail: [email protected] SPADA Gian Piero Alma Master Studiorum, Dipartimento Di Chimica Organica Università di Bologna"A. Mangini" Via S. Giacomo, 11 40126 Bologna Italia E-mail: [email protected]

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SPADONI Luca Reckitt Benckiser Italia S.p.A. R&D Centre P.zza S. Nicolò 12/3 30034 Mira (VE) Italia E-mail: [email protected] STERCHELE Stefano Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 - 35131 Padova Italia E-mail: [email protected] STIVANELLO Mariano Lundbeck Pharmaceuticals Italy S.p.A. Via Quarta Strada, 2 35129 Padova Italia E-mail: [email protected] TADDIA Marco Dipartimento di Chimica "Giacomo Ciamician" Universita' di Bologna Via F. Selmi, 2 40126 Bologna Italia E-mail: [email protected] TONDELLO Eugenio Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] TONELLATO Umberto Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] TROISI Luigino Dip. Disteba Universita' di Lecce Via Monteroni, 73055 Lecce Italia E-mail: [email protected] VALITUTTI Giuseppe Via Macelli, 24 60027 Osimo (AN) E-mail: [email protected] VERSINI Giuseppe Consulente, Unione Italiana Vini Verona Italia E-mail: [email protected] VISCARDI Guido Dip. Di Chim. Generale e Chim. Org. Universita' di Torino C.so Massimo d'Azeglio, 48 10125 Torino Italia E-mail: [email protected]

VOLPE Giulio Lundbeck Pharmaceuticals Italy S.p.A. Via Quarta Strada, 2 35129 Padova Italia E-mail: [email protected] Von BOHLEN Alex ISAS Institut Analytical Sciences Bunsen-Kirchoff-Str., 11 44139 Dortmund Germania E-mail: [email protected] WALTER Philippe Centre de Recherche et de Restauration del Musèes de France Quai Francais Mitterand, 14 75001 Paris France E-mail: [email protected] ZAUPA Giovanni Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] ZECCA Marco Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected] ZONTA Cristiano Dipartimento di Scienze Chimiche Universita' di Padova Via Marzolo, 1 35131 Padova Italia E-mail: [email protected]

PROGRAMME AND ABSTRACT PROGRAMME AND ABSTRACT

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