programme and abstract programme and abstract

Transcription

INTERNATIONAL CONGRESS
“THE CENTENARY”
100th Anniversary of the Italian Chemical Society
Padova, August 31-September 4, 2009
PROGRAMME AND ABSTRACT
by: gianfranco.scorrano@unipd.it - epiaia@unipd.it
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ACKNOWLEDGEMENTS
The organisers greatefully acknowledge the financial support listed below:
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Consiglio Nazionale delle Ricereche-I.T.M
Comune di Padova
Universita- degli Studi di Padova
Societa Chimica Italiana
C.N.R.-Dipartimento di Progettazione Molecolare
Consorzio di Ricerca Laguare
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
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Honour Committee
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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 (20082010).
Rectors of Italian Universities: Mario Pasquali (Pisa); Ezio Pelizzetti (Torino); Antonino
Recca (Catania).
Scientific and Organizing Committee
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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
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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: epiaia@unipd.it
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WELCOME 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 a 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
opportunuties 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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CONTENTS
General Information
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Scientific Programme →
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Abstracts →
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List of Plenary Lectures →
List of Invited Lectures →
List of Posters
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Abstract Plenary Lectures→
Abstract Invited Lectures →
Abstract Posters →
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Appendices
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Author Index →
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List of Participants →
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GENERAL 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 in
Padova. A map of the city is available at: http://www.chimica.unipd.it/the-centenary/
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 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”
11,20-12,00
GIUSEPPE VERSINI (UNIONE ITALIANA VINI) “PARAMETRI ISOTOPICI DELLA GRAPPA INFLUENZATI DALL’ORIGINE E VARIABILI
COMPOSITIVE LEGATE AL MIGLIORAMENTO TECNOLOGICO”
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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”
17,00-17,15
STEFANO SANTORO “PhSeZnCl IN NUCLEOPHILIC VINYLIC SUBSTITUTIONS: REACTIVITY AND THEORETICAL
INVESTIGATION”
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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
12,00-12,30
OSCAR CHIANTORE, UNIVERSITÀ DI TORINO "FROM BAKELITE TO (NANO)COMPOSITES: 100 YEARS OF POLYMERS IN ART".
RENZO BERTONCELLO AND MARINA R.BRUSTOLON, UNIVERSITA’ DI PADOVA - "LA CHIMICA: UN BENE CULTURALE"
15,00-15,20
EMANUELA BERZIOLI, ELISA CAMPANI, 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
16,20-16,40
PAOLO CREMONESI, CESMAR 7 - " A CHEMICAL APPROACH TO THE CLEANING OF PAINTINGS"
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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ABSTRACTS
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LIST OF PLENARY 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: ettore.novellin@unina.it
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: jd@crc.dk
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: rosangela.marchelli@unipr.it
PL4
METALS IN SYSTEMS BIOLOGY
IVANO BERTINI
Dipartimento di Chimica – CERM, Universita’ di Firenze, Via Sacconi, 6, 50019 Sesto Fiorentino (FI) – Italia
E-mail: bertini@cerm.unifi.it
PL5
CHEMISTRY OF THE UNIVERSE
PIERO RAFANELLI
Dipartimento di Astronomia, Università di Padova, Vicolo dell’Osservatorio, 3, 35100 Padova – Italia
E-mail: piero.rafanelli@unipd.it
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: luisi@uniroma3.it
PL7
ENERGIA PER L’ASTRONAVE TERRA
VINCENZO BALZANI
Dipartimento di Chimica “G. Ciamician”, Università di Bologna, Via Selmi, 2, 40126 Bologna – Italia
E-mail: vincenzo.balzani@unibo.it
PL8
ABOUT CHEMISTRY AND PHYSICS OF SOUND
ALEX von BOHLEN
ISAS Institut Analytical Sciences – Bunsen-Kirchhoff-Str. 11 – 44139 Dortmund – Germany
E-Mail: vonbohlen@isas.de
PL9
THE SINDONE AGE
LUIGI CAMPANELLA
Dipartimento di Chimica, Università di Roma “La Sapienza”, P.le Aldo Moro, 5, 00185 Roma – Italia
E-mail: luigi.campanella@uniroma1.it
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: philippe.walter@culture.gouv.fr
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: sgam@thch.unipg.it
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LIST 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: cescon@unive.it
IL2
IL COORDINAMENTO SCIENTIFICO DELLE RICERCHE IN LAGUNA
PIER PAOLO CAMPOSTRINI
Direttore Consorzio CORILA, Palazzo Franchetti, S. Marco, 2847, 30124 Venezia - Italia
E-mail: campostrini@corila.it
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: f.corami@unive.it
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: capoda@unive.it
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: luca.spadoni@reckittbenckiser.com
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: msti@lundbeck.com
IL7
"PROCESS DEVELOPMENT AND ELECTROCHEMICAL FLUORINATION: IS A RATIONAL
APPROACH POSSIBLE?”
ANDREA MISSIO
Miteni, Località Colombara, 91, 36070 Trissino (VI) - Italia
E-mail: andrea.missio@miteni.com
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: livius.cotarca@zambongroup.com
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: andrea.castellin@fisvi.com
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: a.desilva@qub.ac.uk
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: valeria.conte@uniroma2.it
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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: versini@yahoo.it
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: vincenzo.gerbi@unito.it
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: bruno.fedrizzi@unipd.it
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: riccardo.flamini@entecra.it
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: sindona@unical.it
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: procopio@unicz.it
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: marzio.rancan@unipd.it
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: capriati@farmachim.uniba.it
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: allanes@units.it
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: laura.bartali@virgilio.it
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: mariagraziabart@hotmail.com
13
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: davide.bini@unimib.it
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: fra.devin@gmail.com
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: vincenzofino@gmail.com
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: mauromazzella@hotmail.com
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: francesca.rosato@libero.it
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: antoniosalomone@libero.it
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: stefanos80@gmail.com
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: oscar.chiantore@unito.it
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: luca.bertoncello@unipd.it – marinarosa.brustolon@unipd.it
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: michela.berzioli@libero.it
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: rocco.mazzeo@unibo.it
14
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: paolocremonesi57@gmail.com
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: bisco@unive.it
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: marco.taddia@unibo.it
15
LIST 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: luca.ronconi@unipd.it
PO2
NOVEL MITOCHONDRION-TARGETED QUERCETIN DERIVATIVES: SYNTHESIS, OXIDATION POTENTIALS, RADICALSCAVENGING PROPERTIES AND CYTOTOXICITY
ANDREA MATTAREI*, LUCIA BIASIUTTO, ESTER MAROTTA, SPIRIDIONE GARBISIA, MARIO ZORATTI, CHRISTIAN
DURANTE, GIANCARLO SANDONA’, ARMANDO GENANRO, CRISTINA PARADISI
E-mail: andrea.mattarei@unipd.it
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: henriettemolinari@univr.it
PO4
(Zn,Cu)O PHOTOCATALYTIC MATERIAL AND ZnGa22O4:Eu PHOSPHORS: TAILORING STRUCTURE-PROPERTY
RELATIONSHIPS
LAURA BOVO, LIDIA ARMELAO, MARCO BETTINELLI, EUGENIO TONDELLO
E-mail: laura.bovo@unipd.it
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: renato.bonomi@unipd.it
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: francesca.colombo@unipd.it
PO7
3+
II
SUPPORTED BIS(ZN -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: elisa.lubian@unipd.it
PO8
TARGETED SILICA NANOPARTICLES FOR DRUG DELIVERY
A
FRANCESCO SELVESTREL , GAETANO GUARINO, IRIA MARIA RIO-ECHEVARRIA, ELENA REDDI, FABRIZIO MANCIN .
Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova - Italia
E-mail: francesco.selvestrel@unipd.it
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: andrea.biffis@unipd.it
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: serena.berardi@unipd.it
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: martino.gardan@unipd.it
16
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
E-mail: cristina.peggion@unipd.it
PO13
MODELLING THE PARTITIONING OF SOLUTES IN LIPID MEMBRANES
G. PARISIO*, M. STOCCHERO, A. FERRARINI
E-mail: giulia.parisio@unipd.it
P014
PRELIMINARY STUDIES ON STRUCTURE, MORPHOLOGY AND BIODEGRADABILITY OF POLY (€-CAPROLACTONE) BASED
NANOCOMPOSITES
RAMESH NEPPALLI*, VALERIO CAUSIN, CARLA MAREGA, ROBERTA SAINI, ANTONIO MARIGO
E-mail: ramesh.neppalli@unipd.it
PO15
A PEPTIDO[2]ROTAXANE MOLECULAR MACHINE
A.MORETTO, I. MENEGAZZO, M. CRISMA, S. MAMMI, C. TONIOLO
E-mail: alessandro.moretto@unipd.it
PO16
EXPLOITING NON COVALENTG INTERACTIONS FOR THE DISCOVERY OF NEW CATALYSTS: DYNAMIC COVALENT CAPTURE
APPROACH
LEONARD PRINS, MARTA DAL MOLIN*, PAOLO SCRIMIN
E-mail: marta.dalmolin@unipd.it
P017
ROLE OF INTERMOLECULAR INTERACTIONS IN OXYGEN TRANSFER CATALYZED BY SILSESQUIOXANE TRISILANOLATE
VANADIUM(V)
SILVIA LOVAT*, M. MBA, C. ZONTA, G. LICINI
E-mail: silvia.lovat@unipd.it
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: laura.colli@unifi.it
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: roberto.milani@unipd.it
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
PO21
SOLUBLE AND FUNCTIONAL SINGLE-WALLED CARBON NANOTUBES
MARCO DE NARDI*, FABRIZIO CORDELLA, CECILE HEBERT, MARIA ANTONIETTA LOI, ENZO MENNA
E-mail: marco.denardi@unipd.it
PO22
UNIVERSAL GOLD NANOPARTICLES: SYNTHESIS, PURIFICATION, APPLICATION
MATTEO GRAZIANI*, LEONARD PRINS, PAOLO SCRIMIN
E-mail: matteo.graziani@unipd.it
17
PO23
HYDROARYLATION OF ALKYNES CATALYSED BY PD(II) COMPLEXES: OPTIMIZATION OF THE REACTION CONDITIONS
LUCA GAZZOLA*, ANDREA BIFFIS, CRISTINA TUBARO, GABRIELLA BUSCEMI, MARINO BASATO
E-mail: luca.gazzola@unipd.it
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
E-mail: miriam.mba@unipd.it
PO25
ORGANIC SYNTHESIS IN MICROREACTORS
TOMMASO CAROFIGLIO, ANDREA CASTELLIN, PAOLA DONNOLA*, MICHELE MAGGINI, E. ROSSI
E-mail: paola.donnola@unipd.it
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: cristiano.bindoli@unipd.it
PO27
Mo(VI) AMINE TRIPHENOLATE COMPLEXES: SYNTHESIS, STRUCTURE AND CATALYTIC ACTIVITY
1
F. ROMANO , S. LOVAT, M. MBA, C. ZONTA, G. LICINI
E-mail: francesco.romano@unipd.it
PO28
Pd(0) NANOPARTICLES SUPPORTED ONTO MACROPOROUS MONOLITHS FOR CONTINUOUS FLOW CARBON-CARBON
CROSS COUPLINGS IN CAPILLARY MICROREACTORS
PRASENJIT MAITY, TOMMASO CAROFIGLIO, MICHELE MAGGINI
E-mail: prasenjit.maity@unipd.it
PO29
SUPRAMOLECULAR ASSEMBLY OF THE VDE PROTEIN IN MEMBRANES AS REVEALED BY SDSL-EPR AND 4P-DEER
A*
E. SALVADORI , M. DI VALENTIN, G. SAGA, T. MOROSINOTTO, D. CARBONERA
E-mail: enrico.salvadori@unipd.it
PO30
SENSITIVITY TUNING IN INTRACELLULAR Zn PROBES
1*
1
L. BAÙ , F. MANCIN
E-mail: luca.bau@unipd.it
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.
Email: emiliano.rossi@unipd.it.
PO32
NUCLEIC ACID RECOGNITION BY ALANYL-NUCLEOPEPTIDES
PIERO GEOTTI-BIANCHINI, OLIVIER CHALOIN, ALBERTO BIANCO, FERNANDO FORMAGGIO*
E-mail: fernando.formaggio@unipd.it
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
2+
18
PO34
REPLACEMENT OF Ala BY Aib IMPROVES STRUCTURATION AND BIOLOGICAL STABILITY IN THYMINE-BASED
NUCLEOPEPTIDES
A,B
A
A
B
B
PIERO GEOTTI-BIANCHINI, ALESSANDRO MORETTO, CRISTINA PEGGION, JULIEN BEYRATH, ALBERTO BIANCO,
A
FERNANDO FORMAGGIO *
PO35
METAL NANOCLUSTERS STABILISED BY POLYAMIDES: “BOTTOM-UP” PREPARATION AND PRELIMINARY CATALYTIC DATA
A,
A
A
A
a
M. ZECCA *, I. CONCINA , I. DUSE , B. CORAIN, , P. CENTOMO
E-mail :marco.zecca@unipd.it
PO36
COMPARISON OF THE INITIAL DECOMPOSITION STEPS OF HALOGENATED AND NON-HALOGENATED HYDROCARBONS
IN AIR UNDER DIFFERENT PLASMA REGIMES
1*
1
1
2
1
M. SCHIORLIN , E. MAROTTA , M. DAL MOLIN , M. REA , C. PARADISI
E-mail: milko.schiorlin@unipd.it
PO37
SYNTHESIS OF CHIRAL HYBRID ORGANIC-INORGANIC POLYOXOMETALATES
GLORIA MODUGNO*, MAURO CARRARO, ANDREA SARTOREL, MARCELLA BONCHIO, GIANFRANCO SCORRANO,
E-mail: glomod84@libero.it
.
1
PO38
LIPID OXIDATION PRODUCTS GENERATED BY THERMAL STRESS OF CULINARY OILS AND FAT: A KINETIC STUDY BY H NMR
SPECTROSCOPY
ALESSANDRO BAGNO, FEDERICO RASTRELLI, MARCO SALMISTRARO, ADRIANO SILVAGNI
E-mail: adriano.silvagni@unipd.it
PO39
THIOREDOXIN REDUCTASE AS ANTICANCER TARGET. COMPUTATIONAL AND MODEL STUDIES OF INHIBITION
1
2
1
1
3
RICCARDO BINI, GIACOMO SAIELLI, FRANCESCA DI SARRA, * ALESSANDRO BAGNO, VALENTINA GANDIN,
4
FRANCESCO TISATO
Dipartimento di Scienze Chimiche, , Università di Padova, Via Marzolo, 1, 35131 Padova – Italia
E-mail: francesca.disarra@unipd.it
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: morelle.negomkouodom@unipd.it
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: simone.silvestrini@unipd.it
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
19
PLENARY LECTURES
20
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.
21
PL2
100 YEARS OF RESEARCH AT CARLSBERG LABORATORY; FROM pH TO HIGH
FIELD NMR SPECTROSCOPY
Jens Ø. Duus*
1
Carlsberg Laboratory, Gamle Carlsberg Vej 10, DK-2500 Valby, Denmark
*Corresponding Author jd@crc.dk
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.
22
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.
23
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.
24
PL5
CHEMISTRY OF THE UNIVERSE
Piero Rafanelli, Dipartimento di Astronimia, Università di Padova
25
PL6
From the origin of life to cognition
Pier Luigi Luisi
Department of Biology, University. Roma3, Italy
E-mail: luisi@mat.ethz.ch
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).
26
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
27
PL8
VIOLINS – ABOUT CHEMISTRY AND PHYSICS OF SOUND
Alex von Bohlen
Institute for Analytical Sciences ISAS-Dortmund
Bunsen-Kirchhoff-Str. 11
44139 Dortmund, Germany
vonbohlen@isas.de
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.
28
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.
29
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
philippe.walter@culture.gouv.fr
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.
30
PL11
MOLECULAR SCIENCES FOR ART:
FROM RENAISSANCE TO CONTEMPORARY
Antonio Sgamellotti
SMAArt, CNR-ISTM
ISTM and INSTM - Department of chemistry, University of Perugia
sgam@thch.unipg.it
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
port
scientific instrumentation to carry out non-invasive
non
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
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
underdra
of the Rocks (London,
National
Gallery) will be discussed and the palette of the painter il
Perugino
of
the
will be presented. This Renaissance artist, besides using traditional pigments
bronze, or
sixteenth century, also experimented with metal powders, such as
a bismuth or
the effort
minerals with metallic lustre, or even powders of transparent uncoloured glass, in
MOLAB has
to reach more sophisticated chromatic effects. The multi-technique
multi
approach of
been adopted for investigations in modern and contemporary
con
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
ictory Boogie Woogie,
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
investigation of twenty
paintings
by Burri (Fondazione Palazzo Albizzini Collezione Burri,
Burri Città di Castello,
Perugia)
allowed for the characterization of the execution techniques and
materials
used by the artist in the period 1948-1976.
1948
Gino de Dominicis’
monumental sculpture, Calamita Cosmica,, was investigated by employing a
combination of non-invasive
non
and micro-invasive
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
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
chr
properties: brilliant metallic reflections, iridescence and changing effects.
31
INVITED LECTURES
32
IL1
LE PROBLEMATICHE CHIMICO-AMBIENTALI DEL SISTEMA LAGUNARE VENEZIANO
Paolo Cescon, Dipartimento di Scienze Ambientali, Università di Venezia
33
IL2
IL COORDINAMENTO SCIENTIFICO DELLE RICERCHE IN LAGUNA
Pierpaolo Campostrini
CORILA
campostrini@corila.it
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.
34
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: f_corami@unive.it
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.
35
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.
36
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.
37
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
1
Lundbeck Pharmaceuticals Italy SpA, Quarta Strada, 2- 35129-Padova, Italy and
2
H. Lundbeck A/S, OttiliaVej 7-9, CK-2500 Valby, Denmark
*msti@lundbeck.com
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
38
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.
AHF
RHCOX
RFCOF
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.
39
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
*livius.cotarca@zambongroup.com
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.
O
F
H
OH
H
N
OH
H
O
(2)
O
F
F
H
OH
H
N
OH
H
O
(3)
F
(-)-Nebivolol
( RSSS)-Nebivolol
(L-Nebivolol)
(+)-Nebivolol
( SRRR)-Nebivolol
(D-Nebivolol)
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.
40
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.
2.
3.
A. Liljeblad, J. Lindborg, A. Kanerva, J. Katajisto, L. T. Kanerva, Tetr.Lett. 2002, 43, 2471-2474.
M. C. Ng-Youn-Chen, A. N. Serreqi, Q. Huang, R. J. Kazlauskas, J.Org. Chem. 1994, 59, 2075-2081.
E. J. Toone, Bryan Jones Can. J. Chem. 1987, 65, 2722-2726.
41
IL10
THE ROLE OF pH IN CONCEPT-BUILDING FOR MOLECULAR SENSING AND COMPUTING
a
a
b
a
a
Gareth J. Brown, A. Prasanna de Silva,* Kaoru Iwai, Gareth D. McClean, Bernadine O.F. McKinney, David C. Magri,
c
a
Seiichi Uchiyama 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
(a.desilva@qub.ac.uk)
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 deexciting 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).
e
LUMOPHORE
SPACER
RECEPTOR
SPACER
RECEPTOR
νAbs
hν
LUMOPHORE
νAbs
hν
H+
hνLum
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).
42
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: valeria.conte@uniroma2.it
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
1
the deacidification with calcium bicarbonate. Recently, use of magnesium phytate solution was proposed , 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 non2,3,4
aqueous stabilisation of iron gall inks was proposed.
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.
8
factor of stabilisation (kuntreated/ktreated)
7
6
5
4
3
2
1
--
Mg phytate
HMIMCl
Ca phytate
Treatment
HMIMBr
BMIMBr
BDMIMBr
EMIMBr
BBABr
TBABr
MgEtO
0
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 tetrabutylammonium 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 1hexyl-3-methylimidazolium bromide (HMIMBr) or 1-hexyl-3methylimidazolium 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.
43
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 , I36016 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
13 12
C/ C 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.
44
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: vincenzo.gerbi@unito.it; 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 copigmentazione 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.
45
IL14
SULFUR COMPOUNDS IN GRAPE AND WINE: CONTENTS, PRECUROSORS AND SUITABLE
ANALYTICAL TECHNIQUES
Bruno Fedrizzi 1,2,*, Giuseppe Versini 2, Franco Magno 1
1
Chemical Sciences Dept., University of Padova, via Marzolo 1, 35131 – Padova, Italy; 2Unione Italiana Vini
Soc. Coop., viale del Lavoro 8, 37135 – Verona, Italy;
*
bruno.fedrizzi@unipd.it
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.
46
IL15
RECENT ANALYTICAL APPLICATIONS IN GRAPE AND WINE CHEMISTRY
Riccardo Flamini
CRA-VIT Laboratorio Chimico, Viale XXVIII aprile, 26 – 31015 Conegliano (TV), Italy
riccardo.flamini@entecra.it
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-IonChemical-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).
47
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
1-3
and LC-MS/MS has been used to assess the quality of olive oil. 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
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
1.
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
48
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
1
Section 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 antiinflammatory properties. Oleopentadial [ 2-(3, 4-hydroxyphenyl) ethyl (3S,4E)-4-formyl-3-(2-oxoethyl)hex4-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-kBdependent 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.
49
IL18
THE ORGANIC CHEMISTRY OF OLIVE NUTRACEUTICALS
Monica Nardi, a Antonio Procopio,*b Manuela Oliverio,b Giovanni Sindona a
a
b
Dipartimento di Chimica, Università della Calabria, ponte Bucci cubo 12/c, I-87030 Arcavacata di Rende (Cs) Italy. .
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.
R
O
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.
O
COOR'
HO
R = OH: Hydroxytyrosol (1, HTyr)
R = H: Tyrosol (2, Tyr)
O
OGlu
R = OH; R' = CH 3: Oleuropein (3, Ole)
R = H; R' = CH3: Ligstroside 4
Chart 1: Chemical structure of compounds 1-4.
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,5 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.6
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, 90969098; (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.
50
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: marzio.rancan@unipd.it
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.
51
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
*capriati@farmchim.uniba.it
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.1 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.2 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,3 such as the oxazolinyloxiranyllithium 14 and lithiated styrene oxide 2,5 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 noncovalent interactions, which are at the root of different organizational complexities are, indeed, mainly
responsible of the dichotomic reactivity exhibited by such reactive intermediates.
THF
O
Me
Me
Li
O
N
(R)
Li
Me
Me
O
(R)-η3-1
Me
Me
O
(S)
N
Me
Me
Ph
O
Li
(S)
Li
O
(S) Ph
THF
(S)-η3-1
THF
slow
O
Ph
2·(THF)2
O
Li
(R)
(S) Ph
Li
THF
O
H
Ph
H
Li THF
2·(THF)3 THF THF
carbanionic reactivity
carbenoid reactivity
1
Gessner, V. H.; Däschlein, C.; Strohmann, C. Chem. Eur. J. 2009, 15, 3320–3334.
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.
2
52
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: allanes@units.it
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.
53
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: laura.bartali@virgilio.it
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.
2.
3.
Wlesmann C. et al., Nature, 1999, 401, 184-188.
(a) Maliartchouk S. et al., Mol. Pharm., 2001, 57, 385-391; (b) Xie Y. et al., J. Biol. Chem., 2000, 275,
29868-29874.
Trabocchi A. et al., Synlett., 2006, 331-354.
54
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. mariagraziabart@hotmail.com
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 nonradical 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 orthothioquinones, 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.
O
O
+
HO
HO
S
O
HO
Z
α
O
R
HO
Z
R
O
HO
β
R = Phytyl; Z = CH2 : Tocopherols
S
Z
γ
O
R
HO
R
Z
δ
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.
55
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 MilanoItaly, davide.bini@unimib.it
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.
1
H-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.
56
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.
O
R3
H
N A-
H2O
Lg
N
H
R2
R2
HA
R1
R1
R1
NH3A-
Lg N
R2
R3
N
H
AO
1
R
N
Lg
N
H
HA
R2
R2
R3
R3
R1
H 2O
N
Lg
O
R2
N R3
R1
R1
3
N R
Lg H
R2
H 2O
N
H
A-
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
57
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: vincenzofino@gmail.com
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.
F
F
N
F
X
F X
F
Ir
N
N
F
X
F
F
facial
F
F X
F
NF
X
F
F
F
N
Ir
X: F; perfluorinated oligophenyls
Ir
N
N
F
L
Y
F
X
F
X
2
meridianal
HOMOLEPTIC COMPLEXES
HETEROLEPTIC COMPLEXES
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.
58
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;
e-mail: mauromazzella@hotmail.com
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 electrooptics, 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:
HO
R
N
S
O
O
O
1
R=H
2
R=
N
N
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
O
N
O M
R
S
R
O
N
O
O
R=H
R=
S
O
N
N
1a (M=Pd), 1b (M=Cu)
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.
59
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
francesca.rosato@libero.it
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).
Ar
O R'
+ R C CH
N
toluene
reflux
R
O
N R'
Ar
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)
Ar'
.
O
N
Ar
+ Ar C N
O
N
N
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.
60
IL29
ON THE CONFIGURATIONAL STABILITY OF α-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
e-mail: antoniosalomone@libero.it
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.
Li
Li
O
O
k1
Li
O
k -1
R2
R1
R 1= o-, m-, p-F
configurationally stable
R2
R2= o-, m-, p-CF3
configurationally unstable
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.
61
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
e-mail: stefanos80@gmail.com
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.
EWG
X
EWG
PhSeZnCl
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
62
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
e-mail: oscar.chiantore@unito.it
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
63
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.
64
IL33
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
michela.berzioli@libero.it
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
65
IL34
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).
rocco.mazzeo@unibo.it
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.
66
IL35
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.
67
IL36
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.
68
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
marco.taddia@unibo.it
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)
69
POSTERS
70
PO1
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
1
Department of Chemical Sciences, University of Padova, Padova 35131 (ITALY); 2Department of Molecular
Oncology and Translational Research - Division of Experimental Oncology 2, National Cancer Institute (CROIRCCS), Aviano (PN) I-33081 (ITALY); 3Ann Karmanos Cancer Institute and Department of Pathology, School
of Medicine, Wayne State University, Detroit MI-48201 (USA)
e-mail: luca.ronconi@unipd.it
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.
2.
3.
4.
5.
L. Ronconi, C. Marzano, P. Zanello, M. Corsini, G. Miolo, C. Maccà, A. Trevisan, D. Fregona, J. Med.
Chem. 2006, 49, 1648.
V. Milacic, D. Fregona D, Q.P. Dou, Histol. Histopathol. 2008, 23, 101.
V. Milacic, D. Chen, L. Ronconi, K.R. Landis-Piwowar, D. Fregona, Q.P. Dou, Cancer Res. 2006, 66,
10478.
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.
I. Rubio-Aliaga, H. Daniel, Trends Pharmacol. Sci. 2002, 23, 434.
71
PO2
Novel mitochondrion-targeted Quercetin derivatives: synthesis, oxidation potentials, radicalscavenging 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
a
b
Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo 1, 35100 Padova, Italy
Dipartimento di Scienze Biomediche, Università di Padova, Viale G. Colombo 3, 35100 Padova, Italy
c
Istituto di Neuroscienze, Consiglio Nazionale delle Ricerche, Viale G. Colombo 3, 35100 Padova, Italy
andrea.mattarei@unipd.it
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-(4triphenylphosphoniumbutyl)-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
72
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.*
1
Dipartimento di Biotecnologie, Strada le Grazie 15, Università di Verona, 37134 Verona
e-mail: Henriette.Molinari@univr.it
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 tenstranded 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.
2.
3.
4.
Furuhashi, M. and Hotamisligil, G. S., Nat Rev Drug Discov 7, 489-503, 2008.
Eliseo, T., Ragona, L., Catalano, M., Assfalg, M., Paci, M., Zetta, L., Molinari, H. and Cicero, D. O.
Biochemistry 46, 12557-67, 2007.
Tomaselli, S., Zanzoni, S., Ragona, L., Gianolio, E., Aime, S., Assfalg, M. and Molinari, H. J Med Chem
51, 6782-92, 2008.
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.
73
PO4
(Zn,Cu)O PHOTOCATALYTIC MATERIAL AND ZnGa2O4 : Eu3+ PHOSPHORS:
TAILORING STRUCTURE-PROPERTY RELATIONSHIPS
Laura Bovo1*, Lidia Armelao2, Marco Bettinelli3, Eugenio Tondello1
1
Dipartimento Scienze Chimiche, Università di Padova,via Marzolo 1 35131 Padova, INSTM,
e-mail: laura.bovo@unipd.it
2
CNR, ISTM, INSTM, Dipartimento di Scienze Chimiche, Università di Padova,via Marzolo 1 35131 Padova
3
Lab. 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, lanthanidedoped 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
74
PO5
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
1
ITM-CNR and Dipartimento di Scienze Chimiche, Università di Padova
2
Department Materials Physics, University of Leoben
3
EPFL SB-CIME & IPN-LSME, Lausanne
4
Zernike 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.
75
PO6
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
e-mail: renato.bonomi@unipd.it
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
G. K.; Lad, C.; Wyman, P.; Williams, N. H.; Wolfenden, R. Proc. Natl. Acad. Sci. U.S.A103, 40524055, 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.
1. Schroeder,
76
PO7
SUPPORTED BIS(ZNII-PORPHYRIN)
PORPHYRIN) DITOPIC RECEPTORS
R
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
dependent reactivity of cyanuric chloride toward nucleophiles2. This synthetic
procedure takes advantage on the unique temperature-dependent
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
one pot introduction of various
variou
substituents into a triazine ring is also possible, with a minimal recourse to purification based
chromatography techniques. Thus, the
the procedure for preparing porphyrin dyads simply involves a
sequential coupling of two identical or different amino-porphyrin
amino
yrin building blocks (Scheme 1) thus leading to
homo- (PP and MM) or hetero-substituted
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
group functionalities (i.e.
(
polymeric resins, porous glass
lass particles, and aminoamino
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,
s, 2) the chemistries employed for supporting the porphyrin receptors onto
Tentagel-amino
amino resin beads and amino-cellulose
amino cellulose and 3) some preliminary results about the construction of
optical sensors for diamines.
References
1. J.K.M. Sanders, The Porphyrin Handbook,
Handbook Volume 3, Chapter 22, 347-368.
2. a) T. Carofiglio, A. Varotto, U. Tonellato. J. Org. Chem., 69, 8121-8124, 2004;
77
PO8
TARGETED SILICA NANOPARTICLES FOR DRUG DELIVERY
a
Francesco Selvestrel *,a,b Gaetano Guarino,a Iria Maria Rio-Echevarria,a,b Elena Reddi,b Fabrizio Mancina.
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: francesco.selvestrel@unipd.it
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
cal 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
nanotechnologies applied to the
1
human diseases .
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
le
to scarce coverage.
In this work, we describe a new one-step
one step procedure to prepare silica nanoparticles coated with a dense
PEG layer. Size control is achieved in the 10-150
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.
Figure 1: Example of silica nanoparticles targeted with folic acid and amino groups
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,
150 552.
2. P.N. Prasad and other, J Am. Chem. Soc,
Soc 2003, 125, 7860.
3. Ren-Xi Zhuo and other, Bioconjugate Chem,
Chem 2009, 20, 481.
78
PO9
MICROGEL-STABILIZED METAL NANOCLUSTERS
G. Dvorakova,a* S. Piperno,b L. A. Gheber,b A. Biffis a
Dipartimento di Scienze Chimiche, Università di Padova, via Marzolo 1, I-35131 Padova, Italy. Tel. +39049-8275216. FAX +39-049-8275223.
b
Department of Biotechnology Engineering, Ben-Gurion University of the Negev, P.O.BOX 653, Beer-Sheva
84105, Israel
email: andrea.biffis@unipd.it
aa
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, lowviscosity 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.
79
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.
e-mail: serena.berardi@unipd.it
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.
80
PO11
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.
E-mail: martino.gardan@libero.it
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 -
SubO
Fluorous-tagged
POMs
HOOH
O2
O
W
O
O
O
W
O
Sub
hν T
fluorous phase
H 2O
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.
81
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 and C. Toniolo
ICB, Padova Unit, CNR, Department of Chemistry, University of Padova, 35131 Padova, Italy
e-mail: cristina.peggion@unipd.it
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.
82
PO13
MODELLING THE PARTITIONING OF SOLUTES IN LIPID MEMBRANES
G. Parisio1*, M. Stocchero2 , A. Ferrarini1
1
Dipartimento di Scienze Chimiche, Università degli Studi di Padova, via Marzolo 1, 35131 Padova, Italy,
2
S-IN Soluzioni Informatiche, via Salvemini 9, 36100 Vicenza, Italy
e-mail: giulia.parisio@unipd.it
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)
83
PO14
PRELIMINARY STUDIES ON STRUCTURE, MORPHOLOGY AND BIODEGRADABILITY OF POLY (εCAPROLACTONE) 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 (200
*
Presenting author. email address: ramesh.neppalli@unipd.it
84
PO15
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
e-mail: alessandro.moretto.1@unipd.it
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 nonsymmetrical 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.
85
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.
marta.dalmolin@unipd.it
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.
self-selection
+
+
TSA
TSA
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.
86
PO17
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
email: silvia.lovat@unipd.it
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
O
R O
O Si
O V
R Si O
O R Si R O
O Si
O Si
O
O O R
Si
Si
O
R
R
1, R= i-butyl
CO-LIGAND EFFECT
Tol-S-Me
Ph
N
H
NEt3
CHP, 1
Ph CHP, 1
CHP, 1
REACTIVITY
Tol-SO-Me
Ph
N
O
CHEMOSELECTIVITY
Ph
O NEt3
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.
87
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) *laura.colli@unifi.it
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 (Dasparagina (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
88
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
d)
a)
c)
b)
b)
c)
a)
80
70
60
50
40
30
20
10
( ppm )
0
- 10
- 20
- 30
- 40
- 40
- 60
2
Figure 1- 31P{1H} NMR spectra in the solid state of :
- 80
- 100
( ppm )
- 120
- 140
- 160
Figure 2.- 9Si NMR spectra in the solid state of :
a) Dellite-HPS, b) DP-MMT, c) DP-MMT 250
a) DP-Br2 ,b) DP-MMT, c) DP-MMT 250, d) PU/DP-MMT
89
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: roberto.milani@unipd.it
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 plasmatreated 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 OwensWendt 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)
90
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 chemicalphysical 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.
91
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;
Email: matteo.graziani@unipd.it.
Gold nanoparticles are attractive scaffolds for the preparation of multivalent, functional surfaces. Selfassembled 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.
R
O
N
O
O
O2N
O2N
S
S
O
R
O
O
N
S
S
O2N
O2N
R-NH2
Au
Au
S
S
O
O
O
R
N
O2N
O2N
S
S
O
O
O
O2N
O2N
N
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.
92
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.
e-mail: luca.gazzola.1@unipd.it
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
R
H
0.1% [Pd]
+
R1
R2
0.2% AgTFA
R
R2
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
2
3
4
Reviews: a) F. Kakiuchi, N. Chatani, Adv. Synth. Catal. 2003, 345, 1077; b) V. Ritleng, C. Sirlin, M. Pfeffer,
Chem. Rev. 2002, 102, 1731.
Biffis, A.; Tubaro, C.; Buscemi, G.; Basato, M. Adv. Synth. Catal. 2008, 350, 189-196.
Buscemi, G.; Biffis, A.; Tubaro, C.; Basato, M. Catal. Today 2009, 140, 84-89.
Biffis, A.; Gazzola, L.; Gobbo, P.; Buscemi, G.; Tubaro, C.; Basato, M., Eur. J. Org. Chem., in press.
93
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
3
Dep. Organic Chemistry, Université de Genève, Switzerland
email: miriam.mba@unipd.it
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.
Ph
Ph
N
O
Ti
O
Ph
O
O
O
Ph
Ph
Ph
O
Ti
O
N
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
94
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
e-mail: paola.donnola@unipd.it
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 photooxidations with singlet oxygen.
References
1.
2.
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
Carofiglio T.; Donnola P.; Maggini M.;Rossetto M.; Rossi E.; Adv. Synth: Catal., 350, 2815-2822, 2008
95
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
e-mail: cristiano.bindoli@unipd.it
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
R
O
O
Si
V
O
O O
R
Si O
Si R O
O R Si
O Si
O
O
R
O
Si
Si
O
R
R
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
96
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
*francesco.romano@unipd.it
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
R
R
X O O
O Mo O
R
N
R = H, Me, t-Bu, Ph
X = Cl, OMe
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 Noxidation 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.
97
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
1
Dipartimento di Scienze Chimiche, Università di Padova Via Marzolo, 135131 Padova (Italy)
phone: +39-049-8275662 fax: +39-049-8275279
* michele.maggini@unipd.it
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) carbenecomplexes. 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.
98
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
99
PO30
SENSITIVITY TUNING IN INTRACELLULAR Zn2+ PROBES
L. Baù1*, F. Mancin1
1
Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova, Italy
*luca.bau@unipd.it
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
allowing for the same receptor to be used in
a family of sensors covering the whole concentration range.
range A FRET-based
based fluorescent sensor was designed,
which is made of two parts: a fluorophore and a receptor/quencher whose quenching ability is switched off
upon
n 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.
100
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.
Email: emiliano.rossi@unipd.it.
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.).
101
PO32
NUCLEIC ACID RECOGNITION BY ALANYL-NUCLEOPEPTIDES
Piero Geotti-Bianchini,a,b Olivier Chaloin,b Alberto Bianco,b Fernando Formaggioa*
a
Department of Chemical Sciences, University of Padova, via Marzolo 1, 35131 Padova, Italy;
b
Laboratoire 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 alanylnucleopeptides 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.
102
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.
103
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*
a
Department of Chemical Sciences, University of Padova, via Marzolo 1, 35131 Padova, Italy;
b
Laboratoire 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.
104
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 :marco.zecca@unipd.it
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 nbutylacrylate 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.
105
PO36
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
1
Department of Chemical Sciences and 2Department of Electrical Engineering, Università di Padova, 35131
Padova, Italy
e-mail: milko.schiorlin@unipd.it
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.
106
PO37
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 glomod84@libero.it
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 [γSiW10O36]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 Oprotected 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.
RSiCl3 or RPO(OH)2
(2 eqs)
[γ−
−SiW10O36]8-
[RX(γ-SiW10O36)]4RX= (RSi)2O or (RPO)2
CH3CN / H2O
(HCl) TBABr
R
R
R
[(RSi)2O(γ-SiW10O36)]4-
R
[(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.
107
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 degli Studi di Padova, via Marzolo 1, 35131Padova, Italy
e-mail adriano.silvagni@unipd.it
Deep fried foods introduce in the human diet some by-products
by products that originate from the thermal
stress of lipids, and the possibility that a regular intake of such materials has a deleterious
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
radical
auto-oxidation
oxidation of polyunsaturated fatty acids. This
reaction mainly generates
nerates conjugated hydroperoxydienes that are unstable at the standard frying
temperatures (180 °C) and are degraded to a variety of by-products
by products including aldehydes. This class of
compounds, in particular, is known for its ability to exert toxicological effects
effects in vivo because of its high
2
reactivity with most biomolecules.
O
H
O
n
CH3
H
n
CH
H3
O
O
H
H
n
CH
H3
OH
In this communication, we employ enhanced-sensitivity
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,
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,
Chemistry 2nd ed., Springer
108
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
1
Department 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).
OAc
OAc
PEt3
O
AcO
AcO
Au
S
AcO
+ R-XH
O
AcO
AcO
X = S, Se
SH
+ R-X-Au-PEt3
AcO
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.
109
PO40
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
e-mail: Morelle.negomkouodom@unipd.it
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 nonapoptotic 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.
110
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
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
111
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.
1
Although different methods have been introduced for the assay of rotenone , 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.
2.
3.
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
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
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
112
AUTHOR INDEX
BAU'
BALZANI
BARTALI
BARTOLOZZI
BERARDI
BERTINI
BERTONCELLO
BERZIOLI
BINI
BINDOLI
BISCONTIN
BONOMI
BOVO
BRUSTOLON
CAMPANELLA
CAMPOSTRINI
CAPODAGLIO
CAPRIATI
CASTELLIN
CESCON
CHIANTORE
COLLI
COLOMBO
CONTE
CORAMI
COTARCA
CREMONESI
DAL MOLIN
DE NARDI
de SILVA
De VINCENTIIS
DI SARRA
DONNOLA
DUUS
DVORAKOVA
FEDRIZZI
FINO
FLAMINI
FORMAGGIO
GARDAN
GAZZOLA
GERBI
GRAZIANI
LLANES-PALLÀS
LOVAT
LUISI
LUBIAN
Luca
PO30
Domenico
PL7
Laura
IL22
Maria Grazia
IL23
Serena
PO10
Ivano
PL4
Renzo
IL32
Michela
IL 33
Davide
IL24
Cristiano
PO26
Guido
IL37
Renato
PO5
Laura
PO4
Marina
IL32
Luigi
PL9
Pier Paolo
IL2
Gabriele
IL4
Vito
IL20
Andrea
IL9
Paolo
IL1
Oscar
IL31
Laura
PO18
Francesca
PO6
Valeria
IL11
Fabiana
IL3
Livius
IL8
Paolo
IL35
Marta
PO16
Marco
PO21
A. Prasanna
IL10
Francesco
IL25
Francesca
PO39
Paola
PO25
Jens
PL2
Gita
PO9
Bruno
IL14
Vincenzo
IL26
Riccardo
IL15
Fernando
PO32-PO33-PO34
Martino
PO11
Luca
PO23
Vincenzo
IL13
Matteo
PO22
Anna
IL21
Silvia
PO17
Pierluigi
PL6
Elisa
PO7
MAITY
MARCHELLI
MARTINI
MATTAREI
MAZZELLA
MAZZEO
MAZZOTTI
MBA
MILANI
MISSIO
MODUGNO
MOLINARI
MORETTO
NEGOM KOUODOM
NEPPALLI
NOVELLINO
PARISIO
PEGGION
PROCOPIO
RAFANELLI
RANCAN
ROMANO
RONCONI
ROSATO
ROSSI
SALOMONE
SALVADORI
SANTORO
SCHIORLIN
SELVESTREL
SGAMELLOTTI
SILVAGNI
SILVESTRIN
SINDONA
SPADONI
STIVANELLO
TADDIA
VERSINI
VOLPE
Von BOHLEN
WALTER
ZECCA
113
Prasenjit
Rosangela
Elena
Andrea
Mauro
Rocco
Fabio
Miriam
Roberto
Andrea
Gloria
Henriette
Alessandro
Morelle
Ramesh
Ettore
Giulia
Cristina
Antonio
Piero
Marzio
Francesco
Luca
Francesca
Emiliano
Antonio
Enrico
Stefano
Milko
Francesco
Antonio
Adriano
Simone
Giovanni
Luca
Mariano
Marco
Giuseppe
Giulio
Alex
Philippe
Marco
PO28
PL3
IL17
PO2
IL27
IL34
PO42
PO24
PO19-PO20
IL7
PO37
PO3
PO15
PO40
PO14
PL1
PO13
PO12
IL18
PL5
IL19
PO27
PO1
IL28
PO31
IL29
PO29
IL30
PO36
PO8
PL11
PO38
PO41
IL16
IL5
IL6
IL37
IL12
IL6
PL8
PL10
PO35
LIST OF PARTICIPANTS
114
BARTOLOZZI Maria Grazia
Dipartimento di Chimica Organica "U. Schiff"
Università di Firenze
Via della Lastruccia 13
50019 Sesto Fiorentino (FI) Italia
E-mail: mariagraziabart@hotmail.com
ALLEVI Pietro
Dipartimento di Chimia, Biochimica e
Biotecnologie per la Medicina
Università di Milano
Via Saldini, 50
20133 Milano – Italia
E-mail: pietro.allevi@unimi.it
BASATO Marino
Università di Padova
Via Marzolo, 1
35131 Padova Italia
E-mail: marino.basato@unipd.it
ANASTASIA Luigi
IRCCS Policlinico San Donato
Via Morandi, 30
20097 San Donato Milanese (MI) – Italia
E-mail: luigi.anastasia@unimi.it
ANASTASIA Mario
Direttore, Dipartimento di Chimia, Biochimica e
Biotecnologie per la Medicina
Via Saldini, 50
20133 Milano – Italia
E-mail: mario.anastasia@unimi.it
BERARDI Serena
Via Marzolo, 1
35131 Padova Italia
E-mail: serena.berardi@unipd.it
BERTINI Ivano
Dipartimento di Chimica CERM
Universita' di Firenze
Via Sacconi, 6
E-mail: bertini@cerm.unifi.it
BAGNO Alessandro
Universita' di Padova
Via Marzolo, 1
35131 Padova Italia
E-mail: alessandro.bagno@unipd.it
BERTONCELLO Renzo
Via Marzolo, 1
35131 Padova Italia
E-mail: renzo.bertoncello@unipd.it
BAU' Luca
Via Marzolo, 1
35131 Padova Italia
E-mail: luca.bau@unipd.it
BERZIOLI Michela
Dipartimento di Chimica G.I.A.F.
Università di Parma
Viale Usberti 17A
43100 Parma Italia
E-mail: michela.berzioli@libero.it
BALZANI Vincenzo
Dipartimento di Chimica
Universita' di Bologna "G. Ciamician"
Via Selmi, 2
40126 Bologna Italia
E-mail: vincenzo.balzani@unibo.it
BIANCO Armandodoriano
Università di Roma “La Sapienza”
P.le Aldo Moro, 5
00185 Roma – Italia
E-mail: armandodoriano.bianco@uniroma1.it
BARTALI Laura
E-mail: laura.bartali@virgilio.it
BARTOLI Giuseppe
Facoltà di Chimica Industriale
Università di Bologna
Viale Risorgimento, 4
E-mail: bartoli@ms.fci.unibo.it
BINI Davide
Dipartimento dfi Biotecnologia e Bioscienze
Università di Milano -Bicocca
P.zza della Scienza 2
20126 Milano Italia
E-mail: davide.bini@unimib.it
BARNI Ermanno
Dip. Di Chim. Generale e Chi. Org.
Universita' di Torino
C.so Massimo d'Azeglio, 48
10125 Torino Italia
E-mail: ermanno.barni@unito.it
BINDOLI Cristiano
Via Marzolo, 1
35131 Padova Italia
E-mail: cristiano.bindoli@unipd.it
115
BISCONTIN Guido
Dipartimento di Scienze Ambientali
Universita' "Ca Foscari" Venezia
Santa Marta, Dorsoduro, 2137
21137 Venezia Italia
E-mail: bisco@unive.it
CAMPOSTRINI Paolo
Direttore Consorzio CORILA
P.zza S. Marco, 2847
E-mail: campostrini@corila.it
CAPODAGLIO Gabriele
Dipartimento di Scienze Ambientali
Universita' di Venezia "Ca Foscari"
E-mail: capoda@unive.it
BONCHIO Marcella
Istituto Tecnologia delle Membrane Sede Operativa di
Padova
C.N.R.
Via Marzolo, 1
35131 Padova Italia
E-mail: marcella.bonchio@unipd.it
CAPRIATI Vito
Dip. Farmaco-Chimico
Universita' di Bari
Via E. Orabona, 4
70125 Bari Italia
E-mail: capriati@farmchim.uniba.it
BONOMI Renato
Via Marzolo, 1
35131 Padova Italia
E-mail: renato.bonomi@unipd.it
CAPUTO Romualdo
Dip. Chimica Organica e Biochimica
Universita' di Napoli Federico II
Via Cintia, 4
82126 Napoli Italia
E-mail: rocaputo@unina.it
BORTOLOMEI Nicola
Via Marzolo, 1
35131 Padova Italia
E-mail: nicola.bortolomei@unipd.it
CARASSO MOZZI Fausta
Via Montegrappa, 15
31021 Mogiano (TV) – Italia
E-mail: carassof@unive.it
BORTOLINI Olga
Università della Calabria
Via Bucci, 12C
87036 Rende (CS) Italia
E-mail: o.bortolini@unica.it
CARDELLICCHIO Nicola
Istituto per l'Ambiente Marino Costiero - IAMC
Consiglio Nazionale delle Ricerche
Via Roma, 3
74100 Taranto Italia
E-mail: nicola.cardellicchio@iamc.cnr.it
BOVO Laura
Via Marzolo, 1
35131 Padova Italia
E-mail: laura.bovo@unipd.it
CAROFIGLIO Tommaso
Via Marzolo, 1
35131 Padova Italia
E-mail: tommaso.carofiglio@unipd.it
BOZIO Renato
Via Marzolo, 1
35131 Padova Italia
E-mail: renato.bozio@unipd.it
CARRARA Paolo
Via Libero Benedetti, 5
35100 Padova, Italia
E-mail: parachim@virgilio.it
BRUSTOLON Marina
Via Marzolo, 1
35131 Padova Italia
E-mail: marinarosa.brustolon@unipd.it
CARRARO Mauro
Via Marzolo, 1
35131 Padova Italia
E-mail: mauro.carraro@unipd.it
CAMPANELLA Luigi
Universita' di Roma "La Sapienza"
P.le Aldo Moro, 5
00185 Roma Iralia
CASACCIA Luciano
116
COLLI Laura
E-mail: laura.colli@unifi.it
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: antonella.casoli@unipr.it
CASTELLIN Andrea
F.I.S. Fabbrica Italiana Sintetici,
Viale Milano, 26
36075 Alte di Montecchio Maggiore (VI) Italia
E-mail: andrea.castellin@fisvi.com
CONTE Valeria
Dip. Di Scienze e Tecnologie Chimiche
Universita' di Roma "Tor Vergata"
Via della Ricerca Scientifica
00133 Roma Italia
E-mail: valeria.conte@uniroma2.it
CESCON Paolo
Presidente Corila, Dip. Scienze Ambientali
CORAMI Fabiana
IDPA-CNR Venezia
E-mail: f_corami@unive.it
CHIACCHIO Ugo
Dip. Di Scienze Chimiche
Universita' di Catania
V.le Andrea Doria,6
95125 Catania Italia
E-mail: uchiacchio@unict.it
CORSARO Antonio
Dip. Di Scienze Chimiche
V.le Andrea Doria,6
E-mail: acorsaro@unict.it
CHIANTORE Oscar
Dip. di Chimica Inorganica, fisica e dei materiali
Via Pietro Giuria, 7
10125 Torino Italia
E-mail: oscar.chiantore@unito.it
COSTANTINO Umberto
Universita' di Perugia
Via Elce di Sotto, 8
06123 Perugia Italia
E-mail: ucost@unipg.it
CHILIN Adriana
Dip. Scienze Farmaceutiche-Presidente S.C.I. Veneto
Via Marzolo, 5
35131 Padova Italia
E-mail: adriana.chilin@unipd.it
COTARCA Livius
Zambon Advanced Fine Chemicals
Via Dovaro, 2
36045 Lonigo (VI) Italia
E-mail: livius.cotarca@zambongroup.com
CREMONESI Paolo
CESMAR7-Centro per lo Studio di Materiali per il Restauro
Via Lombardia, 41/43
35020 Padova Italia
E-mail: paolocremonesi57@gmail.com
CIMINALE Francesco
Universita' degli Studi di Bari
Via Orabona, 4
70126 Bari Italia
E-mail: ciminale@chimica.uniba.it
CIOFFI Marcella
C.co Vittorio Emanuele, 347
82100 Napoli - Italia
CRISAFULLI Fabrizio
EDISES s.r.l.
Via Nuova San Rocco, 62/A
Parco Soleado (NA)
E-mail: fabrizio.crisafulli@edises.it
COLOMBO Francesca
Via Marzolo, 1
35131 Padova Italia
E-mail: francesca.colombo@unipd.it
DAL MOLIN Marta
Via Marzolo, 1
35131 Padova Italia
E-mail: marta.dalmolin@unipd.it
117
FABRIZI Olga
Via Badile 23
37131 Verona – Italia
E-mail: olga.fabrizi@tin.it
DE LUCCHI Ottorino
E-mail: delucchi@unive.it
FORMAGGIO Fernando
Via Marzolo, 1
35131 Padova Italia
DE NARDI Marco
Via Marzolo, 1
35131 Padova Italia
E-mail: marco.denardi@unipd.it
FEDRIZZI Bruno
Via Marzolo, 1
35131 Padova Italia
E-mail: bruno.fedrizzi@unipd.it
DE NISCO Mauro
Dip. Chimica Organica e Biochimica
Via Cintia, 4
82126 Napoli Italia
de SILVA A. Prasanna
School of Chemistry and Chemical Engineering
Queen's University
Belfast Irlanda
E-mail: a.desilva@qub.ac.uk
FINO Vincenzo
Universita' di Bari
Via E. Orabona, 4
70125 Bari Italia
E-mail: vincenzofino@gmail.com
DESIMONI Giovanni
Dipartimento di Chimica Organica
Universita' di Pavia
V.le Taramelli, 10
27100 Pavia Italia
E-mail: desimoni@unipv.it
FLAMINI Riccardo
Agricoltural Research Council, Viticulture
Research Center, CRA-VIT
Viale XXVII Aprile, 25
31015 Conegliano (TV) Italia
E-mail: riccardo.flamini@entecra.it
De VINCENTIIS Francesco
Dipartimento di Chimica Organica "A. Mangini"
Facoltà di Chimica Industriale, Università di Bologna
V.le Risorgimento, 4, Bologna Italia
E-mail: fra.devin@gmail.com
FLORIO Saverio
Dip. Farmaco-Chimico
Universita' di Bari
Via E. Orabona, 4
70125 Bari Italia
E-mail: florio@farmchim.uniba.it
DI SARRA Francesca
Via Marzolo, 1
35131 Padova Italia
GAITA Elisabetta
Scuola Secondaria Superiore
Via Salvo d'Acquisto, 6, 1
15100 Alessandria Italia
E-mail: gaita@libero.it
DONNOLA Paola
Via Marzolo, 1
35131 Padova Italia
E-mail: paola.donnola@unipd.it
GALVAGNI Marco
F.I.S. Fabbrica Italiana Sintetici,
Viale Milano, 26
36075 Alte di Montecchio Maggiore (VI) Italia
E-mail: marco.galvagni@fisvi.com
DUUS Jens
Carlsberg Laboratory, Gremle Calsberg
Vej 10
2500 Valby Denmark
E-mail: jd@crc.dk
GARDAN Martino
Via Marzolo, 1
35131 Padova Italia
E-mail: martino.gardan@unipd.it
DVORAKOVA Gita
Via Marzolo, 1
35131 Padova Italia
E-mail: gita.dvorakova@unipd.it
GASPARINI Giulio
Via Marzolo, 1
35131 Padova Italia
E-mail: giulio.gasparini@unipd.it
118
LLANES-PALLÀS Anna
Dipartimento di Scienze Farmaceutiche and INSTM UdR
Universita' di Trieste
34127 Trieste Italia
E-mail: allanes@units.it
GASPARRINI Francesco
Dip. Chimica e Tecnologie del Farmaco
Universita' di Roma
P.le Aldo Moro, 5
00185 Roma Italia
E-mail: francesco.gasparrini@uniroma.it
LOVAT Silvia
Via Marzolo, 1
35131 Padova Italia
E-mail: silvia.lovat@unipd.it
GAZZOLA Luca
Via Marzolo, 1
35131 Padova Italia
E-mail: luca.gazzola@unipd.it
LUBIAN Elisa
Via Marzolo, 1
35131 Padova Italia
E-mail: elisa.lubian@unipd.it
GENNARO Armando
Via Marzolo, 1
35131 Padova Italia
E-mail: armando.gennaro@unipd.it
LUISI Pierluigi
Dipartimento di Biologia
Universita' di Roma III
L.go S. Leonardo Murialdo, 1
00146 Roma Italia
E-mail: luisi@uniroma3.it
GERBI Vincenzo
DIVAPRA
Via Leonardo da Vinci, 44
10095 Grugliasco (TO) Italia
E-mail: vincenzo.gerbi@unito.it
GIBERTINI Paolo
Via Bellini, 29/31
20026 Novate (MI) – Italia
E-mail: info@gibertini.com
MAGGINI Michele
Via Marzolo, 1
35131 Padova Italia
E-mail: michele.maggini@unipd.it
GOBBO Marina
Via Marzolo, 1
35131 Padova Italia
E-mail: marina.gobbo@unipd.it
MAGNO Franco
Via Marzolo, 1
35131 Padova Italia
E-mail: franco.magno@unipd.it
GORI Silvio
Via Durante, 36
20133 Milano - Italia
MAITY Prasenjit
Via Marzolo, 1
35131 Padova Italia
E-mail: prasenjit.maity@unipd.it
GRAZIANI Matteo
Via Marzolo, 1
35131 Padova Italia
E-mail: matteo.graziani@unipd.it
MAJORANA Stefano
Dipartimento di Chimica Organica e Industriale
Via Venezian, 21, 20133 Milano
E-mail: stefano.majorana@unimi.it
LICANDRO Emanuela
Via Venezian, 21, 20133 Milano
E-mail: emanuela.licandro@unimi.it
MANCIN Fabrizio
Via Marzolo, 1
35131 Padova Italia
E-mail: fabrizio.mancin@unipd.it
LICINI Giulia
Via Marzolo, 1
35131 Padova Italia
E-mail: giulia.licini@unipd.it
119
MARCHELLI Rosangela
V.le G.P. Usberti, 17A
43100 Parma Italia
MENNA Enzo
Via Marzolo, 1
35131 Padova Italia
E-mail: enzo.menna@unipd.it
MARIGO Antonio
Via Marzolo, 1
35131 Padova Italia
E-mail: antonio.marigo@unipd.it
MILANI Roberto
Dipartimento di Processi Chimici
Via Marzolo, 9
35131 Padova Italia
MARTINI Elena
MISSIO Andrea
Miteni S.p.A.
Loc. Colombara, 91
36070 Trissino (VI) Italia
E-mail: andrea.missio@miteni.com
MAROTTA Ester
Via Marzolo, 1
35131 Padova Italia
E-mail: ester.marotta@unipd.it
MODELLI Manuela
Via Faenza, 15 - 40139 Bologna Italia
E-mail: modman@tiscalinet.it
MATTAREI Andrea
Via Marzolo, 1
35131 Padova Italia
E-mail: andrea.mattarei@unipd.it
MODUGNO Gloria
Via Marzolo, 1
35131 Padova Italia
E-mail: gloria.modugno@unipd.it
MAZZELLA Mauro
Via Cintia, 4
80126 Napoli Italia
E-mail: mauromazzella@hotmail.com
MOLINARI Henriette
Dipartimento di Biotecnologie
Università di Verona
Strada le Grazie, 15
37134 Verona Italia
E-mail: henriette.molinari@univr.it
MAZZEO Pietro
Universita' dell'Aquila
Via Vetoio,
67010 Coppito AQ Italia
E-mail: pietro.mazzeo@univaq.it
MORETTO Alessandro
Via Marzolo, 1
35131 Padova Italia
E-mail: alessandro.moretto.1@unipd.it
MAZZEO Rocco
Dipartimento di Chimica "Giacomo Ciamician"
Via F. Selmi, 2
E-mail: rocco.mazzeo@unibo.it
MUSUMARRA Giuseppe
V.le Andrea Doria,6
E-mail: gmusumarra@unict.it
MAZZOTTI Fabio
Via P. Pucci Cubo 12B
87036 Arcavacata di Rende (CS)
NEGOM KOUODOM Morelle
Via Marzolo, 1
35131 Padova Italia
E-mail: morelle.negomkouodom@unipd.it
MBA Miriam
Via Marzolo, 1
35131 Padova Italia
E-mail: miriam.mba@unipd.it
NEPPALLI Ramesh
Via Marzolo, 1
35131 Padova Italia
E-mail: ramesh.neppalli@unipd.it
120
NOTO Renato
Dip. Chimica Organica
Universita' di Palermo
V.le delle Scienze, Parco d'Orleans, 11
90128 Palermo Italia
E-mail: rnoto@unipa.it
PROCOPIO Antonio
Dip. Scienze Farmacobiologiche
Università "Magna Grecia"
Complesso Ninì Barbieri
88021 Roccelleta di Borgia (CZ) Italia
E-mail: procopio@unicz.it
NOVELLINO Ettore
Dip. di Chimica Farmaceutica e Tossicologia
Università di Napoli
Via D. Montesacro, 49
80131 Napoli Italia
E-mail: ettore.novellino@unina.it
RAFANELLI Piero
Dipartimento di Astronomia
Vicolo Osservatorio
35100 Padova Italia
PARADISI Cristina
Via Marzolo, 1
35131 Padova Italia
E-mail: cristina.paradisi@unipd.it
RANCAN Marzio
Via Marzolo, 1
35131 Padova Italia
E-mail: marzio.rancan@unipd.it
PARISIO Giulia
Via Marzolo, 1
35131 Padova Italia
E-mail: giulia.parisio@unipd.it
RICCI Alfredo
Facoltà di Chimica Industriale
Viale Risorgimento, 4
E-mail: ricci@ms.fci.unibo.it
PAVAN M. Vittoria
Via D. Chiesa, 8
35100 Padova – Italia
E-mail:
ROMANO Francesco
Via Marzolo, 1
35131 Padova Italia
E-mail: francesco.romano@unipd.it
PEGGION Cristina
Via Marzolo, 1
35131 Padova Italia
E-mail: cristina.peggion@unipd.it
RONCONI Luca
Via Marzolo, 1
35131 Padova Italia
E-mail: luca.ronconi@unipd.it
PELIZZI Giancarlo
Dip. Di Chimica Generale
V.le G.P. Usberti
43100 Parma Italia
E-mail: gpelizzi@unipr.it
ROSATO Francesca
Dipartimento di Scienze e Tecnologie Biologiche ed
Ambientali
Università del Salento
Via Prov-le Lecce-Monteroni,
73100 Lecce Italia
E-mail: francesca.rosato@libero.it
POCAR Donato
Universita' di Milano
Via Venezian, 21
20133 Milano Italia
E-mail: donato.pocar@unimi.it
ROSSI Emiliano
Via Marzolo, 1
35131 Padova Italia
E-mail: emiliano.rossi@unipd.it
PRATO Maurizio
Dipartimento di Scienze Farmaceutiche
Università degli Studi di Trieste
Italia
E-mail: prato@units.it
SAIELLI Giacomo
Istituto Tecnologia delle Membrane Sede Operativa di
Padova
C.N.R.
Via Marzolo, 1
35131 Padova Italia
E-mail: giacomo.saielli@unipd.it
PRINS Leonard
Via Marzolo, 1
35131 Padova Italia
E-mail: leonard.prins@unipd.it
121
SEMINO Nadia
Istituto Istruzione Superiore "Marconi"
Viale Einaudi, 6
15057 Tortona Italia
E-mail: clnairsofr@alice.it
SALOMONE Antonio
Dipartimento Farmaco-Chimico
Universita' di Bari
Via E. Orabona, 4
70125 Bari Italia
E-mail: antoniosalomone@libero.it
SGAMELLOTTI Antonio
Via Elce di Sotto, 8
06123 Perugia Italia
E-mail: sgam@thch.unipg.it
SALVADORI Enrico
Via Marzolo, 1
35131 Padova Italia
E-mail: enrico.salvadori@unipd.it
SILVAGNI Adriano
Via Marzolo, 1 - 35131 Padova Italia
E-mail: adriano.silvagni@unipd.it
SANTORO Stefano
Dipartimento di Chimica e Tecnologia del Farmaco-Chim.
Org.
Via del Liceo, 1
06123 Perugia Itaalia
E-mail: stefanos80@gmail.com
SILVESTRINI Simone
Via Marzolo, 1
35131 Padova Italia
E-mail: simone.silvestrini@unipd.it
SARTOREL Andrea
Via Marzolo, 1
35131 Padova Italia
E-mail: andrea.sartorel@unipd.it
SINDONA Giovanni
Via P. Pucci, Cubo 12C,
87036 Arcavacata di Rende (CS) Italia
E-mail: sindona@unical.it
SCAPINELLO Marco
Via Marzolo, 1
35131 Padova Italia
E-mail: marco.scapinello@unipd.it
SPADA Gian Piero
Alma Master Studiorum, Dipartimento Di Chimica Organica
Università di Bologna"A. Mangini"
Via S. Giacomo, 11
E-mail: gianpiero.spada@unibo.it
SCHIORLIN Milko
Via Marzolo, 1
35131 Padova Italia
E-mail: milko.schiorlin@unipd.it
SPADONI Luca
Reckitt Benckiser Italia S.p.A. R&D Centre
P.zza S. Nicolò 12/3
30034 Mira (VE) Italia
E-mail: luca.spadoni@reckittbenckiser.com
SCORRANO Gianfranco
Via Marzolo, 1
35131 Padova Italia
E-mail: gianfranco.scorrano@unipd.it
STERCHELE Stefano
Via Marzolo, 1
35131 Padova Italia
E-mail: stefano.sterchele@unipd.it
SCRIMIN Paolo
Via Marzolo, 1
35131 Padova Italia
E-mail: paolo.scrimin@unipd.it
STIVANELLO Mariano
Lundbeck Pharmaceuticals Italy S.p.A.
Via Quarta Strada, 2
35129 Padova Italia
E-mail: msti@lundbeck.com
SELVESTREL Francesco
Via Marzolo, 1
35131 Padova Italia
E-mail: francesco.selvestrel@unipd.it
TADDIA Marco
Dipartimento di Chimica "Giacomo Ciamician"
Universita' di Bologna
Via F. Selmi, 2
E-mail: marco.taddia@unibo.it
122
TONDELLO Eugenio
Via Marzolo, 1
35131 Padova Italia
E-mail: eugenio.tondello@unipd.it
ZECCA Marco
Via Marzolo, 1
35131 Padova Italia
E-mail: marco.zecca@unipd.it
TONELLATO Umberto
Via Marzolo, 1
35131 Padova Italia
E-mail: umberto.tonellato@unipd.it
ZONTA Cristiano
Via Marzolo, 1
35131 Padova Italia
E-mail: cristiano.zonta@unipd.it
TROISI Luigino
Dip. Disteba
Universita' di Lecce
Via Monteroni,
73055 Lecce Italia
E-mail: luigino.troisi@unisalento.it
VALITUTTI Giuseppe
Via Macelli, 24
60027 Osimo (AN)
E-mail: gvalitutti@virgilio.it
VERSINI Giuseppe
Consulente, Unione Italiana Vini
Verona Italia
E-mail: versini@yahoo.it
VISCARDI Guido
Dip. Di Chim. Generale e Chim. Org.
C.so Massimo d'Azeglio, 48
10125 Torino Italia
E-mail: guido.viscardi@unito.it
VOLPE Giulio
Lundbeck Pharmaceuticals Italy S.p.A.
Via Quarta Strada, 2
35129 Padova Italia
E-mail: givo@lundbeck.com
Von BOHLEN Alex
ISAS Institut Analytical Sciences
Bunsen-Kirchoff-Str., 11
44139 Dortmund Germania
E-mail: vonbohlen@isas.de
WALTER Philippe
Centre de Recherche et de Restauration del Musèes de
France
Quai Francais Mitterand, 14
75001 Paris France
E-mail: philippe.walter@culture.gouv.fr
ZAUPA Giovanni
Via Marzolo, 1
35131 Padova Italia
E-mail: giovanni.zaupa@unipd.it
123

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