Hotel Ambasciatori - Rimini (Italy)
October 27th-29th, 2015
Edited by Federico Bella and Domenico Spinelli for
Società Chimica Italiana
Proceedings of the
XV Sigma-Aldrich Young Chemists Symposium
(SAYCS 2015)
Edited by: Federico Bella and Domenico Spinelli
Copyright © 2015 Società Chimica Italiana, Viale Liegi 48C, 00198-Roma
ISBN: 978-88-86208-94-9
2
Organizing Committee
Academic
Sigma-Aldrich
Federico Bella
Piergiorgio Franceschelli
Domenico Spinelli
Mariarosaria Piscopiello
Scientific Committee
Federico Bella
Julien Bloino
Sandro Cosconati
Alessandro D’Urso
Oscar Francesconi
Paolo Oliveri
Michele Pavone
Luca Rocchigiani
Davide Rosestolato
Giorgia Sciutto
Domenico Spinelli
Student Helpers
Silvia Cino
Gabriele Micheletti
Nicola Zanna
3
Welcome message
Dear participants,
welcome to the XV Sigma-Aldrich Young Chemists Symposium.
SAYCS is an annual scientific event organized by the Italian Chemical
Society (SCI) with the financial support of Sigma-Aldrich. From the
second consecutive year, the Symposium is an international event.
This symposium is fully devoted to young researchers, such as Ph.D.
students, post-doc fellows and young researchers in enterprises. All the
disciplines of Chemistry are covered: analytical, physical, industrial,
organic, inorganic, theoretical, pharmaceutical, biological, macromolecular
and electrochemistry. This year, a special emphasis will be given to new
trends in chemistry: how chemistry is facing emerging sectors in energy,
medicine and nanotechnologies.
This year we have a significant number of 175 participants; we thank
you for the great trust shown towards the Young Group of the Italian
Chemical Society and Sigma-Aldrich.
Enjoy the conference!
HOW TO CITE YOUR WORK
For the first year, SAYCS scientific contributions
are collected in an international volume with ISBN
code.
You can cite your work in this way:
N. Surname, N. Surname, … and N. Surname, Title of
your work, in “Proceeding of the XV Sigma-Aldrich
Young Chemists Symposium (SAYCS 2015), Ed. F.
Bella & D. Spinelli, 2015, page number”.
4
Index
Program
6
Invited talks
11
Oral presentations
17
Flash communications
65
Posters
103
List of participants
179
About SCI
183
5
Program - Tuesday, 27th October
11.00
Registration desk opens @ Hotel Ambasciatori
14.30-15.00
Opening Ceremony @ Conference Hall
Chair: Michele Pavone, Università di Napoli Federico II
15.00-15.40
INV-1 Luisa De Cola, Université de Strasbourg
15.40-15.50
OR-1 Cristina Marucci, Università degli Studi di Milano
15.50-16.00
OR-2 Francesco Merlino, Università di Napoli Federico II
16.00-16.10
OR-3 Valentina Pifferi, Università degli Studi di Milano
16.10-16.20
OR-4 Antonio Valentoni, Università degli Studi di Sassari
16.20-16.30
OR-5 Laura Rotolo, Università degli Studi di Torino
16.30-16.40
OR-6 Marcello La Rosa, Università di Bologna
16.40-16.50
OR-7 Marta Olszówka, Università di Pisa
16.50-17.00
OR-8 Marta Cippitelli, Università degli Studi di Macerata
17.00-17.30
Coffee Break
Chair: Paolo Oliveri, Università degli Studi Di Genova
17.30-17.40
OR-9 Ajiroghene Thomas, Università di Camerino
17.40-17.50
OR-10 Gaetano Fiorillo, Naxospharma srl
17.50-18.00
OR-11 Michele Di Foggia, Università di Bologna
18.00-18.10
OR-12 Francesca Colò, Politecnico di Torino
Chair: Alessandro D’Urso, Università degli Studi di Catania
18.10-19.30
Flash communications: from FL-1 to FL-16
19.30-20.15
Free time. Those who will present a poster in the evening
must hang the poster in Poster Hall (Hotel Ambasciatori)
20.15-21.30
Sigma-Aldrich Dinner @ Hotel Sporting
Dress code: Elegant
21.30-22.30
Poster Session @ Hotel Ambasciatori (Poster Hall)
from POS-1 to POS-40
22.30-
&
from FL-1 to FL-16
Enjoy Rimini! (walking tour looking for something to drink)
6
Wednesday, 28th October - morning
7.30-9.00
Breakfast in your Hotel, then move to Conference Hall
Chair: Sandro Cosconati, Seconda Università degli Studi di Napoli
9.00-9.40
INV-2 Chiara Cappelli, Scuola Normale Superiore
9.40-9.50
OR-13 Rosalba Randazzo, Università degli Studi di Catania
9.50-10.00
OR-14 Emanuela Martino, Università degli Studi di Pavia
10.00-10.10
OR-15 Jorge T. Rodríguez, Università degli Studi di Firenze
10.10-10.20
OR-16 Chiara Gangemi, Università degli Studi di Catania
10.20-10.30
OR-17 Davide Corinti, Sapienza - Università di Roma
10.30-10.40
OR-18 Annamaria Marra, Università degli Studi di Pavia
10.40-10.50
OR-19 Luca A. Andronico, Università di Bologna
10.50-11.00
OR-20 Michela Corricelli, Università degli Studi di Bari
Coffee Break
11.00-11.25
All the posters presented in the previous day must be
removed from Poster Hall
Chair: Domenico Spinelli, Università di Bologna
11.25-12.25
INV-3 Jean-Marie Lehn, Université de Strasbourg
12.25-12.35
OR-21 Gloria Mazzone, Università della Calabria
12.35-12.45
OR-22 Luca Porcarelli, Politecnico di Torino
12.45-12.55
OR-23 Matteo Compagnoni, Università degli Studi di Milano
12.55-13.05
OR-24 Silvia Gaspa, Università degli Studi di Sassari
13.05-13.15
OR-25 Antonio Rodríguez, Università degli Studi di Napoli
13.15-13.25
OR-26 Paolo Piazzetta, Università della Calabria
13.25-13.35
OR-27 Deborah Sementa, Università degli Studi di Napoli
Lunch @ Hotel Sporting
13.35-14.30
Those who will present a poster in the afternoon must
hang the poster in Poster Hall
7
Wednesday, 28th October – afternoon and evening
Chair: Oscar Francesconi, Università degli Studi di Firenze
14.30-16.10
Flash communications: from FL-17 to FL-36
16.10-16.20
OR-28 Irene Ruggeri, Università di Bologna
16.20-16.30
OR-29 Andrea Idili, Università degli Studi di Roma Tor Vergata
Poster Session with Coffee Break @ Poster Hall
16.30-17.45
from POS-41 to POS-75&
from FL-17 to FL-36
Chair: Davide Rosestolato, SIA Industria Accumulatori
17.45-17.55
OR-30 Elena Chugunova, Kazan Scientific Center
17.55-18.05
OR-31 Fabrizio Puleo, Consiglio Nazionale delle Ricerche
18.05-18.15
OR-32 Gaia Fumagalli, Università degli Studi di Milano
18.15-18.25
OR-33 Fabian Jeschull, Uppsala University
18.25-18.35
OR-34 Michele Protti, Università di Bologna
18.35-18.45
OR-35 Omar H. Ismail, Sapienza - Università di Roma
18.45-19.45
Assemblea Ordinaria dei Soci del Gruppo Giovani (ITA)
19.45-20.45
Free time. Posters must be removed from Poster Hall
Social Dinner @ Hotel Sporting
20.45-22.00
22.30-01.30
01.30-…
Dress code: Smart casual
SCI-Night @ DiscoBar Hotel Sporting
Dress code: Disco party
Enjoy Rimini!
8
Thursday, 29th October
7.30-9.00
Breakfast in your Hotel
9.00-9.30
Check-out from Hotel rooms, leave luggage @ Reception
Chair: Federico Bella, Politecnico di Torino
9.30-10.10
INV-4 Anders Hagfeldt, École polytechnique fédérale de Lausanne
10.10-10.20
OR-36 Bianca Cecconi, Università degli Studi di Milano-Bicocca
10.20-10.30
OR-37 Andrea Lamberti, Politecnico di Torino
10.30-10.40
OR-38 Daniele Franchi, Università degli Studi di Firenze
10.40-10.50
OR-39 Simone Galliano, Università degli Studi di Torino
10.50-11.00
Group Picture
11.00-11.20
Coffee Break
Chair: Laura Mercolini, Università di Bologna
11.20-11.30
OR-40 Giuseppina Corrente, Università del Salento
11.30-11.40
OR-41 Annalisa Vigorito, Università di Bologna
11.40-11.50
OR-42 Carmen Cavallo, Sapienza - Università di Roma
11.50-12.00
OR-43 Nicola Zanna, Università di Bologna
12.00-12.10
OR-44 Serena Arnaboldi, Università degli Studi di Milano
12.10-12.20
OR-45 Ali M. Yousif, Università di Napoli Federico II
12.20-12.30
OR-46 Federica Sabuzi, Università di Roma Tor Vergata
Sarah Newton, EYCN-EuCheMS
12.30-12.45
12.45-13.00
13.00-14.00
Poster Prizes
Oral and Flash Prizes
Closing Ceremony
Lunch @ Hotel Sporting
9
10
Invited Talks
INV-1
Luisa DE COLA
INV-2
Chiara CAPPELLI
INV-3
Jean-Marie LEHN
INV-4
Anders HAGFELDT
11
INV-1
Light to see, understand and control chemical processes
Luisa De Cola
Institut de Science et d'Ingénierie Supramoléculaires, Université de Strasbourg, 8 allée
Gaspard Monge, 67083-Strasbourg Cedex, France
E-mail: [email protected]
Self-assembly is one of the most important processes in nature and for technological
developments. Visualization and control of self-assembly processes are therefore very
desirable and the dream of many scientist. A way to “see” the supramolecular organization is
therefore to take advantage of emission properties of molecules able to change their
luminescence color upon the formation of assemblies. These aggregates can form in solution
and their kinetics and we have succeeded to fully understand and control multiple pathways
because of the different emission properties, used as fingerprint, of each of the assembled
species. The full process resembles a biological infection progression and yields micrometerslong emissive supramolecular architectures. A delicate interplay of solvent-non solvent
compositions allowed to unravel all the evolving self-assembling process and to slow down
some of the kinetics in order to have full control of the process (see figure below). Size
control of the aggregates is achieved by growth under living supramolecular polymerization
condition. In addition we can photochemically convert, the uniform in size, species in
thermodynamically unstable species.
The assembly process can occur also inside living cells resulting in a new tool to use the
supramolecular structure as an imaging labels for cells and therefore to use the light for
biomedical applications. In this respect the combination of fluorescent labels and drugs can be
used to monitor the efficacy of drug and oligonucleotide delivery in cells but also in vivo. The
use of carriers and their destruction in vivo will be illustrated and light is used to follow the
degradation of the carriers and their release from the organs of the animals.
[1] M. Mauro, A. Aliprandi, D. Septiadi, N. S. Kehr and L. De Cola, Chem. Soc. Rev., 43 (2014) 41444166.
[2] M. Mauro, A. Aliprandi, C. Cebrián, D. Wang, C. Kübel and L. De Cola, Chem. Commun. 50
(2014) 7269-7272.
[3] A. Aliprandi, M. Mauro and L. De Cola, Nat. Chem., in press.
[4] F. Biedermann, L. De Cola et al., Nature, under review.
12
INV-2
Towards a reliable virtual modeling of molecular properties and
spectroscopies
Chiara Cappelli
Centre Européen de Calcul Atomique et Moléculaire @ Scuola Normale Superiore (CECAMIT-SNS), Piazza dei Cavalieri 7, 56126-Pisa, Italy
E-mail: [email protected]
Effective in silico simulations of response and spectroscopic properties of chiral molecular
systems in their natural environment is among the most significant tasks of contemporary
theoretical and computational chemistry in view of the increasing reliability of the results
coupled to the quite straightforward disentanglement of the role of different effects. However,
the production of calculated spectroscopic data directly comparable to their experimental
counterparts is particularly tricky in the case of solvated systems. In fact, the models should
reliably represent the experimental sample, i.e., the physical model should be as realistic as
possible, which in practice means that all the physical interactions in the sample and between
the sample and the probing field have to be taken into account in the model.
The simultaneous accounting of solvent effects and anharmonicity is among the most
difficult tasks, coupled with the modeling of strong interacting environments. I will give an
overview of the computational methods recently developed in this field.
This work was supported by the Italian MIUR (PRIN 2012 NB3KLK 002).
[1] B. Mennucci, C. Cappelli, R. Cammi and J. Tomasi Chirality 23 (2011) 717-729.
[2] F. Egidi, J. Bloino, C. Cappelli and V. Barone Chirality 25 (2013) 701-708.
[3] C. Cappelli, F. Lipparini, J. Bloino and V. Barone J. Chem. Phys. 135 (2011) 104505:1-15.
[4] C. Cappelli, S. Monti, G. Scalmani and V. Barone J. Chem. Theory Comput. 6 (2010) 1660-1669.
[5] F. Egidi, V. Barone, J. Bloino and C. Cappelli J. Chem. Theory Comput. 8 (2012) 585-597.
[6] C. Cappelli, J. Bloino, F. Lipparini and V. Barone J. Phys. Chem. Lett. 3 (2012) 1766-1773.
[7] F. Lipparini, C. Cappelli, N. De Mitri, G. Scalmani and V. Barone J. Chem. Theory Comput. 8
(2012) 4270-4278.
[8] F. Lipparini, F. Egidi, C. Cappelli and V. Barone J. Chem. Theory Comput. 9 (2013) 1880-1884.
[9] F. Egidi and C. Cappelli Elsevier Reference Module in Chemistry, Molecular Sciences and
Chemical Engineering, DOI:10.1016/B978-0-12-409547-2.10881-9.
13
INV-3
Perspectives in chemistry: from supramolecular chemistry towards
adaptive chemistry
Jean-Marie Lehn
Institut de Science et d'Ingénierie Supramoléculaires, Université de Strasbourg, 8 allée
Gaspard Monge, 67083-Strasbourg Cedex, France
E-mail: [email protected]
Supramolecular chemistry is actively exploring systems undergoing self-organization, i.e.
systems capable of spontaneously generating well-defined functional supramolecular
architectures by self-assembly from their components, on the basis of the molecular
information stored in the covalent framework of the components and read out at the
supramolecular level through specific non-covalent interactional algorithms, thus behaving as
programmed chemical systems.
Supramolecular chemistry is intrinsically a dynamic chemistry in view of the lability of the
interactions connecting the molecular components of a supramolecular entity and the resulting
ability of supramolecular species to exchange their components. The same holds for
molecular chemistry when the molecular entity contains covalent bonds that may form and
break reversibility, so as to allow a continuous change in constitution by reorganization and
exchange of building blocks. These features define a Constitutional Dynamic Chemistry
(CDC) covering both the molecular and supramolecular levels.
CDC introduces a paradigm shift with respect to constitutionally static chemistry. It takes
advantage of dynamic diversity to allow variation and selection and operates on dynamic
constitutional diversity in response to either internal or external factors to achieve adaptation.
CDC generates networks of dynamically interconverting constituents, constitutional
dynamic networks, presenting agonistic and antagonistic relationships between their
constituents, that may respond to perturbations by physical stimuli or to chemical effectors.
The implementation of these concepts points to the emergence of adaptive and evolutive
chemistry, towards systems of increasing complexity.
[1] J. M. Lehn, Supramolecular Chemistry: Concepts and Perspectives, VCH Weinheim, 1995.
[2] J. M. Lehn, Chem. Eur. J. 5 (1999) 2455-2463.
[3] J. M. Lehn, Chem. Eur. J. 6 (2000) 2097-2102.
[4] J. M. Lehn, PNAS 99 (2002) 4763-4768.
[5] J. M. Lehn, Chem. Soc. Rev. 36 (2007) 151-160.
[6] J. M. Lehn, Chapter 1 in Constitutional Dynamic Chemistry, Ed. M. Barboiu, Topics Curr. Chem.
322 (2012) 1-32.
[7] J. M. Lehn, Angew. Chem. Int. Ed. 52 (2013) 2836-2850.
[8] J. M. Lehn, Angew. Chem. Int. Ed. 54 (2015) 3276-3289.
14
INV-4
The versatility of mesoscopic solar cells
Anders Hagfeldt
Laboratory of Photomolecular Science, Swiss Federal Institute of Technology Lausanne
(EPFL), Chemin des Alambics, Station 3, 1015-Lausanne, Switzerland
E-mail: [email protected]
Since the seminal Nature paper by O’Regan and Grätzel in 1991 [1] the highest efficiencies
of dye-sensitized solar cells (DSC) have been achieved using the iodide/tri-iodide redox
system. A disadvantage of this mediator is the large internal losses caused by the fact that it is
a two-electron redox couple. In 2010 we made a breakthrough by using one-electron transfer
redox systems such as cobalt-complexes, in combination with a new generation of organic
dyes, which efficiently prevents recombination losses [2]. This discovery was quickly
embraced by Grätzel and co-workers, and the new world record for DSC is at present 13.0%
by using a Co-complex redox couple and a porphyrin [3]. Our focus now is to develop high
efficiency DSC utilizing different colors such as blue, green, yellow and red aiming for
aesthetically attractive applications in - for example - building integration.
Besides liquid DSC we develop solid-state DSC (ssDSC). In one configuration, we prepare
a conducting polymer by in situ photopolymerization of the monomers in a
photoelectrochemical cell. ssDSCs based on an organic dye, D35, gives together with PEDOT
or PEDOP as hole transporting material (HTM) efficiencies up to 7%. Recently [4], we
showed that copper phenanthroline complexes in the solid phase can act as an efficient HTM.
We prepared ssDSCs with the organic dye LEG4 and copper(I/II)-phenantroline as redox
system and achieved power conversion efficiencies of more than 8%, with open-circuit
potentials of more than 1.0 V.
The phenomenal breakthrough of the so called perovskite solar cells (PSC) originates from
the ideas of replacing the dye layer adsorbed on the mesoporous oxide surface with an
ultrathin inorganic perovskite layer and replacing the liquid electrolyte with a solid-state hole
conductor [5,6]. We will report on our latest work on optimizing the solar cell efficiency that
at present is above 20% in our laboratories. We have developed new hole conductor materials
that reach efficiencies similar to the conventional hole conductor spiro-OMeTAD but with the
advantage of being more easily synthesized.
[1] B. O’Regan and M. Grätzel, Nature 353 (1991) 737-740.
[2] S. M. Feldt, E. A. Gibson, E. Gabrielsson, L. Sun, G. Boschloo and A. Hagfeldt, J. Am. Chem. Soc.
132 (2010) 16714-16724.
[3] S. Mathew, A. Yella, P. Gao, R. Humphry-Baker, B. F. E. Curchod, N. Ashari-Astani, I.
Tavernelli, U. Rothlisberger, M. K. Nazeeruddin and M. Grätzel, Nat. Chem. 6 (2014) 242-247.
[4] M. Freitag, Q. Daniel, M. Pazoki, K. Sveinbjörnsson, J. Zhang, L. Sun, A. Hagfeldt and G.
Boschloo, Energy Environ. Sci. 8 (2015) 2634-2637.
[5] H. S. Kim, C. R. Lee, J. H. Im, K. B. Lee, T. Moehl, A. Marchioro, S. J. Moon, R. HumphryBaker, J. H. Yum, J. E. Moser, M. Grätzel and N. G. Park, Sci. Rep. 2 (2012) 591.
[6] M. M. Lee, J. Teuscher, T. Miyasaka, T. N. Murakami and H. J. Snaith, Science 338 (2012) 643647.
15
16
Oral Presentations
OR-1
Cristina MARUCCI
OR-24
Silvia GASPA
OR-2
Francesco MERLINO
OR-25
Antonio RODRIGUEZ
OR-3
Valentina PIFFERI
OR-26
Paolo PIAZZETTA
OR-4
Antonio VALENTONI
OR-27
Deborah SEMENTA
OR-5
Laura ROTOLO
OR-28
Irene RUGGERI
OR-6
Marcello LA ROSA
OR-29
Andrea IDILI
OR-7
Marta OLSZOWKA
OR-30
Elena CHUGUNOVA
OR-8
Marta CIPPITELLI
OR-31
Fabrizio PULEO
OR-9
Ajiroghene THOMAS
OR-32
Gaia FUMAGALLI
OR-10
Gaetano FIORILLO
OR-33
Fabian JESCHULL
OR-11
Michele DI FOGGIA
OR-34
Michele PROTTI
OR-12
Francesca COLO’
OR-35
Omar H. ISMAIL
OR-13
Rosalba RANDAZZO
OR-36
Bianca CECCONI
OR-14
Emanuela MARTINO
OR-37
Andrea LAMBERTI
OR-15
Jorge T. RODRIGUEZ
OR-38
Daniele FRANCHI
OR-16
Chiara M. A. GANGEMI
OR-39
Simone GALLIANO
OR-17
Davide CORINTI
OR-40
Giuseppina CORRENTE
OR-18
Annamaria MARRA
OR-41
Annalisa VIGORITO
OR-19
Luca A. ANDRONICO
OR-42
Carmen CAVALLO
OR-20
Michela CORRICELLI
OR-43
Nicola ZANNA
OR-21
Gloria MAZZONE
OR-44
Serena ARNABOLDI
OR-22
Luca PORCARELLI
OR-45
Ali M. YOUSIF
OR-23
Matteo COMPAGNONI
OR-46
Federica SABUZI
17
OR-1
Hybrid compounds as new tubulin binders: design and synthesis
Cristina Marucci and Daniele Passarella
Dipartimento di Chimica, Università degli Studi di Milano, Via C. Golgi 19, 20133-Milano,
Italy
E-mail: [email protected]
Microtubules are dynamic polymers which play a central role in a number of cellular process,
most particularly cell division, as they are the key constituents of the mitotic spindle [1]. They
are constituted of a heterodimeric protein named tubulin. It is composed of two polipeptide
called -tubulin and -tubulin, which through polymerization process assembly to form
microtubules. Thus, any molecule which exhibits some interaction with microtubules
dynamics will be able to influence the cell division process [2]. Most of these antimitotic
agents interact with -tubulin. In contrast, the number of products that bind to -tubulin is
very small. One of these compounds that bind -tubulin is the Pironetin 1.
We designed a library of compounds characterized by the presence of the 5,6-dihydro
pyran-2one ring and by exploiting the synthetic plan previosly studied for the preparation of
dumetorine [3].
Figure 1: Dumetorine-Pironetin hybrids.
[1] T. Fojo, The role of Microtubules in Cell Biology, Neurobiology and Oncology, Humana Press,
Totowa, New Jersey, 2008.
[2] J. G. Pla, M. Carda, J. Murga, E. Falomir, C. Trigili, S. Notararigo, F. J. Dìaz and I. Barasoain,
Eur. J. Med. Chem. 46 (2011) 1630-1637.
[3] a) E. Riva, A. Rencurosi, S. Gagliardini, D. Passarella and M Martinelli, Chem. Eur. J. 17 (2011)
6221-6226; b) D. Passarella, S. Riva, G. Grieco, F. Cavallo, B. Checa, F. Arioli, E. Riva, D. Comi and
B. Danieli, Tetrahedron: Asymmetry 20 (2009) 192-197.
18
OR-2
Tour across U-II(4-11) sequence by design and synthesis of new
analogues
Francesco Merlino,a Ali Munaim Yousif,a Stéphane Turcotte,b Salvatore Di
Maro,c Emma Mitidieri,a David Chatenet,d Ettore Novellino,a Paolo Grieco,a and
William D. Lubellb
a
Dipartimento di Farmacia, Università di Napoli Federico II, Via D. Montesano 49, 80131Napoli, Italy
b
Département de Chimie, Université de Montréal, C. P. 6128, succursale Centre-ville,
H3C3J7-Montréal, Canada
c
Dipartimento di Scienze e Tecnologie Ambientali, Biologiche e Farmaceutiche, Via Vivaldi
43, 81100-Caserta, Italy
d
INRS-Institut Armand-Frappier, Université du Québec, 531 Boulevard des Prairies,
H7V1B7-Ville de Laval, Canada
E-mail: [email protected]
Human urotensin-II (hU-II) is a cyclic peptide that can influence cardiovascular homeostasis
as well as blood supply in cancer and metastasis formation [1,2]. The shortest active sequence
required for biological activity of hU-II contains residues 4-11 in a cycle featuring a disulfide
bond between Cys5-Cys10 (Figure 1), and is suggested to adopt a β-hairpin conformation of
prime relevance for interaction with the urotensin-II receptor (UTR) [3].
Employing the minimal active sequence, herein we have developed synthetic strategies to
prepare new derivatives in which peptidomimetic residues have been inserted into the cyclic
peptide core region. Our presentation will discuss about such modifications as chemical tools
to survey their influences on hydrogen bonds, geometry and interaction with UTR. The results
of this structure-activity relationship study offer useful information for the design of further
UTR ligands with enhanced activity.
Figure 1: U-II(4-11) peptide sequence.
[1] H. Vaudry, J. Leprince, D. Chatenet, A. Fournier, D. G. Lambert, J. C. Le Mével, E. H. Ohlstein,
A. Schwertani, H. Tostivint and D. Vaudry, Pharmacol. Rev. 67 (2015) 214-258.
[2] D. Guidolin, G. Albertin and D. Ribatti, Peptides 31 (2010) 1219-1224.
[3] A. Carotenuto, L. Auriemma, F. Merlino, A. Limatola, P. Campiglia, I. Gomez-Monterrey, R.
d’Emmanuele di Villa Bianca, D. Brancaccio, P. Santicioli, S. Meini, C. A. Maggi, E. Novellino and
P. Grieco, J. Pept. Sci. 19 (2013) 293-300.
19
OR-3
Silica-silver-titania engineered sensors: self-cleaning features
for neurotransmitters electroanalysis
Valentina Pifferi,a Guido Soliveri,a Guido Panzarasa,b Silvia Ardizzone,a
Giuseppe Cappelletti,a Daniela Meroni,a and Luigi Falciolaa
a
Dipartimento di Chimica, Università degli Studi di Milano, Via Golgi 19, 20133-Milano,
Italy
b
Dipartimento di Scienze e Innovazione Tecnologica, Università del Piemonte Orientale
“Amedeo Avogadro”, Viale T. Michel 11, 15100-Alessandria, Italy
E-mail: [email protected]
Fouling and passivation are the main challenges faced during electroanalysis of complex
matrices, especially those commonly encountered in the biomedical and environmental fields
[1]. The production of highly engineered devices, designed ad hoc for specific applications, is
the key factor in the direction of overcoming such problems and accessing effective sensors.
A performant, reliable and reusable sensor, that could be cleaned simply by irradiation with
UV light, would perfectly match this goal.
We designed a three-layered transparent electrode, in which silver nanoparticles are
embedded between a bottom silica and a top titania layer [2,3]. Such structure equips the
device with multifunctional properties for a complex biomedical challenge: the detection and
quantification of catecholamine neurotransmitters. The crucial importance of each component
to make our device a robust and efficient electroanalytical system was thoroughly
investigated. The size distribution of silver nanoparticles, the device architecture and surface
homogeneity were inspected by electron microscopy. The overlayer was made of anatase (the
active polymorph of titanium dioxide) as confirmed by X-ray diffraction and by measuring
the photodegradation of model contaminants. Electrochemical techniques (cyclic voltammetry
and electrochemical impedance spectroscopy) revealed that an highly ordered distribution of
silver nanoparticles is the active core of the device, allowing easier electron transfer and better
quantification of the analytes even in the presence of typical interferents, e.g. ascorbic acid
and uric acid.
The high photoactivity of titania top layer allowed total recovery of the device
performance in terms of sensitivity after a fast UV-A cleaning step. This self-cleaning
property, combined with a remarkable resistance against aging, make our sensor also suitable
for on-field applications.
[1] C. M. Welch and R. G. Compton, Anal. Bioanal. Chem. 384 (2006) 601-619.
[2] G. Maino, D. Meroni, V. Pifferi, L. Falciola, G. Soliveri, G. Cappelletti and S. Ardizzone, J.
Nanoparticle Res. 15 (2013) 2087.
[3] G. Soliveri, V. Pifferi, G. Panzarasa, S. Ardizzone, G. Cappelletti, D. Meroni, K. Sparnacci and L.
Falciola, Analyst 140 (2015) 1486-1494.
20
OR-4
Effect of CaH2 on the kinetics properties of Mg(NH2)2-2LiH
Antonio Valentoni,a Francesco Torre,a Chiara Milanese,b Claudio Pistidda,c
Amedeo Marini,b Martin Dornheim,c Stefano Enzo,a Gabriele Mulas,a and
Sebastiano Garronia
a
Dipartimento di Chimica e Farmacia, Università degli Studi di Sassari, Via Vienna 2,
07100-Sassari, Italia
b
Dipartimento di Chimica, Università degli Studi di Pavia, V.le Taramenlli 16, 27100-Pavia,
Italy
c
Institute of Materials and Coastal Research, Helmholtz-Zentrum Geesthacht, Max-Planck,
Str.1, D-21502 Geesthacht, Germany
E-mail: [email protected]
Mg(NH2)2-2LiH has been recognized as one of the most useful mixture for solid state
hydrogen storage. They, infact, can theoretically desorb 5.58 wt.% of hydrogen under
moderate conditions (<150 °C) forming the ternary imide Li2Mg(NH)2. Unfortunately several
kinetic constrains limit its pratical application [1]. In the present work we focused on the
catalytic effect of CaH2 on the dehydrogenation process of the Mg(NH2)2–2LiH system [2].
The synthesis, hydrogen storage properties and energy barriers were investigated by X-ray
diffraction (XRD), temperature-programmed desorption (TPD) and differential scanning
calorimetry (DSC). The TPD measurements proved that desorption of the Mg(NH2)2–2LiH
system milled with CaH2 started at temperature of 78 °C, lower if compared with the 125 °C
observed in the pristine material. Furthermore, Kissinger analysis revealed that CaH2 acted as
a catalyst to decrease the activation energy of the first dehydrogenation step from a value of
133.8 ± 4.1 kJ/mol for the pristine material to 105.1 ± 3.2 kJ/mol when CaH2 was dispersed
into the mixture [2].
Figure 1: Kissinger plot of Mg(NH2)2-2LiH undoped (a) and doped with CaH2 (b).
[1] J. Wang, H. W. Li and P. Chen, MRS Bull. 38 (2013) 480-487.
[2] F. Torre, A. Valentoni, C. Milanese, C. Pistidda, A. Marini, M. Dornheim, S. Enzo, G. Mulas and
S. Garroni, J. Alloys Compd. 645 (2015) S284-S287.
21
OR-5
Selective hydrogenation of alkynes to (Z-)alkenes with lead-free
Pd/Boehmite catalysts under ultrasound and microwaves
Laura Rotolo, Zhilin Wu, Emanuela Calcio Gaudino, and Giancarlo Cravotto
Dipartimento di Scienza e Tecnologia del Farmaco e Centro Interdipartimentale NIS,
Università degli Studi di Torino, Via P. Giuria 9, 10125-Torino, Italy
E-mail: [email protected]
The development of green and efficient catalytic procedures for the semi-hydrogenation of
alkynes to alkenes remains a hot research topic in organic and pharmaceutical chemistry, in
particular for the synthesis of natural products and vitamins [1, 2]. We confirmed the pivotal
role of ultrasound (US) and microwaves (MW) in the preparation of eco-friendly
heterogeneous catalysts [3] and their use in selective hydrogenations [4]. Pd/Boehmite
catalysts have been prepared exploiting MW and/or US reduction of Pd(II) and dispersion of
Pd(0) on the solid support. For the sake of comparison the semi-hydrogenation of
phenylacetylene, diphenylacetylene and 2-butyne-1,4-diol have been tested both under US
(bath and pressure reactor) and silent conditions. The use of US under H2 pressure (0.1-0.5
MPa) dramatically improved the hydrogenation rate, activity and selectivity to semihydrogenated products.
Unconventional techniques are an irreplaceable tool in heterogeneous catalysis and can be
expected to bring even greater successes in the near future as processes are scaled up with
suitable flow-reactors equipped with on-line analytical monitoring. This research was funded
by the EU project MAPSYN (CP-IP 309376 7th Framework Program).
[1] V. Hessel, G. Cravotto P. Fitzpatrick, B. S. Patil, J. Lang and W. Bonrath, Chem. Eng. Process 71
(2013) 19-30.
[2] Z. Wu, E. Borretto, G. Cravotto, J. Medlock and W. Bonrath, ChemCatChem 6 (2014) 2762-2783.
[3] S. Schüßler, N. Blaubacha, A. Stolle, G. Cravotto and B. Ondruschka, Appl. Catal. A 445-446
(2012) 231-238.
[4] Z. Wu, E. Borretto, N. Cherkasov, G. Cravotto, J. Medlock and W. Bonrath, ChemCatChem 7
(2015) 952-959.
22
OR-6
Surface modification and solubility modulation of semiconductor
nanocrystals
Marcello La Rosa, Christophe Lincheneau, Tommaso Avellini, Serena Silvi, and
Alberto Credi
Dipartimento di Chimica “Giacomo Ciamician”, Università di Bologna, Via Selmi 2, 40100Bologna, Italy
E-mail: [email protected]
Inorganic semiconductor nanocrystals, also called quantum dots (QDs), are single crystals a
few nanometers in diameter, whose size and shape can be controlled by adjusting the
experimental parameters used during the synthesis [1]. Therefore, owing to their peculiar
photophysical properties, QDs are attractive nanomaterials for application in several fields,
such as medicine, diagnostics, materials science and optoelectronic devices.
Commonly synthesized QDs are hydrophobic but several uses need water soluble and/or
biocompatible nanoparticles, so it could be necessary to replace the native hydrophobic
ligands (amines or phosphines with long alkyl chains) with hydrophilic ones after the
synthesis. Molecules with multiple thiol groups, such as dihydrolipoic acid (DHLA), are very
useful for the ligand exchange. DHLA, generally, can be obtained from lipoic acid (LA) upon
reduction with NaBH4 [2] or by irradiation with UV light [3].
However, we have developed a three-step method based on a borohydride-loaded ionexchange resin [4,5] for the chemical activation of lipoic acid and its successive utilization for
phase transfer of QDs in polar and aqueous solvents.
This procedure is handly and has several practical advantages, for example avoid preparing
DHLA stock solutions and their storage at low temperature under inert atmosphere.
We also want to show how we can modulate the solubility of the nanoparticles by
modifying the experimental conditions of the ligand exchange.
[1] Semiconductor Nanocrystal Quantum Dots, Ed. A. L. Rogach, Springer-Verlag, Wien, 2008.
[2] H. Mattoussi, J. M. Mauro, E. R. Goldman, G. P. Anderson, V. C. Sundar, F. V. Mikulec and M.
G. Bawendi, J. Am. Chem. Soc. 122 (2000) 12142-12150.
[3] G. Palui, T. Avellini, N. Zhan, F. Pang, D. Gray, I. Alabugin and H. Mattoussi, J. Am. Chem. Soc.
134 (2012) 16370-16378.
[4] A. Credi, S. Silvi, T. Avellini and C. Lincheneau, Italian patent RM2013A000269,
PCT/IB2014/061230.
[5] T. Avellini, C. Lincheneau, M. La Rosa, A. Pertegás, H. J. Bolink, I. A. Wright, E. C. Constable,
S. Silvi and A. Credi, Chem. Commun. 50 (2014) 11020-11022.
23
OR-7
A computational approach to the resonance Raman spectra of
doxorubicin in aqueous solution
Marta Olszówka, Rosario Russo, and Chiara Cappelli
Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via G. Moruzzi 13,
56124-Pisa, Italy
E-mail: [email protected]
In this study a computational approach to model spectroscopic properties of doxorubicin in
aqueous solution is presented. As a widely used anti-cancer drug, doxorubicin is a popular
object of both experimental [1] and theoretical investigations [2] aiming to describe its
properties and explain the mechanism of its biological activity. The structure of the drug
consists of a planar part (chromophore) of three condensed aromatic rings, an aliphatic ring
and an aminosugar moiety situated out of plane of the chromophore (Figure 1).
Tumor-inhibiting behavior of doxorubicin may be explained by the process of intercalation
of the drug molecule into DNA helix. This effect, possible due to pi-stacking between
nucleobases and doxorubicin, can be observed by means of Resonance Raman spectroscopy.
We show that our approach, rooted in DFT and TD-DFT, which models Resonance Raman
spectra at the Franck-Condon level with the further inclusion of solvent effects within the
Polarizable Continuum Model (PCM) [3], is able to describe the main features of vibrational
Resonance Raman spectra, as well as IR and UV-Vis spectra. While this method enables us to
study systems in various complex environments, in the present work we focus on the water
solution. The prospect of using molecular dynamics to include the interaction with explicit
water molecules is also discussed.
Figure 1: One of the stable conformers of doxorubicin.
[1] G. Das, A. Nicastri, M. L. Coluccio, F. Gentile, P. Candeloro, G. Cojoc, C. Liberale, F. De Angelis
and E. Di Fabrizio, Microsc. Res. Tech. 73 (2010) 991-995.
[2] H. Lei, X. Wanga and C. Wu, J. Mol. Graph. Model. 38 (2012) 279-289.
[3] J. Tomasi, B. Mennucci and R. Cammi, Chem. Rev. 105 (2005) 2999-3094.
24
OR-8
Finding drugs in tooth matrix: analytical method
Marta Cippitelli, Giovanni Ottaviani and Paolo Silvestrini
Laboratorio di Chimica Tossicologica Forense e Medicina Forense, Università degli Studi di
Macerata, Via D. Minzoni 9, 62100-Macerata, Italy
E-mail: [email protected]
In post-mortem forensic toxicology, in conditions in which a body is poorly conserved,
because it has been burned, skeletonized, remained a long time in water, or exhumed after a
long period, sometimes teeth are the only samples which can be analysed for useful
information. Many substances accumulate in the dental matrix, which can provide much
information on the habits of the person when alive. Some authors have reported that many
substances, such as nicotine and drugs of abuse, can be efficiently incorporated and
accumulated in the humans teeth [1,2,3]. There are very few studies in this field.
The purpose of this work was to find a method for identifying drugs of abuse, such as
cocaine, morphine and cannabinoids, in teeth, for routine analysis in forensic toxicology and
forensic medicine. Fourteen teeth from drug addicts, both alive and deceased, were analysed,
and showed at least one positivity to one of the three substances sought.
The extraction procedure followed the method used in our laboratory for searching for
drugs of abuse in hair samples [4]. Each tooth was pulverized and incubated for two days in 2
mL of 0.1 N HCl solution at 50 ºC, with internal standards (SKF-525A for cocaine and
benzoylecgonine; nalorphine for opiates) to detect cocaine, opiates and their metabolites. The
resulting mixtures were neutralized with 2 mL of phosphate buffer solution at pH 6 and
extracted by an SPE technique. The eluates were completely evaporated and then derivatized
with 30 µl of BSTFA + 1% TMCS at 60 ºC for 20 min. One µl of the derivatized eluate was
analysed by GC/MS. Residual tooth samples from previous analyses were used for detection
of Δ9-THC and its metabolites. The samples, to which the internal standard (Δ9-THC-D3)
was added, were subjected to basic hydrolysis, cooled to room temperature, and subjected to
a liquid-liquid extraction method with a hexane/ethyl acetate solution (9:1). The organic
phases were separated. The eluates were completely evaporated, and then derivatized with 30
µl of BSTFA + 1% TMCS at 60 ºC for 20 min. One µl was analysed by GC/MS.
The 14 analyses showed at least one positivity to one of substances sought. The method
used turned out to be of particular validity, allowing the recovery of both illicit substances and
their metabolites. It was also possible to use the same sample aliquot to extract various kinds
of drugs, first by acid hydrolysis and then basic hydrolysis, as confirmed by Tassoni et al. [4].
The method showed good efficacy, mainly during the extraction time from such complex
matrices as teeth, and was linear and reproducible.
[1] O. Garcia-Algar, O. Vall, J. Segura, J. A. Pascual, D. Diaz, L. Mutnoz, P. Zuccaro, R. Pacifici and
S. Pichini, JAMA 290 (2003) 196-197.
[2] C. Cattaneo, F. Gigli, F. Lodi and M. Grandi, J. Forensic Odontostomatol. 21 (2003) 1-5.
[3] M. Pellegrini, A. Casà, E. Marchei, R. Pacifici, R. Maynè, V. Barbero, O. Garcia-Algar and S.
Pichini, J. Pharm. Biomed. Anal. 40 (2006) 662-668.
[4] G. Tassoni, D. Mirtella, M. Zampi, L. Ferrante, M. Cippitelli, E. Cognigni, R. Froldi and M.
Cingolani, Forensic Sci. Int. 244 (2014) 16-19.
25
OR-9
Design, synthesis, and biological evaluation of new GPR17 ligands
Ajiroghene Thomas,a Maria Pia Abbracchio,b Michela Buccioni,a Diego Dal
Ben,a Catia Lambertucci,a Claudia Martini,c Gabriella Marucci,a Claudia
Santinelli,a Andrea Spinaci,a and Rosaria Volpinia
a
School of Pharmacy, Medicinal Chemistry Unit, Università di Camerino, Via S. Agostino 1,
62032-Camerino, Italy
b
Dipartimento di Scienze Farmacologiche e Biomolecolari, Università degli Studi di Milano,
Via Balzaretti 9, 20133-Milano, Italy
c
Dipartimento di Psichiatria, Neurobiologia, Farmacologia e Biotecnologie, Università degli
Studi di Pisa, Via B. Pisano 6, 56126-Pisa, Italy
E-mail: [email protected]
The Gi protein-coupled receptor GPR17 shows a peculiar dual pharmacology for being
activated by two unrelated families of endogenous ligands: extracellular nucleotides and
cysteinyl-leukotrienes [1].
GPR17 expression is markedly increased at the site of damage upon central nervous
system injury, suggesting its possible role as “danger signal”. At very early times after injury,
GPR17 seems to mediate cell death and, at later stages, GPR17 may promote cell repair
mechanisms [2].
Based on the observation that 2-phenylethynylATP behaves as a strong agonist (EC50 =
0.036 nM) of GPR17 while N6-methylATP and some bisphosphate analogues behave as
antagonists [3], new 2-phenylethynyladenine nucleotide derivatives, including stable
analogues, have been designed and synthesized.
The new derivatives were tested on GPR17 transfected cells by using a non-radioactive
functional cAMP assay [4]. Furthermore, in order to test the selectivity of these compounds
versus P2 purinergic receptors coupled with Gi-proteins, the new nucleotides were tested also
at HEK cells transiently transfected with the P2Y12-14 receptors, using P2Y reference
compounds for comparison.
[1] P. Ciana, M. Fumagalli, M. L. Trincavelli, C. Verderio, P. Rosa, D. Lecca, S. Ferrario, C.
Parravicini, V. Capra, P. Gelosa, U. Guerrini, S. Belcredito, M. Cimino, L. Sironi, E. Tremoli, G. E.
Rovati, C. Martini and M. P. Abbracchio, The EMBO Journal 25 (2006) 4615-4627.
[2] S. Ceruti, G. Villa, T. Genovese, E. Mazzon, R. Longhi, P. Rosa, P. Bramanti, S. Cuzzocrea and
M. P. Abbracchio, Brain 132 (2009) 2006-2218.
[3] E. Calleri, S. Ceruti, G. Cristalli, C. Martini, C. Temporini, C. Parravicini, R. Volpini, S. Daniele,
G. Caccialanza, D. Lecca, C. Lambertucci, M. L. Trincavelli, G. Marucci, I. W. Wainer, G. Ranghino,
P. Fantucci, M. P. Abbracchio and G. Massolini, J. Med. Chem. 53 (2010) 3489-3501.
[4] M. Buccioni, G. Marucci, D. Dal Ben, D. Giacobbe, C. Lambertucci, L. Soverchia, A. Thomas, R.
Volpini and G. Cristalli, Pur. Sign. 7 (2011) 463-468.
26
OR-10
Novel 13-(di)arylalkyl berberines with antiproliferative activity
Gaetano Fiorillo, Franco Buzzetti, Paolo Lombardi, Tanjia Monir Syeda
Naxospharma srl, Via G. Di Vittorio 70, 20026-Novate Milanese, Italy
E-mail: [email protected]
Berberine chloride (1) is an isoquinoline quaternary plant alkaloid which has been used in the
Ayurvedic and Chinese medicines since hundreds of years [1]. The diverse pharmacological
properties exhibited by berberine indicate that the alkaloid has a definite potential in a wide
spectrum of clinical applications. It represents a biologically interesting skeleton by providing
an attractive natural lead compound for the introduction of chemical modifications in search
for more selective and specific medical indications [2,3]. Anticancer properties of berberine
have also been reported [4,5].
In this respect we discovered novel 13-(di)arylalkyl berberines (2) with improved
anticancer properties [6], several of which show remarkable antiproliferative effects on a
variety of human cancer cell lines refractory to chemotherapy. The derivatives can be
prepared starting from 7,8-dihydroberberine precursors by using various synthetic
methodologies, including an uncommon aldehyde-enamine condensation.
Although the precise molecular basis of the biological activities of berberine is still
debated, at least for the anticancer activity we present informations and data regarding
downregulation of cancer related protein expression as a putative major biological effect of
this class of compounds which is exploitable for clinical applications. These new derivatives
are believed to have the property to bind to oligonucleotides and to function as selecting
suppressors of protein synthesis [7,8].
[1] M. Imanshahidi and H. Hosseinzadeh, Phytother. Res. 22 (2008) 999-1012.
[2] G. A. Cordell, M. L. Quinn-Beattle and N. R. Farnsworth, Phytother. Res. 15 (2001) 183-205.
[3] M. Tillhon, L. M. Guamàn Ortiz, P. Lombardi and A. I. Scovassi, Biochem. Pharmacol. 84 (2012)
1260-1267.
[4] Y. Sun, K. Xun, Y. Wang and X. Chen, Anti-Cancer Drugs 20 (2009) 757-769.
[5] L. M. Guamàn Ortiz, P. Lombardi, M. Tillhon and A. I. Scovassi, Molecules 19 (2014) 1234912357.
[6] US Pat 8,188,109B2 to Naxospharma.
[7] G. Marverti, A. Ligabue, P. Lombardi, S. Ferrari, M. G. Monti, C. Frassineti and M. P. Costi, Int.
J. Oncology 43 (2013) 1269-1280.
[8] N. Wang, H. Y. Tan and Y. Feng, Int. J. Mol. Med. 34 (2014) 409-419.
27
OR-11
It’s all about the surface! Vibrational spectroscopy applied to the
study of biomimetic surfaces for tissue engineering
Michele Di Foggia,a Armida Torreggiani,b Paola Taddei,a Sergio Bonora,a
Monica Dettin,c and Anna Tintia
a
Dipartimento di Scienze Biomediche e Neuromotorie, Università di Bologna, Via Belmeloro
8/2, 40126-Bologna, Italy
b
Istituto per la Sintesi Organica e la Fotoreattività, Consiglio Nazionale delle Ricerche, Via
Gobetti 1, 40100-Bologna, Italy
c
Dipartimento di Ingegneria Industriale, Università degli Studi di Padova, Via Marzolo 9,
35131-Padova, Italy
E-mail: [email protected]
Tissue engineering is a multidisciplinary field aimed at the creation of biological substitutes
that restore and maintain the biological function of a damaged tissue. The key of the success
of these biomedical devices lies into surface interactions with living tissues, therefore a
common strategy is to create biomimetic surfaces that help cells to colonize the biomaterial,
leading to tissue healing.
Raman and FT-IR vibrational spectroscopies, apart from being mainly surface and nondestructive techniques, are extremely sensitive to changes in structure and molecular
interactions; thus, they have been increasingly used to investigate biomimetic devices.
In particular, we have used vibrational spectroscopies to investigate different biomimetic
materials and to test some of their proprieties:
 self-assembling peptides adsorbed on titanium surfaces for bone implants [1], analyzed
before and after attack from free radicals (obtained by gamma-radiolysis and mimicking
inflammation processes) [2], with the aim to evaluate their capability in resisting to
oxidative stress;
 composite (ceramic-polymer, polymer-polymer) bioresorbable biomaterials [3,4];
 hydroxyapatite nanomaterials functionalized with proteins to increase biocompatibility
[5-7].
[1] M. Di Foggia, P. Taddei, A. Torreggiani, M. Dettin and A. Tinti, J. Raman Spectrosc. 42 (2011)
276-285.
[2] M. Di Foggia, A. Torreggiani, P. Taddei, M. Dettin and A. Tinti, J. Raman Spectrosc. 44 (2013)
1446-1450.
[3] V. Guarino, F. Causa, P. Taddei, M. Di Foggia, G. Ciapetti, D. Martini, C. Fagnano, N. Baldini
and L. Ambrosio, Biomaterials 29 (2008) 3662-3670.
[4] V. Guarino, P. Taddei, M. Di Foggia, C. Fagnano, G. Ciapetti and L. Ambrosio, Tissue Eng. A 15
(2009) 3655-3668.
[5] M. Iafisco, B. Palazzo, G. Falini, M. Di Foggia, S. Bonora, S. Nicolis, L. Casella and N. Roveri,
Langmuir 24 (2008) 4924-4930.
[6] M. Iafisco, M. Di Foggia, S. Bonora, M. Prat and N. Roveri, Dalton Trans. 40 (2011) 820-827.
[7] M. Iafisco, E. Varoni, M. Di Foggia, S. Pietronave, M. Fini, N. Roveri, L. Rimondini and M. Prat,
Colloids Surf., B 90 (2012) 1-7.
28
OR-12
Polymer electrolytes for green, safe and robust all solid Na-ion
batteries
Francesca Colò,a Federico Bella,a Jijeesh R. Nair,a Matteo Destro,b Giuseppina
Meligrana,a and Claudio Gerbaldia
a
GAME Lab, Dipartimento di Scienza Applicata e Tecnologia, Politecnico di Torino, Corso
Duca degli Abruzzi 24, 10129-Torino, Italy
b
Lithops Batteries s.r.l., Via della Rocca 27, 10123-Torino, Italy
E-mail: [email protected]
The modern life style that we are enjoying depends on energy storage systems in which the
role of Li-ion batteries (LiBs) is peerless. However, state-of-the-art LiBs are approaching the
verge of possible technological imagination, particularly in terms of energy density. Some
researchers argue that next-gen secondary batteries should switch to heavier elements such as
sodium. Indeed, when it comes to gigantic energy storage systems for the electricity grid
and/or other non-portable applications where size does not matter, Na-based systems can be
an effective and intelligent choice. Nevertheless, research on NiBs’ components is at the very
beginning, particularly for what concerns the electrolyte, where standard organic liquid
electrolytes are mainly used. Unfortunately, their flammable nature jeopardizes the safety of
these large scale systems, which in case of failure may lead to thermal runaways.
In this work, an overview is provided on quasi-solid polymer electrolytes specifically
conceived and developed for Na-ion secondary cells, based on polyethylene oxide (PEO),
acrylates/methacrylates and/or mixtures thereof. Eventually, pyranose ring based natural
additives and/or low volatile plasticizers are added along with supporting sodium salts to
improve specifically defined characteristics. All the sample are thoroughly characterized in
the physic-chemical and electrochemical viewpoint. The performances in lab scale devices are
presented, evaluated by means of cycling voltammetry and galvanostatic charge/discharge
cycling exploiting different electrode materials. We also present preliminary aging resistance
tests of the devices inherited by different solid electrolytes, as well as the cell response upon
various temperatures and current regimes.
So far, work on Na-ion polymer batteries for moderate temperature application is at an
early stage, only lab-scale small battery cells are demonstrated. Nevertheless, with the
appropriate choice and development of electrode/electrolyte materials, the overall
characteristics of the SPEs here developed postulates the possibility of their effective
implementation in safe, durable and high energy density secondary Na-based polymer devices
conceived for green-grid storage and operating at ambient and/or sub-ambient temperatures
[1,2].
[1] F. Bella, F. Colò, J. R. Nair and C. Gerbaldi, ChemSusChem (2015) DOI:
10.1002/cssc.201500873.
[2] F. Colò, F. Bella, J. R. Nair, M. Destro and C. Gerbaldi, Electrochim. Acta 174 (2015) 185-190.
29
OR-13
Mechanical stirring affects the chirality of supramolecular
complex
Rosalba Randazzo,a Alessandro D’Urso,a Maria Elena Fragalà,a Norberto
Micali,b Giuseppe Compagnini,a Roberto Paolesse,c and Roberto Purrelloa
a
Dipartimento di Scienze Chimiche, Università degli Studi di Catania, V.le A. Doria 6,
95125-Catania, Italy
b
Istituto per i Processi Chimico Fisici, Consiglio Nazionale delle Ricerche, V.le F. Stagno
d'Alcontres 37, 98158-Messina, Italy
c
Dipartimento di Scienze e Tecnologie Chimiche, Università degli Studi di Roma Tor
Vergata, Via Orazio Raimondo 18, 00173-Roma, Italy
E-mail: [email protected]
The relationship between vortexes and chirality of large assemblies is a very intriguing
problem, which might lead to understanding fundamentals of nature and, from this, to
possible technological applications [1]. The effects of vortexes (obtained by mechanical
stirring) on chirality are both static or dynamic: in the first condition the stirring can induce
the formation of one enantiomeric form decided by the stirring sense, in the second situation
clock wise (CW) and counter clock wise (CCW) stirring of non covalent assembly solutions
causes an increase of circular dichroism (CD) intensity and a dependence of the CD signs on
the stirring sense. [2-8] In the latter case effects disappear by stopping the stirring.
We studied the effects of mechanical stirring on chirality at supramolecular level of two
systems: the protonated form of H2TPPS4 that self-assemblies spontaneously to form chiral
aggregates (the so called J-aggregates) and Graphene oxide. Both this systems respond to
vortexes in a dynamic fashion by inverting the CD signal with stirring sense.
[1] D. B. Amabilino, Nat. Mater. 6 (2007) 924-925.
[2] D. K. Kondepudi, R. J. Kaufman and N. Singh, Science 250 (1996) 975-976.
[3] J. M. Rib, J. Crusats, F. Sague, J. Claret and R. Rubires, Science 292 (2001) 2063-2066.
[4] W. Dzwolak, A. Loksztejn, A. Galinka-Rakoczj, R. Adachi, Y. Goto and L. Rupnicki, J. Am.
Chem. Soc. 129 (2007) 7517-7522.
[5] O. Ohno, Y. Kaizu and H. Kobayashi, J. Chem. Phys. 99 (1993) 4128-4139.
[6] T. Yamaguchi, T. Kimura, H. Matsuda and T. Aida, Angew. Chem. Int. Ed. 43 (2004) 6350-6355.
[7] A. Tsuda, Md. Akhtarul Alam, T. Harada, T. Yamaguchi, N. Ishii and T. Aida, Angew. Chem. Int.
Ed. 46 (2007) 8198-8202.
[8] M. Wolffs, S. J. George, Z. Tomovic´, S. C. J. Meskers, A. P. H. J. Schenning and E. W. Meijer,
Angew. Chem. Int. Ed. 46 (2007) 8203-8205.
30
OR-14
GC-MS analysis as fingerprint to characterize kernel oil from six
different hazel (Corylus avellana L.) populations in Italy
Emanuela Martino,a Francesco Bracco,a Mirko Umberto Granata,a Barbara
Mannucci,b Federica Corana,b Daniela Rossi,c Rosangela Catoni,d and Loretta
Gratanid
a
Dipartimento di Scienze della Terra e dell'Ambiente, Università degli Studi di Pavia, Via S.
Epifanio 14, 27100-Pavia, Italy
b
Centro Grandi Strumenti, Università degli Studi di Pavia, Via Bassi 21, 27100-Pavia, Ital
c
Dipartimento di Scienze del Farmaco, Università degli Studi di Pavia, Viale Taramelli 12,
27100-Pavia, Italy
d
Dipartimento di Biologia Ambientale, Sapienza - Università di Roma, Piazzale A. Moro 5,
00185-Roma, Italy
E-mail: [email protected]
Hazelnut kernels play a relevant role in the agricultural market, mainly because of their use to
provide flavor in dairy, bakery, candy, confectionery, and chocolate products. Moreover they
exhibit functional properties due to their content in fatty acids, phenols and other compounds
that could positively affect human health [1].
Italy is the second world hazelnut producer after Turkey [2]. About 90% of the world crop
is sold as kernels and processed in the food industry and the remaining 10% is sold as in-shell
product and consumed fresh, blanched, or roasted [3].
In this study, the GC-MS fingerprint of kernel oil from six hazel populations of Italy was
investigated. The 3 sites of Northern Italy are: Bosco Siro Negri (BN – Lombard), Lequio (L)
and Alba (A) in Piedmont. The 3 sites in Central Italy, Lazio region on Tuscia hills, are 2
Nepi (N1 – N2) and Capranica (C).
Fully ripe hazelnuts were collected in each site and then the oil extracted. Briefly, crude oil
was obtained from finely chopped nuts, using the Soxtherm automatic extraction instrument
(Gerhardt Analytical system, Germany) and the fatty acid composition of hazelnut oil samples
was determined from total lipid extract as methyl esters (FAMEs) by gas chromatography
(GC) coupled to a mass spectrophotometer [4,5].
In summary, herein we report: 1) the GC fingerprint of the kernel oil, 2) the comparison of
kernel oils obtained from the six sites.
[1] E. Ros, Nutrients 2 (2010) 652-682.
[2] FAOstat Agriculture data, http://faostat.fao.org/site/408/default.aspx, accessed 08/04/2014.
[3] N. Valentini, L. Rolle, C. Stevigny and G. Zeppa J. Sci. Food Agric. 86 (2006) 1257-1262.
[4] AOAC: Official Methods of Analysis, Washington DC, 1990.
[5] L. Li, R. Tsao, R. Yang, J.K.G. Kramer and M. Hernandez, J. Agric. Food Chem. 55 (2007) 11641169.
31
OR-15
Surfactant-templated self-assembled synthesis of mesoporous
materials using a geothermal waste as silicon source
Jorge Tovar Rodríguez and Emiliano Fratini
Dipartimento di Chimica “Ugo Schiff”, Università degli Studi di Firenze, Via della
Lastruccia 13, 50019-Sesto Fiorentino, Italy
E-mail: [email protected]
A series of surfactant-templated hexagonally-ordered mesoporous MCM-41 materials were
successfully obtained by means of a novel green hydrothermal synthesis, using geothermal
waste as silicon source to avoid the use of toxic reagents. All prepared materials exhibit
hexagonal structure and high surface areas and could be used as catalytic supports or for
adsorption purposes.
A sample of inorganic waste from a geothermal field was used in substitution of the
conventionally used alkoxides and colloidal silica to synthesize the surfactant-templated
mesoporous structure MCM-41, following the methodology reported elsewhere [1]. This new
green synthesis approach enabled to yield high surface area solids (over 600m2/gr), exhibiting
at least two small angle scattering peaks, as it can be seen on figure 1. These peaks can be
assigned to the (100) and (110) reflections in the hexagonal structure, space group p6mm [2],
changing from an amorphous solid to an ordered one. According to the nitrogen isotherms
shown in figure 2, all materials exhibit a type IV isotherm, typical in mesoporous materials
and have a narrow pore size distribution. Given their characteristics, and considering the
revalorization of a very cheap raw material, this methodology could be scaled-up into a
realistic industrial process to synthesize oxides with catalytic utility or as adsorption matrixes.
[1] C. T. Kresge, M. E. Leonowicz, W. J. Roth, J. C. Vartuli and J. S. Beck, Nature 359 (1992) 710712.
[2] J. S. Beck, J. C. Vartuli, W. J. Roth, M. E. Leonowicz, C. T. Kresge, K. D. Schmitt, C. T. W. Chu,
D. H. Olson and E. W. Sheppard, J. Am. Chem. Soc. 114 (1992) 10834-10843.
32
OR-16
ZnTCPPSpm4: a single molecule as probe, catalyzer & stabilizer
toward Z-DNA
Chiara Maria Antonietta Gangemi,a,b Nina Berova,b Gaetano Andrea Tomaselli,a
Alessandro D’Urso,a and Roberto Purrelloa
a
Dipartimento di Scienze Chimiche, Università degli Studi di Catania, Viale Andrea Doria
6, 95125-Catania, Italy
b
Department of Chemistry, Columbia University, 3000 Broadway, 10027-NY, USA
E-mail: [email protected]
DNA containing an alternation of purine and pyrimidine repeats has the potential to adopt the
Z structure, a left-handed double helix characterized by a high-energy structure [1]. It has
been shown that Z-DNA can exist in vivo under physiological conditions as a transient
structure, occasionally induced by a biological process. Therefore, tracts of Z-DNA can exist
within a single duplex of segments of right-handed B-DNA if the conditions and sequences
are appropriate [2]. Several research groups have studied the possible correlation between
chromosomal breakpoints in human tumours with potential Z-DNA forming sequences [3].
For these reasons the possibility to recognize, to induce or in some cases to stabilize this
conformation could represent an important goal to understand the mechanism of action of this
important structure of DNA. Porphyrinoids are ideal compounds to interact with DNA due to
their peculiar characteristics [4]. In this work, we developed a new achiral zinc-spermineporphyrin conjugate that shows a catalytic and a stabilizer effect toward the changing of BDNA into Z-DNA of poly(dG-dC) sequence. In addition, it works as probe, showing an
intense ICD signal.
Figure 1: Schematic representation of transition.
[1] A. H. Wang, G. J. Quigley, F. J. Kolpak, J. L. Crawford, J. H. van Boom, G. van der Marel and A.
Rich, Nature 282 (1979) 680-686.
[2] A. Rich, A. Nordheim and A. H. J. Wang, Annu. Rev. Biochem. 53 (1984) 791-846.
[3] M. Adachi and Y. Tsujimoto, Oncogene 5 (1990) 1653-1657.
[4] a) M. Balaz, M. De Napoli, A. E. Holmes, A. Mammana, K. Nakanishi, N. Berova and R.Purrello,
Angew. Chem. Int. Ed. 44 (2005) 4006-4009; b) A. D’Urso, S. Nardis, G. Pomarico, M. E Fragala, R.
Paolesse and R. Purrello, J. Am. Chem. Soc. 135 (2013) 8632-8638.
33
OR-17
Ion chemistry of cisplatin with biological ligands at the encounter
complex level
Davide Corinti,a Cecilia Coletti,b Nazzareno Re,b Barbara Chiavarino,a Maria
Elisa Crestoni,a and Simonetta Fornarinia
a
Dipartimento di Chimica e Tecnologia del Farmaco, Sapienza - Università di Roma, P.le A.
Moro 5, 00185-Roma, Italy
b
Dipartimento di Farmacia, Università degli Studi "G. d'Annunzio" Chieti - Pescara, Via dei
Vestini 31, 66100-Chieti, Italy
E-mail: [email protected]
Platinum complexes belonging to the cisplatin family, a widely used antineoplastic drug, are
extensively explored in the current literature and sustained effort is devoted to reach deeper
insight into the mechanism of their reaction with biological targets and carriers. IRMPD
spectroscopy has recently shown great potentiality in the investigation of cisplatin-derived
complexes of biological relevance [1-3]. In this contribution mass spectrometry and IRMPD
spectroscopy, supported by DFT calculations, are employed to investigate the interactions of
pyridine, trimethylphosphate and 4(5)-methylimidazole with the primary intermediate in the
hydrolysis of cisplatin, namely the cis[PtCl(NH3)2(H2O)]+ cation. Ionic products obtained by
addition and/or substitution by the selected ligands have been isolated in the gas phase and
characterized by IRMPD spectroscopy. The IR spectroscopic analysis has covered both the
fingerprint region (1000-2000 cm-1) and the N-H/O-H stretch region (2800-3800 cm-1). The
assignment of the vibrational features in the experimental IRMPD spectra has been assisted
by computations employing the classical B3LYP functional, and the ωB97XD one, which has
been shown to better take into account long range
and dispersion effects.
Direct evidence has been obtained for the
substitution reaction of the coordinated water
molecule by the selected ligand in the isolated
addition complex, activated by the absorption of IR
photons. Calculations of the potential energy
profile have successfully clarified the behavior of
the different complexes.
[1] B. Chiavarino, M. E. Crestoni, S. Fornarini, D. Scuderi and J. Y. Salpin, J. Am. Chem.
Soc. 135 (2013) 1445-1455.
[2] A. De Petris, A. Ciavardini, C. Coletti, N. Re, B. Chiavarino, M. E. Crestoni and S. Fornarini, J.
Phys. Chem. Lett. 4 (2013) 3631-3635.
[3] B. Chiavarino, M. E. Crestoni, S. Fornarini, D. Scuderi and J. Y. Salpin, Inorg. Chem. 54 (2015)
3513-3522.
34
OR-18
Towards sigma1 receptor agonists as neuroprotective agents.
Chemical and pharmacological studies of RC-33 enantiomers
Annamaria Marra,a Daniela Rossi,a Daniela Curti,b and Simona Collinaa
a
Dipartimento di Scienze del Farmaco, Università degli Studi di Pavia, Viale Taramelli 12,
27100-Pavia, Italy
b
Dipartimento di Biologia e Biotecnologie "L. Spallanzani", Università degli Studi di Pavia,
Via Ferrata 9, 27100-Pavia, Italy
[email protected]
Over the years there has been a growing interest in the therapeutic potential of sigma receptor
modulators for treating several CNS pathologies. Sigma1 receptor agonists have been proved
to prevent neuronal death caused by glutamate toxicity, and to promote in vitro neurite
sprouting and elongation [1]. In this scenario, our recent research led to identified racemic
RC-33 (Figure 1) as a potent and metabolically stable S1R agonist [2-4].
Figure 1: Chemical structure of (R/S)-RC-33.
In this communication we will describe the preparation of RC-33 enantiomers, their
absolute configuration assignment and pharmacological study, in order to address the role of
chirality in their biological activity and metabolic processes. On the bases of this results, (R)RC-33 was selected as optimal candidate for proof of concept in vivo studies in animal model
of CNS-mediates diseases.
[1] S. Collina, R. Gaggeri, A. Marra, A. Bassi, S. Negrinotti, F. Negri and D. Rossi, Expert. Opin.
Ther. Pat. 23 (2013) 597-613.
[2] D. Rossi, A. Marra, P. Picconi, M. Serra, L. Catenacci, M. Sorrenti, E. Laurini, M. Fermeglia, S.
Pricl, S. Brambilla, N. Almirante, M. Peviani, D. Curti and S. Collina, Bioorg. Med. Chem. 21 (2013)
2577-2586.
[3] D. Rossi, A. Pedrali, R. Gaggeri, A. Marra, L. Pignataro, E. Laurini, V. DalCol, M. Fermeglia, S.
Pricl, D. Schepmann, B. Wünsch, M. Peviani, D. Curti and S. Collina, ChemMedChem 8 (2013) 15141527.
[4] D. Rossi, A. Pedrali, A. Marra, L. Pignataro, D. Schepmann, B. Wünsch, L. Ye, K. Leuner, M.
Peviani, D. Curti, O. Azzolina and S. Collina, Chirality 25 (2013) 814-822.
35
OR-19
Influence of structural variations over the synthesis and
fluorescent properties of new thermochemiluminescent labels
Luca Alfio Andronico,a Massimo Di Fusco,a,b Arianna Quintavalla,a Marco
Lombardo,a Massimo Guardigli,a Mara Mirasoli,a,b Claudio Trombini,a and Aldo
Rodaa
Dipartimento di Chimica “Giacomo Ciamician”, Università di Bologna, Via Selmi 2,
40100-Bologna, Italy
b
Centro di Ricerca Interdipartimentale di Ricerca Industriale di Meccanica Avanzata e
Materiali, Viale Risorgimento 2, 40136-Bologna, Italy
E-mail: [email protected]
a
Thermochemiluminescence (TCL) is the process by which a thermolabile molecule generates
a light emission after heating above a threshold temperature.
Recently, we synthesized new 1,2-dioxethane derivatives, characterized by remarkably
TCL properties in terms of lower triggering temperature and high fluorescence efficiency [13]. Both the synthesis and the thermal decomposition of these new TCL-labels is shown in
Figure 1.
Figure 1: Scheme of the synthesis and thermal decomposition of TCL-labels.
We will present the impact of structural modifications both on the photo-oxygenation step
and on TCL properties of a small library of 1,2-dioxetanes, and preliminary results on the
application of these molecules in the development of TCL-based immunoassay.
[1] A. Roda, M. Di Fusco, A. Quintavalla, M. Guardigli, M. Mirasoli, M. Lombardo and C. Trombini,
Anal. Chem 84 (2012) 9913-9919.
[2] M. Di Fusco, A. Quintavalla, C. Trombini, M. Lombardo, A. Roda, M. Guardigli and M. Mirasoli,
J. Org. Chem. 78 (2013) 11238-11246.
[3] M. Di Fusco, M. Guardigli, M. Lombardo, M. Mirasoli, A. Quintavalla, A. Roda and C. Trombini,
Patent WO2014024106 A1 (2014).
36
OR-20
Collective optical properties arising from colloidal nanoparticles
self-assembled into 2 and 3D functional materials
Michela Corricelli,a,b Nicoletta Depalo,b Elisabetta Fanizza,a Davide Altamura,c
Cinzia Giannini,c Andrea Falqui,d Angela Agostiano,a,b Marinella Striccoli,b and
M. Lucia Currib
a
Dipartimento di Chimica, Università degli Studi di Bari "Aldo Moro", Via E. Orabona 4,
70125-Bari, Italy
b
Istituto per i Processi Chimico-Fisici, Consiglio Nazionale delle Ricerche, Via E. Orabona
4, 70125-Bari, Italy
c
Istituto di Cristallografia, Consiglio Nazionale delle Ricerche, Via Amendola 122/O, 70126Bari, Italy
d
King Abdullah University of Science & Technology, 4700-Thuwal, Saudi Arabia
E-mail: [email protected]
In the last decades the enormous development of colloidal synthetic routes allowed to obtain
metallic and semiconductor colloidal nanoparticles (NPs) with high control on their size and
shape and with their surface coordinated by organic molecules that ensure their dispersibility in a
range of solvent. Slowly evaporating the solvent of a drop cast NP dispersion, make NPs selfassembly into superlattices, thanks to a delicate balance between interparticle forces and
crystallization energy. The tremendous interest of such NP superlattices is driven by novel
collective properties arising from inter-NP interactions that emerge in these artificial solids, with
promising application in opto-electronics, photonics and biomedicines.
Superlattices based on PbS nanocrystals (NCs) and Au NPs, respectively, were fabricated: the
influence of parameters such as NP size and concentration, dispersing solvent and substrate on the
superlattice formation, was investigated [1,2]. An integrated approach, including both small and
wide angle XRD as well as TEM analysis, allowed to retrieve the full 3D organization of the PbS
NCs in the superlattice. Interestingly, the comparison between the absorption and emission
features of the PbS NCs in solution and organized in thin film, pointed out the occurrence of a
FRET energy transfer between the close-packed NCs, only under specific geometrical constrains
[3]. On the other hand, SEM and grazing-incidence small-angle X-ray scattering investigations
validated the Au NP organization in crystalline domains and confirmed the role played by the
surface chemistry of the substrate onto the 2D lattice assembly. Indeed, a combined analysis of
reflection and transmission spectroscopy, as well as ellipsometric data demonstrated that the
plasmonic properties of the Au NP assemblies strongly depend on the substrate, which was found
influence NP ordering and near-field interactions between neighboring NPs [2].
[1] M. Corricelli, D. Altamura, L. De Caro, A. Guagliardi, A. Falqui, A. Genovese, A. Agostiano, C.
Giannini, M. Striccoli and M. L. Curri, CrystEngComm 13 (2011) 3988-3997.
[2] M. Corricelli, N. Depalo, E. Fanizza, D. Altamura, C. Giannini, D. Siliqi, R. Di Mundo, F.
Palumbo, V. G. Kravets, A. N. Grigorenko, A. Agostiano, M. Striccoli and M. L. Curri, J. Phys.
Chem. C 118 (2014) 7579-7590.
[3] M. Corricelli, F. Enrichi, D. Altamura, L. De Caro, C. Giannini, A. Falqui, A. Agostiano, M. L.
Curri and Marinella Striccoli, J. Phys. Chem. C 116 (2012) 6143-6152.
37
OR-21
Theoretical investigation of methane activation by transitionmetal cations M+
Gloria Mazzone,a Adriana Pérez-González,b Jenny Pirillo,a Annia Galano,b Nino
Russo,a and Emilia Siciliaa
a
Dipartimento di Chimica e Tecnologie Chimiche, Università della Calabria, 87036-Rende,
Italy
b
Departamento de Quimica, Division de Ciencias Basicas e Ingenieria, Universidad
Autonoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco No. 186, Col. Vicentina, 09340Mexico D.F., Mexico
E-mail: [email protected]
With the depletion of petroleum reserves, the rational utilization of methane become of
primary importance in commercial field. Actually, the effective use of such abundant and
readily accessible natural resource as a raw material for industrial processes still remains one
of the long standing problems in the scientific community. Nevertheless, in the last decades,
the methane conversion into value-added chemicals, such as methanol and higher
hydrocarbons, has received much attention.
Fruitful interplay between theory and experiments in this field has allowed a great deal of
detailed information in terms of involved intermediates, energetics, kinetics and
thermochemical data. It is well known, that third-row (5d) transition metals are able to
activate methane exothermically by dehydrogenation, as they form much stronger bonds than
do first-row (3d) and second-row (4d)
transition metals [1].
To gain more information about the ability
of metal ions to activate methane for hydrogen
production, the detailed mechanism promoted
by Nb+ and Ta+ has been fully explored by
means of Density Functional Theory
calculations. The reaction mechanisms have
been investigated following the general
schemes proposed for these reactions (Scheme)
that involve the formation of a metal−ligand
adduct, as the first step of the process, followed
by an oxidative insertion of the metallic centre
into one C−H bond of the alkane molecule
(root 1). Furthermore also the possibility that M+(CH4) adducts react further with methane to
produce M+(CH4)n cluster ions has been investigated (root 2).
[1] A. Shayesteh, V. V. Lavrov, G. K. Koyanagi and D. K. Bohme, J. Phys. Chem. A 113 (2009) 56025611.
38
OR-22
New polymeric single-ion conductors for rechargeable lithiumbattery
Luca Porcarelli,a Alexander S. Shaplov,b Maitane Salsamendi,c Federico Bella,a
Jijeesh R. Nair,a David Mecerreyes,c and Claudio Gerbaldia
a
Dipartimento di Scienza Applicata e Tecnologia, Politecnico di Torino, Corso Duca degli
Abruzzi 24, 10129-Torino, Italy
b
Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov str. 28,
119991-Moscow, Russia
c
POLYMAT, University of the Basque Country UPV/EHU, Avda. Tolosa 72, 20018-DonostiaSan Sebastian, Spain
E-mail: [email protected]
In recent years, wide research efforts have been devoted to the development of solid polymer
electrolytes (SPEs) with the goal to enhance the intrinsic safety and replace the traditional
flammable liquid electrolytes employed in the lithium-ion battery technology. Very
commonly, SPEs are composed of a lithium salt dissolved either in a neutral polymer (e.g.,
PEO) or in an ion-conducting polymer matrix. The latter usually is represented by a new class
of polyelectrolytes, namely poly(ionic liquid)s (PILs) [1,2]. Although significant progresses
have already been achieved with cationic PILs, the motion of lithium ions carriers in such
PIL/Li salt composite separators constitutes only a small fraction (1/5th) of the overall ionic
current. This leads to the formation of a strong concentration gradient during battery
operation, with deleterious effects such as favored dendritic growth and limited power
delivery. Anionic PILs or polymeric single-ion conductors have been recently suggested as an
alternative. Differently from other SPEs, a single-ion conductor is composed of a polymeric
backbone bearing a covalently bonded anionic moiety and a Li counter-ion free to move and
responsible for the ionic conductivity. Given the single-ion nature of the above-mentioned
systems, the lithium-ion transport number is noticeably close to the unity.
In this work, we present an innovative family of single-ion polymer electrolytes based on
specifically developed lithium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethanesulfonyl)imide ionic monomer. Varying the macromolecular architecture of the
polyelectrolytes (i.e., random or block copolymers with poly(ethylene glycol) methyl ether
methacrylate or crosslinked networks with poly(ethylene glycol)dimethacrylate) it was
possible to develop the SPE with the tailored highest ionic conductivity. A full overview of
the electrochemical and thermal properties for the synthesized SPEs will be presented.
Finally, the performance of prototype lithium-ion batteries using the best PILs will be shown,
which demonstrates their highly promising prospects as next-gen all-solid safe electrolytes.
[1] J. Yuan, D. Mecerreyes and M. Antonietti, Prog. Polym. Sci. 38 (2013) 1009-1036.
[2] A. S. Shaplov, R. Marcilla and D. Mecerreyes, Electrochim. Acta 175 (2015) 18-34.
39
OR-23
Flame spray pyrolysis: catalysts for the steam reforming of bioethanol
Matteo Compagnoni,a Ilenia Rossetti,a Josè Lasso,a Valentina Nichele,b and
Michela Signorettob
a
Dipartimento di Chimica, Università degli Studi di Milano, Via C. Golgi 19, 20133-Milano,
Italy
b
Dipartimento di Scienze Molecolari e Nanosistemi, Università Cà Foscari Venezia, and
INSTM Unit Venezia, Calle Larga S. Marta, 30100-Venezia, Italy
E-mail: [email protected]
Flame Spray Pyrolysis (FSP) is a one step high temperature synthesis able to impart strong
metal-support interaction [1], besides high thermal resistance. A set of Ni catalysts supported
over ZrO2 doped with different basic oxide (CaO, MgO) were prepared by this innovative
technique. Steam Reforming catalytic tests were carried out for the production of hydrogen
using bio-ethanol. The catalytic activity was compared with catalysts of the same
composition, but prepared with a traditional precipitation/impregnation method (multistep
synthesis). Very high activity has been observed at high reaction temperature (>600°C), but
further kinetic studies were done under milder conditions (500-300°C), in order to lower the
energy input to the process and to improve H2 productivity favoring the water gas shift
reaction [2]. Two different bioethanol samples, 50 and 90 vol%, produced and supplied by
Mossi&Ghisolfi, have been used for 8 h-on-stream at each temperature. Attention was paid to
the catalyst resistance towards deactivation by coking, besides its activity and selectivity. The
acidity of the support was tuned by doping ZrO2 with basic oxides, helping to prevent ethanol
dehydration and coking by ethylene polymerization. Fresh and spent samples were
characterized by XRD, TPR, TPO, TEM, FE-SEM and Raman analysis.
Figure 1: Scheme and image of Flame Spray Pyrolysis.
[1] G. Ramis, I. Rossetti, E. Finocchio, M. Compagnoni, M. Signoretto and A. Di Michele, Progress
in Clean Energy, I. Dincer, Ed. Springer, in press.
[2] I. Rossetti, J. Lasso, E. Finocchio, G. Ramis, V. Nichele, M. Signoretto and A. Di Michele, Appl.
Catal. B: Environmental, 150-151 (2014) 257-267.
40
OR-24
Metal-free oxidation of aldehydes and alcohols using TCCA to
esters and anhydrides
Silvia Gaspa,a Andrea Porcheddu,b and Lidia De Lucaa
a
Dipartimento di Chimica e Farmacia, Università degli Studi di Sassari, Via Vienna 2,
07100-Sassari, Italy
b
Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari,
Cittadella Universitaria, 09042-Monserrato, Italy
E-mail: [email protected]
Trichloroisocyanuric acid (TCCA) is an inexpensive and easily available reagent with low
toxicity and it has been widely used in organic reactions such as oxidation and chlorination
reactions of alkenes [1]. Based on its remarkable properties we have decided to use it for the
generation of acyl chlorides in situ from starting unconventional molecules as alcohols and
aldehydes to obtain molecules with high added value such as esters and anhydrides. The
classical synthesis of acyl chlorides involve the use of toxic and expensive reagents (thionyl
chloride, chlorine) also have a poor applicability to a wide range of aldehydes and alcohols
[2].
We develop a one pot metal-free and eco-friendly protocol to convert aldehydes [3] or
alcohols in situ into acyl chlorides, that subsequently react with other alcohols to give a
variety of esters in high yields, or with carboxylic acid to obtained anhydrides.
Figure 1: Synthesis of esters and anhydrides from aldehydes or alcohols.
[1] U. Tilstam and H. Weinmann, Org. Process Res. Dev. 6 (2002) 384-393.
[2] (a) H. Gautier, Ann. Chim. Phys. 14 (1888) 362. (b) F. Loth and A. Michaelis, Chem. Ber. 27
(1894) 2540-2548.
[3] S. Gaspa, A. Porcheddu and L. De Luca Org. Lett.17 (2015) 3666-3669.
41
OR-25
Ab initio study on microsolvatation of melamine on graphene
Antonio M. Rodríguez,a Ana B. Muñoz-Garcia,a Orlando Crescenzi,a
Ester Vázquez,b and Michele Pavonea
a
Dipartimento di Scienze Chimiche, Università degli Studi di Napoli Federico II, Via Cintia
26, 80126-Napoli, Italy
b
Instituto Regional de Investigación Científica Aplicada, University of Castilla La-Mancha,
Avd Camilo José Cela, 13071-Ciudad Real, Spain
E-mail: [email protected]
Graphene has attracted enormous interest thanks to its inherent mechanical and electronic
properties [1], which make it very attractive for a wide variety of applications, ranging from
microelectronics to biosensing and nano-medicine [2,3]. However, these high-value
applications require high-quality graphene dispersions. In this context, non-covalent
interactions of graphene with small molecules present several advantages: they can facilitate
graphene exfoliation from graphite [4] and permit the modulation of graphene electronic
properties [5] by acting as effective dopants, but avoiding chemical modifications. Many
molecules have been proposed as exfoliating agents, but few have successfully stabilised
graphene in aqueous media: one example is 2,4,6-triamino-1,3,5-triazine, also known as
melamine [4].
Extending recent work on melamine-graphene interactions [4], here we addressed the role
of water in tuning the properties of melamine-graphene systems. To this end, we performed
stat-of-the-art first-principles calculations, with periodic boundary conditions, on different
coverages of melamine onto graphene. We observed how clusters of water molecules can
effectively interact with both the graphene [6,7] surface and the network of co-adsorbed
melamine molecules. Our objective is to find the most convenient coverage of microsolvated
melamine that stabilizes graphene moieties in water. Our results will provide useful insights
for the rational design of new non-toxic molecules that can conveniently adsorb with water on
graphene, thus enabling its effective use in aqueous media.
[1] K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, S. V. Dubonos, I. V. Grigorieva
and A. A. Firsov, Science 306 (2004) 666-669.
[2] K. S. Novoselov, V. I. Fal'ko, L. Colombo, P. R. Gellert, M. G. Schwab and K. Kim, Nature 490
(2012) 192-200.
[3] V. Palermo, Chem. Commun. 49 (2013) 2848-2857.
[4] V. Leon, A. M. Rodriguez, P. Prieto, M. Prato and E. Vazquez, ACS Nano 8 (2014) 563-571.
[5] S. Y. Zhou, D. A. Siegel, A. V. Fedorov and A. Lanzara, Phys. Rev. Lett. 101 (2008) art. no.
086402.
[6] F. Yavari, C. Kritzinger, C. Gaire, L. Song, H. Gulapalli, T. Borca-Tasciuc, P. M. Ajayan and N.
Koratkar, Small 6 (2010) 2535-2538.
[7] R. R. Freitas, R. Rivelino, B. Mota Fde and C. M. de Castilho, J. Phys. Chem. A 115 (2011) 1234812356.
42
OR-26
Direct hydrogenation of carbon dioxide by an artificial reductase
obtained by substituting rhodium for zinc in the carbonic
anhydrase catalytic center. A mechanistic study
Paolo Piazzetta,a Tiziana Marino,a Nino Russo,a and Dennis R Salahubb
Dipartimento di Chimica e Tecnologie Chimiche, Università della Calabria, Via Pietro
Bucci, 87036-Rende, Italy
b
Department of Chemistry, Institute for Quantum Science and Technology, Centre for
Molecular Simulation, University of Calgary, 2500 University Dr NW, Calgary, AB T2N 1N4,
Canada
E-mail: [email protected]
a
Recently, a new artificial carbonic anhydrase enzyme in which the native zinc cation has been
replaced with a Rh(I) has been proposed as a new reductase able to efficiently catalyze the
hydrogenation of olefins [1,2]. We propose the possible use of this modified enzyme in the
direct hydrogenation of carbon dioxide.
In our theoretical investigation we have considered different reaction mechanisms such as
reductive elimination and -bond metathesis. In addition, the release of the formic acid and
the restoring of the catalytic cycle has also been studied. Results show that the -bond
metathesis potential energy surface lies below the reactant species. The rate-determining step
is the release of the product with an energy barrier of 12.8 kcal mol-1. On the basis of our
results we conclude that this artificial enzyme can efficiently catalyze the conversion of CO2
to HCOOH by a direct hydrogenation reaction.
Figure 1: Rhodium substituted carbonic anhydrase active site.
[1] Q. Jing, K. Okrasa and J. Kazlauskas, Chem. Eur. J. 15 (2009) 1370-1376.
[2] Q. Jing, K. Okrasa and J. Kazlauskas, ChemCatChem 2 (2010) 953-957.
43
OR-27
Development of serum proteases-resistant cyclic peptides as
potent CXCR4 antagonists
Deborah Sementa,a Salvatore Di Maro,b Anna Maria Trotta,c Diego Brancaccio,a
Crescenzo D’Alterio,c Francesco Saverio Di Leva,a Ettore Novellino,a Stefania
Scala,c and Luciana Marinellia
a
Dipartimento di Farmacia, Università di Napoli Federico II, Via D. Montesano 49, 80131Napoli, Italy
b
Dipartimento di Scienze e Tecnologie Ambientali, Biologiche e Farmaceutiche, Via Vivaldi
43, 81100-Caserta, Italy
c
Dipartimento di Immunologia Oncologica, Istituto Nazionale per lo Studio e la Cura dei
Tumori “Fondazione Giovanni Pascale”, Via Mariano Semmola 52, 80131-Napoli, Italy
E-mail: [email protected]
The CXCR4/CXCL12 axis plays a pivotal role in cancer development of metastases, stem cell
mobilization and chemosensitization [1]. The interest about this pathway triggers the
discovery of a broad range of both peptidical and non peptidical structures [2]. Altough some
CXCR4 antagonists have reached preclinical and clinical stages, the discovery of new
inhibitors suitable for anticancer therapy is still necessary.
Definite, methodical and robust rearrangements of hit peptides [3] were carried out with
the aim of develop new potent and plasma stable CXCR4 antagonists. The systematic design
strategy (including e.g. Ala- and D- scan, N- and C- terminal modifications, conversion in
peptidomimetics) have enabled the generation of a promising library of peptides: new analogs
exhibit improved potency and metabolic properties suggestive of reasonable in vivo studies.
Figure 1: General structure of new potent and serum stable CXCR4 antagonists.
[1] D. Mukherjee and J. Zhao, Am. J. Cancer Res. 3 (2013) 46-57.
[2] O. Demmer, I. Dijkgraaf, U. Schumacher, L. Marinelli, S. Cosconati, E. Gourni, H. Wester and H.
Kessler, J. Med. Chem. 54 (2011) 7648-7662.
[3] L. Portella, R. Vitale, S. De Luca, C. D’Alterio, C. Ieranò, M. Napolitano, A. Riccio, M. Polimeno,
L. Monfregola, A. Barbieri, A. Luciano, A. Ciarmiello, C. Arra, G. Castello, P. Amodeo and S. Scala,
PLoS One 8 (2013) 745-748.
44
OR-28
A novel concept of semi-solid, flow Li-O2 battery
Irene Ruggeri, Catia Arbizzani, and Francesca Soavi
Dipartimento di Chimica “Giacomo Ciamician”, Università di Bologna, Via Selmi 2, 40100Bologna, Italy
E-mail: [email protected]
Although still at their infant state, Li/O2 batteries are considered the next generation of
batteries due to the significant higher energy than “conventional” Li-ion batteries of 2 or 3
times.
In Li/O2 batteries, O2 redox reaction (ORR) takes place at the solid electrode/electrolyte
interface, this process involves the formation of insulating superoxide and peroxide of lithium
that clog the electrode, highly increasing overpotentials and determining battery losses.
The limit of the conventional cell configurations, furthermore, is the sudden capacity drop
at high discharge rate, mainly due to the kinetics and mass transport issues in the cathode side
[1].
A radically new battery concept, a non-aqueous semi-solid flow Li-O2 battery which
combines the high energy density of Li/O2 battery with the flexible and scalable architecture
of redox flow batteries is here proposed [2].
The cell operates with a flowable O2-satured catholyte, which is pumped through the
battery, having lithium metal as anode. The catholyte is a suspension of high surface area
carbon in oxygen-saturated non-aqueous electrolyte.
In this cell, ORR takes place on the semi-solid electroactive particles dispersed in the
catholyte, avoiding the electrode passivation, enhancing the capacity and, in turn, the generate
energy.
The results of electrochemical test demonstrates the exceptionally high capacity at cathodic
voltages >2.6 V vs Li/Li+ and a high discharge rated (> 2.5 mA/cm2) of certainly interest for
practical applications [3].
[1] S. Monaco, F. Soavi and M. Mastragostino, J. Phys.Chem. Lett. 4 (2013), 1379-1382.
[2] F. Soavi, C. Arbizzani and I. Ruggeri, Patent Application (102015000040796).
[3] I. Ruggeri, C. Arbizzani and F. Soavi, manuscript under review.
45
OR-29
DNA Switches based on triple helices formation: design and
applications in nanotechnology
Andrea Idili,a Alessia Amodio,a,b Kevin W. Plaxco,c Alexis Vallée-Bélisle,d and
Francesco Riccia
a
Dipartimento di Scienze e Tecnologie Chimiche, Università degli Studi di Roma Tor
Vergata, Via della Ricerca Scientifica 1, 00173-Roma, Italy
b
Dipartimento di Fisica, Università degli Studi di Trieste, Via Valerio 2, 34127-Trieste, Italy
c
Department of Chemistry and Biochemistry, University of California, 93106-Santa Barbara,
USA
d
Departement of Chemistry, University of Montreal, 2900 Boulevard Edouard-Montpetit,
QCH3T1J4-Montréal, Canada
E-mail: [email protected]
DNA-based switches that shift between two or more conformations upon binding to a specific
target, or for a change in the environment, can be used to build robust, sensitive, and specific
sensors or use to engineer functional nanodevices. Among the various structure-switching
strategies employed by DNA-based sensors, those based on the formation of triple helices
structure seem very interesting and promising. Exploiting the features of parallel triplex
structure, we first designed and explored a DNA clamp-like molecular receptor that
recognizes a specific complementary oligonucleotide target through two recognition elements
that both bind and recognize the target. These two distinct recognition elements are based on
Watson−Crick and triplex-forming Hoogsteen interactions, which lead to the formation of a
triplex DNA structure. We fully realize and exploit the advantages of such molecular “doublecheck” mechanism, by adapting this clamp-like sensing strategy to a DNA-based
electrochemical biosensor. We demonstrate that this target-binding mechanism can improve
both the affinity and specificity of recognition as opposed to classic probes solely based on
Watson−Crick recognition. By using electrochemical signaling to report the conformational
change, we demonstrate a signal-on E-DNA sensor with up to 400% signal gain upon target
binding. We were able to detect with nanomolar affinity a perfectly matched target as short as
10 bases. Moreover, exploiting the pH-dependence of parallel triplex structure we have
designed programmable DNA-based nanoswitches whose closing/opening can be triggered
over specific different pH windows. These nanoswitches form an intramolecular triplex DNA
structure through pH-sensitive parallel Hoogsteen interactions. We demonstrate that by
simply changing the relative content of TAT/CGC triplets in the switches, we can rationally
tune their pH dependence over more than 5 pH units. The ability to design DNA-based
switches with tunable pH dependence provides the opportunity to engineer pH nanosensors
with unprecedented wide sensitivity to pH changes.
46
OR-30
Benzofuroxans – perspective platform for creation of potential
biologically active compounds
Elena Chugunova,a Alexander Burilov,a Rezeda Mukhamatdinova,b Alexandra
Voloshina,a Vladimir Zobov,a and Vladimir Samsonovc
a
A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center of
Russian Academy of Sciences, Arbuzov str., 8, 420088-Kazan, Russia
b
Kazan National Research Technological University, 68 Karl Marx st, 420015-Kazan, Russia
c
N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian
Academy of Sciences, 9 prosp. Akad. Lavrentґeva, 630090-Novosibirsk, Russia
E-mail: [email protected]
Benzofuroxans and their derivatives not only have established themselves as active
compounds with different spectrum of action, but attract attention as a precursor for the
synthesis of a number of heterocyclic compounds. Thus, substances, possessing antibacterial
and antifungal activity, were prepared on the basis of the interaction of
(di)сhloro(di)nitrobenzofuroxans with different aliphatic, aromatic amines, amino acids,
aminoalcohol nitrates, sulfanilamides, polyene antibiotics and other nucleophiles [1]. New
2H-benzimidazole 1,3-dioxides were also prepared on the base of benzofuroxans upon the
interaction with alcohols in sulfuric or perchloric acid. Under heating 2H-benzimidazole 1,3dioxides are rearranged to 3H-[2,1,4]benzoxadiazine 4-oxide which under irradiation
converted back to 2H-benzimidazole 1,3-dioxides. More prolonged heating causes sequential
elimination oxygen atom from oxadiazine cycle to form 2H-benzimidazole mono N-oxide [2].
This work was supported by the Russian Fundamental Research Fund (grants 14-03-31365
and 15-43-02088).
[1] E. A. Chugunova, A. D. Voloshina, R. E. Mukhamatdinova, I. V. Serkov, A. N. Proshin, E. M.
Gibadullina, A. R. Burilov, N. V. Kulik, V. V. Zobov, D. B. Krivolapov, A. B. Dobrynin and R.
Goumont, Lett. Drug Des. Discov. 11 (2014) 502-512.
[2] E. Chugunova, V. Samsonov, T. Gerasimova, T. Rybalova and I. Bagryanskaya, Tetrahedron 21
(2015) 7233-7244.
47
OR-31
Structural and electrochemical properties of
La0.6Sr0.4Co1-xFex-0.03M0.03O3-δ (x=0.2-0.8; M=Pd,Ni) perovskites
as IT-SOFCs cathodes
Fabrizio Puleo,a Alessandro Longo,a,b Valeria La Parola,a Concetta Lo Cascio,a
and Leonarda Francesca Liottaa
a
Istituto per lo Studio dei Materiali Nanostrutturati, Consiglio Nazionale delle Ricerche,
90146-Palermo, Italy
b
Dutch-Belgian Beamline, European Synchrotron Radiation Facility, B.P. 220, 38043Grenoble, France
E-mail: [email protected]
Thanks to their mixed ionic/electronic conductivity and high catalytic activity for oxygen
exchange reaction, La1−xSrxCo1−yFeyO3-δ (LSCF) perovskites have received much attention as
cathode materials for intermediate solid oxide fuel cells (IT-SOFCs) operating at relatively
low-temperature, 600-800 °C. Lowering the operating temperature, however, decreases the
electrode kinetics, in particular the oxygen reduction at the cathode.
It is widely accepted that the rate-limiting step of O2 reduction process is the solid state
diffusion of oxygen anions through the vacancies of the cathode lattice. LSCF oxides with
metal substitution in B-site prepared by different methods, such as solid-state reaction or by
impregnation of the perovskite with the metal dopant precursor, have been extensively
investigated as new cathodes with enhanced oxygen reduction activity [1]. The promotion of
redox properties of La0.6Sr0.4Co0.8Fe0.2O3-δ and of La0.6Sr0.4Co0.2Fe0.8O3-δ by incorporation of
Pd4+ into the B-site of the perovskite lattice, through one pot citrate synthesis, has been
recently demonstrated by some of us [2]. The present work aims to get more insight into the
B-site metal promotion by investigating the effect of two metals (Pd and Ni) and by using
citrate method that provides a good control of the microstructural properties.
Perovskites with compositions La0.6Sr0.4Co1-xFex-0.03M0.03O3-δ (x=0.2-0.8; M=Pd/Ni) have
been prepared and compared with the un-promoted La0.6Sr0.4Co0.2Fe0.8O3-δ cathode material.
Characterizations by XRD, EXAFS, TPR, XPS, TGA and EIS techniques have been carried
out. Addition of Pd and Ni to La0.6Sr0.4Co0.2Fe0.8O3-δ was found to be effective in improving
the redox and electrochemical properties.
[1] S. Guo, H. Wu, F. Puleo and L. F. Liotta, Catalysts 5 (2015) 366-391.
[2] F. Puleo, L. F. Liotta, V. La Parola, D. Banerjee, A. Martorana and A. Longo, Phys. Chem. Chem.
Phys. 16 (2014) 22677-22686.
48
OR-32
Hetero-nanoparticles as a useful tool for cancer therapy
Gaia Fumagalli,a Davide Mazza,b and Daniele Passarellaa
a
Dipartimento di Chimica, Università degli Studi di Milano, Via Golgi 19, 20133-Milano,
Italy
b
Centro di Imaging Sperimentale, San Raffaele Scientific Institute - Ospedale San Raffaele,
Via Olgettina 28, 20132-Milano, Italy
E-mail: [email protected]
Our continuous interest in the field of chemical approaches to target cancer cells moved us to
study the preparation of a novel class of squalene conjugates with paclitaxel, podophyllotoxin,
camptothecin and epothilone A. All of them were characterized by a squalene tail that makes
them able to self-assemble in water and a linker to secure the release inside the cells [1]. The
need to demonstrate the internalization of the drugs pushed us toward the formation of
heterogeneous fluorescent nanoassemblies by mixing a paclitaxel-squalene conjugate and
fluorescein-squalene conjugate [2].
The following application of hetero-nanoparticles is in the combined therapy. Mixing a
paclitaxel-squalene conjugate and a cyclopamine-squalene conjugate we were able to obtain
hetero-nanoparticles able to induce Hedgehog inhibition. The preparation of fluorescent
hetero-nanoparticles containing a paclitaxel-squalene conjugate, a cyclopamine-squalene
conjugate and tetramethylrhodamine-sqalene conjugate serves to demonstrate the
internalization of the nanoassemblies.
Figure 1: Hetero-nanoparticles internalization.
[1] S. Borrelli, M. S. Christodoulou, I. Ficarra, A. Silvani, G. Cappelletti, D. Cartelli, G. Damia, F.
Ricci, M. Zucchetti, F. Dosio and D. Passarella, Eur. J. Med. Chem 85 (2014) 179-190.
[2] S. Borrelli, D. Cartelli, F. Secundo, G. Fumagalli, M. S. Christodoulou, A. Borroni, F. Dosio, G.
Cappelletti and D. Passarella, ChemPlusChem 80 (2015) 47-49.
49
OR-33
Improving the stability of graphite anodes in ether-based
electrolytes for lithium batteries
Fabian Jeschull, Matthew. J. Lacey, and Daniel Brandell
Department of Chemistry – Ångström Laboratory, Uppsala University, Box 538, 75121Uppsala, Sweden
E-mail: [email protected]
Lithium-ion batteries quickly dominated the market of mobile applications after their
introduction in the early 90’s. This “rocking chair” battery typically uses a graphite negative
electrode and a transition metal oxide positive electrode, with lithium ions moving back and
forth between anode and cathode respectively. These electrodes typically comprise the active
material, a conductive additive and a binder.
At low potentials, electrolyte components decompose and deposit on the graphite, thus
rendering the electrode kinetically stable. This so called solid-electrolyte interface (SEI) is
crucial for the stability and durability of the battery. Until recently, stable SEI layers were
limited to carbonate-based electrolytes [1].
This talk will outline how the surface chemistry of graphite particles alters the SEI formation
by replacing traditional binders, such as poly(vinylidene difluoride) (PVdF), by the functional
polymer poly(acrylic acid) (PAA). In combination with LiNO3, the electrodes cycle stable
even in ether-based electrolytes. This opens new opportunities for low temperature
applications and other cell chemistries. Especially lithium-sulfur batteries, where lithium
metal anodes and sulfur-carbon composite cathodes are applied, receive renewed interest in
recent years by virtue of the earth abundance of sulfur and high energy density, potentially 23 times greater than current Li-ion batteries. Lithium metal, however, is problematic, as
morphological changes upon repeated cycling cause rapid cell failure [2]. Using a graphite
electrode can help to mitigate parasitic reactions at the negative electrode and reduce selfdischarge through formation of a more stable electrode-electrolyte interface (Figure 1).
Figure 1: Self-discharge experiments of a Li-S (red) and a graphite-S battery (blue).
[1] F. Jeschull, M. J. Lacey and D. Brandell, Electrochim. Acta 175 (2015) 141-150.
[2] S. Urbonaite, T. Poux and P. Novák, Adv. Energy Mater. 5 (2015) art. no. 201500118.
50
OR-34
Development of StAGE tips sample pretreatment for UHPLCMS/MS analysis of Candida albicans quorum-sensing molecules
Michele Protti,a Veronika Pilařová,b Pavel Svoboda,b Laura Mercolini,a and
Lucie Novákováb
a
Dipartimento di Farmacia e Biotecnologie, Università di Bologna, Via Belmeloro 6, 40126Bologna, Italy
b
Department of Analytical Chemistry, Charles University in Prague, Heyrovského 1203,
50005-Hradec Králové, Czech Republic
E-mail: [email protected]
Candida albicans is a commensal fungi as member of the gastrointestinal, oropharyngeal and
female genital flora. However, it is also an opportunistic pathogen in humans, causing
diseases in immunodeficient and immunocompetent individuals that can be life-threatening.
C. albicans can grow as budding yeast, hyphae or pseudohyphae and its morphological
conversion from yeast form to pseudohyphal or hyphal stage is often characterized by the
shift from commensal status to an invasive form. Quorum sensing molecules (QSMs) are
extracellular chemical signals, continuously produced in response to increasing density of
microbial population to coordinate action of the cells, thus participating in such
transformation processes, together with some physical-chemical factors. Two main QSMs in
C. albicans under study are farnesol and tyrosol (Fig.1). While farnesol blocks the dimorphic
transition from yeast to mycelial, tyrosol supports the development of its filamentous form
[1].
For this research, a fast and reliable analytical
method, based on ultra high performance liquid
chromatography coupled to tandem mass
spectrometry (UHPLC-MS/MS), was developed
for the simultaneous determination of farnesol and
tyrosol as quorum-sensing molecules of C.
albicans.
In order to minimize the required amount of
biological samples and maximize sample
preparation throughput, a feasible yet advanced miniaturized pretreatment procedure based on
Stop And Go Extraction (StAGE) tips was developed, as a novel powerful Pipette Tip Solid
Phase Extraction (PT-SPE) approach to complex matrix analysis. The optimized method
provided good results in terms of sensitivity and selectivity and is being fully validated, for its
application to vaginal washing samples, in order to study the role of quorum sensing
molecules in potentially pathogenic yeasts.
The work was supported by the project AZV 15-29225A MZ ČR.
[1] M. Kruppa, Mycoses 52 (2009) 1-10.
51
OR-35
Characterization and applications in seconds time scale of new
totally porous sub-2micron CSPs: brush-type and macrocyclic
selectors
Omar H. Ismail, Alessia Ciogli, Claudio Villani, and Francesco Gasparrini
Dipartimento di Chimica, Sapienza - Università di Roma, Piazzale A. Moro 5, 00185-Roma,
Italy
E-mail: [email protected]
Over the last ten years, the technological progress has led to the development of stationary
phases on ever smaller silica particles and instuments (UHPLC/UHPSFC) with a reduced
extra-column volume able to reach very high pressure. These innovations allow higher
efficiencies, resolutions and permit to reduce the analysis time and the eluent consumption.
For these reasons also chiral stationary phases (CSPs) are moving to sub-2µm particles
diameter. This talk concerns the development of two different sub-2µm CSPs based on the
WhelkO-1 [1] and on the teicoplanin selectors [2]. The first selector was covalently bonded
on fully porous 1.8 µm Kromasil and the second one on totally porous and monodispersed 1.9
µm Titan silica particles. Both CSPs were packed in columns with an I.D. of 4.6 mm and
different lengths, from 10 cm down to 1 cm, the latter geometry permitting very short analysis
time. The UHPLC columns packed with the WhelkO-1-CSP were evaluated using normal
phase and supercritical fluid eluents. Kinetic performances were estimated using transstilbene oxide as a probe, and resulted in efficiencies up to 250’000 plates/m under normal
phase conditions. To evaluate the thermodynamic performances a large library screening [3]
was performed under sub-critical fluid conditions: in one working day, 81 out of 129
randomly collected racemates were resolved under identical eluting conditions. The new
UHPC-Titan120-Chirobiotic-TZWIT-1.9 showed a broad field of application in different
environments (reversed phase, polar organic mode, HILIC, sub-critical fluid and normal
phase). The thermodynamic performances of the new TEICO-Titan 1.9 µm have been
evaluated with several N-protected amino acids, aryloxy acids, pharmaceutical compounds,
sulfoxides and phosphine oxides. This CSP frequently showed high enantio-selectivity values:
downsizing in column length, from 10-cm down to 1-cm was easily possible maintain high
efficiency obtaining baseline separations and providing a considerable reduction of the
analysis time. Ultra-fast enantiomeric separations in less than 60 seconds could get a routine
in the chiral screening methods.
[1] D. Kotoni, A. Ciogli, C. Molinaro, I. D’Acquarica, J. Kocergin, T. Szczerb, H. Ritchie, C. Villani
and F. Gasparrini, Anal. Chem. 84 (2012) 6805-6813.
[2] A. Berthod, X. Chen, J. P. Kullman, D. W. Armstrong, F. Gasparrini, L. D’Acquarica, C. Villani
and A. Carotti, Anal. Chem. 72 (2000) 1767-1780.
[3] L. Sciascera, O. Ismail, A. Ciogli, D. Kotoni, A. Cavazzini, L. Botta, T. Szczerba, J. Kocergin, C.
Villani and F. Gasparrini, J. Chromatogr. A 1383 (2015) 160-168.
52
OR-36
Phenothiazine dyes in hydrogen production: tuning performances
through dye design
Bianca Cecconi,a Norberto Manfredi,a Tiziano Montini,b Paolo Fornasiero,b and
Alessandro Abbottoa
a
Dipartimento di Scienza dei Materiali, Università degli Studi di Milano-Bicocca, Via Cozzi
55, 20125-Milano, Italy
b
Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Trieste, Via L.
Giorgieri 1, 34127-Trieste, Italy
E-mail: [email protected]
In recent years many research groups showed interest in hydrogen production from renewable
sources. Splitting water molecules is an energy demanding process and solar radiation could
provide such request. Inspired by DSSC technology, an analogous mechanism can be
envisaged for water splitting, as it is illustrated in Figure 1a.
In such devices dyes are the first interface towards solar radiation, so we focused in the
design of organic metal-free sensitizers, since they have been scantly investigated in the
literature. We selected the dye-architecture of the multi-branched multi-anchoring D(-π-A)2
geometry, firstly introduced by us a few years ago and now widely used in the DSSC field
[1], we selected phenothiazine core as a donor unit.
Here we present the effect of different modifications on the dye structure in the
photocatalytic production of hydrogen in presence of a sacrificial donor. The proper design of
the heteroaromatic -spacer (Figure 1b) afforded significant enhancement of optical
properties, improved stability under irradiation, and enhanced hydrogen production rates in
the long-term. Modulation of the hydrophilicity of the catalyst:dye system, by exploiting the
R group (Figure 1b) on the phenothiazine core, gave important influences on the surface
wettability properties and improved photocatalytic performances.
Figure 1: left) Dye-sensitized H2 production; right) Structure of a phenothiazine dye.
[1] a) A. Abbotto, N. Manfredi, C. Marinzi, F. De Angelis, E. Mosconi, J. H. Yum, Z. Xianxi, M. K.
Nazeeruddin and M. Grätzel, Energy Environ. Sci. 2 (2009) 1094-1101; b) N. Manfredi, B. Cecconi
and A. Abbotto, Eur. J. Org. Chem. 32 (2014) 7069-7086.
53
OR-37
Multi-functional TiO2 nanotubes arrays by anodic oxidation: from
energy to bio-sensing
Andrea Lamberti,a Adriano Sacco,b Stefano Bianco,a Alessandro Virga,a
Alessandro Chiadò,a Federico Bella,a Angelica Chiodoni,b Katarzyna Bejtka,b
Paola Rivolo,a Elena Tresso,a Fabrizio Giorgis,a and Candido Fabrizio Pirria,b
a
Dipartimento di Scienza Applicata e Tecnologia, Politecnico di Torino, C.so Duca degli
Abruzzi 24, 10129-Torino, Italy
b
Center for Space Human Robotics, Istituto Italiano di Tecnologia, C.so Trento 21, 10129Torino, Italy
E-mail: [email protected]
Since the first report of Zwilling and coworkers [1], vertically aligned titanium dioxide (TiO2)
nanotube (NT) arrays by anodic oxidation have been largely investigated as active element for
dye-sensitized solar cells [2], Li-ions batteries, water photoelectrolysis, artificial
photosynthesis, biomedical devices, molecular sensors [3], gas sensors, and photocatalytic
degradation of pollutants. Thanks to their quasi one-dimensional arrangement, TiO2 NTs are
able to provide high surface area and superior electron transport properties resulting in a
performance enhancement in the different fields of application. The electrochemical oxidation
of Ti foil in a fluorine-based electrolyte is a simple, cheap and green process, easy to be
scaled up towards massive production and with a low energy payback time if used for energy
harvesting applications. We present and discuss the integration of these arrays as efficient
photoanodes into dye-sensitized solar cells - DSCs (see Figure 1a) - and as ultra-sensitive
SERS substrate for bio-sensing application (see Figure 1b).
Figure 1: Electrical characterization of TiO2 NTs based DSCs (a) and SERS spectra collected
on Ag-decorated TiO2 substrates (b). Inset in (a) shows electron microscope cross-section of
the TiO2 NT arrays.
[1] V. Zwilling, M. Aucouturier and E. Darque-Ceretti, Electrochim. Acta 45 (1999) 921-929.
[2] A. Lamberti, A. Sacco, S. Bianco, D. Manfredi, F. Cappelluti, S. Hernandez, M. Quaglio and C. F.
Pirri, Phys. Chem. Chem. Phys. 15 (2013) 2596-2602.
[3] A. Lamberti, A. Virga, A. Chiadò, A. Chiodoni, K. Bejtka, P. Rivolo and F. Giorgis, J. Mater.
Chem. C 3 (2015) 6868-6875.
54
OR-38
Synthesis and application of new, pyridine-containing D-π-A
organic photosensitizers for DSSCs
Daniele Franchi,a,b Massimo Calamante,a,b Alessandro Mordini,a,b Gianna
Reginato,b and Lorenzo Zanib
Dipartimento di Chimica “Ugo Schiff”, Università degli Studi di Firenze, Via della
Lastruccia 13, 50019-Sesto Fiorentino, Italy
b
Istituto di Chimica dei Composti Organometallici, Consiglio Nazionale delle Ricerche, Via
Madonna del Piano 10, 50019-Sesto Fiorentino, Italy.
E-mail: [email protected]
a
Dye-sensitized solar cells (DSSC) have been considered a potential alternative for buildingintegrated PV devices [1], but their industrial development has been hampered by their low
efficiency and limited lifetime. We synthesize new D-π-A structured DSSC organic
sensitizers [2] bearing pyridine-based anchoring groups and we compare efficiency and
stability with dyes having a traditional cyanoacrylic acceptor (named DF15). Pd-catalyzed
cross-coupling reaction were used to build up the common D-π scaffold and to introduce the
novel anchoring units. We prepare the target dyes having three regioisomeric
carboxypyridines as acceptor groups. Spectroscopic, electrochemical and computational
characterization were carried out and compared with DF15. Test devices prepared with these
new sensitizers provided power conversion efficiencies corresponding to 54-63% of those
obtained with DF15. More significantly, device stability tests carried out on transparent,
larger area cells and determination of desorption pseudo-first order rate constants showed that
some of these new compounds were removed from TiO2 more slowly than DF15 suggesting a
possible cooperative effect of the two functional groups on semiconductor binding [3]. We
increased the electron-withdrawing character of the pyridine rings with N-methylpyridinium
derivation. Despite more favorable photophysical properties, the cells built with the cationic
sensitizers provide lower efficiencies than their neutral counterparts does.
[1] A. Hagfeldt, G. Boschloo, L. Sun, L. Kloo and H. Pettersson, Chem. Rev. 110 (2010) 6595-6663.
[2] Y. Ooyama and Y. Harima, ChemPhysChem. 13 (2012) 4032-4080.
[3] D. Franchi, M. Calamante, G. Reginato, L. Zani, M. Peruzzini, M. Taddei, F. Fabrizi de Biani, R.
Basosi, A. Sinicropi, D. Colonna, A. Di Carlo and A. Mordini, Tetrahedron 70 (2014) 6285-6295.
55
OR-39
Multivariate approaches for dye-sensitized solar cells
Simone Galliano,a Nadia Barbero,a Valentina Gianotti,b Claudio Gerbaldi,c
Claudia Barolo,a and Federico Bellac
a
Dipartimento di Chimica e Centro Interdipartimentale NIS, Università degli Studi di Torino,
Via Pietro Giuria 7, 10125-Torino, Italy
b
Dipartimento di Scienze ed Innovazione Tecnologica, Università degli Studi del Piemonte
Orientale “Amedeo Avogadro”,Viale Teresa Michel 11, 15121-Alessandria, Italy
c
Dipartimento di Scienza Applicata e Tecnologia, Politecnico di Torino, Corso Duca degli
Abruzzi 24, 10129-Torino, Italy
E-mail: [email protected]
Dye-sensitized Solar Cells (DSCs) represent a promising and emerging technology because of
their simple and easily scalable fabrication process, low cost of the components, color
tunability, possibility of transparency and flexibility. However, efficiency and stability of
DSCs are still limited, especially if compared to Si-based solar cells, and some of the
components are often not environmental friendly and even dangerous [1]. These issues
prevent the large-scale industrialization of practical devices and solving them has become a
key objective. To make it possible, we think it is necessary to consider the DSC as a complex
system
assembled
with
different
and
heterogeneous
layers
(FTO/semiconductor/sensitizer/electrolyte/Pt-FTO), each of them affected by intrinsic
variability. It is clear that a classical OVAT (One-Variable-At-Time) method is not adequate
and a comprehensive approach is strongly required. In particular, considering a higher number
of experimental factors concurrently would be a better strategy to analyze in dept the
multivariate DSC system [2].
In this work, we show how chemometrics and multivariate design of experiments (DoE)
can be used to study and optimize some components or fabrication procedures of DSCs in
order to enhance their performance, long term stability [3] and environmental compatibility
(Figure 1).
Figure 1: Example of DoE and DSC performances.
[1] F. Bella, C. Gerbaldi, C. Barolo and M. Grätzel, Chem. Soc. Rev. 44 (2015) 3431-3473.
[2] V. Gianotti, G. Favaro, L. Bonandini, L. Palin, G. Croce, E. Boccaleri, E. Artuso, W. Van Beek, C.
Barolo and M. Milanesio, ChemSusChem 7 (2014) 3039-3052.
[3] J. Park, N. Barbero, J. Yoon, E. Dell’Orto, S. Galliano, R. Borrelli, J. H. Yum, D. Di Censo, M.
Grätzel, Md Nazeeruddin, C. Barolo and G. Viscardi, Phys. Chem. Chem. Phys. 16 (2014) 2417324177.
56
OR-40
Effect of different length chains on DSSCs performance
Giuseppina Anna Corrente,a,b Agostina Lina Capodilupo,c Luisa De Marco,b and
Giuseppe Ciccarellaa
a
Dipartimento di Ingegneria dell'Innovazione, Università del Salento, Via per Monteroni,
73100-Lecce, Italy
b
Center for Biomolecular Nanotechnologies, Istituto Italiano di Tecnologia, Via Barsanti 1,
73010-Arnesano, Italy
c
Istituto di Nanotecnologia, Polo di Nanotecnologie c/o Campus Ecotekne, Consiglio
Nazionale delle Ricerche, Via Monteroni, 73100-Lecce, Italy.
E-mail: [email protected]
Dye-sensitized solar cells (DSSCs) have attracted considerable attention in scientific research
and practical applications. These devices show high conversion of sunlight to electricity and
low-cost production. The organic sensitizing. plays a significant role in DSSCs, because its
light-harvesting ability determines the upper limit of the conversion efficiency.
Organic sensitizers for DSSCs are mainly classified as metal-containing and metal-free
dyes. Compared to the first class, metal-free sensitizers have advantages such as low cost and
structural design flexibility. By a careful molecular design, photovoltaic performance of
DSSCs can be widely improved [1-3].
We have designed and synthesized a series of organic dyes containing two donor moieties
bonded to the dibenzofulvene core, with two thiophene spacer-linker forming a 2D-π-A pushpull system, to improve the performance of the solar cells. Starting from a “model molecule”
TK3 we evaluated the effects caused by the introduction of an alkyl chain on thiophene ring
and two alkoxy chains of different length in p-position of the aryl rings of donor units.
Figure 1: Structures of the dyes.
[1] A. L. Capodilupo, L. De Marco, E. Fabiano, R. Giannuzzi, A. Scrascia, C. Carlucci, G. A.
Corrente, M. P. Cipolla, G. Gigli and G. Ciccarella, J. Mater. Chem. A 2 (2014) 14181-14188.
[2] A. Scrascia, L. De Marco, S. Laricchia, R. A. Picca, C. Carlucci, E. Fabiano, A. L. Capodilupo, F.
Della Sala, G. Gigli and G. Ciccarella, J. Mater. Chem. A 1 (2013) 11909-11921.
[3] A. Scrascia, M. Pastore, L. Yin, R. A. Picca, M. Manca, Y.-C. Guo, F. De Angelis, F. Della Sala,
R. Cingolani, G. Gigli and G. Ciccarella, Curr. Org. Chem. 15 (2011) 3535-3543.
57
OR-41
Laboratory spectroscopy of species of astrochemical interest
Annalisa Vigorito, Assimo Maris, Camilla Calabrese, and Sonia Melandri
Dipartimento di Chimica “Giacomo Ciamician”, Università di Bologna, Via Selmi 2,
40100-Bologna, Italy
E-mail: [email protected]
The research of molecular species in the interstellar medium arouses great interest. By
these investigations, it is believed to trace the origin of the life and its evolution. The
molecular species in gas phase are identified, principally, by theirs rotational spectra.
The free jet microwave spectroscopy results on some promising molecular systems
(fluorenone, acrylic acid, gamma-lactams and 1,2-butanediol) to search in the interstellar
medium will be presented.
Although molecular adducts have never been observed in the space, it is likely that in
appropriate conditions they can be formed. Due to the abundance of the monomeric
species, it is supposed that adducts involving nitriles can be good candidates to be
observed.
For this reason the millimeter spectra of molecular adducts between acrylonitrile with
water and methanol are assigned, while the measurements on acetonitrile-water complex
were extended in the 59.6-74.4 GHz frequency region. Some considerations on the ways of
interactions of the two subunits will be done.
58
OR-42
Effect of rare-earth doping of anatase on the performances of
dye sensitized solar cells
Carmen Cavallo,a Alessandro Latini,a Alberto Salleo,b and Daniele Gozzia
a
Dipartimento di Chimica, Sapienza - Università di Roma, Piazzale A. Moro 5, 00185Roma, Italy
b
Department of Materials Science and Engineering, Stanford University, 94305-Stanford,
USA
E-mail: [email protected]
In a recent paper [1] we obtained a reproducible behavior and a significant improvement of
the efficiency of dye sensitized solar cell by substitution of pure anatase semiconductor in the
photoanode with solid solutions of scandium in anatase. In the similar way the improvement
of the performance of Dye-Sensitized Solar Cells (DSSCs) has been obtained by doping
anatase with Er3+or Yb3+ cations. In this work, the mesoporous TiO2 samples were
synthesized by controlled hydrolysis of titanium isopropoxide and the corresponding rare
earth isopropoxide in presence of a templating agent. The cells prepared using these materials
and a non-volatile electrolyte [2] were tested by means of I-V curves under simulated solar
radiation (AM 1.5G), electrochemical impedance spectroscopy, dark current and IPCE
measurements. The highest performing cell (Fig. 1) (0.2% Er metal atoms) showed the
following photovoltaic performances: a short circuit current density of 16.45 mA cm‒2, an
open circuit voltage of 0.731 V and a FF of 0.71 for an overall energy conversion efficiency
of 8.7%. For undoped TiO2 the same parameters were: 13.99 mA cm‒2, 0.725 V, 0.69 and 7%.
A discussion of the obtained results as a function of the dopant and its concentration will be
presented.
Figure 1. J-V polarization curve of DSSC with anatase undoped and doped Er3+ at 0.2%.
[1] A. Latini, C. Cavallo, F. K. Aldibaja and D. Gozzi, J. Phys. Chem. C 117 (2013) 25276-25289.
[2] A. Latini, F. K. Aldibaja, C. Cavallo and D. Gozzi, J. Power Sources 269 (2014) 308-316.
59
OR-43
Synthesis, characterization and applications of new dipeptide
based hydrogelators
Nicola Zanna, Lorenzo Milli, and Claudia Tomasini
Dipartimento di Chimica “Giacomo Ciamician”, Università di Bologna, Via Selmi 2, 40100Bologna, Italy
E-mail: [email protected]
Hydrogels are solid like materials composed mainly by water, as they are formed by a water
phase immobilized by a scaffold that results in a gel. Their applications range from the
preparation of new materials, drug delivery, biomineralization, growth of cultured cells,
mimicking the extracellular matrix, etc. [1].
Low molecular weight gelators (LMWGs) are small molecules able to gelate water and/or
organic solvents by the formation of reversible supramolecular architectures governed by
interactions such as π–π stacking, non-covalent interactions, hydrophobic and hydrogen bond,
that favor the formation of layers that in turn get organized into fibers able to trap liquids.
Recently, the gelation behavior of Fmoc-protected dipeptides has been studied and
reported [2]. Now we want to show here the gelation properties of some Fmoc-protected
peptidomimetics, containing the L-Phe-D-Oxd unit (or the isosteric L-Phe-D-pGlu unit), that
is a privileged scaffold for the preparation of supramolecular materials [3].
[1] R. J. Wade, E. J. Bassin, W. M. Gramlich and J. A. Burdick, Adv. Mater. 27 (2015) 1356-1362.
[2] V. Jayawarna, M. Ali, T. A. Jowitt, A. E. Miller, A. Saiani, J. E. Gough and R. V. Ulijn, Adv.
Mater. 18 (2006) 611-614.
[3] a) C. Tomasini, G. Angelici and N. Castellucci, Eur. J. Org. Chem. 2011 (2011) 3648-3669; b) G.
Angelici, G. Falini, H. J. Hofmann, D. Huster, M. Monari and C. Tomasini, Angew. Chem. Int. Ed. 47
(2008) 8075-8078.
60
OR-44
Versatile inherently chiral materials for electrochemistry
Serena Arnaboldi,a Patrizia Mussini,a Franceso Sannicolò,a and Tiziana
Benincorib
a
Dipartimento di Chimica, Università degli Studi di Milano, Via Golgi 19, 20133-Milano,
Italy
b
Dipartimento di Scienze Chimiche ed Ambientali, Università degli Studi dell’Insubria, Via
Valeggio 11, 22100-Como, Italy
E-mail: [email protected]
The usual approaches to chiral electroactive molecular materials, relying on attaching chiral
pendants to an electroactive polyconjugated backbone, generally result in modest chirality
manifestations; other approaches, such as chiral templating agents, chiral counteranions, etc.
actually imply the chirality source to be external to the electroactive material. Very recently,
our research group has unveiled by electrochemical experiments the unprecedented
enantioselectivity properties of molecular films based on a new family of "inherently chiral"
polyheterocycles, where chirality is not external to the electroactive backbone, but inherent to
it, resulting from a tailored torsion produced by the periodical presence of atropoisomeric,
conjugatively active biheteroaromatic scaffolds [1]. The electroactive films obtained by
electrooligomerization mostly consist of cyclic electroactive oligomers, constituted by several
fully conjugated thiophene units. These ringlets, which can also be obtained by chemical
oligomerization are endowed with an outstanding pool of attractive properties both as
racemates and as enantiopure antipodes [1,2]. The neat peak separation for two enantiomers
of electroactive chiral probes together with the linearity of the peak currents with enantiomer
concentration affords estimation of the enantiomeric excess when both enantiomers are
present. The new electrodes have been tested with very good results towards several chiral
probes, quite different in molecular structure and of applicative interest, on different supports,
and in different media. Moreover, we have verified that the same spectacular
enantioselectivity is obtained on surfaces prepared starting from monomers designed
according to the same structural concept but chemically different, which demonstrates the
general validity of the new strategy. Albeit preliminary, such unprecedented outstanding
results open the way to chiral voltammetry.
Considering the outstanding enantioselectivity obtained with inherently chiral surfaces, our
research group has been started to investigate whether the "inherently chiral" concept can also
yield enantioselectivity when implemented in ionic liquids or supporting electrolytes. This
study is still in its early stage, but preliminary tests seem to indicate that, also in this case,
significant enantioselectivity could be achieved by applying the inherent chirality concept.
[1] F. Sannicolò, S. Arnaboldi, T. Benincori, V. Bonometti, R. Cirilli, L. Dunsch, W. Kutner, G. Longhi, P.
R. Mussini1, M. Panigati, M. Pierini and S. Rizzo, Angew. Chem. Int. Ed. 53 (2014) 2623-2327.
[2] F. Sannicolò, P. R. Mussini, T. Benincori, R. Cirilli, S. Abbate, S. Arnaboldi, S. Casolo, E. Castiglioni,
G. Longhi, R. Martinazzo, M. Panigati, M. Pappini, E. Quartapelle Procopio and S. Rizzo, Chem. Eur. J. 20
(2014) 15298-15302.
61
OR-45
Optimization of urokinase receptorderived peptide SRSRY by
head-to-tail cyclization
Ali Munaim Yousif,a Vincenzo Ingangi,b Francesco Merlino,a Maria Vincenza
Carriero,b Ettore Novellino,a and Paolo Griecoa
a
Dipartimento di Farmacia, Università di Napoli Federico II, Via D. Montesano 49, 80131Napoli, Italy
b
Dipartimento di Immunologia Oncologica, Istituto Nazionale per lo Studio e la Cura dei
Tumori “Fondazione Giovanni Pascale”, Via Mariano Semmola 52, 80131-Napoli, Italy
E-mail: [email protected]
The urokinase-type plasminogen activator receptor (uPAR) is a widely recognized master
regulator of cell migration and uPAR88-92 is the minimal sequence required to induce cell
motility. Studies has documented that the S88RSRY92 peptide, even in the form of synthetic
linear form, interacts with the formyl peptide receptor type 1 (FPR1), henceforth inducing cell
migration of several cell lines [1]. FPR1 plays a crucial role in chemotaxis. In this present
work, we provide evidence that the constriction of S88RSRY92 into macrocyclic conformation
revealed to be an efficient approach to develop novel peptide analogues [2]. These
compounds resulted to be as potent and stable inhibitors of cell migration. After the
elongation of the linear peptide on solid support by solid phase synthesis, the
macrocyclization was carried out using head to tail cyclization strategy (C-terminus to Nterminus) in solution phase. To advance our knowledge about the features of uPAR/FPR
interaction inhibitors, a small library of cyclic peptides has been designed and successfully
synthesized. The synthesized compounds contain a phosphorylated L-serine, and/or Glutamic
residue in both 88 and 90 positions to mimic the revisable phosphorylation process.
Furthermore, modifications at the aromatic moiety in position 92 into macrocyclic
conformation has been introduced by using different aromatic amino acids such as Phe, Trp,
Nal(1’), and Nal(2’) (Figure 1).
Figure 1. General structure of cyclic peptides, and side chains substitutions.
[1] M. Resnati, I. Pallavicini, J. M. Wang, J. Oppenheim, C. N. Serhan and M. Romano, Proc. Natl.
Acad. Sci. 99 (2002) 1359-1364.
[2] A. M. Yousif, M. Minopoli, K. Bifulco, V. Ingangi, G. Di Carluccio, F. Merlino, M. L. Motti, P.
Grieco and M. V. Carriero, PLoS One 10 (2015) e0126172.
62
OR-46
Novel quinoid compounds as photosensitizers on ITO
Federica Sabuzi, Emanuela Gatto, Valeria Conte, Barbara Floris, Mariano
Venanzi, and Pierluca Galloni
Dipartimento di Scienze e Tecnologie Chimiche, Università degli Studi di Roma Tor Vergata,
Via della Ricerca Scientifica, 00133-Roma, Italia
E-mail: [email protected]
KuQuinones belong to a new class of pentacyclic quinoid compounds, synthesized for the
first time few years ago in our research group [1]. KuQuinones are characterized by a broad
absorption spectrum in the visible region, due to the extended electronic conjugation over the
five rings [1]; in particular, UV-vis spectrum shows two intense and broad absorption bands
between 450 and 600 nm. This class of molecules is also characterized by a low reduction
potential compared to simpler quinoid compounds: the first reduction process appears at −0.3
V vs. Ag/AgCl and it can be reasonably assigned to the formation of a radical monoanionic
species, while the second, reversible, process (at -1,2 V) is a broad peak, probably due to two
sequential reduction processes characterized by similar reduction potential values. This
evidence suggested that the pentacyclic diquinoid compound might be an efficient electron
acceptor molecule.
In this regard, we are testing KuQuinone as dye in photoelectrochemical devices, in which
photoinduced electron transfer processes occur.
Preliminary studies on the efficiencies of the cells made by using KuQuinones as sensitive
material have been carried out. Photocurrent generation mechanism will be proposed.
Figure 1: Left: KuQuinones general structure. Right: Absorption spectrum of 1EthylKuQuinone in CH2Cl2. Cyclic voltammetry of 1-EthylKuQuinone in CH2Cl2 0.1 M
TBAP vs. Ag/AgCl. (Inset: Cyclic voltammetry of the first reduction process occurring at
−0.26 V.).
[1] A. Coletti, S. Lentini, V. Conte, B. Floris, O. Bortolini, F. Sforza, F. Grepioni and P. Galloni, J.
Org. Chem. 77 (2012) 6873-6879.
63
64
Flash communications
FL-1
Francesca ARCUDI
FL-19
Jessica MANZI
FL-2
Alessio CARETTO
FL-20
Giulia MARIANETTI
FL-3
Maria C. CATAPANO
FL-21
Domenico A. CRISTALDI
FL-4
Rita NASTI
FL-22
Giulia MARTELLI
FL-5
Lisa CATTELAN
FL-23
Elia MATTEUCCI
FL-6
Valeria CRISCUOLO
FL-24
Stefania MIRABELLA
FL-7
Marta DA PIAN
FL-25
Devis MONTRONI
FL-8
Rossella DE MARCO
FL-26
Chiara PALUMBO
FL-9
A. Evelyn DI MAURO
FL-27
Davide PERRINO
FL-10
Marta RUI
FL-28
Carlotta PONTREMOLI
FL-11
Luka DORDEVIC
FL-29
Luca PRATI
FL-12
Federica FAROLDI
FL-30
Giovanni ROVIELLO
FL-13
Lucia FERRAZZANO
FL-31
Susanna SAMPAOLESI
FL-14
Lucia FORTE
FL-32
Remo SIMONETTI
FL-15
Giorgio GRILLO
FL-33
Janeth TAFUR M.
FL-16
Elena LENCI
FL-34
Edoardo TORTI
FL-17
Giulia MAGNABOSCO
FL-35
Giorgio VOLPI
FL-18
Mirko MAGNI
FL-36
Stefano VOLPI
65
FL-1
A facile route to carbon dots and their application in electrically
driven devices
Francesca Arcudi,a Serena Carrara,b Elena Longhi,b Matteo Mauro,b Maurizio
Prato,a and Luisa De Colab
a
Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Trieste,
Piazzale Europa 1, 34127-Trieste, Italy
b
Institut de Science et d'Ingénierie Supramoléculaires, Université de Strasbourg, 8 rue
Gaspard Monge, 67083-Strasbourg Cedex, France
E-mail: [email protected]
Carbon Dots (CDs) are a recently discovered class of nanocarbon structures that comprise
discrete, quasispherical carbon nanoparticles with sizes below 10 nm. Their great success is
mainly due to their benign, abundant and inexpensive nature, compared to traditional
semiconductor quantum dots (QDs) and organic dyes. Photoluminescent CDs are superior in
terms of aqueous solubility, chemical inertness, resistance to photobleaching, low toxicity and
good biocompatibility. They can be obtained from both top-down and bottom-up routes, but
achievement of large-scale quantities as well as easy preparation methods are still
challenging. To date, most of the synthetic routes usually involve complex processes, severe
reaction conditions, extensive post-synthetic purification, lack of control over the CDs surface
chemistry, sample polydispersity, size distributions. This inhomogeneity leads to poor
photophysical properities such as very low photoluminescence quantum yields.
Among all preparation methods reported in the literature, the microwave-assisted synthesis
provides simultaneous, homogeneous and efficient heating that guarantees fast reaction rates
and uniform-sized CDs [1].
In this contribution, we report a simple bottom-up method for the preparation of nitrogendoped CDs starting from carbon and nitrogen sources and employing a microwave reactor.
The resulting CQDs are highly water soluble, monodispersed in size and surfacefunctionalized with amino groups. Therefore, they are promptly suitable for further
modifications and fascinating application as platforms for engineering biologically
compatible nano-probes and biofunctional nano-sensors with enhanced analytical
performances. In particular, we describe the modification of the surface with iridium and
ruthenium complexes aiming to develop novel hybrid nano-systems for
electrochemiluminescent (ECL) based biosensors and immunoassays [2]. We envisage that
such new hybrid materials will allow improvement in the ECL efficiency thanks to the
presence of more emissive labels on a single dot.
[1] S. Y. Lim, W. Shen and Z. Gao, Chem. Soc. Rev. 44 (2015) 362-381.
[2] a) A. J. Bard, Electrogenerated Chemiluminescence. Marcel Dekker: New York, 2004; b) L. Hu
and G. Xu, Chem. Soc. Rev. 39 (2010) 3275-3304.
66
FL-2
HELIV: light in transparency
Alessio Carettoa and Luca Bellottoa
HELIV Group s.r.l., Via delle Industrie 9, 30175-Venezia, Italy
E-mail: [email protected]
Heliv LIT (Light in Transparency) [1] is the innovative technology that allows transparent
materials, such as glass or polymers, to transform into illuminating graphic displays of
unlimited design upon command, and immediately convert back to transparent when switched
off. Its basis is a transparent surface, either glass or plastic, to which a power source is added
in the form of an edge-lit LED configuration that activates the surface printed inks (or the
surface adhesives). The inks can be applied to the surface using various techniques, including
digital printing which allows for a multitude of graphic forms and colours, thus generating
text, pictures and logos.
By using Heliv LIT, the glass or polymer surface can be transformed into a source of light
– either full surface coverage or selected areas only – with transparent or slightly translucent
colours: monochrome, multi-coloured, graphics or text.
Heliv uses its innovative printing technologies to offer a professional service that is aimed
at large manufacturers and SMEs, seeking to enhance their existing products or to generate
new ones, in which transparent surfaces are innovated by adding illuminating displays of
visual communication or decorative graphics.
Figure 1: Scheme of HELIV’s LIT technology.
[1] P. Riello, F. Enrichi, L. Bellotto, I. Freris and S. Bellan, WO2013068997 (2013).
67
FL-3
Antidoping analysis in athlete urine samples: endogenous and
exogenous glucocorticoids
Maria Carmen Catapano,a Michele Protti,a Michela Tendi,a Francesca
Bugamelli,a Angelo Sberna,b and Laura Mercolinia
a
Dipartimento di Farmacia e Biotecnologie, Università di Bologna, Via Belmeloro 6, 40126Bologna, Italy
b
Commissione per la vigilanza ed il controllo sul doping e per la tutela della salute nelle
attività sportive, Ministero della Salute, Viale Ribotta 5, 00144-Roma, Italy
E-mail: [email protected]
Glucocorticoids are largely used in clinical practice and possess pain-relieving, antiinflammatory and ergogenic effects. For these reasons, these compounds have been recently
abused with the purpose to enhance and intensify athletic performance. According to the list
of prohibited substances, published by the World Anti-Doping Agency (WADA), all
glucocorticoids are prohibited “in competition” and in “particular sports” when administered
by oral, intravenous, intramuscular or rectal routes 1.
The continuous evolution of doping practices requires a constant update and optimisation
of analytical techniques: the development of fast, effective and repeatable methods with a
simple workflow and increased sensitivity and selectivity are never ending challenges for
researchers.
In the workframe of antidoping activities, urine is by far the most widely used biological
matrix because of the advantages of large specimen volume and relatively high drug
concentrations, its collection is considered non-invasive and provides wide detection
windows. Nevertheless, several relevant issues are still unanswered within sampling
procedures and analysis, including the limitations inherent to the biological fluid itself.
The aim of this study is the optimisation and application of an original volumetric
absorptive microsampling technique coupled to LC-MS/MS for the identification and
quantitation of the main glucocorticoids in 10 µL of dried urine for sport drug testing
purposes. All the steps involved in the analytical methodology have been investigated in order
to develop and test standardised procedures to be further applied in specific doping control
protocols. The simultaneous determination of 4 exogenous glucocorticoids, alongside with 2
endogenous ones, may allow to detect the use of prohibited substances or methods in sport
practices. The proposed original method is under validation and the preliminary results are
very satisfactory, proving its suitability for athlete monitoring in- and out-of competition.
1 World Anti-Doping Agency (WADA), The 2015 prohibited list of substances and methods.
68
FL-4
Beyond the affinity fort he protein kinase C: a critica evaluation
of 2-phenyl-3-hydroxypropyl pivalate analogues targeting the C1
domain
Rita Nasti,a Annamaria Marra,a Gustav Boije Gennäs,b Virpi Talman,c Jari YliKauhaluoma,c Raimo K. Tuominen,c Jeewoo Lee,d Daniela Rossi,a and Simona
Collinaa
a
Dipartimento di Scienze del Farmaco, Università degli Studi di Pavia, Viale Taramelli 12,
27100-Pavia, Italy
b
Division of Pharmaceutical Chemistry and Technology, Faculty of Pharmacy, University of
Helsinki, Viikinkaari 5 E, 00014-Helsinki, Finland
c
Division of Pharmacology and Pharmacotherapy, Faculty of Pharmacy, University of
Helsinki, Viikinkaari 5 E, 00014Helsinki, Finland
d
Laboratory of Medicinal Chemistry, College of Pharmacy, Seoul National University,
151742-Seoul, Korea
E-mail: [email protected]
In the last fifteen years, numerous compounds having as target the C1 domain of protein
kinase C were projected and synthetized [1]. Among those, our attention was focused on
compound 1, promising PKCα ligand (Ki= 0.7 μM) (Figure 1). On the base of this template,
thirteen novel analogues were designed and synthetized to better understand which structural
modifications are allowed to preserve the affinity for C1 domain of PKC and their interaction
was evaluated in silico. The affinity of all compounds was evaluated for the α and δ isoforms
of PKC. For the most interesting PKC ligand, the role of chirality in the ligand-target
interaction was investigate. Taken together, results of biological assays indicate that only few
chemical structure modifications are allowed in such series of compounds and that the C1
domain of PKC doesn’t exhibit enantiopreference for the pure stereoisomers of tested
compounds [2].
Figure 1
[1] a) Y. Baba, Y. Ogoshi, G. Hirai, T. Yanagisawa, K. Nagamatsu, S. Mayumi, Y. Hashimoto and M.
Sodeoka, Bioorg. Med. Chem. Lett. 14 (2004) 2963-2967; b) J. H. Lee, S. Y. Kim, N. A. Perry, N. E.
Lewin, J. A. Ayres and P. M. Blumberg, Bioorg. Med. Chem. 14 (2006) 2022-2031.
[2] a) D. Rossi, V. Talman, G. Boije Af Gennäs, A. Marra, P. Picconi, R. Nasti, M. Serra, J.Ann, M.
Amadio, A. Pascale, R. K. Tuominen, J. Yli-Kauhaluoma, J. Lee and S. Collina, Med. Chem. Comm. 6
(2015) 547-554.
69
FL-5
Dimethylcarbonate for the catalytic upgrading of bio-based
derivatives
Lisa Cattelan, Sandro Guidi, and Alessio Caretto
Dipartimento di Scienze Molecalari e Nanosistemi, Università Ca' Foscari Venezia,
Via Torino 155, 30172-Mestre, Italy
E-mail: [email protected] [email protected] [email protected]
In the past three decades, the use of dialkyl carbonates (DAlCs) as greener solvents and as
non-toxic reagents has gradually improved. For instance, dimethylcarbonate (DMC) has
widely be employed as non-toxic reagent for catalytic alkylation, carboxyalkylations and
transesterification processes.
Starting from different bio-based chemicals it is possible to obtain a wide variety of
derivatives depending on the type of catalyst employed.
Inorganic catalysts including alkaline carbonates, faujasites, and hydrotalcites were proved
to be active towards the selective alkylation of glycerol-based derivatives [1], [2], whereas
organic catalysts (ionic liquids, ILs) promote, starting from diols, the synthesis of cyclic
organic carbonates [3].
Asymmetric methyl carbonates can be obtained within a catalyst-free protocol from simple
alcohols [4]. With solid heterogeneous catalysts, it has been improved the feasibility to work
under continuous flow (CF) conditions.
Figure 1: Selective reactions of bio-based derivatives with DMC.
[1] M. Selva, V. Benedet and M. Fabris, Green Chem. 14 (2012) 188-200.
[2] A. Caretto, M. Noè, M. Selva and A. Perosa, ACS Sustainable Chem. Eng. 2 (2014) 2131-2141.
[3] M. Selva, A. Caretto, M. Noè and A. Perosa, Org. Biomol. Chem. 12 (2014) 4143-4155.
[4] M. Selva, S. Guidi and M. Noè, Green Chem. 17 (2015) 1008-1023.
70
FL-6
Synthesis and photochemical properties of new melanin-inspired
electroluminescent materials for OLED applications
Valeria Criscuolo,a Paola Manini,a Alessandro Pezzella,a Pasqualino
Maddalena,b Salvatore Aprano,c Maria Grazia Maglione,d Paolo Tassini,d Carla
Minarini,d and Marco d’Ischiaa
a
Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia 4, 80126Napoli, Italy
b
Dipartimento di Fisica, Università di Napoli Federico II, Via Cintia 4, 80126-Napoli, Italy
c
SESMAT S.r.l., S.S.7 Appia 36, 82018-San Giorgio del Sannio, Italy
d
Laboratorio di Nanomateriali e Dispositivi, Agenzia Nazionale per le Nuove Tecnologie,
l’Energia e lo Sviluppo Economico Sostenibile, P.le E. Fermi 1, 80055-Portici, Italy
E-mail: [email protected]
In recent years increasing interest has been devoted to the synthesis of electroluminescent
organic materials for the development of efficient organic light-emitting diodes (OLEDs) or
light-emitting electrochemical cells (LEECs) for displays and lighting applications [1].
In the frame of a research line aimed at studying the potentiality of melanins in organic
electronics [2], we report herein for the first time the synthesis of two different type of
electroluminescent materials inspired to the melanin precursors 5,6-dihydroxyindole (DHI)
and dopamine (DA). In particular, DHI has been used to prepare fluorescent asymmetric
triazatruxenes (I) and DA has been involved in the synthesis of phosphorescent
cyclometalated iridium(III) complexes (II) containing a novel set of 6,7-dihydroxy-3,4dihydroisoquinoline ancillary ligands (DHQ) deriving from the catecholic neurotransmitter
[3].
Reported is also a survey of the optoelectronic properties of I and II, both in solution and
as thin films, and the fabrication and characterization of the corresponding OLED/LEEC
devices.
[1] J. M. Fernandez-Hernandez, J. I. Beltran, V. Lemaur, M. D. Galvez-Lopez, C. H. Chien, F. Polo,
E. Orselli, R. Fröhlich, Jeróme Cornil and L. De Cola, Inorg. Chem. 52 (2013) 1812-1824.
[2] P. Manini, V. Criscuolo, L. Ricciotti, A. Pezzella, M. Barra, A. Cassinese, O. Crescenzi, M. G.
Maglione, P. Tassini, C. Minarini, V. Barone and Marco d’Ischia, ChemPlusChem 80 (2015) 919-927.
[3] P. Manini, L. Panzella, I. Tedesco, F. Petitto, G. L. Russo, A. Napolitano, A. Palumbo and M.
d’Ischia, Chem. Res. Toxicol. 17 (2004) 1190-1198.
71
FL-7
Cation templated improved synthesis of pillar[6]arene
Marta Da Pian, Fabrizio Fabris, and Alessandro Scarso
Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca’ Foscari Venezia, Via
Torino 155, 30170-Mestre, Italy
E-mail: [email protected]
Pillar[n]arene is emerging as a new class of cyclic semi-rigid arenes with new intriguing hostguest properties. Herein we present an improved high yield synthesis of the larger
pillar[6]arenes P[6] through cation template synthesis using tetramethylammonium chloride,
bis(cyclopentadienyl)cobalt(III) hexafluorophosphate and (ferrocenylmethyl)trimethylammonium hexafluorophosphate.
72
FL-8
Tuning the activity profiles of the naturally occurring peptide Kopioid receptor ligand CJ-15,208
Rossella De Marco,a Andrea Bedini,b and Luca Gentiluccia
Dipartimento di Chimica “Giacomo Ciamician”, Università di Bologna, Via Selmi 2,
40100-Bologna, Italy
b
Dipartimento di Farmacia e Biotecnologie, Università di Bologna, Via S. Giacomo 46,
40128-Bologna, Italy
E-mail: [email protected]
a
The cyclotetrapeptide c[D-Pro-Phe-Trp-Phe], CJ-15,208, is a naturally occurring opioid
compound isolated as a metabolite of a fungus by Saito in 2002 [1]. CJ-15,208 is a modestly
selective KOR/MOR ligand (IC50 = 35 and 619 nm, respectively), behaving as an antagonist
at the guinea pig brain membrane test. Unexpectedly, a significant antinociceptive agonist
activity in vivo was observed for CJ-15,208 and some analogues in the warm water tail
withdrawal antinociceptive assay, mediated predominantly by MOR. An alanine scan and a
D-amino acid scan were performed by Dolle et al. [2] and by J. Aldrich et al. [3,4], to
determine which residues contribute to the in vivo agonist activity observed for the parent
peptide.
In this work, we present a SAR study aimed at
investigating the role exerted by ring size and backbone
conformation, towards the pharmacological profile of the
opioid cyclopeptide. The new cyclic tetrapeptides were
synthesized from the linear precursors obtained by solidphase peptide synthesis, followed by cyclization in solution.
Receptor affinity was determined by competitive binding
experiments using receptor-selective radioligands. Unlike the parent peptide, some of the
analogues exhibited low-nanomolar affinity for MOR or for DOR, and agonist activity in the
cAMP test. Extensive conformational analyses generally allowed to correlate the affinity and
selectivity of the compounds to the different 3D shape. These analyses led to an
unprecedented model of ligand-receptor interaction.
[1] T. Saito, H. Hirai, Y. J. Kim, Y. Koima, Y. Matsunaga, H. Nishida, T. Sakakibara, O. Suga, T.
Sujaku and N. Kojima, Antibiotics J. 55 (2002) 847-854.
[2] R. E. Dolle, M. Michaut, B. Martinez-Teipel, P. R. Seida, C. W. Ajello, A. L. Muller, R. N.
DeHaven and P. J. Carroll, Bioorg. Med. Chem. Lett. 19 (2009) 3647-3650.
[3] J. V. Aldrich, S. S. Kulkarni, S. N. Senadheera, N. C. Ross, K. J. Reilley, S. O. Eans, M. L. Ganno,
T. F. Murray and J. P. McLaughlin, Chem. Med. Chem. 6 (2011) 1739-1745.
[4] J. V. Aldrich, S. N. Senadheera, N. C. Ross, K. J. Reilley, S. O. Eans, M. L. Ganno and J. P.
McLaughlin, J. Nat. Prod. 76 (2013) 433-438.
73
FL-9
Synthesis of luminescent amine-capped carbon dots
A. Evelyn Di Mauro,a Annamaria Panniello,a Elisabetta Fanizza,b M. Lucia
Curri a, and Marinella Striccolia
a
Istituto per i Processi Chimico-Fisici, Consiglio Nazionale delle Ricerche, Via E. Orabona
4, 70125-Bari, Italy
b
Dipartimento di Chimica, Università degli Studi di Bari "Aldo Moro", Via E. Orabona 4,
70125-Bari, Italy
E-mail: [email protected]
Carbon dots (C-dots) draw increasing attention as new luminescent nanomaterials in different
applications, including bioimaging and biosensing, thanks to their high quantum yield (QY),
biocompatibility, low toxicity and inexpensive sources [1]. Here, nano-sized highly
luminescent C-dots have been synthesized via the injection of citric acid (CA) in a hot
mixture of non-coordinating solvent and alkylamine [2]. During the reaction, the CA carbonyl
groups convert into amide groups by passivating with the amine, as demonstrated by infrared
spectroscopy. The surface passivation makes the dots soluble in various organic solvents,
such as acetone and chloroform. Their large band emission is strongly dependent on the
excitation wavelength. Indeed the amine-capped C-dots show the highest absolute quantum
yield (QY) of 30% when excited at 360 nm and, at increasing excitation wavelength, a redshift in the emission band is observed. The effect of the carbonization conditions, temperature
and time, and surface passivation on the C-dot optical properties has been investigated and the
results presented and discussed.
Figure 1: C-dots in chloroform: (a) Absorption spectrum (b) emission spectra at different
excitation wavelengths and photograph under UV light (365 nm).
[1] S. Zhu, Q. Meng, L. Wang, J. Zhang, Y. Song, H. Jin, K. Zhang, H. Sun, H. Wang and B. Yang,
Angew. Chem. Int. Ed. 52 (2013) 3953-3957.
[2] F. Wang, S. Pang, L. Wang, Q. Li, M. Kreiter and C. Liu, Chem. Mater. 22 (2010) 4528-4530.
74
FL-10
On the study of stereoselectivity in the ligand - Sigma1 receptor
interaction.
Marta Rui,a Annamaria Marra,a Daniela Rossi,a Erik Lurini,b Sabrina Pricl,b and
Simona Collinaa
a
Dipartimento di Scienze del Farmaco, Università degli Studi di Pavia, Viale Taramelli 12,
27100-Pavia, Italy
b
MOlecular Simulation Engineering, Department of Engineering and Architecture,
Università degli Studi di Trieste, Via Valerio 10, 34127-Trieste, Italy
E-mail: [email protected]
Sigma1 (S1) agonists represent promising molecules to treat neurodegenerative diseases. One
of the most intriguing aspect of the interaction between S1 receptor and their ligands is the
stereoselectivity. In the case of RC-33, we have already evidenced that the RC-33
enantiomers do not show any difference in the interaction towards the molecular target [1].
According to the latest and more specific pharmacophore model for S1 receptor ligands
[2], we hypothesized that the absence of enantioselectivity in the interaction with the S1
receptor is due to the lack of an hydrogen bond center in the structure of the lead compound.
In order to deepen the role of chirality in the ligand-S1 receptor interaction, herein we
evaluate - both in silico and in vitro – a series of enantiomeric arylalkylaminoalcohols and
arylpyrrolidinols in targeting S1 receptor. All these compounds are structurally related to RC33 and characterized by the presence of an –OH group as additional pharmacophore feature.
Overall, theoretical and experimental results are in agreement to affirm that S1 presents
enantiopreference toward compounds characterized by (S)-configuration. Although numerous
questions on this enigmatic receptor need to be answered our efforts represent a step-forward
in future development of more specific and effective σ1 agonists [3].
Figure 1: Representative snapshot of the ligand – S1 receptor interaction.
[1] D. Rossi, A. Marra, P. Picconi, M. Serra, L. Catenacci, M. Sorrenti, E. Laurini, M. Fermeglia, S.
Pricl, S. Brambilla, N. Almirante, M. Peviani, D. Curti and S. Collina, Bioorg. Med. Chem. 21 (2013)
2577-2586.
[2] D. Zampieri, M. G. Mamolo, E. Laurini, C. Florio, C. Zanette, M. Fermeglia, P. Posocco, M.S.
Paneni, S. Pricl and L. Vio, J. Med. Chem. 52 (2009) 5380-5393.
[3] D. Rossi, A. Marra, M. Rui, E. Laurini, M. Fermaglia, S. Pricl, D. Schepmann, B. Wuensch, M.
Peviani, D. Curti and S. Collina, Med. Chem. Commun. 6 (2015) 138-146.
75
FL-11
Templating porphyrin anisotropy via magnetically-aligned carbon
nanotubes
Luka Đorđević,a Tomas Marangoni,a Mingjie Liu,b Andrea Minoia,c Roberto
Lazzaroni,c Yasuhiro Ishida,b and Davide Bonifazia,d
a
Dipartimento di Scienze Chimiche e Farmaceutiche, Piazzale Europa 1, 34127-Trieste, Italy
RIKEN Center for Emergent Matter Science, 2-1 Hirosawa, Wako, 3510198-Saitama, Japan
c
Laboratory for Chemistry of Novel Materials, Université de Mons, Place du Parc 20, 7000Mons, Belgium
d
Namur Research College and Department of Chemistry, University of Namur, Rue de
Bruxelles 61, 5000-Namur, Belgium
E-mail: [email protected]
b
We report the design, preparation and characterisation of a novel three-dimensional organic
material consisting of porphyrin arrays / carbon nanotubes (CNTs) / organogel. Firstly, the
porphyrin array was prepared through metal – ligand coordination of a ditopic ligand
(bispyridyl) and a pyrene core comprising two Zn(II) porphyrins and was studied throught
UV-Vis, NMR and Diffusion spectroscopies. Secondly, the porphyrin arrays were absorbed
on unfuctionalised carbon nanotubes, greatly improving their solubility in organic solvents
and the hybrid material was characterisated by both UV-Vis and microscopic techniques and
by thermogravimetric analysis (TGA). Finally, owing to the anisotropic magnetic
susceptibility of the carbon nanotubes, the hybrid material was aligned under a magnetic field,
where the temporal alignment could be fixed by in-situ gelation.
The resultant hybrid organogel exhibits notable optical anisotropy, suggesting anisotropic
arrangement of the porphyrin arrays due to the templating effect of the carbon nanotubes.
Figure 1: Templating chromophores onto carbon nanotubes and, by exploiting the intrinsic
magnetic properties of the latter, the alignment of the hybrid material. The final material
exhibits notable optical anisotropy.
76
FL-12
New calixarenes functionalised with N-acetyl-D-mannosamine for
immunostimulation
Federica Faroldi,a Marta Giuliani,a Silvia Fallarini,c Alessandro Casnati,a
Federica Compostella,b Grazia Lombardi,c and Francesco Sansonea
a
Dipartimento di Chimica, Università degli Studi di Parma, Parco Area delle Scienze 17/A,
43124-Parma, Italy
b
Dipartimento di Biotecnologie Mediche e Medicina Traslazionale, Università degli Studi di
Milano, Via Saldini 50, 20133-Milano, Italy
c
Dipartimento di Scienze del Farmaco, Università degli Studi del Piemonte Orientale
"Amedeo Avogadro", Largo Donegani 2, 20100-Novara, Italy
E-mail: [email protected]
Streptococcus Pneumoniae 19F is an encapsulated bacterium responsible of several, harsh
deseases and it is characterised by the presence on its capsule of a polysaccharide whose Nacetyl-D-mannosamine residue seems to play the major role in immunostimulation and thus
can constitute the minimal antigenic unit.
We are currently synthesizing different glycocalixarenes decorated with N-acetyl-Dmannosamine in order to obtain immunological active compounds, exploiting multivalency.
We synthesized N-acetyl-D-mannosamine from glucose in several steps. The sugar unit was
then conjugated with the proper isothiocyanate calixarenes to give the glycocalixarenes 3a, 3c
and 3b in cone and 1,3-alternate conformation, and conformationally mobile respectively
(Figure 1). As reported in previous works, in fact, varying the display and number of sugar
units on a calixarene platform determines interesting selectivities in the interactions with
protein receptor [1,2]. Biological properties of compounds 3a, 3b and 3c have been
investigated in terms of capability to inhibit the interaction between the polysaccharide 19F
and its antibody.
HO
OH
OH
HO
OH
HO
HO
OH
NHAc
O
NHAc
O
NHAc
O
O
O
O
NH S
OR
NH
OR
NH
OR
OH
NHAc
O
O
NH
NH
NH
S
HO
OH OH
S HN
NH
S
3a R = Me, conformationally mobile
3b R = Pr, fixed cone
3c R = Pr, 1,3-alternate
RO
Figure 1: Calixarenes decorated with N-acetyl-D-mannosamine
[1] F. Sansone, E. Chierici, A. Casnati and R. Ungaro, Org. Biomol. Chem. 1 (2003) 1802-1809.
[2] S. Andrè, F. Sansone, H. Kaltner, A. Casnati, J. Kopitz, H. J. Gabius and R. Ungaro,
ChemBioChem 9 (2008) 1649-1661.
77
FL-13
Integrin-interacting molecular shuttles: a smart tool for selective
drugs and fluorescent molecules delivery
Lucia Ferrazzano, Angelo Viola, and Alessandra Tolomelli
Dipartimento di Chimica “Giacomo Ciamician”, Università di Bologna, Via Selmi 2, 40100Bologna, Italy
E-mail: [email protected]
In the field of theranostic of tumours, one of the main goal of medicinal chemistry is the
development of systems for selective and targeted delivery of drugs and diagnostic molecules
towards the pharmacologic target, for the reduction of side effects associated to an
uncontrolled distribution of drugs during treatments and the localization of tumours using
fluorescent molecules and nanoparticles. This is possible through overexpression on cancer
cells of several receptors, which became the anchoring points of cancer therapy. Among them,
integrins are receptors involved in cell signalling, cell adhesion and cell motility, three of the
upregulated phenomena in cancer cells [1]. Since integrins recognize RGD sequence, our
purpose is to develop an RGD peptidomimetic functionalized with drugs, fluorescent
molecules and nanoparticles [2]. The RGD mimetic have been designed to have an alkyne
side chain to link amino-, acidic- and PEG-azides by Click chemistry.
Figure 1: Structure of RGD mimetic molecules.
[1] K. Chenr and X. Chen, Theranostics 1 (2011) 189-200.
[2] F. Danhier, A. Le Breton and V. Préat, Mol. Pharmaceutics 9 (2013) 2961-2973.
78
FL-14
Functionalization of octacalcium phosphate with bisphosphonates
Lucia Forte,a Elisa Boanini,a Massimo Gazzano,b and Adriana Bigia
Dipartimento di Chimica “Giacomo Ciamician”, Università di Bologna, Via Selmi 2,
40100-Bologna, Italy
b
Istituto per la Sintesi Organica e la Fotoreattività, Consiglio Nazionale delle Ricerche, Via
Gobetti 1, 40100-Bologna, Italy
E-mail: [email protected]
a
In this work we have investigated the interaction of octacalcium phosphate (OCP) - a
precursor phase of biological apatites - with two different Bisphosphonates (BPs), namely
zoledronate (ZOL) and alendronate (AL), in order to obtain new composite materials useful
for bone repair.
BPs represent the major class of drugs used for the treatments of disorders of bone
metabolism characterized by abnormally increased bone resorption [1]. The properties of
individual BPs depend on the two covalently bound sidechains, R1 and R2, attached to the
central carbon atom (Scheme 1). The presence of nitrogen atoms in the R2 side group is
associated with the ability of an individual bisphosphonate to inhibit farnesyl pyrophosphate
synthase (FPP) enzyme within the mevalonate pathway in osteoclasts [2]. As a matter of fact,
alendronate and zoledronate are the most potent antiresorptive BPs [3].
We modified the classical procedure of
OCP synthesis in order to prepare composite
OCP–AL and OCP-ZOL crystals at different
concentration of the BPs. In both cases we
obtained OCP as the unique crystalline phase,
as confirmed by the results of XRD analysis.
AL and ZOL content in the solid products
increased on increasing their concentration in
solution up to 5.5% and 3.5%, respectively.
BPs presence caused a reduction of the
Scheme 1 Molecular structure of two
mean length of the coherently scattering
amino-bisphosphonate.
domains. Moreover, SEM images showed
reduced dimensions of the composite crystals compared to those of pure OCP. Release tests,
performed in PBS solution at pH of 7.4, indicated no BP release from OCP-ZOL , whereas
almost half of AL amount adsorbed on OCP was released into solution. The data suggest
different mechanisms of interaction of ZOL and AL with OCP structure.
[1] R. G. G. Russell, Bone 49 (2011) 2-19.
[2] M. J. Rogers, J. C. Crockett, F. P. Coxon and J. Mönkkönen, Bone 49 (2011) 34-41.
[3] G. H. Nancollas, R. Tang, R. J. Phipps, Z. Henneman, S. Gulde and W. Wu, Bone 38 (2006) 617627.
79
FL-15
Microwave assisted processes for biomass valorisation
Giorgio Grillo, Silvia Tabasso, Diego Carnaroglio, and Giancarlo Cravotto
Dipartimento di Scienza e Tecnologia del Farmaco e Centro Interdipartimentale NIS,
Università degli Studi di Torino, Via P. Giuria 9, 10125-Torino, Italy
E-mail: [email protected]
The production of high added value products from residual biomass is gaining increasing
interest in the last years, overthrowing fossil sources and the problem of waste disposal [1].
New technologies such as microwaves (MW), strongly promote chemical modifications
enabling biomass valorization through a sustainable process.
We designed a flash MW-assisted protocol (2 min only) to obtain with high selectivity
lactic and glycolic acid from agricultural residues. This acids mixture was efficiently reacted
under MW to synthesize an oligomer [2]. The batch protocol was then adapted to a flow
process, paving the way to scaling up design.
The modification of bio-derived platform chemicals plays a key role in biomass
valorization. A new solvent-free protocol for the one-pot hydrogenation/dehydration of
levulinic acid to γ-valerolactone (GVL) was studied. GVL is considered a green solvent and
an intermediate in the production of biofuels and food additives [3].
The synthesis of adipic acid from γ-valerolactone was studied (Fig.1), performing the first
step under MW irradiation. Versatile intermediate was obtained.
Figure 1: Synthesis of adipic acid from levulinc acid.
Modern MW reactors (batch and flow) can rapidly reach high pressures and temperatures,
eventually with modified atmosphere by gas inlets, enhancing reaction rates with a lower
energy consumption.
[1] R. A. Sheldon, I. W. C. E. Arends and U. Hanefeld, Green Chemistry and Catalysis, Wiley-VCH,
Weinheim, 2007.
[2] D. Carnaroglio, S. Tabasso, B. Kwasek, D. Bogdal, E. Calcio Gaudino and G. Cravotto,
ChemSusChem 8 (2015) 1342-1349.
[3] D. M. Alonso, J. Q. Bond and J. A. Dumesic, Green Chem. 12 (2010) 1493-1513.
[4] W. Fang and H. Sixta, ChemSusChem 8 (2015) 73-76.
80
FL-16
New trends in diversity-oriented synthesis: use of mannose for
the development of polyhydroxylated scaffolds
Elena Lenci, Gloria Menchi, and Andrea Trabocchi
Dipartimento di Chimica “Ugo Schiff”, Università degli Studi di Firenze, Via della
Lastruccia 13, 50019-Sesto Fiorentino, Italy
E-mail: [email protected]
Diversity-Oriented Synthesis (DOS) is a new approach to drug discovery which has proven to
be very effective for the synthesis of large compound libraries [1]. It combines the generation
of a functionalized precursor with further synthetic elaborations, in order to generate the
maximum diversity and complexity from simple starting material.
In this context, carbohydrates are attractive building blocks for DOS strategies, taking
advantage of their stereochemical diversity, structural bias and polyfunctional opportunities.
The application of D-mannose, as a multipurpose starting material from the chiral pool,
enabled the diversity-oriented synthesis of an array of cyclic and bicyclic scaffolds with
polyhydroxylated appendages [2]. These compounds, containing glyco and peptidomimetic
moieties, could open the way to novel hit chemical entities, with potential therapeutic
applications as protein-protein interactions inhibitors.
Figure 1: Glycopeptidomimetic scaffolds obtained starting from D-mannose.
[1] (a) S. L. Schreiber, Science 17 (2000) 1964-1969; (b) “Diversity-Oriented Synthesis – Basics and
Applications in Organic Synthesis, Drug Discovery, Chemical Biology”, Trabocchi, A.; Wiley, 2013.
[2] E. Lenci, G. Menchi, A. Guarna and A. Trabocchi, J. Org. Chem. 80 (2015) 2182-2191.
81
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Bio-driven synthesis of cellulose/SWCNT-COOH composites
Giulia Magnabosco, Stefania Rapino, Giuseppe Falini, and Matteo Calvaresi
Dipartimento di Chimica “Giacomo Ciamician”, Università di Bologna, Via Selmi 2, 40100Bologna, Italy
E-mail: [email protected]
Biomaterials are one of the major inspirations for developing new materials of technological
interest; scientists try to emulate structures created by Nature to reach their extraordinary
proprieties. In this work the opposite concept is used: we take advantage of Nature to
synthetize a new material [1-2].
Arabidopsis thaliana is a plant used as a model organism in biology for its well-known
structure, life cycle and genome.
Single wall carboxylated carbon nanotubes (SWCNT-COOH) are 1-D carbon
nanoparticles with incredible electrical, thermal and mechanical proprieties; they are able to
pass phospholipidic membranes.
In this work we used the hierarchical structure of the root of A. thaliana and the incredible
flux of solution into their inner channels to synthetize a new composite made of cellulose and
SWCNT-COOH.
To obtain the composite plants were grown using hydroponic technique with water
containing nutrients for 28 days, then roots were submerged in a solution containing SWCNTCOOH for 4 days. After this time roots become black and their resistance diminish of 5 times.
To understand if SWCNT-COOH penetrate inside roots it is necessary to cut sections
perpendicular to the elongation axis; Raman microscopy has been performed on the section to
study the distribution on SWCNT-COOH and it is possible to see that the specie is localized
into root’s channels.
Mechanical proprieties of the composite have been studied: there are no differences
between treated and untreated roots but the stress strain curve of treated samples present steps
that are due to the presence of two different materials in the sample.
The presence of nanotubes wires into the roots has been evidenced even with optical
microscopy imaging: after mechanical test it is possible to see regions in which the external
part of the root is broken while the inner SWCNT-COOH coated channel is still intact. There
are also difference in the way this materials broke: the untreated sample shows neat edges
while the treated one presents fibrous ends.
In conclusion, this is a demonstration of how plant nanobionics can be used to obtain a
new composite with enhanced mechanical and electrical proprieties [1-2].
[1] R. Di Giacomo, C. Daraio and B. Maresca, PNAS 112 (2015) 541-545.
[2] J. P. Giraldo, M. P. Landry, S. M. Faltermeier, T. P. McNicholas, N. M. Iverson, A. A.
Boghossian, N. F. Reuel, A. J. Hilmer, F. Sen, J. A. Brew and M. S. Strano, Nat. Mater. 13
(2014) 400-408.
82
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Copper complexes as electron shuttles in DSSCs
Mirko Magni,a Alessia Colombo,a Maria Pia Cipolla,b Claudia Dragonetti,a
Patrizia Romana Mussini,a Stefano Caramori,c Roberto Giannuzzi,b Carlo
Alberto Bignozzi,c Michele Manca,b and Dominique Robertoa
a
Dipartimento di Chimica, Università degli Studi di Milano, Via C. Golgi 19, 20133- Milano,
Italy
b
Centro per le Nanotecnologie Biomolecolari, Istituto Italiano di Tecnologia, Via Barsanti
snc, 73010-Arnesano, Italy
c
Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Ferrara, Via
Fossato di Mortara 17, 44121-Ferrara, Italy
E-mail: [email protected]
One of the challenges that humanity will soon have to face is the problem of the increasing
energy demand. Depletion and environmental impact of fossil fuels necessitate abandoning
them in favor of alternative, possibly cleaner and renewable, energy sources. Among these the
sunlight is probably the optimal task being ubiquitous, abundant, and practically
inexhaustible. Since 90’s of the last century dye-sensitized solar cells, DSSCs, have been
studied as light-to-electricity-conversion devices alternative to the already mature siliconbased photovoltaic technology. Researches started in the last decade have identified in firstrow transition metal complexes promising redox mediators alternative to the most common
I3|I redox couple.
In this contribution we will focus on substituted bis(1,10-phenanthroline) copper
complexes which revealed to be effective redox mediators characterized by i) a simple and
high yielding synthesis, ii) a high chemical and electrochemical reversibility, and iii) an
oxidation half-wave potential E1/2(Cu2+|Cu+) and an electron transfer rate easy-tunable
through modification of the diimine chelating scaffold.
Starting from the electrochemical rationalization of their thermodynamic and kinetic features as a
function of the ligand structure (and of the related complex geometry), solvent and counteranion
nature [1], and electrode material we tested some complexes in liquid-type DSSCs. Variations of
the dye [2], of the counter electrode material and of the electrolyte formulation were
performed reaching a 4.5% efficiency under 100 mW/cm2 AM1.5 G illumination with the
homolepctic [Cu(2-mesityl-4,7-dimethyl-phenanthroline)2]+/2+ redox couple. It improved by
almost 50% the performance of an equimolar iodine-based control electrolyte.
[1] M. Magni, A. Colombo, C. Dragonetti and P. Mussini, Electrochimica Acta 141 (2014) 324-330.
[2] A. Colombo, C. Dragonetti, M. Magni, D. Roberto, F. Demartin, S. Caramori and C. A. Bignozzi,
ACS Appl. Mater. Interfaces 6 (2014) 13945-13955.
83
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Self discharge in LiCoPO4 electrodes
Jessica Manzi,a Daniele Di Lecce,b Stefania Panero, and Sergio Bruttib
Dipartimento di Scienze, Università degli Studi della Basilicata, Via dell’Ateneo Lucano 10,
85100-Potenza, Italy
b
Dipartimento di Chimica, Sapienza - Università di Roma, Piazzale A. Moro 5, 00185-Roma,
Italy
E-mail: [email protected]
a
LiCoPO4 (LCP) is a promising candidate as cathode material for high energy density Li-ion
batteries. Unfortunately after charge in Li cells, it suffers a remarkable self-discharge (i.e.
spontaneous open circuit voltage decrease) [1]. Bramnik et al. [2] suggested the possible
spontaneous re-lithiation of CoPO4:
CoPO4 + 0.7Li+ + 0.7e-  Li0.7CoPO4
Li0.7CoPO4 + 0.3Li+ + 0.3e- LiCoPO4
LCP used for this research has been synthesized by a solvothermal route developed in our
laboratory [3]. After characterization LCP pellets have been used as cathode material versus
lithium metal as the anode. LiPF6 in EC:DMC (LP30, Solvionic) has been adopted as the
electrolyte. Cells have been charged up to 5 V at several C-rates and then self-discharged.
After electrochemical experiments, electrodes have been recuperated for the post-mortem
analysis [4]. X-ray diffraction patterns (registered at the ELETTRA synchrotron radiation
source) confirm the spontaneous lithium reincorporation: in fact from charge to selfdischarged materials, CoPO4, Li0.7CoPO4 and finally LiCoPO4 phases are observed.
Concerning the role of the electrolyte, TEM images reveal the formation of an instable
solid electrolyte interphase (SEI), whose composition has been evaluated through XPS.
Moreover, gas-phase FTIR measurements indicate the release of CO2, thus suggesting the
parallel oxidation of the electrolyte carbonaceous components.
Methods to minimize the self-discharge consequences are currently under study.
[1] S. Brutti and S. Panero, “Recent advances in the development of LiCoPO4 as high voltage cathode
material for Li-ion batteries”, in Nanotechnology for Sustainable Energy, Washington, DC, ACS
Symposium Series, Chapter 4, pp 67-99, 2013, DOI: 10.1021/bk-2013-1140.ch004.
[2] N. Bramnik, K. Nikolowski, C. Baehtz, K. Bramnik and H. Ehrenberg, Chem. Mater. 19 (2007)
908-915.
[3] S. Brutti, J. Manzi, A. De Bonis, D. Di Lecce, F. Vitucci, A. Paolone, F. Trequattrini and S.
Panero, Mater. Lett. 145 (2015) 324-327.
[4] J. Manzi, F. M. Vitucci, A. Paolone, F. Trequattrini, D. Di Lecce, S. Panero and S. Brutti,
Electrochim. Acta (2015) DOI: 10.1016/j.electacta.2015.03.071.
84
FL-20
2,5-diaryl substituted azoles as promising organic fluorescent
dyes for luminescent solar concentrators
Giulia Marianetti,a Fabio Bellina,b Vincenzo Barone,a Marco Lessi,b Pierpaolo
Minei,a and Andrea Puccib
a
Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Moruzzi 13, 56124Pisa, Italy
b
Scuola Normale Superiore, Piazza dei Cavalieri 7, 56126-Pisa, Italy
E-mail: [email protected]
In the past two decades lot of research has focused on Luminescent Solar Concentrators
(LSCs) as a way to decrease the cost of solar photovoltaics [1]. LSC devices usually consist in
a thin slab of transparent material (glass or polymer) doped with a fluorescent dye. Upon solar
irradiation, a fraction of the luminescence emitted by the dye remains trapped inside the slab
though means of internal reflection and is collected at the edges of the device by photovoltaic
cells. Compared to traditional concentrators, which make use of mirrors and lenses, this kind
of devices show numerous advantages, such as theoretical higher concentration factors, the
ability to work with both diffuse and incident light and no need for tracking devices or
cooling apparatuses [1,2]. Moreover, the simplicity and the low cost of this devices make
them particularly appealing. In this insight, efforts can be directed towards the synthesis of
novel organic dyes which not only display interesting optical features, but are also attainable
through cheap and scalable procedures. Organic fluorescent dyes bearing π-conjugated
electron-donor and -acceptor moieties exhibit intramolecular charge-transfer (ICT) properties
[3], and can therefore show the optical properties required by LSCs such as high quantum
yield and high Stokes shift. On account of this, in the present communication it will be
discussed the synthesis and UV- Vis characterization of a set of novel symmetrical push-pull
azole-based dyes of general structure 1. These compounds are characterized by a central 1,3azole core substituted at its 2 and 5 positions with two aromatic rings bearing typical electron
withdrawing (EWG) functional groups. Remarkably, the heteroatoms have a positive impact
on the overall polarizability, and the introduction of an heteroaromatic ring usually improves
the thermal and chemical stability required for fabrication processes of the final device.
Figure 1: General structure of push-pull azole-based dyes 1.
The 2,5-diaryl substituted azoles 1 were prepared through a robust synthetic pathway
involving a palladium-catalyzed direct arylation reaction as key step. In order to rationalize
the experimental results we carried out TD-DFT studies is solution and in a polymeric matrix,
with the aim of selecting the best candidate to be employed in LSC devices.
[1] W. G. J. H. M. van Sark, K. W. J. Barnham, L. H. Slooff, A. J. Chatten, A. Büchtemann, A.
Meyer, S. J. McCormack, R. Koole, D. J. Farrell, R. Bose, E. E. Bende, A. R. Burgers, T. Budel, J.
Quilitz, M. Kennedy, T. Meyer, C. De Mello Donegá, A. Meijerink and D. Vanmaekelbergh, Optics
Express 16 (2008) 21773-21792.
[2] R. Reisfeld and K. C. Jørgensen, Sol. Energy Mater. 49 (1982) 1-36.
[3] A. Hagfeldt, G. Boschloo, L. Sun, L. Kloo and H. Pettersson, Chem. Rev. 110 (2010) 6595-6663.
85
FL-21
Fingerprint for ligands and proteins (FLAP): proteasomeporphyrins systems
Domenico Andrea Cristaldi,a Alessandra Cunsolo,a Cosimo Fortuna,a Anna
Maria Santoro,b Danilo Milardi,b Rosalba Randazzo,a Maria Elena Fragalà,a
Alessando D'Urso,a and Roberto Purrelloa
a
Dipartimento di Scienze Chimiche, Università degli Studi di Catania, Viale Andrea D'oria 6,
95125-Catania, Italy
b
Istituto di Biostrutture e Bioimmagini, Unità Organizzativa di Supporto di Catania Consiglio Nazionale delle Ricerche, Via Gaefami, 95125-Catania, Italy
E-mail: [email protected]
The in silico studies are nowadays crucial in several research fields. The Fingerprints for
Ligands And Proteins (FLAP) [1] is a algorithm, performed by Molecular Discovery, based
on GRID force field to calculate molecular interaction fields. FLAP is able to describe
molecules and protein structures which are used to identify particular target locations where
an energetic interaction with small molecular features would be very favourable. Our attention
is directed to the screening analysis, the prediction and evaluation of biological activities, or
possible mechanisms, studying the interactions between ligands and proteins. In particular, we
are using this approach on constitutive proteasome (cCP) and immunoproteasome (iCP), in
order to predict and/or verify the activities of different class of compounds as proteasome
inhibitors.
Proteasomes are important regulator of all physiological processes and thus in last decade
they became important pharmacological targets, either in oncological and neurodegenerative
fields. In this work, in order to validate this method, we start with a comparative analysis of
iCP in free form and bound with PR-957 (a selective iCP inhibitor) [2]. Then we will focus
our research on the interactions between porphyrinoids and cinnamic acid derivatives either
with iCP.
Figure 1: Porphyrin derivatives studies on the iCP.
[1] M. Baroni, G. Cruciani, S. Sciabola, F. Perruccio and J. S. Mason, J. Chem. Inf. Model. 47 (2007)
279-294.
[2] E. M. Huber, M. Basler, R. Schwab, W. Heinemeyer, C. J. Kirk, M. Groettrup and M. Groll, Cell.
148 (2012) 727-738.
86
FL-22
Targeting integrins with new beta-lactam derivatives
Giulia Martelli,a Paola Galletti,a Roberto Soldati,a Monica Baiula,b Samantha
Deianira Dattoli,b Santi Spampinato,b and Daria Giacominia
Dipartimento di Chimica “Giacomo Ciamician”, Università di Bologna, Via Selmi 2,
40100-Bologna, Italy
b
Dipartimento di Farmacia e Biotecnologie, Università di Bologna, Via Irnerio 48, 40126Bologna, Italy
E-mail: [email protected]
a
Beta-lactam compounds are really evergreen molecules [1]. Because of the unique properties of
the azetidinone ring, the β-lactam structure is a versatile building block in the synthesis of several
biologically active compounds. Notably, in the last decades monocyclic β-lactams gained
importance as effective enzymatic inhibitors; among them there are only few examples of
azetidinones that demonstrated activity against integrins [2].
Integrins are heterodimeric α/β transmembrane receptors that mediate dynamic adhesive cellcell and cell-matrix interactions. Because of their important roles in intracellular signalling,
immune responses, leukocyte traffic, haemostasis and cancer, their potential as a therapeutic
target is now widely recognized.
We recently reported the synthesis of some monocyclic β-lactams specifically designed to
target integrins acting like mimetics of the RGD (Arg-Gly-Asp) peptide sequence, the key portion
for the recognition of ligands. All the tested molecules resulted biologically active showing good
affinity and specificity towards αvβ3 and α5β1 integrin classes [3].
After first biological data, a library of new beta-lactams derivatives with a wider structural
variability was developed. New compounds were designed especially to deepen a preliminary
SAR study on their agonist or antagonist activities and to develop new promising active
molecules that can be selective towards different integrin isoforms.
Figure 1: Previously reported beta-lactams as integrin ligands
[1] For recent reviews see: a) N. Arya, A. Y. Jagdale, T. A. Patil, S. S. Yeramwar, S. S. Holikatti, J.
Dwivedi, C. J. Shishoo and K. S. Jain, Eur. J. Med.Chem. 74 (2014) 619-656; b) P. Galletti and D.
Giacomini, Curr. Med. Chem. 18 (2011) 4265-4283.
[2] J. M. Aizpurua, J. I. Ganboa, C. Palomo, I. Loinaz, J. Oyarbide, X. Fernandez, E. Balentova, R. M.
Fratila, A. Jimenez, J. I. Miranda, A. Laso, S. Avila and J. L. Castrillo, ChemBioChem 12 (2011) 401405.
[3] P. Galletti, R. Soldati, M. Pori, M. Durso, A. Tolomelli, L. Gentilucci, S. D. Dattoli, M. Baiula, S.
Spampinato and D. Giacomini, Eur.J. Med. Chem. 83 (2014) 284-293.
87
FL-23
New luminescent Ir(III) complexes with 1,2,3-triazolylidenes as
NHC-type ligand
Elia Matteucci,a Andrea Baschieri,a Filippo Monti,b Andrea Mazzanti,a Nicola
Armaroli,b and Letizia Sambria
a
Dipartimento di Chimica Industriale "Toso Montanari", Università di Bologna, Viale
Risorgimento 4, 40136-Bologna, Italy
b
Istituto per la Sintesi Organica e la Fotoreattività, Consiglio Nazionale delle Ricerche, Via
Gobetti 1, 40100-Bologna, Italy
E-mail: [email protected]
Triazolylidene derivatives have found a wide range of application, especially in
organometallic chemistry and catalysis, due principally to the relatively high covalent
contribution to the M–NHC bond and to their strong donating abilities. The success of this
class of ligand can be also attributed to easily preparation of the triazole precursor via the
readily accessible Cu(I) catalysed ‘click’ cycloaddition of an alkyne and azide (CuAAC) [1].
Subsequent alkylation of the triazole with a suitable alkylating agent is generally selective and
yields the 1,3,4-substituted triazolium salt. Metal complexation is ready available too via
direct metallation with Ag2O and subsequent transmetallation with a wide range of metal
precursors, giving a whole library of metal-triazolylidene complexes [2].
Only few examples of triazolylidene metal complexes that show photochemical properties
have been reported [3].
Here we report the first examples of luminescent Ir(III) complexes bearing two
triazolylidene ligands.
[1] a) V. V. Rostovtsev, L. G. Green, V. V. Fokin and K. B. Sharpless, Angew. Chem. Int. Ed. 41
(2002) 2596-2599; b) F. Himo, T. Lovell, R. Hilgraf, V. V. Rostovtsev, L. Noodleman, K. B.
Sharpless and V. V. Fokin, J. Am. Chem. Soc. 127 (2005) 210-216.
[2] K. F. Donnelly, A. Petronilho and M. Albrecht, Chem. Commun. 49 (2013) 1145-1159.
[3] a) B. Schulze, D. Escudero, C. Friebe, R. Siebert, H. Görls, U. Köhn, E. Altuntas, A. Baumgaertel,
M. D. Hager, A. Winter, B. Dietzek, J. Popp, L. Gonzalez and U. S. Schubert, Chem. Eur. J. 17 (2011)
5494-5498; b) V. Leigh, W. Ghattas, R. Lalrempuia, M. Pryce, H. Müller-Bunz and M. Albrecht,
Inorg.Chem. 52 (2013) 5395-5402.
88
FL-24
Exploring multivalent architectures based on a
trihydroxypiperidine iminosugar
Stefania Mirabella, Camilla Matassini, Andrea Goti, and Francesca Cardona
Dipartimento di Chimica “Ugo Schiff”, Università degli Studi di Firenze, Via della
Lastruccia 13, 50019-Sesto Fiorentino, Italy
E-mail: [email protected]
Iminosugars, natural products widely found in plants and microorganisms, are well-known
glycosidase inhibitors and thus present a great potential in the treatment of several pathologies
[1]. We recently developed a straightforward double reductive amination strategy, that,
starting from a D-mannose derived aldehyde, allows to obtain diversely functionalized
trihydroxypiperidines, among which the trihydroxypiperidine with an azido moiety at the
terminal N-alkyl chain 1 [2,3]. The multimerization of derivative 1 onto dendrimeric scaffolds
was addressed by exploiting the CuI-catalyzed azide-alkyne cycloadditions (CuAAC), using
microwave heating. Herein we present the total synthesis of
tetra- and nonavalent
thrihydropiperidine iminosugars (2 and 3, Figure 1) and their preliminary biological
evaluation towards commercially available and human glycosidases of therapeutic interest.
Figure 1: Tetravalent and nonavalent trihydroxypiperidines.
[1] P. Compain and O. R. Martin, Iminosugars: from Synthesis to Therapeutic Applications, Wiley
VCH, New York, 2007.
[2] C. Matassini, S. Mirabella, A. Goti and F. Cardona, Eur. J. Org. Chem. 2012 (2012) 3920-3924.
[3] C. Matassini, S. Mirabella, X. Ferhati, C. Faggi, I. Robina, A. Goti, E. Moreno-Clavijo, A.-J.
Moreno-Vargas and F. Cardona, Eur. J. Org. Chem. 2014 (2014) 5419-5432.
89
FL-25
Synthesis and characterization of byssus films from Mytilus
galloprovincialis for technological applications
Devis Montroni,a Francesco Valle,b Stefania Rapino,a Matthew Harrington,c
Nicola Pugno,d Matteo Calvaresi,a and Giuseppe Falinia
Dipartimento di Chimica “Giacomo Ciamician”, Università di Bologna, Via Selmi 2,
40100-Bologna, Italy
b
Area della Ricerca di Bologna, Consiglio Nazionale delle Ricerche, Via Piero Gobetti 101,
40129-Bologna, Italy
c
Max Planck Institute for Colloids and Interfaces, Am Mühlenberg 1 OT Golm, 14476Potsdam, Germany
d
Dipartimento di Ingegneria Civile, Ambientale e Meccanica, Università degli Studi di
Trento, Via Calepina 14, 38122-Trento, Italy
E-mail: [email protected]
a
The byssus is a proteic fibrous material synthetized by mussels to anchor themselves to a
surface and to resist to waves and currents. To fulfil these tasks this material is characterized
by a high mechanical resistance, elasticity and self-healing properties [1]. The last one is the
most interesting and is due to a high number of coordination bonds between His-rich domains
and transition metals (mainly Cu2+ and Zn2+) [2].
In this work we synthesized films for technological applications using the byssus of
Mytilus galloprovincialis.
After a wide screening of chemical and physical conditions we defined a simple and fast
procedure for the films synthesis. The film characterization with atomic force microscopy
showed the presence of two different dimensions fiber populations. The observation by
optical microscope, using different dyes, showed a composition similar to the natural thread.
The use of polarized light demonstrated the presence of a large number of intact fibers
demonstrating how part of the supramolecular structure of the pristine material is conserved.
In order to further improve the mechanical properties of the films, many treatments were
done: carbon nanoparticles doping, reticulation and coordination metal exchange.
Finally, the film was tested on cell cultures and appeared completely biocompatible. This
feature makes this film a good candidate also for drug delivery systems. In fact, the film is i)
able to load a drug from a water solution (140% of its mass), ii) trap it during desiccation and
iii) release the drug in a controlled way.
[1] M. J. Harrington, H. S. Gupta, P. Fratzl and J. H. Waite, J. Struct. Biol. 167 (2009) 47-54.
[2] S. Schmidt, A. Reinecke, F. Wojcik, D. Pussak, L. Hartmann and M. J. Harrington,
Biomacromolecules 15 (2014) 1644-1652.
90
FL-26
Epoxidation of terminal alkenes by an unprecedented
catalyst/oxidant/solvent combination
Chiara Palumbo, Cristina Tiozzo, Rinaldo Psaro, Nicoletta Ravasio, and Matteo
Guidotti
Istituto di Scienze e Tecnologie Molecolari, Consiglio Nazionale delle Ricerche, Via C. Golgi
19, 20133-Milano, Italy
E-mail: [email protected]
The derivatization of unsaturated fatty acid methyl esters (FAMEs) from biomasses has been
extensively studied in order to achieve valuable products. In the case of the metathesis of
FAMEs, terminal olefins are obtained [1]. In this context, a sustainable epoxidation of
terminal alkenes is an interesting target, even though it represents a challenge because they
are poorly-activated towards electrophilic epoxidation and can undergo to rearrangements.
Here we report about a selective, heterogeneous, catalytic epoxidation of 1-octene, as a model
substrate, by an unprecedented Catalyst/Oxidant/Solvent combination. To the purpose, a
series of Ti-containing catalysts was prepared via liquid-phase grafting (ca. 2% wt. metal),
starting from a selection of silicon dioxide supports [2]. In particular, supports with different
morphology were used for the catalytic species, in order to evaluate their influence on the
catalytic performances. The catalytic activity was tested in a discontinuous batch reactor, in a
heterogeneous phase, and with various COS combinations. The best conditions, required TiDavisil as catalyst, tert-butyl hydroperoxide (TBHP) as an oxidant, and PhCF3 as a solvent.
Remarkably, the use of PhCF3, which is considered a “green” alternative to dichloromethane
[3], led to high selectivity and good conversions of 1-octene (76% conversion, 98%
selectivity to epoxide). The procedure was successfully applied to other linear terminal and
internal alkenes, such as 1-hexene, trans-2-octene, cis-2-octene, 1,9-decadiene and cis-1,4hexadiene (selectivity to epoxides up to 99%).
Figure 1: Epoxidation of 1-octene as a model substrate.
[1] M. A. R. Meier, J. O. Metzger and U. S. Schubert, Chem. Soc. Rev. 36 (2007) 1788-1802.
[2] A. Gallo, C. Tiozzo, R. Psaro, F. Carniato and M. Guidotti, J. Catal. 298 (2013) 77-83.
[3] J. M. Fraile, N. García, J. A. Mayoral, F. G. Santomauro and M. Guidotti. ACS Catal. 5 (2015)
3552-3561.
91
FL-27
Degradation of organic waste in microbial fuel cells
Davide Perrino,a Pierangela Cristiani,b Matteo Grattieri,a,c Alessandra Colombo,a
Edoardo Guerrini,a and Stefano Pierpaolo Marcello Trasattia
a
Dipartimento di Chimica, Università degli Studi di Milano, Via Golgi 19, 20133-Milano,
Italy
b
Dipartimento Sviluppo Sostenibile e Fonti Energetiche, RSE – Ricerca sul Sistema
Energetico S.p.A., Via Rubattino 54, 20134-Milano, Italy
c
Dipartimento di Chimica, Materiali e Ingegneria Chimica "Giulio Natta", Politecnico di
Milano, Piazza L. Da Vinci 32, 20133-Milano, Italy
E-mail: [email protected]
Microbial Fuel Cells (MFCs) represent an innovative electrochemical bio-technology capable
of generating electricity from organic substances [1]. The application of microbial
electrogenic phenomena in wastewater plants as well as to specific industrial biomass
substrates (e.g. corn stover, landfill leachate, lignocellulosic biomass) have been already
investigated [2]. In this study food waste was used as organic substrate in single chamber
microbial fuel cells. The inoculated bacteria came from an anaerobic sludge of a biogas
production plant.
Two approaches were used for the characterization of the microbial fuel cells: the first was
related to the study of biological degradation of the organic waste; the second was related to
the electrochemical study on the electrodes.
Every cell was fed with the food cited previously and the degradation of the organic waste
was followed by COD (chemical oxygen demand) analysis. When the value of COD fell
down below 500 mg O2 L‒1, a new addition of food was performed. At the same time, the
power production of the microbial fuel cells was recorded and was strictly related with the
biodegradation process of the food waste.
Potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS)
were used to study the electrochemical behaviour of the electrodes, showing interesting
evolution along the tests. SEM (Scanning Electron Microscopy) analyses were performed at
the end of the tests, reinforcing the electrochemical results.
Based on the obtained results, the application of microbial fuel cells will be presented.
[1] P. Cristiani, M. L. Carvalho, E. Guerrini, M. Daghio, C. Santoro and B. Li, Bioelectrochemistry
92 (2013) 6-13.
[2] D. Pant, G. Van Bogaert, L. Diels and K. Vanbroekhoven, Bioresour. Technol. 101 (2010) 15331543.
92
FL-28
Mucin-drugs interaction: the case of theophylline, prednisolone
and cephalexin
Carlotta Pontremoli,a Nadia Barbero,b Guido Viscardi,b and Sonja Visentina
a
Dipartimento di Biotecnologie Molecolari e Scienze per la Salute, Università degli Studi di
Torino, Via Quarello 15, 10135-Torino, Italy
b
Dipartimento di Chimica e Centro Interdipartimentale NIS, Università degli Studi di
Torino, Via Pietro Giuria 7, 10125-Torino, Italy
E-mail: [email protected]
The binding of mucin with three commercially available drugs (theophylline,cephalexin and
prednisolone) belonging to different pharmaceutical classes was investigated. The studied
drugs are normally used to treat the symptomatology of cystic fibrosis. The interaction
between drugs and mucin has been investigated using fluorescence and UV-Vis absorption
spectroscopy; quenching mechanism, binding constants, binding sites, thermodynamic
parameters and binding distance of the interaction were obtained.
Figure 1: Quenching of mucin fluorescence by drugs.
93
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Long-range bonding/nonbonding interactions: a donor−acceptor
resonance studied by dynamic NMR
Luca Prati,a Michele Mancinelli,a Silvia Ranieri,a Andrea Mazzanti,a Renzo
Ruzziconi,b Susan Lepri,b Federica Buonerba,b and Manfred Schlosserc
a
Dipartimento di Chimica Industriale "Toso Montanari", Università di Bologna, Viale
Risorgimento 4, 40136-Bologna, Italy
b
Dipartimento di Chimica, Biologia e Biotecnologie, Università degli Studi di Perugia, Via
Elce di Sotto 10, 06100-Perugia, Italy
c
Institute of Chemical Sciences, Ecole Polytechnique Fédérale de Lausanne, CH-1015
Lausanne, Switzerland
E-mail: [email protected]
Long-range bonding interactions were evaluated [1] using variable temperature NMR
spectroscopy and suitable 2′-CH2X-substituted phenylpyridines (X = Me, NMe2, OMe, F).
This study has revealed that the aryl-pyridyl rotational barriers were lower as much as the
atom bound to the α carbon of the 2′ moiety were electronegative. This effect was ascribed to
a stabilizing interaction in the transition state due to the lone pair of the heterocyclic nitrogen
with the α carbon of the aryl. Computational support for this hypothesis was produced from
CCSD(T)/6-31+G(d) DFT calculations.
The comparison with the rotational barrier of the analogous biphenyl has allowed to rule
out the steric effect of the X substituent in this process.
Figure 1: Interaction studied in the transition state of the aryl-pyridine system.
[1] R. Ruzziconi, S. Lepri, F. Buonerba, M. Schlosser, M. Mancinelli, S. Ranieri, L. Prati and A.
Mazzanti, Org. Lett. 17 (2015) 2740-2743.
94
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Cationic nucleobase-derivatised peptides and nucleic acid binding
properties
Giovanni Roviello,a Caterina Vicidomini,a Valentina Roviello, b Domenica
Musumecia,c and Gaetano Alfanoa
a
Istituto di Biostrutture e Bioimmagini, Consiglio Nazionale delle Ricerche, Via
Mezzocannone 16, 80134-Napoli, Italy
b
Dipartimento di Ingegneria Chimica, dei Materiali e della Produzione Industriale,
Università degli Studi di Napoli Federico II, Piazzale V. Tecchio 80, 80125-Napoli, Italy
c
Dipartimento di Scienze Chimiche, Università degli Studi di Napoli Federico II, Via Cintia
26, 80126-Napoli, Italy
E-mail: [email protected]
The development of new DNA analogues able to interact with natural nucleic acids and
proteins has gained a great scientific interest in recent years leading to a number of artificial
nucleotidic molecules, bearing various modifications both in the DNA backbone and
nucleobases, that in some cases presented hybridization properties even better than natural
oligonucleotides. Among these, peptide nucleic acids emerged as powerful DNA analogues
forming complexes endowed with a great thermal stability and sequence specificity[1].
Nevertheless, some drawbacks of these analogues like scarce water-solubility and poor
strand-orientation selectivity during binding were soon reported.
nucleobase
B
l=1,2..
n=0,1..
O
HN
H
m=5,6..
l
H
N
OH
*
n
m
O
Figure 1: Schematic representation of a nucleobase-containing peptide
One way to overcome these limits consists in introducing chiral residues, possibly carrying
charged moieties, in the peptide skeleton. Our recent efforts in this field have focused on the
realization of chiral nucleoaminoacids, suitably protected for solid phase oligomerization, the
realization of cationic chiral nucleopeptides[2] and the study of their interaction with
molecules of biological relevance[3]. In this work we present the synthesis, purification and
characterization of both a chiral nucleoaminoacid and the corresponding cationic
nucleopeptide, as well as some preliminary results on its hybridization ability towards natural
targets in view of a possible use in biomedical applications.
[1] P. E. Nielsen and M. Egholm Science 254 (1991) 1497-1500.
[2] G. N. Roviello, D. Musumeci, V. Roviello, M. Pirtskhalava, A. Egoyan and M. Mirtskhulava,
Beilstein J Nanotech 6 (2015) 1338-1347.
[3] G. N. Roviello, D. Musumeci, C. D’Alessandro and C. Pedone, Bioorg Med Chem. 22 (2014) 9971002.
95
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A new efficient strategy for the one-pot synthesis of
substituted quinolines
Susanna Sampaolesi, Alessandro Palmieri, Serena Gabrielli, and Roberto Ballini
Scuola di Scienze e Tecnologie, Chemistry Division, Università di Camerino, Via
Sant’Agostino 1, 62032-Camerino, Italy
E-mail: [email protected]
Substituted quinolines are important scaffolds that occur in many biologically active
compounds, including natural products and synthetic drugs. Indeed quinoline derivatives have
been found to possess antimalarial, antimicrobial, antifungal, anticancer, antiinflammatory
activity [1]. Moreover some quinoline derivatives display a relevant role in the formation of
conjugated molecules and polymers with suitable electronic, optoelectronic or non-linear
optical properties [2]. As a consequence of their fundamental importance, a number of
synthetic procedures have been reported in literature [3], however the development of new
more efficient methodologies still to be welcomed.
With this aim, herein we report an alternative one-pot process for the synthesis of
quinolines, starting from 2-amminobenzaldehyde 1 and β-nitroacrylates 2, which are an
emerging class of electron-poor alkenes, largely studied by our research group [4].
Figure 1: One-pot synthesis of substituted quinolines.
[1] a) O. Afzala, S. Kumara, M. R. Haidera, M. R. Alia, R. Kumara, M. Jaggib and S. Bawa, Eur. J.
Med. Chem. 97 (2015) 871-910; b) S. Mukherjee and M. Pal, Drug Discov. Today 18 (2013) 389-398;
c) K. Kaur, M. Jain, R. P. Reddy and R. Jain, Eur. J. Med. Chem. 45 (2010) 3245-3264.
[2] a) S. Tao, L. Li, J. Yu, Y. Jiang, Y. Zhou, C. S. Lee, S.-T. Lee, X. Zhang and O. Kwon, Chem.
Mater. 21 (2009) 1284-1287; b) I. H. Jung, D. Zhao, J. Jang, W. Chen, E. S. Landry, L. Lu, D. V.
Talapin and L. Yu, Chem. Mater. 27 (2015) 5941-5948.
[3] a) R. I. Khusnutdinov, A. R. Bayguzina and U. M. Dzhemilev, J. Organomet. Chem. 768 (2014)
75-114; b) Z. Huo, I. D. Gridnev and Y. Yamamoto, J. Org. Chem. 75 (2010) 1266-1270.
[4] R. Ballini, S. Gabrielli and A. Palmieri, Curr. Org. Chem. 14 (2010) 65-83; b) S. Gabrielli, A.
Palmieri, D. S. Panmand, D. Lanari, L. Vaccaro and R. Ballini, Tetrahedron 68 (2012) 8231-8235; c)
A. Palmieri, S. Gabrielli, C. Cimarelli and R. Ballini, Green Chem. 13 (2011) 3333-3336.
96
FL-32
Has your ancient stamp been “regummed”? A FT-Raman study
Remo Simonetti,a,b Adrien Henry,c and Ludovic Duponchelb
a
Dipartimento di Farmacia, Università degli Studi di Genova, Via Brigata Salerno 13,
16147-Genova, Italy
b
Laboratoire de Spectrochimie Infrarouge et Raman (LASIR), Université de Lille, Sciences et
Technologies - Bâtiment C5, 59655-Villeneuve d'Ascq Cedex, France
c
École Polytechnique Universitaire de Lille, Avenue Paul Langevin, 59655-Villeneuve d’Ascq
Cedex, France
E-mail: [email protected]
Since the beginning of postage stamp production, counterfeiters started their activities by
altering genuine stamps in some way to make them more desirable. These activities include
the application of new gum on the back side of non-cancelled stamps, whose condition greatly
influences the stamp value. If a stamp is identified as “regummed” by a philatelic expert, it is
downgraded and considered as a stamp without gum, considerably decreasing its value [1,2].
Because these counterfeits are not always easily detected by philatelic expert visual
inspection, a reliable scientific detection method is desirable. It is well documented that the
three main glues used in Italian stamps during the period investigated were animal glue
(before 1901), Arabic gum (1901-1973), and polyvinyl acetate glue (PVAc) (after 1974) [3].
It has also been reported that many counterfeits have been performed in recent years by
applications of modern synthetic glues, such as PVAc, on ancient stamps [3,4].
The aim of this work was to study and to develop, for the first time, a rapid and nondestructive methodology able to study the stamp gum composition and to unmask regummed
stamps by means of FT-Raman spectroscopy.
A total number of 108 non-cancelled Italian stamps, covering the period 1861-2001 were
analysed and eight ancient specimens (period 1862-1932) were purposely regummed with a
PVAc thin layer, to simulate counterfeit and used as test samples.
The results obtained indicate that FT-Raman spectroscopy, coupled with exploratory
pattern recognition methods, is able to detect the compositional chemical differences between
the different gum and is able to detect ancient stamps artificially regummed with PVAc glue.
[1] Bolaffi, Il catalogo dei francobolli (2014), G. Bolaffi Editore, Torino.
[2] Sassone, Catalogo Sassone Blu (2015), Sassone Editore, Milano.
[3] E. Imperio, G. Giancane and L. Valli, Anal. Chem. 85 (2013) 7085-7093.
[4] A. Bandini Buti, Manuale di filatelia (1973), U. Mursia Editore, Milano.
97
FL-33
Pyrogasification of woodstocks: characterization of solid and
liquid byproducts
Janeth Tafur-Marinos, Marco Ginepro, Mara Cantamessa, and Vincenzo Zelano
Dipartimento di Chimica, Università degli Studi di Torino, Via P. Giuria 7, 10125-Turin,
Italy
E-mail: [email protected]
Woody biomass is gaining attention as a potential source of alternative energy to increase
energy independence on fossil fuels and reduce environmental pollution [1]. Biomass
pyrogasification is a complex thermochemical process that converts lignocellulosic materials
into a valuable gas by means of a partial oxidation process at high temperature. The gas
mixture obtained can be utilized to produce electrical energy and thermal power [2].
However, during this process liquid (process water and tar) and solid (biochar) byproducts are
formed. The process water, tar and biochar, which can be used as soil amendment in
agriculture, must be characterized since they may contain hazardous organic compounds, such
as phenols and PAHs [3].
This study was carried out on a pyrogasification industrial plant fueled with wood pellets.
So the process water, tar and biochar were characterized. Then pyrogasification biochar and
other commercial biochars were further characterized for potential use as ammendant.
The organic component analyses of the process water, tar and biochar were made by GCMS. Additionally, pH, water content, ash content, and contents of water extractable metals
and anions (by ICP-OES and IC) were determined on biochar samples.
Phenols, PAHs and VOCs were mainly found in the process water, tar and biochar,
respectively. Moreover, the metals extracted were mainly Al, Ca, K, Mg and Na; the heavy
metal contents extracted were very low, even though their concentrations in the biochar is
four times higher than woodstocks.
The liquid byproducts, namely process water and tar have to be disposed of as waste.
Biochar obtained from virgin wood, doesn’t have problems with regard to metals harmful to
the environment, whereas the organic components depend on several factors related to the
production and it is therefore necessary the analysis of this one.
[1] N. Jendoubi, F. Broust, J. M. Commandre, G. Mauviel, M. Sardin and J. Lédé, J. Anal. Appl.
Pyrol. 92 (2011) 59-67.
[2] I. De Bari, D. Barisano, M. Cardianle, D. Matera, F. Nanna and D. Viggiano, Energy Fuels 14
(2000) 889-898.
[3] K. A. Spokas, J. M. Novak, C. E. Stewart, K. B. Cantrell, M. Uchimiya, M. G. DuSaire and K. S.
Ro, Chemosphere 85 (2011) 869-882.
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Photogeneration of methanesulfonic acid from Narylmethanesulfonimides: application in cationic
photopolymerization
Edoardo Torti,a Maurizio Fagnoni,a Stefano Protti,a Daniele Merli,a Gioia Della
Giustina,b and Giovanna Brusatinb
a
Dipartimento di Chimica, Università degli Studi di Pavia, Viale Taramelli 12, 27100-Pavia,
Italy
b
Dipartimento di Ingegneria Industriale, Università degli Studi di Padova, Via Marzolo 9,
35131-Padova, Italy
E-mail: [email protected]
Compounds able to release acid upon light absorption (photoacid generators, PAGs) find
wide application in photoresists and other similar devices [1]. In the last few years our group
demonstrated that aryl sulfonates are able to release the corresponding sulfonic acid under UV
irradiation [2,3]. We present herein a photochemical investigation of Narylmethanesulfonimides (1).
Irradiation of 1 in N2 saturated acetonitrile resulted in the formation of Narylmethanesulfonamides, anilines and thia-Fries rearrangement products along with
methanesulfinic acid (0-116%). In O2 saturated media, methanesulfonic acid was released in
high yields (up to 2 equiv for one equiv of 1). The photochemical behaviour is consistent with
a homolytic cleavage of the ArN-S bond with the formation of a radical pair (2) (see Figure
1). Compounds 1 are also suitable as photoinitiators for cationic polymerization, as
demonstrated by photopolymerization experiments performed on an epoxy based hybrid
organic-inorganic material [4].
This work has been supported by the Fondazione Cariplo (grant no. 2012-0186).
Figure 1: Photochemical behaviour of N-arylmethanesulfonimides 1.
[1] S. Y. Moon and J. M. Kim, J. Photoch. Photobio. C 8 (2007) 157-173.
[2] M. Terpolilli, D. Merli, S. Protti, V. Dichiarante, M. Fagnoni and A. Albini, Photochem.
Photobiol. Sci. 10 (2011) 123-127.
[3] E. Torti, G. Della Giustina, S. Protti, D. Merli, G. Brusatin and M. Fagnoni, RSC Adv. 5 (2015)
33239-33248.
[4] G. Brusatin and G. Della Giustina, J. Sol-Gel Sci. Technol. 60 (2011) 299-314.
99
FL-35
1,3-substituted-imidazo[1,5-a]pyridine: new series of
fluorescent derivatives
Giorgio Volpi,a Claudio Garino,a Eleonora Conterosito,b Claudia Barolo,a
Roberto Gobetto,a and Guido Viscardia
a
Dipartimento di Chimica e Centro Interdipartimentale NIS, Università degli Studi di Torino,
Via Pietro Giuria 7, 10125-Torino, Italy
b
Dipartimento di Scienze e Innovazione Tecnologica, Università degli Studi del Piemonte
Orientale "Amedeo Avogadro", Viale T. Michel 11, 15121-Alessandria, Italy
E-mail: [email protected]
A new general synthetic method, developed both through standard and microwave heating,
provides a versatile one step approach for the synthesis of multidentate nitrogen heterocyclic
ligands, containing a pair of biologically relevant imidazo[1,5-a]pyridine moieties (Figure 1).
These compounds show considerable optical properties, with good fluorescent emissions,
moderate quantum yields and large Stokes’ shifts enabling their technological application.
Figure 1. General structures of synthesized compounds
The photofunctional diversity of the synthesized compounds imply that the bis(1-(pyridin2-yl)imidazo[1,5-a]pyridin-3-yl)benzene and their derivatives can potentially be used as
easily tuneable photofunctional materials and as tetradentate ligands of interest in the fields of
DSCs, OLED, NLO and for pharmaceuticals applications.
Figure 2. Absorption (left) and Emission spectra (right) for compounds 1–6.
Moreover, quantitative yields, absence of catalysts, high accessibility and stability, ease of
handling and preparation, no toxicity of reagents and derivatives render this synthetic
approach particularly useful for a systematic screening and full-scale production and make the
products inexpensive and affordable.
100
FL-36
A guanidino-triazacyclononane calix[4]arene as a novel and
efficient catalyst for the cleavage of phosphodiesters
Stefano Volpi,a Riccardo Salvio,b Roberta Cacciapaglia,b Luigi Mandolini,b
Francesco Sansone,a and Alessandro Casnatia
a
Dipartimanto di Chimica, Università degli Studi di Parma, Viale delle Scienze 17/A, 43124Parma, Italy.
b
Dipartimento di Chimica and Istituto di Metodologie Chimiche, Università degli Studi di
Roma "La Sapienza" and Consiglio Nazionale delle Ricerche, P.le A. Moro 5, 00185-Roma,
Italy
E-mail: [email protected]
An important goal of supramolecular chemistry is the design of artificial catalysts able to
mimic the activity of enzymes. Recent studies showed that effective artificial
phosphodiesterases can be obtained by functionalizing the upper rim of cone-calix[4]arenes
with two or more guanidinium units or metal cations coordinated via appropriate N-ligands
[1]. However, no examples of calix[4]arenes decorated with these two different units are
reported in the literature. We therefore synthesized the guanidino-triazacyclononanecalix[4]arene 1(H+)4 to test the ability of its ZnII and CuII complexes to cleave phosphodiesters
[2].
These systems show high activity in the cleavage of the RNA model HPNP thanks to the
cooperation of the two units at the upper rim (Figure 1). The monoprotonated species 1H+ZnII and 1H+-CuII enhance the intramolecular transesterification rate by 2.1∙103 and 3.2∙105
folds, respectively. The catalysts, in DMSO/H2O (8/2), turn to be active at pH 8.8 for 1H+CuII and 9.8 for 1H+-ZnII, when the deprotonation of a water molecule coordinated to the
metal center takes place. These data support the hypothesis that a metal ion-bound hydroxide
ion participates to the catalytic process.
The most reactive 1H+-CuII was also tested in the cleavage of some diribonucleoside
monophosphates, leading, in the case of GpA, to an acceleration factor of 1.3∙107-fold.
Figure 1: Mechanism proposed for the cleavage of HPNP by 1H+-M2+.
[1] R. Cacciapaglia, S. Di Stefano, L. Mandolini and R. Salvio, Supramol. Chem. 25 (2013) 537-554.
[2] R. Salvio, S. Volpi, R. Cacciapaglia, A. Casnati, L. Mandolini and F. Sansone, J. Org. Chem. 80
(2015) 5887-5893.
101
102
Posters
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POS-36
POS-37
POS-38
Francesco ALLETTO
Francesco BARSOTTI
Federico BELLA
Andreas BERGFELT
Lorenzo CANTI
Daria CAPONE
Enrico CASAMASSA
Alessia CASO
Pietro CASSOTTA
Valentina CAUDA
Andrea CHIMINAZZO
Silvia CINO
Claudia CIOCE
Doretta CUFFARO
Massimo C. D’ALTERIO
Federico DAPIAGGI
Chiara DASSO
Rita M. C. DI MARTINO
Carlo DIAFERIA
Alessandro EMENDATO
Giuseppe FERRARO
Claudia FINAMORE
Antonio FOGLIA
Oscar FRANCESCONI
Claudio FREZZA
Francesca GADO
Mattia G. GENTILE
Giulia GIACONA
Alessandra GRAZIADIO
Lorenzo GUALANDI
Giulia IOVENITTI
Silvia MANFRIN
Piero MARGARI
Davide MARIOTTINI
Arianna MASSARO
Dario MASULLO
Thomas MATULLI C.
Laura MERCOLINI
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Andrea MEZZETTA
Gabriele MICHELETTI
Elirosa MINNITI
Alessio MOLINARI
Emanuele MORGANTI
Ana B. MUNOZ-GARCIA
Alexandra NEAGU-CHIVU
Federica NOVELLI
Paolo OLIVERI
Francesco OROFINO
Alice PAIOTTA
Emanuele PARIS
Luca PARISE
Carolina PASERO
Eleonora PAVONI
Stefano PIERACCINI
Luca PIERSANTI
Maria Augusta RAGGI
Giulia RAINOLDI
Arianna ROSSETTI
Marianna ROSSETTI
Sebastiano RUPIANI
Veronica SANTACROCE
Carla SAPPINO
Eduardo SCHIAVO
Mirko SCORTICHINI
Maria SENESE
Denise SIGHEL
Alberto SINIBALDI
Ilaria SORRENTINO
Andrea SPINACI
Mattia STUCCHI
Bernardino TIRRI
Leonardo TRIGGIANI
Giuseppe TRUSSO
Giampiero VALENTE
Marina ZENZOLA
POS-1
Regioselective synthesis of triazole-5-boronates
Francesco Alletto, Emilia Caselli, and Fabio Prati
Dipartimento di Scienze della Vita, Università degli Studi di Modena e Reggio Emilia, Via G.
Campi 103, 41125-Modena, Italy
E-mail: [email protected]
In the last decades the interest for organic compounds bearing the boronic moiety has grown
considerably. Aside from their well-known utility as intermediate in C-C, C-N and C-O
bound forming reactions (e.g. Suzuki-Miyaura and Chan-Lam coupling), their use in
medicinal chemistry as protease inhibitors is quickly increasing [1].
Although at the state of art there are several methods to insert the boronic moiety, in
literature are described only two cases of formation of triazole with the boronic function in
position 4 or 5 [2,3]; this was achieved by cycloaddition of alkynylboronates and organic
azides. Nevertheless, the reaction wasn’t regioselective or it introduced the boronic moiety as
methylimminodiacetate (MIDA) thus confining their application to Suzuki-Miyaura
couplings. During our investigations on the application of boronic acids to the inhibition of βlactamases, we demonstrated the positive contribution of the triazole to the bioavailability of
the boronic inhibitor [4], but we faced the scarce accessibility of triazoles presenting the
boronic group in position 5.
Here we report our contribution to the synthesis of this class of compounds. Our approach
exploits the efficiency of the copper-catalyzed cycloaddition of SEM-azide with several
alkynes to build the 4-substituted triazole, as well as the assistance of the SEM protecting
group to the direct metalation of the position 5 for the insertion of the boronate group.
This method allows to obtain several triazole-5-boronates whose application in Suzuki
coupling as well as in β-lactamase inhibition is currently under investigation.
[1] R. Smoum, A. Rubinstein, V. M. Dembitsky and M. Srebnik, Chem. Rev. 112 (2012) 4156-4220.
[2] J. Huang, S. J. F. Macdonald and J. P. A. Harrity, Chem. Commun. (2009) 436-438.
[3] J. E. Grob, J. Nunez, M. A. Dechantsreiter and L. G. Hamann, J. Org. Chem. 76 (2011) 1024110248.
[4] E. Caselli, C. Romagnoli, R. Vahabi, M. A. Taracila, R. A. Bonomo and F. Prati, J. Med. Chem. 58
(2015) 5445-5458.
104
POS-2
Computational assessment of the fluorescence emission of phenol
oligomers: A possible insight into the fluorescence properties of
humic-like substances (HULIS)
Francesco Barsotti, Giovanni Ghigo, and Davide Vione
Dipartimento di Chimica, Università degli Studi di Torino, Via Giuria 7, 10125-Torino, Italy
E-mail: [email protected]
Compounds with fluorescence in the humic-like substances (HULIS) region are known to be formed
under conditions where the oligomerization of phenolic compounds is operational, because of the
formation of phenoxy radicals [1]. However, there was no evidence to date that such fluorescence
emission was really due to phenol oligomers. In this work, the fluorescence of phenol and some of its
oligomers was studied by computational methods (TD-DFT [2] [3] with the PCM approximation [4])
and it was compared with experimental data, when allowed by the availability of commercial
standards. The oligomer fluorescence depends on the contribution of different stable conformers,
which differ from one another for the dihedral angles between the aromatic rings. Differences in the
dihedral angles are also observed between the round states and the corresponding excited singlet
states. The predicted wavelengths of fluorescence emission increase with increasing the number of
aromatic rings, up to a plateau at around 450 nm. Compounds with more than three-four aromatic
rings are not expected to show emission in a different range, because the transitions causing
fluorescence involve only three consecutive rings. These results support the hypothesis that oligomers
account for the fluorescence emission in the HULIS region, which has been observed under the
photochemical and photosensitized transformation of phenolic compounds.
In this work it has been showed which phenol oligomers formed by two, three and four rings are
characterized by the presence of different conformers, which differ for the dihedral angles between the
aromatic rings. Each conformer gives its own contribution to the absorption and fluorescence spectra
of the investigated compounds. In particular, 4PP and 4PPP have three stable conformers each, while
4PPPP has six conformers. The predicted wavelengths of fluorescence emission, which correspond to
S1 -> S0 transitions, increase up to a plateau with increasing the number of aromatic rings.
Considering that the transitions producing fluorescence involve at most three aromatic rings, important
changes in the emission wavelength are not expected when further increasing the molecular size. This
issue is further supported by the calculated fluorescence emission of one of the conformers of the five
rings oligomer. The plateau in the predicted emission wavelengths is at around 450 nm, which is quite
in the fluorescence range of HULIS. The oligomeric compounds might thus account for the HULIStype fluorescence, which has been observed under conditions where phenol oligomerization was
operational due to the formation of phenoxy radicals [1]. Interestingly, the plateau in the emission
wavelengths predicts that a mixture of phenol oligomers could not show fluorescence in a different
spectral interval than that experimentally observed: the increasing molecular size would initially shift
fluorescence from the phenolic region to the HULIS one, but further increases of the ring number are
not expected to produce important modifications in the wavelengths of the emission signal.
[1] E. De Laurentiis, B. Sur, M. Pazzi, V. Maurino, C. Minero, G. Mailhot, M. Brigante and D. Vione, Atmos. Environ. 70
(2013) 318-317 .
[2] D. Jacquemin, V. Wathelet, E. A. Perpète and C. Adamo, J. Chem. Theory Comput. 5 (2009) 2420-2435.
[3] M. Cossi and V. Barone, J. Chem. Phys. 115 (2001) 4708-4717.
[4] M. Cossi, N. Rega, G. Scalmani and V. Barone, J. Chem. Phys. 114 (2001) 5691-5701.
105
POS-3
Nanostructured anode materials for high-energy Li-/Na-ion
large-scale energy storage
Federico Bella,a Giuseppina Meligrana,a Francesca Colò,a Andrea Lamberti,a
Matteo Destro,a Jijeesh R. Nair,a Sonia Fiorilli, Paolo Pescarmona,b and Claudio
Gerbaldia
a
Dipartimento di Scienza Applicata e Tecnologia, Politecnico di Torino, Corso Duca degli
Abruzzi 24, 10129-Torino, Italy
b
Department of Chemical Engineering, University of Groningen, Nijenborg 4, 9747Groningen, Netherlands
E-mail: [email protected]
Due to their high volumetric and gravimetric capacities, Li-ion batteries (LiBs) are currently
considered as the only viable energy storage solution for portable electronics and hybrid
vehicles. Nevertheless, concerns on the availability of Li resources and their uneven
distribution across the world are growing. As an alternative, Na-ion batteries (NiBs) are
highly attractive due to the abundance of Na as well as its electrochemical similarity with Li.
Na is also environmentally benign, thus promising a more sustainable energy storage.
Although NiBs are unlikely to outperform LiBs in energy density, they are being actively
pursued for low-cost grid storage where size or weight is not the most critical factor.
The identification of a high-performance anode is a key challenge, particularly for NiBs
[1]. Anode materials investigated so far for NiBs can be classified into three categories: (i)
layered materials, such as titania or titanates and transition metal dichalcogenides with a
specific capacity of 50-250 mAh g–1; (ii) carbon-based materials, such as hard carbons; and
(iii) nanostructures like nanowires and graphene-based carbon nanosheets offering capacities
exceeding 300 mAh g–1.
Here, we present our recent results regarding novel nanostructured negative electrodes,
comprising TiO2 nanotubes, Ga2O3 nanorods and graphene-based carbon nanowalls. The
resulting Li-/Na-ion cells exploting the newly elaborated nanostructures as working electrodes
provide very high capacity retention even upon highly stressful conditions and very long-term
cycling (up to > 2000 cycles). High surface area, self-induced doping, short diffusion path and
fast kinetics of the nonostructured arrays are intriguing features, which can account for the
noticeable electrochemical performance. Moreover, the characteristics and electrochemical
behaviour of the annealed samples in comparison with the non-annealed ones were
thoroughly investigated.
These results demonstrate that stable, long-term performing nanostructured anodes, which
can be obtained by fast and low cost procedures, are suitable for Li-/Na-ion battery
application.
[1] D. Larcher and J. Tarascon, Nat. Chem. 7 (2015) 19-29.
106
POS-4
An amino ester based solid polymer electrolyte
Andreas Bergfelt and Tim Bowden
Department of Chemistry - Ångström Laboratory, Uppsala University, Lägerhyddsvägen 1,
75121-Uppsala, Sweden
E-mail: [email protected]
The mobile world depends on lithium-ion batteries; it is probably the most used battery
system of today. The main concern today is to increase safety (liquid electrolytes are very
flammable) and energy density for these types of batteries. Solid polymer electrolytes (SPEs)
using polymers with pendant ion-conducting groups are of interest since the solvating group
is dynamically detached from the main chain and are solvent free [1]. The main challenge
with a solid system is to tailor the mechanical integrity and still achieve high conductivity,
lithium salt dissolving properties and a high cationic transport number. The most studied solid
polymer electrolyte system until now is the polyethylene glycol (PEO) based polymer
electrolyte. The main drawback with this system is that it is not efficient enough.
Block co-polymers and phase separated morphologies could potentially change the
mechanical properties and still retain good conductivity [2]. Moving the dissolving group
from the main chain should favor a more flexible system with a lower Tg, and thus increase
the ionic conductive. Introducing nitrogen as a dissolving group should favor ionic
dissociation, and thus increase the amount of free lithium ions in the system; this is a problem
for the PEO system, where the salt is not fully dissociated [3].
Figure 1: The butyl amino ester monomer.
[1] J. Britz, W. H. Meyer and G. Wegner, Macromolecules 40 (2007) 7558-7565.
[2] W. S. Young, W. F. Kuan and T. H. Epps III, J. Polym. Sci., Part B: Polym. Phys. 52 (2014) 1-16.
[3] R. P. Doyle, X. Chen, M. Macrae, A. Srungavarapu, L. J. Smith, M. Gopinadhan, C. O. Osuji and
S. Granados-Focil, Macromolecules 47 (2014) 3401-3408.
107
POS-5
Microporous hypercrosslinked aromatic polymers: experimental
and grand canonical Monte Carlo study
Lorenzo Canti, Alberto Fraccarollo, Mina Errahali, Giorgio Gatti, Maurizio
Cossi, and Leonardo Marchese
Dipartimento di Scienze e Innovazione Tecnologica, Università degli Studi del Piemonte
Orientale “Amedeo Avogadro”, Viale T. Michel 11, 15121-Alessandria, Italy
E-mail: [email protected]
Hypercrosslinked polymers (HCPs) are characterized by a low-density, rigid network with
extended microporosity (i.e. with pore size smaller than 2 nm) [1,2]. Depending on the
synthesis conditions, the structure and hence the properties of HCPs can vary widely. In our
research group we have synthesized a number of HCPs for these different applications: at the
same time, we used various molecular design techniques to describe the morphology of these
materials. The adsorption isotherms of Ar at 87 K were measured on the real sample UPO-8
and simulated with Monte Carlo techniques in the crystalline and amorphous models. The
simulations were performed with a purposely adapted force field [3]. The NLDFT procedure
was applied to the experimental and simulated isotherms.
[1] J. Urban, F. Svec and J. M. J. J. Frechet, Chromatogr. A, 1217 (2010) 8212-8221.
[2] S. Xu, Y. Luo and B. Tan, Macromol. Rapid Commun. 34 (2013) 471-484.
[3] M. Errahali, G. Gatti, L. Tei, G. Paul, G. A. Rolla, L. Canti, A. Fraccarollo, M. Cossi, A. Comotti,
P. Sozzani and L. Marchese, J. Phys. Chem. C 118 (2014) 28699-28710.
108
POS-6
Crystallization properties, morphology and mechanical properties
of isotactic poly(1-butene) in the presence of nucleating agents
Daria Capone, Claudio De Rosa, Finizia Auriemma, and Oreste Tarallo
Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia 26, 80126Napoli, Italy
E-mail: [email protected]
We report a study of the effect of nucleating agents on the crystallization and mechanical
properties of isotactic poly(1-butene) (iPB) prepared with Ziegler-Natta catalysts. It is well
known that iPB crystallizes in three crystalline forms, denominated forms I, II, III,
characterized by different physical and mechanical properties [1]. Form II is the kinetically
preferred modification and generally crystallizes form the melt. Form II transforms at room
temperature into the more stable form I [1,2].
The crystallization from the melt and solutions and the kinetics of form II → form I
transition have been studied in the presence of organic compounds carrying amide
functionalities, as 1,3,5-tris[2,2-dimethylpropionylamino]benzene (IrgaclearXT), that could
act as nucleating agents for iPB.
We found that the crystallization from the melt of iPB by cooling the melt to room
temperature is affected by the presence of IrgaclearXT and, when the melt is cooled to room
temperature at cooling rate of 10 °C/min, an increase of crystallization temperature of about
10-15 °C is observed. This indicates that this additive is a good nucleating agent for iPB.
However, the presence of IrgaclearXT does not affect the normal crystallization from the melt
of form II that, indeed, crystallizes from the melt in any condition of crystallization, but the
kinetics of the form II → form I transition at room temperature is accelerated. The
morphology of crystals of form II is also affected by the presence of IrgaclearXT with
formation of spherulites smaller than those of the pure iPB. The same effect has been
observed in the case of crystallization from the melt by quenching to low temperature. The
analysis of mechanical properties has shown that the presence of the nucleating agent does not
modify the good mechanical properties of both form II and form I, regardless of the condition
of crystallization from the melt of form II and successive aging at room temperature.
[1] a) G. Natta, P. Corradini and I. W. Bassi, Nuovo Cimento (Suppl.) 15 (1960) 52-67; b) A. Turner
Jones, J. Polym. Sci., Part B: Polym. Lett. B1 (1963) 455-456.
[2] L. Luciani, J. Seppälä and B. Löfgren, Prog. Polym. Sci. 13 (1988) 37-62.
109
POS-7
Synthesis and characterization of Cu(I) complexes
Enrico Casamassa,a Giorgio Volpi,a Claudia Barolo,a Guido Viscardi,a Michael
D. Weber,b and Rubén D. Costab
a
Dipartimento di Chimica e Centro Interdipartimentale NIS, Università degli Studi di Torino,
Via Pietro Giuria 7, 10125-Torino, Italy
b
Department of Chemistry and Pharmacy, University of Erlangen-Nuremberg, Egerlandstr.
3, 91058-Erlangen, Germany
E-mail: [email protected]
In the last years, Cu(I) complexes have been identified as favourable candidates as active
materials in light-emitting electrochemical cells (LECs) [1]. A series of Cu(I) complexes with
N,N-bidentate ligands, based on imidazo[1,5-a]pyridines, with absorption in the ultraviolet
region and emission in the visible were synthesized. These ligands have been obtained
through a simple one-pot procedure [2,3] and for each ligand both the corresponding
heteroleptic (with POP, bis[2-(diphenylphosphino)-phenyl]ether) and homoleptic complexes
were synthesized. In both cases, the coordination environment around CuI should results in a
tetrahedral geometry, the resolution of the crystal structures of some of these complexes are in
progress.
Figure 1: Homoleptic and heteroleptic complexes general structure.
We optimized the synthetic procedure in order to obtain these complexes in mild condition
(i.e: room temperature, short reaction time, and nitrogen atmosphere with degassed solvent)
with high yields (superior to 70%), and through simple purification step.
Ligands and complexes have been characterized by classical techniques, 1H and 13C NMR,
mass spectrometry, UV-Visible absorption and emission and by electrochemistry.
These complexes have, as a main feature, ultraviolet to visible absorption, and an
interesting emission in visible, with more than 70 nm of Stokes Shift. Their application in
LEC has also been tested, with interesting results within this series.
[1] R. D. Costa, E. Ortí, H. J. Bolink, F. Monti, G. Accorsi and N. Armaroli, Angew. Chemie Int. Ed.
51 (2012) 8178-8211.
[2] J. M. Crawforth and M. Paoletti, Tetrahedron Lett. 50 (2009) 4916-4918.
[3] V. S. Arvapalli, G. Chen, S. Kosarev, M. E. Tan, D. Xie and L. Yet, Tetrahedron Lett. 51 (2010)
284-286.
110
POS-8
Toward the total synthesis of smenamide A
Alessia Caso,a Valeria Costantino,a Alfonso Mangoni,a Giorgia Oliviero,a
Gennaro Piccialli,a and Vincenzo Picciallib
a
Dipartimento di Farmacia, Università di Napoli Federico II, Via D. Montesano 49, 80131Napoli, Italy
b
Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia 26, 80126Napoli, Italy
E-mail: [email protected]
An in-depth study of the secondary metabolites contained in the Caribbean sponge
Smenospongia aurea led to the isolation of smenamide A [1], a hybrid peptide/polyketide
showing potent cytotoxic activity at nanomolar level on lung cancer Calu-1 cells, which is
exerted through a clear pro-apoptotic mechanism.
In this communication, a convergent asymmetric total synthesis of smenamide A is
presented. Retrosynthetic analysis led us to disconnect the molecule in two main building
blocks, fragment A (C12-C26) and fragment B (C1-C11), as shown in figure.
Shortly, the synthetic plan involves construction of fragment A from the commercial
available S-citronellene as chiral precursor using oxidative oxidations, Wittig and Grignard
reactions. Fragment B is prepared through cyclisation and asymmetric alkylation of (E)methyl 4-chloro-3-methoxybut-2-enoate with the aid of a chiral auxiliary. Coupling between
the two fragments, leading to the formation of an imide bond, will complete the synthesis.
Total synthesis of smenamide A, which is present only in microgram amounts in the
natural source, will provide larger quantities of the compound needed for pharmacological
development. In addition, it will allow elucidation of the as yet undetermined configuration at
C16.
[1] R. Teta, E. Irollo, G. della Sala, G. Pirozzi, A. Mangoni and V. Costantino, Mar. Drugs 11 (2013)
4451-4463.
111
POS-9
Heavy metals (Pb, Cd, Hg) concentration and distribution in
Murex sp. tissues
Pietro Cassotta,a,b Maria Augusta Raggi,a Annunziata Cannavacciuolo,b
Simonetta Menotta,b and Giorgio Fedrizzib
a
Dipartimento di Farmacia e Biotecnologie, Università di Bologna, Via Belmeloro 6, 40126Bologna, Italy
b
Reparto Chimico degli Alimenti, Istituto Zooprofilattico Sperimentale della Lombardia e
dell’Emilia Romagna, Via P. Fiorini 5, 4012-Bologna, Italy
E-mail: [email protected]
Cadmium (Cd), lead (Pb) and mercury (Hg) are heavy metals that could be found as
environmental contaminants, both through natural occurrence and from industrial and
agricultural sources; in particular, foodstuffs are the main source of exposure population. The
International Agency for Research on Cancer has classified cadmium and lead as human
carcinogens, while mercury poisoning could cause central nervous system disorders.
In the last years, the consumption of the Murex sp. (special gastropods that have different
biological characteristics from bivalve) is remarkably increased in the diet, therefore a
monitoring plan for a better control of heavy metals in these molluscs was advised by the
Emilia-Romagna Region.
The purpose of this investigation was the analysis of heavy metals in Murex sp. tissues in
order to evaluate the concentrations of Cd, Pb, Hg.
Figure 1: Murex sp.
The Murex sp. analyzed were from Rimini, Cesenatico and Ferrara. The samples is
homogenate and mineralized by acidic digestion in nitric acid at 75°C for 12 hours. The
analytical method is based on the use of inductively plasma coupled mass spectrometry (ICPMS). The sensitivity of the method is good, being the Limit of Quantitation 0.005 mg/kg for
all the analytes.
The determination of heavy metals has been carried out on the “foot” and on the “organs”
of the Murex sp. tissues. Cd, Pb, and Hg were found in all examined samples from Murex sp.
The results showed a higher concentration of heavy metals in the “organs” in comparison with
the “foot” (ANOVA; P<0.05). The Pb concentration was always lower than the maximum
residues limits (LMR) both in foot and organs; on the other hand, the concentrations of
cadmium were always over the LMR in organs and below the same limit in “foot” (Reg.
488/EU/2014).
112
POS-10
Doping of nanobranched ZnO films
Marco Laurenti,a Giancarlo Canavese,b Adriano Sacco,a Marco Fontana,a
Katarzyna Bejtka,a Micaela Castellino,a Candido Fabrizio Pirri,a,b and Valentina
Caudaa
a
Center for Space Human Robotics@PoliTo, Istituto Italiano di Tecnologia, C.so Trento 21,
10129-Torino, Italy
b
Dipartimento di Scienza Applicata e Tecnologia, Politecnico di Torino, C.so Duca degli
Abruzzi 24, 10129-Torino, Italy
E-mail: [email protected]
In this work we afford the preparation of both Mn- and Sb-doped zinc oxide (ZnO)
nanobranched thin films and we demonstrate the arise of ferroelectric properties, piezoelectric
voltage generation and, for the first time, ferroelectric-driven photovoltaic effect in the case of
the Sb-doped ZnO porous film [1].
We first synthesized the doped nanobranched structures with an innovative approach, first
depositing by magnetron sputtering a nanobranched zinc film on transparent conductive
substrates, then impregnating it in either manganese acetate or antimony acetate solutions for
different time periods and then thermally treating the impregnated samples. In this way we
achieved at the same time the oxidation of Zn to ZnO and the insertion of the doping element
in the wurtzite structure of ZnO, leading to doped nanostructured materials at different ratio
depending on the impregnation time.
The crystalline structure and chemical composition analyses reported the lattice
substitution of Zn2+ with either Mn2+, maintaining a n-type doping in case of ZnO:Mn
nanobranched films, or with Sb3+ and Sb5+ species, leading to a p-type doping of the ZnO:Sb
porous films. This resulted in the successful use of ZnO:Sb porous films as piezoelectric
nanogenerators, obtaining up to 10.6 V output voltage under compressive force. As a
reference, the undoped nanobranched ZnO showed lower piezoelectric output voltage of 3.3
V. In contrast, ZnO:Mn films showed a high resistive behavior and leakage currents, since the
introduced Mn dopant was unable to compensate the intrinsic n-type conductivity of the ZnO
and lowered the crystallinity of the samples, together with the formation of additional lattice
defects.
The arise of ferroelectricity was observed only upon Sb doping together with a non-zero
spontaneous polarization: this was found to give rise to the ferroelectric-photovoltaic effect,
here reported for the first time for a ZnO-based nanomaterial.
[1] M. Laurenti, G. Canavese, A. Sacco, M. Fontana, K. Bejtka, M. Castellino, F. C. Pirri and V.
Cauda, Adv. Mater. 27 (2015) 4218-4223.
[2] M. Laurenti, S. Stassi, M. Lorenzoni, M. Fontana, G. Canavese, V. Cauda and C. F. Pirri,
Nanotechnology 26 (2015) 215704.
[3] S. Stassi, V. Cauda, C. Ottone, A. Chiodoni, C. F. Pirri and G. Canavese, Nano Energy 13 (2015)
474-481.
113
POS-11
1,2,3-triazole fluorescent bisphosphonates as osteoporosis
probes drugs
Andrea Chiminazzo,a Boris A. Kashemirov,b Charles E. McKenna,b and
Alessandro Scarsoa
Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca’ Foscari Venezia, Via
Torino 155, 30170-Mestre, Italy
b
Department of Chemistry, University of Southern California, 810 Downey Way, 90089-Los
Angeles, USA
E-mail: [email protected]
a
Thanks to their structural similarity with pyrophosphate, bisphosphonates (BPs) ensure
specific bone targeting and are widely employed as drugs for the treatment of bone disorders,
in particular osteoporosis. Recent studies have demonstrated that zoledronic acid, one of the
most potent drugs under use, characterized by the presence of a 1,3-diazole bisphosphonate
strucutre, is among the most efficient inhibitor of specific enzymes [1] leading to osteoclast
inactivation and apoptosis.
In the present contribution we present the syntheses of - and -azido-BP “Click reaction
reagents” in order to obtain a new potentially highly efficient class of 1,2,3-triazole BPs. The
synthesis of the -azido BP proceeded readily via Pd(II)-catalyzed addition of
azidotrimethylsilane [2] to vinylidenebisphosphonate tetraethylesters (VBP), providing a
quantitative yield of the desired compound, using an improved procedure.
-Azido BP can be obtained by Cu(II)-assisted diazo-transfer reaction to a -amino-BP
using imidazole-1-sulfonyl azide hydrochloride as a safe diazo-transfer reagent compared to
the commonly employed triflyl azide [3]. These efficient syntheses allowed the preparation
of the azido-BPs in multigram scale that were tested in click chemistry reactions (Cu(I)catalyzed azide-alkyne cycloadditions), giving 1,4-di-substituted 1,2,3-triazoles BP products
with high regioselectivity. Reaction with several terminal alkynes, including a triple-bond
functionalized diketopyrrolopyrrole (DPP) fluorescent dye, gave a new class of fluorescent
BP probes for bone imaging.
[1] Y. Zhang, R. Cao, M. P. Hudock and E. Oldfield, J. Am. Chem. Soc. 131 (2009) 5153-5162.
[2] M. Ferrer-Casal, A. Barboza, H. Szajnman and J. Rodriguez, Synthesis 45 (2013) 2397-2404.
[3] H. Johansson and D. S. Pedersen, Eur. J. Org. Chem. 23 (2012) 4267-4281.
114
POS-12
Novel structural hybrids from the reaction between benzofuroxan
and benzothiazole derivatives
Silvia Cino,a Gabriele Micheletti,a Elena Chugunova,b and Carla Bogaa
a
Dipartimento di Chimica Industriale "Toso Montanari", Università di Bologna, Viale
Risorgimento 4, 40136-Bologna, Italy
b
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian
Academy of Sciences, ul. Akad. Arbuzova 8, 420088-Kazan, Russia
E-mail: [email protected]
Furoxan and benzofuroxan derivatives are heterocyclic compounds of wide interest both in
theoretical and applied, fields.1
In the meantime the benzothiazole scaffold is a key constituent of many drugs.2
Based on the above considerations, it was in our interest the synthesis of novel structural
hybrids containing both heterocyclic ring systems, benzofuroxan and benzothiazole.
Hereafter, we report the results obtained from the combination of 7-chloro-4,6dinitrobenzofuroxan (1) with 2-thio- and 2-aminobenzothiazole derivatives (2 and 3a-f,
respectively) (see Scheme 1).
Scheme 1
The reaction between 1 and 2 gave compound 4 in high yield while the combination of 1
with 3a-f gave a mixture of mono-adducts 5a-f and di-adducts 6a-d.
The reactions between 1 and 3a-f were also carried out directly in the NMR spectroscopy
tube and from this study we found that mono- or di-adduct can be almost selectively obtained
with a tuning of the experimental conditions.
Finally, the bioactivity of the new structural hybrids was evaluated. Of all the compounds
synthesized, biological activity was displayed by compounds 4 and 5e.
[1] H. Cerecetto and W. Porcal, Mini Rev. Med. Chem. 5 (2005) 57-71.
[2] D. Seenaiah, P. R. Reddy, G. M. Reddy, A. Padmaja, V. Padmavathi and N. S. Krishna, Eur. J.
Med. Chem. 77 (2014) 1-7.
115
POS-13
Nanoporous block-copolymers based materials for biosensing
applications
Claudia Cioce, Claudio De Rosa, Finizia Auriemma, Rocco Di Girolamo, Anna
Malafronte, and Chiara Santillo
Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia 26, 80126Napoli, Italy
E-mail: [email protected]
In recent times interest towards block copolymers based materials has experienced an
explosive growth thanks to their applicability in the fields of nanotechnologies and
nanomaterials.
Block copolymers (BCP) consist of two or more polymer chains linked at one end by
chemical bonds. The chemical incompatibility of blocks generates phase separation and
consequent segregation of the blocks into different domains the geometries and dimensions of
which depend on the volume fraction and the molecular mass of blocks, respectively [1,2].
Regular and periodic nanostructures (of lamellar, cylindrical or body-centered morphology)
can be obtained for domains having uniform nanometric size.
In this work BCPs have been used for the fabrication of nanoporous materials able to act as
substrates for the immobilization of biological macromolecules such as enzymes, with the aim
to probe their applicability in the field of biosensors. The nanoporous material has been
obtained using a nanostructured blend of poly(styrene)-b-poly(L-lactide) (PS-b-PLLA) and
poly(styrene)-b-poly(oxyethylene) (PS-b-PEO), able to generate via self-assembly a lamellar
morphology, after selective removal of PLLA block via alkaline hydrolysis [3]. It has been
shown that this material is able to physically adsorb Myoglobin and Horse Radish Peroxidase
(HRP) and that the enzymatic activity of immobilized HRP onto this support is not impaired.
Immobilization onto the nanoporous support of the enzyme Esterase 2 (EST2) from
Aliciclobacillus Acidocaldarius has been also conducted, in order to develop the active layer
of a biosensor for detection of organophosphorous compounds, such as diethyl 4-nitrophenyl
phosphate (paraoxon). Paraoxon is one of the most potent acetylcholinesterase-inhibiting
insecticides available, of high risk to humans and animals health, because of its high power as
nerve agent.
Therefore, the potential of our approach in enzyme immobilization while preserving high
enzymatic activity over long time has been validated, also identifying a viable tool in
numerous biosensing applications.
[1] F. S. Bates and G. H. Fredrickson, Annu. Rev. Phys. Chem. 41 (1990) 525-557.
[2] M. J. Fasolka and A. M. Mayes, Annu. Rev. Mater. Res. 31 (2001) 323-355.
[3] A. S. Zalusky, R. Olayo-Valles, C. J. Taylor and M. A. Hillmyer, J. Am. Chem. Soc. 123 (2001)
1519-1520.
116
POS-14
Sugar-based arylsulfonamide carboxylates as selective and
water-soluble MMP12 inhibitors
Doretta Cuffaro,a Elisa Nuti,a Felicia D’Andrea,a Enrico A. Stura,b and Armando
Rosselloa
a
b
Dipartimento di Farmacia, Università di Pisa, Via Bonanno 6, 56126-Pisa, Italy
Institute of Biology Technologies - Saclay, Service d’Ingenierie Moleculaire des Proteines,
CEA Saclay, Orme des Merisiers, 91191-Gif-sur-Yvette, France
E-mail: [email protected]
Matrix metalloproteinases (MMPs) constitute a family of more than 20 enzymes which are
involved in tissue remodeling and wounds healing [1]. Among these, macrophage
metalloelastase (MMP12) is mainly produced by macrophages and seems to be involved in
acute and chronic pulmonary inflammatory diseases [2]. In fact, MMP12 is able to degrade
different substrates, among which is elastin, the major constituent of alveolar walls. MMP12
can be considered as an attractive target to study selective inhibitors useful in the
development of new therapies for COPD and other inflammatory diseases. The principal
issues in clinical development of MMP inhibitors (MMPI) are related to the inadequate
selectivity for the designed target enzyme inside the family, to the poor solubility in water and
consequent poor oral bioavailability of many compounds. Therefore, to overcome these
drawbacks and identify novel potent and selective MMP-12 inhibitors, we undertook the
synthesis of a series of arylsulfonamide carboxylates with increased hydrophilicity due to the
conjugation with a β-N-acetyl-D-glucosamine (GlcNAc) moiety. The conjugation between
GlcNAc and the MMP inhibitor scaffold was achieved through the introduction of a
thioureido group or a 1,2,3-triazole group.
The new carboxylates were tested on recombinant human MMPs by in vitro fluorimetric
assay. Among these, two nanomolar MMP-12 inhibitors selective over MMP-1, MMP-9 and
MMP-14 were identified with an improved water solubility. X-ray crystallographic studies
helped us to elucidate the binding mode of the novel sugar-based inhibitors to MMP-12 active
site.
[1] R. Visse and H. Nagase, Circ. Res. 92 (2003) 827-839.
[2] C. Le Quément, I. Guénon, J. Y. Gillon, S. Valença, V. Cayron-Elizondo, V. Lagente and E.
Boichot, Br. J. Pharmacol. 154 (2008) 1206-1215.
117
POS-15
Ab initio study of electrocatalysis at mixed Cr/Mn oxide surfaces
Massimo C. D’Alterio, Ana B. Muñoz-García, and Michele Pavone
Dipartimento di Scienze Chimiche, Università degli Studi di Napoli Federico II, Via Cintia
26, 80126-Napoli, Italy
E-mail: [email protected]
In the context of intermediate temperature solid oxide fuel cells (IT-SOFCs), the rational
design of innovative and effective low-cost materials with high catalytic activity toward
oxygen reduction reaction (ORR) requires a deep understanding of the underlying reaction
mechanisms for oxygen incorporation into the cathodes. In this contribution, we discuss our
first-principles study of the surface chemistry and oxygen reaction reduction ORR mechanism
for the perovskite-type mixed oxide La0.75Sr0.25Cr0.5Mn0.5O3 (LSCM), which has been
proposed in recent studies as both anode and cathode for high-temperature SOFCs thanks to
its excellent catalytic properties, high stability in either oxidant and reducing environments,
good electronic conductivity and mechanical compatibility with common electrolyte (YSZ)
and interconnector (LaCrO3) materials [1,2].
In particular, we use the density functional theory (DFT)+U method, which correctly
describes tightly localized d electrons on transition metals, to analyze the specific roles of
each transition metals (TM), i.e. Cr and Mn, in three main processes of the ORR: (1)
formation of surface oxygen vacancies - needed for the oxygen incorporation after O2
dissociation and reduction; (2) O2 adsorption; and (3) O2 dissociation. We studied Cr/Mn-O2
(001) active surfaces with ordered and disordered Cr/Mn distributions, in order to take into
account the effect of TM local concentrations on the properties under study.
Our results suggest that Cr is an active element in LSCM electrocatalytic activity for both
the reduction of O2 and the inclusion of O2- into the electrode. This result rules out the
established idea of Cr playing only a redox stabilyzing role in LSCM [1,2]. This indication is
of particular relevance because current nanotechnology-based experimental techniques allow
for manipulating inorganic surfaces at the atomic level, enabling the effective synthesis of
catalysts with specific, optimal structural features, as reported from theoretical ab initio
simulations.
[1] S. Tao and J. T. S. Irvine, Nat. Mater. 2 (2003) 320-323.
[2] D. M. Bastidas, S. Tao and J. T. S. Irvine, J. Mater. Chem. 16 (2006) 1603-1605.
118
POS-16
In silico study of VP35 inhibitors
Federico Dapiaggi,a Stefano Pieraccini,a,b and Maurizio Sironia,b
a
Dipartimento di Chimica, Università degli Studi di Milano, Via Golgi 19, 20133-Milano,
Italy
b
Istituto di Scienze e Tecnologie Molecolari, Consiglio Nazionale delle Ricerche, Via Golgi
19, 20133-Milano, Italy
E-mail: [email protected]
In recent years the Ebola virus has spread through several countries in Africa, highlighting the
need to develop new treatments for this disease and boosting a new research effort on this
subject. The Ebola virus Viral Protein 35 (VP35) carries out multiple functions necessary for
virus replication and infection, in particular interfering with (IFN)-α/β signaling [1]. In a
recent work [2], VP35 has been crystallized in complex with small organic molecules able to
inhibit its interaction with viral nucleoproteins, thus reducing Ebola infections of cultured
cells. Starting from these structures, we carried out a computational study aimed at
investigating the energetic and dynamical aspects of the interaction between VP35 and its
ligands at the atomic level [3]. Molecular dynamics simulations, computational alanine
scanning, root mean square fluctuations bootstrap analysis and essential dynamics analysis
were performed. Our results expand the experimental ones obtained in previous works, adding
information about the interactions landscape with the identification of a set of new hot-spots
residues exerting a critical function in the protein–ligand interaction. Moreover we
characterized the dynamics of the complexes, showing that the presence of ligands modifies
the overall protein dynamics as well as the behavior of particular protein segments.
Figure 1: An overview of the hot-spot residues in one of the simulated protein-ligand complexes.
[1] W. B. Cárdenas, Y-M. Loo, M. Gale Jr., A. L. Hartman, C. R. Kimberlin, L. Martinez-Sobrido, E.
O. Saphire and C. F. Basler, J. Virol. 80 (2006) 5168-5178.
[2] C. S. Brown, M. S. Lee, D. W. Leung, T. Wang, W. Xu, P. Luthra, M. Anantpadma, R. S.
Shabman, L. M. Melito, K. S. MacMillan, D. M. Borek, Z. Otwinowski, P. Ramanan, A. J. Stubbs, D.
S. Peterson, J. M. Binning, M. Tonelli, M. A. Olson, R. A. Davey, J. M. Ready, C. F. Basler and G. K.
Amarasinghe, J. Mol. Biol. 426 (2014) 2045-2058.
[3] F. Dapiaggi, S. Pieraccini and M. Sironi, Mol. BioSyst. 11 (2015) 2152-2157.
119
POS-17
Functional and structural characterization of
2-amino-4-phenylthiazole inhibitors of the HIV-1 nucleocapsid
protein with antiviral activity
Chiara Dasso,a Mattia Mori,a Alessandro Nucci,a Nicholas Humbert,b Christian
Boudier,b Francois Dabaene,b Sarah Sanglier-Cianferani,b Marjorie Catala,c
Patricia Schult-Dietrich,d Ursula Dietrich,d Carine Tisné,c Yves Mely,b and
Maurizio Bottaa,e
a
Dipartmento di Biotecnologie, Chimica e Farmacia, Università degli studi di Siena, Via A.
Moro 2, 53100-Siena, Italy
b
Laboratoire de Biophotonique et Pharmacologie, Centre national de la recherche
scientifique, 74 route du Rhin, 67401-Illkirch Cedex, France
c
Laboratoire de Cristallographie et RMN Biologiques, Centre national de la recherche
scientifique, Paris Sorbonne Cité, 4 avenue de l’Observatoire, 75006-Paris, France
d
Georg-Speyer-Haus, Institute for Tumor Biology and Experimental Therapy, Paul Ehrlich
Str. 42-44, 60596-Frankfurt, Germany
e
Sbarro Institute for Cancer Research and Molecular Medicine, Temple University, BioLife
Science Bldg., Suite 333, 19122-Philadelphia, USA
E-mail: [email protected]
The nucleocapsid protein (NC) is a highly conserved protein in diverse HIV-1 subtypes that
plays a central role in virus replication, mainly by interacting with conserved nucleic acid
sequences. NC is thought to protect the nascent vDNA against nucleases, assist Integrase for
the integration of the viral DNA into the host genome and select the genomic RNA and
promote its dimerization and packaging during virus assembly.
NC can hardly mutate, so that NC mutants are generally nonfunctional and result in
noninfectious viruses. Therefore, specific inhibition of NC is thought to generate a sustained
antiretroviral activity [1].
NC is considered a highly profitable drug target to inhibit multiple steps in the HIV-1 life
cycle with just one compound, a unique property not shown by any of the other antiretroviral
classes. However, most of NC inhibitors developed so far act through an unspecific and
potentially toxic mechanism (zinc ejection) and are mainly being investigated as topical
microbicides [2,3]. In an effort to provide specific NC inhibitors that compete for the binding
of nucleic acids to NC, here we combined molecular modeling, organic synthesis, biophysical
studies, NMR spectroscopy, and antiviral assays to design, synthesize, and characterize an
efficient NC inhibitor endowed with antiviral activity in vitro, a desirable property for the
development of efficient antiretroviral lead compounds [4].
[1] R. J. Gorelick, T. D. Gagliardi, W. J. Bosche, T. A. Wiltrout, L. V. Coren, D. Chabot, J. D. Lifson, L. E.
Henderson and L. O. Arthur, Virology 256 (1999) 92-104.
[2] M. Mori, F. Manetti, and M. Botta, Curr. Pharm. Des. 17 (2011) 3713-3728.
[3] V. Shvadchak, S. Sanglier, S. Roche, P. Villa, J. Haiech, M. Hibert, A. Van Dorsselaer, Y. Mely and H. de
Rocquigny, Biochimie 91 (2009) 916-923.
[4] H. Beltz, C. Clauss, E. Piemont, D. Ficheux, R. J. Gorelick, B. Roques, C. Gabus, J. L. Darlix, H. de
Rocquigny, and Y. Mely, J. Mol. Biol. 348 (2005) 1113-1126.
120
POS-18
Curcumin-based analogues as multi-potent
neuroprotective agents
Rita M. C. Di Martino,a Andrea Tarozzi,b Angela Rampa,a Silvia Gobbi,a
Alessandra Bisi,a and Federica Bellutia
a
Dipartimento di Farmacia e Biotecnologie, Università di Bologna, Via Belmeloro 6, 40126Bologna, Italy
b
Dipartimento di Scienze per la Qualità della Vita, Università di Bologna, Corso D'Augusto
237, 47921-Rimini, Italy
E-mail: [email protected]
Multifunctional compounds (MFCs), also called multitarget-directed ligands (MTDLs), are
single chemical entities able to efficiently modulate several molecular targets or pathways
involved in complex diseases, including those affecting central nervous system (CNS) such as
Alzheimer’s disease (AD) [1]. Inflammatory processes and oxidative stress are important
pathogenic features of CNS disorders, responsible for a number of detrimental effects. In this
context, the Keap1-Nrf2-ARE signalling pathway was shown to be a valuable defence
mechanism and it emerged as a validated therapeutic target. A variety of ARE modulators
have been discovered, some of them endowed with a common α,β-unsaturated carbonyl core
structure, responsible for the mechanism of action based on a Michael reaction with critical
cysteine thiol functions of the target [2]. Among this class, curcumin, a naturally occurring
product, proved to be a privileged structure, due to its capability to interact with several
biological macromolecules. Aimed at developing new disease-modifying AD drug candidates,
the curcumin’s scaffold has been suitably exploited to obtain effective MFCs as BACE-1 and
GSK-3β inhibitors [3]. In this study, fragments endowed with additional biological activities
for AD treatment were introduced. These hybrid molecules were evaluated to assess their
ability to interact with some common AD-related targets, and to affect some networked
neurodegenerative pathways.
Figure 1: General structure of the newly synthetized curcumin-based compounds.
[1] A. Cavalli, M. L. Bolognesi, A. Minarini, M. Rosini, V. Tumiatti, M. Recanatini and C.
Melchiorre, J. Med. Chem. 51 (2008) 347-372.
[2] A. J. Wilson, J. K. Kerns, J. F. Callahan and C. J. Moody, J. Med. Chem. 56 (2013) 7463-7476.
[3] R. M. C. Di Martino, A. De Simone, V. Andrisano, P. Bisignano, A. Bisi, S. Gobbi, A. Rampa, R.
Fato, C. Bergamini, D. I. Perez, A. Martinez, G. Bottegoni, A. Cavalli and F. Belluti, J. Med. Chem.,
submitted.
121
POS-19
Aromatic peptide conjugates as potential MRI contrast agents
Carlo Diaferia,a Eliana Gianolio,b Marilisa Leone,c Flavia Mercurio,c Giancarlo
Morelli,a and Antonella Accardoa
a
Dipartimento di Farmacia, Università di Napoli Federico II, Via Mezzocannone 16, 80134Napoli, Italy
b
Dipartimento di Biotecnologie Molecolari e Scienze per la Salute, Università degli Studi di
Torino, Via Nizza 52, 10125-Turin, Italy
c
Istituto di Biostrutture e Bioimaging, Consiglio Nazionale delle Ricerche, Via
Mezzocannone 16, 80134-Napoli, Italy
E-mail: [email protected]
Diphenylalanine (FF) is able to self-assemble into many different nanostructures (NSs) from
nanotubes to organogels [1]. FF-NSs have been investigated for their mechanical,
electrochemical and optical properties, but only few studies have been devoted to investigate
their abilities for potential biomedical applications until now [2]. Moreover, the use of FFbased compounds as diagnostic tools remains largely unexplored, overall for the low intrinsic
water solubility of these derivatives. Very recently [3], we proposed novel di-phenylalanine
and tetra-phenylalanine conjugates as potential contrast agents (CAs) in Magnetic Resonance
Imaging (MRI). Here, we describe two novel peptide CAs (Figure 1) based on the 1Nal and
2Nal aromatic residues, here indicated as DOTA(Gd)-L6-(1Nal)2 and DOTA(Gd)-L6-(2Nal)2.
In these conjugates the phenylalanine residues are replaced with the 1-Naphtylanaline (1-Nal)
or 2-Naphtylanaline (2-Nal). Their aggregation properties and relaxometric behaviour, as free
bases and as gadolinium complexes, have been studied. Moreover, 1HNMR studies provides
evidence for their capability to encapsulate anticancer drugs such as doxorubicin.
Figure 1: Schematic representation of di-aromatic compounds containing an aromatic
framework consisting of two Phenylalanine (Phe) or 1-Naphthylalanine (1-Nal) or 2Naphthylalanine (2-Nal) residues, an ethoxylic linker (L6) at six PEG units and a bifunctional
chelating agent DOTA for gadolinum (III) coordination.
[1] M. Reches and E. Gazit, Nature 300 (2003) 625-627.
[2] X. Yan, P. Zhu and J. Li, Chem. Soc. Rev. 39 (2010) 1877-1890.
[3] C. Diaferia, E. Gianolio, P. Palladino, F. Arena, C. Boffa, G. Morelli and A. Accardo, Adv. Fuct.
Mater, just accepted.
122
POS-20
Omega3 lipid amount in liposomes modulates their interaction with
Abeta(1-42) peptide
Alessandro Emendato,a Roberta Spadaccini,b Augusta De Santis,a,c Gerardino
D’Errico,a,c and Delia Piconea
a
Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia 26, 80126Napoli, Italy
b
Dipartimento di Scienze e Tecnologie, Università degli Studi del Sannio, Via Traiano, 3,
82100-Benevento, Italy
c
Consorzio interuniversitario per lo sviluppo dei Sistemi a Grande Interfase, Via Cintia 26,
80126-Napoli, Italy
The insurgence of Alzheimer Disease (AD), and also of many other age-related
neurodegenerative diseases, is elicited by the interplay of genetic, environmental and dietary
factors. Regular ingestion of fresh fish, vegetables and fruits, which are rich in Omega-3 fatty
acids, seems to reduce the incidence of AD [1]. However, in spite of an impressive research
effort, the physiopathological mechanism of AD is still unknown, therefore it is not clear how
to prevent, halt or cure this pathology. Membrane interaction of Amyloid beta peptides (Aβ)
are certainly crucial in the neuronal cell damages, although the molecular entity leading to
cellular death is still unclear. In vitro studies indicate that Aβ and phospholipid membranes
are able to reciprocally affect their respective structures [2]. Lipid membranes modulate
aggregation and dissolution processes of Aβ [3]. In turn, Aβ affect the integrity of the
membrane, ultimately leading to cytotoxicity. These processes are influenced by membrane
structure, charge, size, composition and fluidity. In the search of a possible explanation for the
influence of Omega-3 fatty acids on AD, we have investigated by CD and ESR studies the
interaction between the Alzheimer peptide Aβ-(1-42) and lipid bilayers whose composition
mimics neuronal membranes. Here, we show that the inclusion of an Omega-3 phospholipid
(1,2-didocosahexaenoyl-sn-glycero-3-phosphocholine) does not change significantly the
liquid crystalline organization of lipid bilayers. However, the presence of the polyunsaturated
fatty acids significantly favours the Aβ interaction with lipid bilayers, and the peptide
aggregation process. Moreover, the amount of Omega3 inside the liposomes modulates the
interaction kinetics. Our results open the way to possible nutraceutical and therapeutical
implications.
[1] B. Singh, A. K. Parsaik, M. M. Mielke, P. J. Erwin, D. S. Knopman, R. C. Petersen and R. O.
Roberts, J. Alzheimers Dis. 39 (2014) 271-282.
[2] K. Matsuzaki, Biochim.Biophys. Acta 1768 (2007) 1935-1942.
[3] I. C. Martins, I. Kuperstein, H. Wilkinson, E. Maes, M. Vanbrabant, W. Jonckheere, P. Van
Gelder, D. Hartmann, R, D'Hooge, B. De Strooper, J. Schymkowitz and F. Rousseau, EMBO J. 27
(2008) 224-233.
123
POS-21
Formulation and characterizations of magnetic inks for
flexographic printing employed as electromagnetic shields
Giuseppe Ferraro,a Gabriele Barrera,b Federica Celegato,c Marco Coïsson,c Paola
Tiberto,c Paola Martino,d Marco Cotto,d Paola Rivolo,e Angelica Chiodoni,a and
Alessandro Chiolerioa
a
Center for Space Human Robotics, Istituto Italiano di Tecnologia, Corso Trento 21, 10129Torino, Italy
b
Dipartimento di Chimica, Università degli Studi di Torino, Via Pietro Giuria 9, 10125Torino, Italy
c
Sezione Elettromagnetismo, Istituto Nazionale di Ricerca Metrologica, Strada delle Cacce
91, 10135-Torino, Italy
d
Politronica srl, Via Livorno 60, 10144-Torino, Italy
e
Dipartimento di Scienza Applicata e Tecnologia, Politecnico di Torino, Corso duca degli
Abruzzi 24, 10129-Torino, Italy
E-mail: [email protected]
The purpose of the project is the formulation and characterization of magnetic inks for
flexographic printing to evaluate their applicability as electromagnetic shields, assessing the
effects of micro/nano particles featuring different sizes.
The smallest magnetite based nanoparticles ware synthesized by precipitation of iron salts
in an alkaline aqueous medium or by using sonochemistry process [1].
The formulation is based on the mixing of the different micro/nano powders with a
compatible UV/EB curable polymer so forming the related composite material.
The so-obtained inks were characterized morphologically by scanning electron microscopy
(SEM) or transmission electron microscope (TEM). The magnetic characterization was
performed by vibrating sample magnetometer (VSM) both in liquid and and on flexible
substrates after printing.
Finally, the absorption properties of different inks were evaluated by means of RF-based
techniques.
Figure 1. Magnetic inks for EM-shielding printed by flexography.
[1] S. Laurent, D. Forge, M. Port, A. Roch, C. Robic, L.V. Elst and R. N. Muller, Chem. Rev. 108
(2008) 2064-2110.
124
POS-22
Discovery of cholanoic acid derivatives as new modulators of bile
acid receptors
Claudia Finamore,a Valentina Sepe,a Barbara Renga,b Carmen Festa,a Dario
Masullo,a Adriana Carino,b Sabrina Cipriani,b Eleonora Distrutti,c Stefano
Fiorucci,b and Angela Zampellaa
a
Dipartimento di Farmacia, Università di Napoli Federico II, Via D. Montesano 49, 80131Napoli, Italy
b
Dipartimento di Medicina Sperimentale, Università degli Studi di Perugia, Via Gambuli 1,
06132-Perugia, Italy
c
Ospedale S. Maria della Misericordia, Piazza Menghini 1, 06126-Perugia, Italy
E-mail: [email protected]
Bile acids, the end-products of cholesterol catabolism, are signaling molecules activating
several cellular networks [1,2] through the recognition of nuclear and membrane receptors,
such as the farnesoid-x-receptor (FXR) and a G-proteins coupled receptor (GP-BAR1). BAs
are generated in the liver as primary bile acids, cholic acid (CA) and chenodeoxycholic acid
(CDCA), conjugated with glycine and taurine, and then secreted in the small intestine and
transformed by the intestinal microbiota into secondary bile acids, deoxycholic acid (DCA)
and lithocholic acid (LCA). CDCA is the endogenous agonist of FXR while LCA and its
corresponding tauro- and glyco-conjugates (GLCA and TLCA) are the most potent natural
agonists for GP-BAR1.
The main physiological role of FXR is the regulation of bile acids absorption, synthesis
and secretion in the intestine, liver and kidney and it is considered a promising target in
cholestasis. Although, GP-BAR1 agonists represent a novel opportunity in the treatment of
entero-hepatic and metabolic disorders, a recent study has provided evidence that this receptor
is the physiologic mediator of pruritus [3], a common symptom observed in cholestasis. In
this contest, we have manipulated the bile acids scaffolds to obtain a potential lead compound
in the treatment of entero-hepatic and metabolic disorders [4].
[1] S. Fiorucci and F. Baldelli, Curr. Opin. Gastroenterol. 25 (2009) 252-259.
[2] S. Fiorucci, S. Cipriani, A. Mencarelli, F. Baldelli, G. Bifulco and A. Zampella, Mini Rev. Med.
Chem. 11 (2011) 753-762.
[3] S. Fiorucci, A. Mencarelli, G. Palladino and S. Cipriani, Trends Pharmacol. Sci. 30 (2009) 570580.
[4] C. Festa, B. Renga, C. D’Amore, V. Sepe, C. Finamore, S. De Marino, A. Carino, S. Cipriani, M.
C. Monti, A. Zampella and S. Fiorucci, J. Med. Chem. 57 (2014) 8477-8495.
125
POS-23
Inhibition of microsomal prostaglandin E2 synthase1: focused
design of new anti-inflammatory and anticancer drugs
Antonio Foglia, Stefania Terracciano, Gianluigi Lauro, Carmela Saturnino,
Raffaele Riccio, Ines Bruno, and Giuseppe Bifulco
Dipartimento di Farmacia, Università degli Studi di Salerno, Via Giovanni Paolo II, 132,
84084-Fisciano, Italy
E-mail: [email protected]
Arachidonic acid metabolism is a critical process mediated by several enzymes, which lead to
the formation of different classes of eicosanoids [1]. mPGES-1 catalyzes the biosynthesis of
Prostaglandin E2 (PGE2), a key bioactive lipid which mediates a variety of biological effects
associated with inflammation, pain, fever and cancer [2]. Recently, mPGES-1 has emerged as
a promising target for therapeutic application in light of the possibility of overcoming the
classical side effects commonly associated with use of traditional anti-inflammatory drugs [3].
mPGES-1 is a homotrimer and the active site is located at the interface of the three
asymmetric monomers, which are formed by four α-helices and are partially occupied by the
glutathione (GSH) cofactor [4]. Although many structurally different compounds able to
efficiently inhibit mPGES-1 have been developed, the discovery of new and more potent
mPGES-1 inhibitors is strongly required [5]. With the aim of discovering a new potential
class of mPGES-1 inhibitors, we have accomplished a virtual screening on a huge number of
synthetically accessible molecules in order to select the best candidates for the subsequential
steps of chemical synthesis and biological evaluation. Computational calculations were
performed by using the X-ray crystallographic structure of mPGES-1 solved in 2014 [6].
Computational results suggest that 1,3,4-trisubstituted-5-pyrazolones seems to be a potential
scaffolds able to interact with the catalytic site of mPGES-1. The synthetic approach used for
the synthesis of these compounds includes a first step of condensation between β-ketoester
and hydrazines and subsequently a Knoevenagel condensation with aromatic aldehydes. The
next step was to use a combinatorial approach using the starting synthons for the construction
of a library of compounds, afterwards we evaluated the binding affinity and the key
interactions with target protein.
The biological studies on the synthesized compounds are currently under evaluation.
[1] W. L. Smith, Y. Urade and P. J. Jakobsson, Chem. Rev. 111 (2011) 5821-5865.
[2] J. Y. Park, M. H. Pillinger and S. B. Abramson, Clin. Immunol. 119 (2006) 229-240.
[3] M. Nakanishia, V. Gokhaleb, E. J. Meuilletc and D. W. Rosenberg, Biochimie 92 (2010)
660-664.
[4] H. Chang and E. J. Meuillet, Future Med Chem 3 (2011) 1909-1934.
[5] S. He, C. Li, Y. Liu and L. Lai, J. Med. Chem. 56 (2013) 3296-3309.
[6] D. Li, N. Howe, A. Dukkipati, S. T. Shah, B. D. Bax, C. Edge, A. Bridges, P. Hardwicke, O. M.
Singh, G. Giblin, A. Pautsch, R. Pfau, G. Schnapp, M. Wang, V. Olieric and M. Caffrey, Cryst.
Growth. Des. 14 (2014) 2034-2047.
126
POS-24
Synthetic receptors for mannosides as carbohydrate binding
agents targeting the glycans of HIV gp120
Oscar Francesconi,a Cristina Nativi,a Gabriele Gabrielli,a Irene De Simone,a Sam
Noppen,b Jan Balzarini,b Sandra Liekens,b and Stefano Roelens a,c
Dipartimento di Chimica “Ugo Schiff”, Università degli Studi di Firenze, Via della
Lastruccia, 3, 50019-Sesto Fiorentino, Italy
b
Rega Institute for Medical Research, KU Leuven, B-3000 Leuven, Belgium
c
Istituto di Metodologie Chimiche (IMC), Consiglio Nazionale delle Ricerche (CNR), Via
della Lastruccia, 3, 50019-Sesto Fiorentino, Italy
E-mail: [email protected]
a
The densely mannosylated glycans of the viral envelope of the human immunodeficiency
virus (HIV) play a crucial role in viral transmission. Recently, they have been proposed as a
potential target for new therapeutic strategies [1]. Lectins capable of interacting with the
highly-mannosilated glycoprotein gp120 of the HIV envelope were shown to effectively
inhibit infection and transmission of HIV by blocking the virus entry process. Unfortunately,
lectins present many drawbacks, which prevent their development as therapeutic agents.
Therefore the development of small-size, nonpeptidic molecules as carbohydrate binding
agents (CBAs) is recently emerging as a promising strategy for antiviral therapies and
vaccines. In the last few years we have developed a family of structurally-related synthetic
aminopyrrolic receptors that are able to recognize mono- and dimannosides in competitive
organic solvents with affinities in the low micromolar range by exploiting a combination of
hydrogen bonding and van der Waals/CH-π interactions [3]. Recently we have investigated
their biological activity toward several strains of yeast and yeast-like microorganisms bearing
mannoproteins on their cell surface, and found that they show antifungal activity through the
interaction with the surface glycans [4]. Because of the close similarity of the mannan portion
of yeast cell wall with the HIV gp120 glycans, we carried out an investigation of their binding
properties towards the highly mannosilated gp120 and gp41 glycoproteins of the HIV
envelope together with an evaluation of the antiviral activity of this family of synthetic
receptors [5]. The cytostatic activities of the investigated compounds were also examined. In
the present communication, we report the results of such a study and discuss the potential
application as CBAs
[1] J. Balzarini, Nat. Rev. Microbiol. 5 (2007) 583-597.
[2] A. Ardá, C. Venturi, C. Nativi, O. Francesconi, G. Gabrielli, F.J. Cañada, J. Jiménez-Barbero and
S. Roelens, Chem. Eur. J. 16 (2010) 414-418.
[3] C. Nativi, O. Francesconi, G. Gabrielli, I. De Simone, B. Turchetti, T. Mello, L. Di Cesare
Mannelli, C. Ghelardini, P. Buzzini and S. Roelens, Chem. Eur. J. 18 (2012) 5064-5072.
[4] O. Francesconi, C. Nativi, G. Gabrielli, I. De Simone, S. Noppen, J. Balzarini, S. Liekens and S.
Roelens, Chem. Eur. J. 21 (2015) 10089-10093.
127
POS-25
Polar fraction composition of Sideritis montana L.
Claudio Frezza,a Alessandro Venditti,b Ginevra Giacomello,b Filippo Maggi,c
Domenico Lucarini,d Mauro Serafini,a and Armandodoriano Biancob
a
Dipartimento di Biologia Ambientale, Sapienza - Università di Roma,
P. le Aldo Moro 5, 00185-Roma, Italy
b
Dipartimento di Chimica - Edificio "Cannizzaro", Sapienza - Università di Roma,
P. le Aldo Moro 5, 00185-Roma, Italy
c
Scuola di Scienze del Farmaco e dei Prodotti della Salute, Università di Camerino, Via
Sant’Agostino 1, 62032-Camerino, Italy
d
Scuola di Bioscienze e Medicina Veterinaria, Università di Camerino, Via Sant’Agostino 1,
62032-Camerino, Italy
E-mail: [email protected]
Sideritis montana L., locally known as ‘stregonia montana’, is a species belonging to the
Lamiaceae family (subfamily Lamioideae) occurring mostly in north and central Italy where it
grows on arid meadows and uncultivated lands up to 1000 m of altitude. In the folk medicine,
it is widely utilized as beverage in brew form for its antibacterial properties [1]. In this work
we report the first study on the total polar fraction content of a sample of this plant collected
in Monte Capolapiaggia (Camerino, central Italy, at 700 m a.s.l.).
Nine compounds were identified: two flavonoids, isoscutellarein derivatives [2]; one
caffeoylquinic derivative, chlorogenic acid [2]; one glycosidic hydroquinone, methyl-arbutin
[3]; five iridoids, harpagide [2], 8-O-acetyl-harpagide [4], 5-allosyloxy-aucubin [5],
melittoside [6] and 8-epiloganic acid [7]. Beside melittoside, all the other compounds were
evidenced for the first time in this species [8]. On the other side, the two isoscutellarein
derivatives together with 5-allosyloxy-aucubin and melittoside have been already found only
in the genus [9] as well as harpagide and 8-O-acetyl-harpagide [10]. Indeed, clorogenic acid,
methyl-arbutin and 8-epiloganic acid were isolated for the first time in Sideritis and, if the
presence of the first two compounds may explain the use of this plant, the presence of the
third one is important from a phytochemical point of view since it’s the precursor of
compounds owning iridoidic skeletons.
[1] S. Pignatti, Flora d’Italia, 451-620, 1982.
[2] A. Venditti, A. Bianco, M. Nicoletti, L. Quassinti, M. Bramucci, G. Lupidi, L. A. Vitali, F. Papa, S. Vittori,
D. Petrelli, L. Maleci Bini, C. Giuliani and F. Maggi, Chem. Biodivers. 11 (2014) 245-261.
[3] R. Lutterbach and J. Stöckigt, Phytochemistry 40 (1995) 801-806.
[4] M. L. Scarpati, M. Guiso and L. Panizzi, Tetrahedron Lett. 39 (1965) 3439-3443.
[5] A. Venditti, A. M. Serrilli, M. Di Cecco, G. Ciaschetti, T. Andrisano and A. Bianco, Nat. Prod. Res. 27
(2013) 190-193.
[6] M. L. Scarpati and P. Esposito, Gazz. Chim. Ital. 97 (1967) 1209.
[7] A. Venditti, C. Frezza, M. Serafini and A. Bianco, Nat. Prod. Res. (2015) DOI:
10.1080/14786419.2015.1060230.
[8] I. I. Koleva, J. P. H. Linssen, T. A. van Beek, L. N. Evstatieva, V. Kortenska and N. Handjieva, J. Sci. Food
Agric. 83 (2003) 809-819.
[9] A. Venditti, A. Bianco, F. Maggi and M. Nicoletti, Nat. Prod. Res. 27 (2013) 1408-1412.
[10] E. N. Gritsenko, O. I. Kostyuchenko, I. M. Fefer, E. N. Gritsenko and A. Y. Kobzar, Mater. S'ezda Farm. B.
SSR 3 (1977).
128
POS-26
Rational design and synthesis of analogs of 2-oxo-1,2dihydropyridine-3-carboxamide derivatives as CB2R ligands
Francesca Gado,a Chiara Arena,a Andrea Chicca,b Jürg Gertsch,b Marco
Macchia,a and Clementina Maneraa
a
b
Dipartimento di Farmacia, Università di Pisa, Via Bonanno 6, 56126-Pisa, Italy
Institute of Biochemistry and Molecular Medicine, University of Bern, Bühlstrasse 28, 3012Bern, Switzerland
E-mail: [email protected]
Cannabinoid receptors (CB1R and CB2R) are key components of a ubiquitous complex lipid
signaling system, the endocannabinoid system (ECS). As CB1R probably mediates most of
the psychotropic effects of cannabinoids , CB2R selective ligands are attractive as
therapeutics [1]. 1,2-dihydro-2-oxopyridine-3-carboxamide derivatives A (Fig.1) exhibited
good CB2 receptor affinity and selectivity. Furthermore, it was showed that the nature of the
substituent in position C5 of the heterocyclic nucleus controls the switch among the different
types of pharmacological modulation (agonism, inverse agonism and antagonism) of the
receptor (compounds B, Fig.1) [2]. Subsequently, a methyl in 6 position was introduced. The
CB2 receptor affinity and selectivity resulted very similar but, interestingly, some of these
compounds showed also potent inhibition of AEA and 2-AG uptake with IC50 values in the
nanomolar range (compounds C, Fig.1). In the light of these good results, in this work the aim
is to deepen the structure activity relationship of this class of compounds, converting the
amide group into the corresponding reverse amide (compounds D, Fig.1). The new
compounds were tested to determine their affinities towards both subtypes of CBRs.
Figure 1: Compounds with general structures A, B, C and D
[1] R. G. Pertwee, Br. J. Pharmacol. 156 (2009) 397-411.
[2] V. Lucchesi, T. Parkkari, J. R. Savinainen, A. M. Malfitano, M. Allarà, S. Bertini, F. Castelli, S.
Del Carlo, C. Laezza, A. Ligresti, G. Saccomanni, M. Bifulco, V. Di Marzo, M. Macchia and C.
Manera, E. J. of Med. Chem.74 (2014) 524-532.
129
POS-27
Marbled texture of sputtered Al thin film on Si
Mattia Gianfranco Gentile,a,b Ettore Vittone,a Josè Alejandro Munoz Tabares,c
Giovanni Richieri,b Rossano Carta,b and Luigi Merlinb
Dipartimento di Fisica and NIS Interdepartmental Center, Università degli Studi di Torino,
Via P. Giuria 1, 10125-Torino, Italy
b
Vishay Semiconductor Italiana S.p.A., Via Liguria 49, 10071-Borgaro, Italy
c
Center for Space Human Robotics, Istituto Italiano di Tecnologia, Corso Trento 21, 10129Torino, Italy
E-mail: [email protected]
a
Aluminum DC magnetron sputtering is a commonly used technique for the fabrication of
silicon based electronic devices, since it provides high deposition rates and uniform large area
metallization. However, in addition to the thickness uniformity, coating optical uniformity is a
crucial need for semiconductor industrial processes, for the wide use of optical recognition
tools. It is shown in this paper, that under certain standard process conditions, Al
metallization on a [100] Si wafer does not match this latter requirement, since it presents a
non-uniform reflectivity, with a marbled texture caused by flakes with milky appearance
adjacent to specular regions. These optical inhomogeneity are found to be induced by the
random orientation of Al grains, which coexist with Al crystals, heteroepitaxially grown on Si
with a small lattice mismatch. Based on this microstructural analysis, some strategies to
mitigate or suppress this marbled texture of the Al thin film are proposed and discussed.
130
POS-28
Aqueous electrolytes for dye-sensitized solar cells
Giulia Giacona,a,b Simone Galliano,a Claudia Barolo,a Claudio Gerbaldi,b
Michael Grätzel,c and Federico Bellab
a
Dipartimento di Chimica e Centro Interdipartimentale NIS, Università degli Studi di Torino,
Via Pietro Giuria 7, 10125-Torino, Italy
b
GAME Lab, Dipartimento di Scienza Applicata e Tecnologia, Politecnico di Torino, Corso
Duca Degli degli Abruzzi 24, 10129-Torino, Italy
c
Laboratory of Photonics and Interfaces, École polytechnique fédérale de Lausanne, Station
6, 1015-Lausanne, Switzerland
E-mail: [email protected]
Dye sensitized solar cells (DSSCs) are photovoltaic systems able to convert solar energy into
electricity and, nowadays, represent the most investigated alternative to conventional Si-based
devices. The first cells have been fabricated with organic solvent-based liquid electrolytes,
achieving high efficiency performance [1].
However, these solvents not only present high vapor pressure, but are also toxic and
flammable. In the last few years, the idea of moving towards a water-based system clearly
emerged, especially for a large scale diffusion of this technology.
DSSCs fabricated with water-based electrolytes may offer reduced costs, non-flammability
and environmental compatibility, but the presence of water in the cell may reduce the longterm stability as well as the photovoltaic performance [2,3,4].
In this work, the study of different truly aqueous electrolytes is presented and a
chemometric approach, useful to investigate and optimize their efficiency and stability, is
effectively demonstrated.
Figure 1: Aqueous photovoltaics: a new era in 3rd generation devices [2].
[1] B. O’Regan and M. Grätzel, Nature 353 (1991) 737-740.
[2] F. Bella, C. Gerbaldi, C. Barolo and M. Grätzel, Chem. Soc. Rev. 44 (2015) 3431-3473.
[3] W. Xiang, F. Huang, Y. B. Cheng, U. Bach and L. Spiccia, Energy Environ. Sci. 6 (2013) 121-127.
[4] C. H. Law, S. C. Pathirana, X. Li, A. Y. Anderson, P. R. F. Barnes, A. Listorti, T. H. Ghaddar and
B. O’Regan, Adv. Mater. 22 (2010) 4505-4509.
131
POS-29
p53-dependent and p53-independent anticancer activity of a new
indole derivative in human osteosarcoma cells
Alessandra Graziadio, Alessandra Locatelli, Alberto Leoni, Rita Morigi, Mirella
Rambaldi, Concettina Cappadone, Lucia Merolle, and Azzurra Sargenti
Dipartimento di Farmacia e Biotecnologie, Università di Bologna, Via Belmeloro 6, 40126Bologna, Italy
E-mail: [email protected]
Osteosarcoma (OS) is the most common primary malignant bone tumor.
Tumor suppressor pathways governed by p53 gene are known to be involved in the
pathogenesis of osteosarcoma [1]. Moreover, loss of wild-type p53 activity is thought to be a
major predictor of failure to respond to chemotherapy in various human cancers.
In this communication we wish to describe the activity profile of the indole derivative NSC
743420 that emerged as a new lead from a small library of Knoevenagel adducts [2]. These
derivatives were synthesized by reacting benzoindolinones with imidazothiazole aldehydes
properly substituted.
The compound NSC 743420 showed an antiproliferative activity in the preliminary
screening in the NCI 60 cell panel, with mean GI50 value of 0.21 μM. However, this molecule
has never been tested on OS cell lines.
Here we address the activity of NSC 743420 in OS cell lines with different p53 status, by
studying how this difference could influence the effects of indole derivatives on the
proliferation and death of these cancer cells.
In particular, we compared the effect of the tested molecule on p53 wild-type and p53silenced U2OS cells, and on SaOs cell line which is null
for p53.
The results suggest that the mechanism of action of the
compound is not exclusive, but it involves p53-dependent
and p53-independent molecular targets.
Also the synthesis of analogues of NSC 743420 and the
relationship between the structural changes and the
antiproliferative activity will be described.
[1] A. Spina, L. Sorvillo, A. Esposito, A. Borgia, L. Sapio and S. Naviglio, Curr. Pharm. Des. 19
(2013) 5394-5403.
[2] A. Andreani, M. Granaiola, A. Locatelli, R. Morigi, M. Rambaldi, L. Varoli, N. Calonghi,
C. Cappadone, G. Farruggia, C. Stefanelli, L. Masotti, T. L. Nguyen, E. Hamel and R. H. Shoemaker,
J. Med. Chem. 55 (2012) 2078-2088.
132
POS-30
Supramolecular control of spin exchange in spin labelled
[2]rotaxane incorporating a tetrathiafulvalene unit
Lorenzo Gualandi, Francesco Romano, Roberta Manoni, Valentina Bleve, Paola
Franchi, Elisabetta Mezzina, and Marco Lucarini
Dipartimento di Chimica “Giacomo Ciamician”, Università di Bologna, Via Selmi 2, 40100Bologna, Italy
E-mail: [email protected]
Exchange-coupled oligoradicals are of great importance and interest in many fields of
chemistry and related sciences [1]. An essential parameter in such structures is represented by
the magnitude and sign of the spin−spin coupling interaction (J). This interaction can be
through-bond and/or through-space, and its value depends on the extent of electronic
communication which is sensitive to their relative orientation between molecules. In this
contest, mechanically interlocked molecules (MIMs), such as catenanes and rotaxanes,
containing paramagnetic species provided stimulating framework in consideration of their
capacity to vary the relative positions of the dumbbell and ring components in response to
external stimuli [2]. Very recently, we prepared a [2]rotaxane, where spin exchange between
two nitroxide units located both at the ring and the dumbbell could be switched on/off by
changing the pH [3].
In the present communication, differently from the previous paramagnetic MIM,3 we
report novel examples of nitroxide-spin-labelled bistable rotaxanes containing both
tetrathiafulvalene (TTF) and 1,5-dioxynaphthalene (DNP) units, and cyclobis(paraquat-pphenylene) ring (CBPQT4+) in which the paramagnetic centers are directly involved in the
shuttling process. In this case the movement of the ring induced by single electron oxidation
of the TTF station provides important differences in the electronic communication between
TTF+ radical cation and a spin label introduced “ad hoc” as a stopper in the dumbbell,
highlighting the effect of rotaxanation on through-space magnetic interactions between radical
fragments [4]. Introduction of a spin label also on the CBPQT4+ ring in the rotaxane structure
will also be discussed.
[1] M. Abe, Chem. Rev. 113 (2013) 7011-7088.
[2] V. Bleve, C. Schäfer, P. Franchi, S. Silvi, E. Mezzina, A. Credi and L. Lucarini, ChemistryOpen 4
(2015) 18-21.
[3] A. Coskun, J. M. Spruell, G. Barin, W. R. Dichtel, A. H. Flood, Y. Y. Botrosghi and J. F. Stoddart,
Chem. Soc. Rev. 41 (2012) 4827-4859.
[4] F. Romano, R. Manoni, P. Franchi, E. Mezzina and M. Lucarini, Chem. Eur. J. 21 (2015) 27752779.
133
POS-31
Rhodanine derivatives as potent anti-HIV microbicides
Giulia Iovenitti,a Cristina Tintori,a Marika Tiberi,a Claudio Zamperini,a Filippo
Canducci,b and Maurizio Bottaa
a
Dipartmento di Biotecnologie, Chimica e Farmacia, Università degli studi di Siena, Via A.
Moro 2, 53100-Siena, Italy
b
Ospedale San Raffaele & Università degli Studi dell’Insubria, Via Olgettina 60, 20132Milano, Italy
E-mail: [email protected]
Considering the adverse side effects and the emergence of resistant mutant strains, new
therapies against the HIV virus are urgently required [1,2]. In this context, the use of a vaginal
microbicide can be considered an excellent strategy to prevent transmission of the disease.
As a continuation of our previous work, which resulted in the identification of a new hit
compound as an HIV-1 inhibitor [2,3], a novel series of rhodanines derivatives was
synthesized. Biological evaluation showed that these compounds are able to inhibit HIV-1
replication at nanomolar concentration. However, the activity of such inhibitors decreased of
several times (from 20 to 100) once they were pre-incubated with serum before the in vitro
assay.
In order to better elucidate this behavior, the binding affinities of the new derivatives to
Serum Albumin were determined by a fluorescence-spectroscopy measurement. The high
affinity binding to albumin prevents their use as oral drugs for HIV. On the other hand,
ADME studies showed that this compounds are promising candidates as anti-HIV
microbicides: excellent cell permeability; stability higher than 90% at pH between 4 and 7;
acceptable solubility at pH 4.2.
It has recently been shown that the complexity of sexual transmission of viral pathogens
requires the identification of compounds able to block the early events during the cycle of
viral infection.[4] Being able to inhibit the very early stage of HIV entry process, as
demonstrated by a time of addition experiment, rhodanines are rather suitable for the use as
microbicide. On this basis a vaginal gel formulation of the best anti-HIV candidate, MAS510,
was developed and evaluated in vitro.
[1] Q. A. Karim, C. Baxter and S. A. Karim, BJOG 121 (2014) 53-61.
[2] M. Rinaldi, C. Tintori, L. Franchi, G. Vignaroli, A. Innitzer, S. Massa, J. A. Esté, E. Gonzalo, F.
Christ, Z. Debyser and M. Botta, ChemMedChem 6 (2011) 343-352.
[3] C. Tintori, V. Corradi, M. Magnani, F. Manetti and M. Botta, J. Chem. Inf. Model. 48 (2008) 21662179.
[4] J. A. Fernández Romero, P. I. Gil, V. Ré, M. Robbiani and G. Paglini, Rev. Argent. Microbiol. 46
(2014) 256-268.
134
POS-32
How to improve the efficiency of sensitizers: a study on the
behavior of co-adsorbents in DSSCs
Silvia Manfrin, Simone Galliano, Alessandra Smarra, Claudio Magistris,
Roberto Buscaino, Claudia Barolo, and Guido Viscardi
Dipartimento di Chimica e Centro Interdipartimentale NIS, Università degli Studi
di Torino, Via Pietro Giuria 7, 10125-Torino, Italy
E-mail: [email protected]
Dye-sensitized solar cells (DSSCs) have attracted great interest as one of the most promising
alternatives to the conventional Si-based devices in the solution of global energy demand. The
main advantages are easy assembly, low manufacturing cost, environmentally friendly
character and, recently, considerable energy conversion efficiency. However, DSSCs are not
yet commercialized on a large scale because of their long-term stability problems [1].
The sensitizer, one of the core component of the device, presents three unwanted process
that hinder their operation: dye aggregation, semiconductor surface protonation and charge
recombination. The most successful solution is to use substances that can be adsorbed
simultaneously onto the photoanode competitively with the dye molecules, thus blocking the
vacant spots on the semiconductor surface. Due to their function they are called co-adsorbents
[2]. Co-adsorbents were mentioned for the first time in the article of Kay and Gratzel of 1993.
In this work they used the deoxycholic acid (DCA) with chlorophyll and related molecules as
sensitizers [3].
The present work aims to study the effects of different co-adsorbents on the efficiency of
DSSC, starting from the classic chenodeoxycholic acid (CDCA) and considering also new
molecules properly synthesized, coupled with various sensitizers, from the conventional
donor-acceptor systems (i.e. D5) to NIR dyes [4]. Due to the multivariate nature of this kind
of devices we choose the experimental design approach [5]. In fact it allows to draw some
interesting observations on the effect of the experimental conditions of co-adsorption process
(soaking time and temperature, dye and co-adsorbent concentration, type of solvent, etc.).
[1] C. Chen, X. Yang, M. Cheng, F. Zhang and L. Sun, ChemSusChem 6 (2013) 1270-1275.
[2] V. S. Manthon, E. K. Pefkianakis, P. Falaras and G. P. Vougioukalakis, ChemSusChem 8 (2015)
588-599.
[3] A. Key and M. Gratzel, J. Phys. Chem. 97 (1993) 6272-6277.
[4] J. Park, N. Barbero, J. Yoon, E. Dell'Orto, S. Galliano, R. Borrelli, J. H. Yum, D. Di Cosenzo, M.
Grätzel, M. K. Zazeeruddin, C. Barolo and G. Viscardi, Phys. Chem. Chem. Phys. 16 (2014) 2417324177.
[5] V. Gianotti, G. Favaro, L. Bonandini, L. Palin, G. Croce, E. Boccaleri, E. Artuso, W. van Been, C.
Barolo and M. Milanesio, ChemSusChem 7 (2014) 3039-3052.
135
POS-33
Arrangements of enantiopure and racemic ionic liquids at the
liquid/air interface: the role of chirality on self-assembly and
layering
Piero Margari,a Stefano Caporali,b Cinzia Chiappe,a Tiziana Ghilardi,a Anna
Iuliano,c Giovanna Longhi,d and Christian Silvio Pomellia
a
Dipartimento di Farmacia, Università di Pisa, Via Bonanno 33, 56126-Pisa, Italy
Dipartimento di Chimica “Ugo Schiff”, Università degli Studi di Firenze, Via della
Lastruccia 13, 50019-Sesto Fiorentino, Italy
c
Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Moruzzi 13, 56124Pisa, Italy
d
Dipartimento di Medicina Molecolare e Traslazionale, Università degli Studi di Brescia,
Viale Europa 11, 25123-Brescia, Italy
E-mail: [email protected]
b
A series of chiral ionic liquids (CILs), have been prepared in high yield and high purity using
commercial propylene oxide and natural chiral alcohols (citronellol and nopol) as building
blocks is presented. The impact of alkyl chain length and the chiral center in cation on the
physico-chemical properties of the resulting salts is evaluated. Circular Dichroism (CD) and
X-ray Photoelectron Spectroscopy (XPS) have been used to demonstrate the assembly and
layering of these ionic liquids.
The self-assembly at the interface IL/vacuum, investigated for some couples of enantiopure
and racemic CILs, show that the presence of a chiral centre on the cation side chain and the
enantiomeric purity of the related imidazolium based CILs can affect the orientation and
layering of the liquid components in the outmost regions of the interface.
136
POS-34
Rational design of Hill-type cooperative DNA-based nanodevices
Davide Mariottini, Andrea Idili, Francesco Ricci, and Giuseppe Palleschi
Dipartimento di Scienze e Tecnologie Chimiche, Università degli Studi di Roma Tor Vergata,
Via della Ricerca Scientifica 1, 00173-Roma, Italy
E-mail: [email protected]
In nature, the control of molecular responsiveness is often achieved using “Hill-type”
cooperativity, a mechanism in which sequential binding events on a multivalent receptor are
coupled such that the first enhances the affinity of the next, producing a steep, higher-order
dependence on target concentration. Here, we rationally designed a synthetic DNA
nanodevice that mimics such cooperativity mechanism and respond to its specific target with
a Hill-type curve. To do so, we designed a clamp-like DNA nanoswitch that contains multiple
interacting binding sites. The first binding event affects the affinity of the subsequent binding
events thus resulting in a steeper dose-response curve with Hill coefficients experimentally
indistinguishable from the theoretically expected maximums.
137
POS-35
Structure-properties relationship in inorganic pigments: a
computational study of Van Gogh Yellow
Arianna Massaro, Ana B. Muñoz-García, and Michele Pavone
Dipartimento di Scienze Chimiche, Università di Napoli Federico II,
Via Cintia 26, 80126-Napoli, Italy
E-mail: [email protected]
Van Gogh Yellow (VGY) is the name given to a family of yellow inorganic pigments used by
numerous painters, and, in particular, by Van Gogh in his late period. VGY is basically
composed by lead chromate PbCrO4, with sulphur added in different amounts to form paler
shades of yellow. The resulting VGY PbCr(1-x)SxO4 solid solution tends to darken on exposure
to sunlight: brownish deteriorated areas are evident in some versions of Van Gogh’s famous
Sunflowers. A series of recent studies have shown that the degradation occurs by formation of
greenish Cr2O3 and that the degradation rate increases with sulphate concentration [1,2].
This work aims at answering the following open questions: Why sulphur induces
degradation? To what extent degradation is a purely surface process or depends on the
underlying bulk structure of VGY solid solution?
On one hand, our objective is to establish an ab initio (DFT) computational framework for
the correct prediction of structure-property relationships in inorganic pigments of interest for
cultural heritage. On the other, we aim at elucidating the origin of crystalline structures,
stability and optical properties of VGY.
From our calculations, we find that the dispersion forces play a crucial role in determining
the crystal structure of inorganic pigments, while trends in electronic band-gaps with
increasing sulphur content can be determined with affordable PBE and PBE+U approaches.
We also find that VGY PbCr(1-x)SxO4 solid solution is not stable for any Cr:S ratio. Thus, we
can predict that the presence of sulphur represents a cause of thermodynamic instability
leading to long-term phase separation of VGY into PbCrO4 and PbSO4. Since VGY results to
be yellow, even for the highest sulphur content explored, we can state that the paler hue of
sulphur-containing VGY arises not from the color of the solid solution itself, but from mixing
of VGY with white pure sulfate. Our study paves the route toward the characterization of
VGY surface chemistry and degradation reactions.
[1] L. Monico, K. Janssens, F. Vanmeert, M. Cotte, B. G. Brunetti, G. Van der Snickt, M.
Leeuwestein, J. S. Plisson, M. Menu and C. Miliani, Anal. Chem. 86 (2014) 10804-10811, and
references therein.
[2] H. Tan, H. Tian, J. Verbeeck, L. Monico, K. Janssens and G. Van Tendeloo, Angew. Chem. Int.
Ed. 52 (2013) 11360-11363.
138
POS-36
Synthesis of new bile acids derivatives as selective FXR/GPBAR1
ligands
Dario Masullo,a Valentina Sepe,a Carmen Festa,a Barbara Renga,b Adriana
Carino,b Sabrina Cipriani,b Claudia Finamore,a Federica Del Gaudio,c Maria
Chiara Monti,c Stefano Fiorucci,b and Angela Zampellaa
a
Dipartimento di Farmacia, Università di Napoli Federico II, Via D. Montesano 49, 80131Napoli, Italy
b
Dipartimento di Scienze Chirurgiche e Biomediche, Università degli Studi di Perugia, P.zza
L. Severi, 06132-Perugia, Italy
c
Dipartimento di Farmacia, Università degli Studi di Salerno, Via Giovanni Paolo II, 132,
84084-Fisciano, Italy
E-mail: [email protected]
Farnesoid-X-receptor (FXR) and GP-BAR1 are bile acids receptors mainly expressed in
entero-hepatic tissues that regulates some metabolic and non-metabolic functions [1]. In the
last ten years, this two receptors gained an increasing importance because they are involved in
many physiological and physio-pathological human conditions. One of the main problem of
these receptors is that bile acids are promiscuous ligand for both receptors. Even if the dual
activation could be a promising pharmacological opportunity for several metabolic diseases,
often it is associated to several side effects. Starting from the results obtained in several our
previous works, [2, 3] in this contest, we decide to manipulate bile acids scaffold in order to
produce new selective FXR and GP-BAR1 modulators.
Figure 1: Endougenous (compounds 1 and 2) and semi-synthetic(compounds 3-6) bile acids.
[1] S. Fiorucci, S. Cipriani, A. Mencarelli, F. Baldelli, G. Bifulco and A. Zampella, Mini Rev. Med.
Chem. 11 (2011) 753-762.
[2] V. Sepe, B. Renga, C. Festa, C. D’Amore, D. Masullo, S. Cipriani, F. S. Di Leva, M. C. Monti, E.
Novellino, V. Limongelli, A. Zampella and S. Fiorucci, J. Med. Chem 57 (2014) 7687-7701.
[3] C. Festa, B. Renga, C. D’Amore, V. Sepe, C. Finamore, S. De Marino, A. Carino, M. C. Monti, A.
Zampella and S. Fiorucci, J. Med. Chem. 57 (2014) 8477-8495.
139
POS-37
A LC-MS/MS method for the rapid identification of toxic drugs
in biological and clinical samples
Thomas Matulli Cavedagna,a,b Matteo Conti,a Daniela Patrono,a Rita Mancini,a
and Maria Augusta Raggib
a
Laboratorio Centralizzato, Policlinico Sant'Orsola-Malpighi, Via Massarenti 9, 40138Bologna, Italy
b
Dipartimento di Farmacia e Biotecnologie, Università di Bologna, Via Belmeloro 6, 40126Bologna, Italy
E-mail: [email protected]
Nowadays, the need for rapid screening methods to identify drugs in biological samples is
becoming more and more urgent in clinical toxicology, since drug consumption is increasing
steadily in western society. At present urine immunoassays are widely employed to this purpose
because they are convenient and commercially available [1]. However, they are available only for
a few classes of compounds (such as amphetamines, opiates, cannabinoids, a few
benzodiazepines, cocaine, barbiturates and tricyclic antidepressants), and, even in these cases,
they suffer from lack of analytical specificity and sensitivity resulting in medical mistreatment
and/or social and legal wrong consequences. Therefore, a more efficient analytical option to
clinical toxicology is required.
In recent years, liquid chromatography-tandem mass spectrometry (LC-MS/MS) has become
the gold standard technique for drug analysis. This is linked to the possibility of obtaining high
sensitivity (in the ppb-ppt range) and specificity (recording collision induced dissociation (CID)
mass spectra of the analytes) without the need of time consuming sample preparations, that had
limited the application of MS in drug analysis so far [2].
Applying the LC-MS/MS approach in our clinical investigation, we developed a rapid method
for simultaneous analysis of drugs in biological samples that exploits ultra-high pressure
chromatography (UHPLC) and quadrupole-ion trap (QTRAP) MS/MS detection. CID MS spectra,
obtained in these conditions, can be searched in software libraries available both commercially
and open source on the Internet, in order to provide identification of unknown compounds.
We also spiked in human serum and urine more than 200 drugs characterized by dangerous
toxicological profiles. In these cases, quantitation in addition to identification could be provided.
We are currently implementing and testing this type of approach to toxicological screening in a
larger number of clinical samples sent to our laboratory from emergency room in St. OrsolaMalpighi hospital.
Figure: Positive match for codeine spectrum on the left,hardware configuration on the right.
[1] K. E. Moeller, K. C. Lee and J. C. Kissack, Mayo. Clin. Proc. 83 (2008) 66-76.
[2] Y. Lee, Clin. Psychopharmacol. Neurosci. 11 (2013) 158-164.
140
POS-38
Volumetric absorptive microsampling (VAMS) as a new challenge in
biological sample analysis
Laura Mercolini,a Michele Protti,a Maria Carmen Catapano,a
Silvia Zago,a Roberto Mandrioli,b and Anna Ferrantia
a
Dipartimento di Farmacia e Biotecnologie, Università di Bologna, Via Belmeloro 6, 40126Bologna, Italy
b
Dipartimento di Scienze per la Qualità della Vita, Università di Bologna, Corso D'Augusto
237, 47921-Rimini, Italy
E-mail: [email protected]
Volumetric absorptive microsampling (VAMS) is a novel technique that can be used to obtain
dried biological samples for qualitative and quantitative analysis.
VAMS devices have been marketed since 2014 and designed to overcome important issues
related to conventional blood sampling, such as hematocrit bias, high sample volumes, high
costs and complicated shipping and storage procedures. However, VAMS technique has the
potential to be also successfully applied to biological fluids other than blood, in fact this
research project has the purpose of studying the application of VAMS to urinary samples for
the identification and quantitation of some psychotropic compounds, like for example
psychiatric drugs, drugs of abuse or doping agents belonging to list of prohibited substances
in sport, published by the World Anti-Doping Agency (WADA) [1].
In the last few years, bioanalysis has not always granted satisfactory results, considering
the significant percentages of false positive and false negative results, or the large number of
samples to be processed in routine analysis settings. It is thus clear that new, faster and more
feasible but reliable procedures are needed, in terms of both sampling and pre-analytical
procedures. In the present study, a VAMS approach is proposed for the first time as a possible
alternative to traditional urine sampling; moreover, all process parameters are investigated in
order to test VAMS suitability for urinary matrix. The results obtained from method
validation prove that the proposed methodology represents a significant improvement in the
field of drug quantitative analysis and could be suitable for application to different classes of
compounds.
[1] World Anti-Doping Agency, The World Anti-Doping Code, 2015.
141
POS-39
A new class of sustainable hydrophobic ionic liquids
Andrea Mezzetta,a Cinzia Chiappe,a Maurizia Seggiani,b and Sandra Vitolob
a
b
Dipartimento di Farmacia, Università di Pisa, Via Bonanno 33, 56126-Pisa, Italy
Dipartimento di Ingegneria Civile e Industriale, Università di Pisa, Largo Lucio Lazzarino
1, 56122-Pisa, Italy
E-mail: [email protected]
In the last 15 years, ionic liquids (ILs) have attracted considerable attention. Through
continuous efforts of numerous researchers, ILs have achieved not only a consolidated
popularity as “green” solvents for synthesis and extraction processes, but also as powerful
catalysts, electrolytes, precursors or additives for smart materials employed in numerous
important areas of research as well as in industrial applications [1]. The most attractive feature
of these salts, liquid at or near room temperature, is the possibility to modify the principal
physico-chemical and biological properties varying cation and/or anion structure.
Herein, we report a halogen free procedure to prepare fluorine-free hydrophobic ILs. ILs
composed by an imidazolium or ammonium cation and a fatty acid anion, with different chain
length and saturation degree, have been synthesized by simple addition of a fatty acid to
methylcarbonate based ILs in methanol. The acidity of the fatty acid is indeed sufficient to
decompose the methylcarbonate anion to methanol and carbon dioxide.
With respect to the classical procedure to prepare carboxylic ILs, this synthetic pathway
starts from methycarbonates, prepared by alkylation of the proper base with the “green”
dimethylcarbonate, and avoids metathesis reactions through silver salts.
These highly hydrophobic ILs with surfactant properties are characterized by good thermal
and chemical stability. Studies for their application as organized media are in progress as well
as their possible use as diathermic fluids. The thermal properties of the synthesized ILs such
as thermal stability and heat capacity are evaluated by differential scanning calorimetry
(DSC) and Thermogravimetric Analysis (TGA), respectively.
[1] M. Biswas, M. Dule, P. N. Samanta, S. Ghoshc and T. K. Mandal, Phys. Chem. Chem. Phys. 16
(2014) 16255-16263.
142
POS-40
Azo-coupling reactions between diazonium salts and anisole
derivatives: formation of fluorescent compounds
Gabriele Micheletti, Silvia Cino, and Carla Boga
Dipartimento di Chimica Industriale "Toso Montanari", Università di Bologna, Viale
Risorgimento 4, 40136-Bologna, Italy
E-mail: [email protected]
Since they discovery in 1858, diazonium salts are used, principally, in the industry of
colorants, for their ability to form colored compounds by azo-coupling reaction with aromatic
derivatives [1].
In the last years, diazonium salts were used to study the azocoupling reaction from a
mechanistic point of view, in combination with tris(N,N-dialkylamino)benzenes [2].
Very recently, they have been used in the field of material chemistry as grafting agents for
the graphene [3].
X
N2 BF4
X
N
N
+
H3CO
Z
H3CO
OCH3
Y
X= OH, OCH3
Y= OCH3, H, NO2
OCH3
Y
Z
Z= NO2, Br, OCH3
Scheme 1
The reaction between diazonium salts and anisole derivatives (Scheme 1) gave new azocompounds in good yield, and only the mono adduct was obtained also when an excess of
diazonium salt was used.
Moreover, in some cases we have obtained compounds displaying fluorescence in solid
state.
[1] a) S. Patai, Chemistry of the Diazonium and Diazo Groups: Part 1, Wiley-Blackwell, 1978; b) S.
Patai, Chemistry of the Diazonium and Diazo Groups: Part 2, Wiley-Blackwell, 1978.
[2] C. Boga, E. Del Vecchio, L. Forlani and S. Tozzi, J. Org. Chem. 72 (2007) 8741-8747.
[3] J. Greenwood, T. H. Phan, Y. Fujita, Z. Li, O. Ivasenko, W. Vanderlinde, H. Van Gorp, W.
Frederickx, G. Lu, K. Tahara, Y. Tobe, H. Uji-I, S. F. L. Mertens and S. De Feyter, ACS Nano 5
(2015) 5520-5535.
143
POS-41
An optimized polyamine moiety boosts the potency of human type
II topoisomerase poisons as quantified by comparative analysis
centered on the clinical candidate F14512
Elirosa Minniti,ac Giulia Palermo,a Maria Laura Greco,b Laura Riccardi,a Elena
Simoni,c Marino Convertino,a Chiara Marchetti,c Michela Rosini,c Claudia
Sissi,b Anna Minarinic, and Marco De Vivoad
a
Department of Drug Discovery and Development, Istituto Italiano di Tecnologia, Via
Morego 30, 16163-Genoa, Italy
b
Dipartimento di Scienze del Farmaco, Università degli Studi di Padova, Via Marzolo 5,
35131-Padova, Italy
c
Dipartimento di Farmacia e Biotecnologie, Università di Bologna, Via Belmeloro 6, 40126Bologna, Italy
d
Computational Biomedicine, Institute for Advanced Simulations, Forschungszentrum Jülich,
Wilhelm-Johnen-Straße, 52428-Jülich, Germany
E-mail: [email protected] [email protected]
Topoisomerase–targeted drugs are considered poisons when they act by trapping the covalent
enzyme/DNA cleavage complex, which is formed during the catalytic cycle required for DNA
topology modification. The spermine-vectorized F14512 is one of the most promising
anticancer agents currently in clinical trials for the treatment of refractory/relapsing acute
myeloid leukemia (AML) [1]. Remarkably, F14512 is reported to be 10-fold more potent than
etoposide in inhibiting cell proliferation. This is partly attributed to the spermine-mediated
F14512 uptake by the polyamine transport system, which is overactive in many tumor cells
[2]. However, the conserved epipodophyllotoxin core and the mechanism of action suggest
that the enhanced efficacy of F14512 in comparison to that of etoposide might also come
from favourable interactions of its spermine moiety within the topoII/DNA cleavage complex
[3]. To demonstrate that spermine also boosts drug binding to the topoII/DNA cleavage
complex, rather than to the DNA alone, we have designed and synthesized newly polyamineconjugated by varying the polyamine chain of F14512. Modeling and simulations of the
structurally uncharacterized F14512/topoII/DNA complex identified key drug-target
configurations and interactions. Combined computational-experimental analyses of F14512,
etoposide, and newly synthesized derivatives confirmed that the spermine tail of F14512
gives the optimal binding to the topoII/DNA cleavage complex.
[1] A. Kruczynski, A. Pillon, L. Creancier, I. Vandenberche, B. Gomes, V. Brel, E. Fournier, J.P.
Annereau, E. Currie, Y. Guminski, D. Bonnet, C. Bailly and N. Guilbaud, Leukemia 27 (2013) 21392148.
[2] J. M. Barret, A. Kruczynski, S. Vispe, J. P. Annereau, V. Brel, Y. Guminski, J. G. Delcros, A.
Lansiaux, N. Guilbaud, T. Imbert and C. Bailly, Cancer Res. 68 (2008) 9845-9853.
[3] C. Bailly, Chem. Rev. 112 (2012) 3611-3640.
144
POS-42
Hck inhibitors as potential therapeutic agents in leukemia and
HIV-1 infection
Alessio Molinari,a.Cristina Tintori,a Francesca Musumeci,b Silvia Schenone,b
Chiara Brullo,b Emmanuele Crespan,c Giovanni Maga,c José A. Esté,d and
Maurizio Bottaa,e
a
Dipartimento Biotecnologie, Chimica e Farmacia, Università degli Studi di Siena, Via De
Gasperi 2, 53100-Siena, Italy
b
Dipartimento di Farmacia, Università degli Studi di Genova, Viale Benedetto XV 3, 16132Genova, Italy
c
Istituto di Genetica Molecolare, Consiglio Nazionale delle Ricerche, Via Abbiategrasso 207,
27100-Pavia, Italy
d
Irsicaixa, Hospital Germans Trias i Pujol, Universitat Autònoma de Barcelona, Crta. Can
Ruti-Camí Escoles, 08916-Badalona, Spain
e
Biotechnology College of Science and Technology Temple University, 1900 North 12th
Street, 19122-Philadelphia, USA
E-mail: [email protected]
Hematopoietic cell kinase (Hck) is a member of the Src-family of non-receptor tyrosine kinases,
which plays many roles in signalling pathways involved in the regulation of cell processes [1].
Hck is expressed in cells of hematopoietic origin, specifically myelomonocytic cells and B
lymphocytes [2]. It participates in phagocytosis, adhesion, migration, regulation of protrusion
formation on cell membrane, lysosome exocytosis, podosome formation and actin polymerization.
More importantly from a medicinal chemistry point of view, high levels of Hck are involved in
chronic myeloid leukemia and other hematologic tumors [3]. Furthermore, Hck activity has been
associated with viral infections including HIV-1 [4]. In particular, Hck is activated by the HIV-1
accessory protein Nef, a multifunctional HIV-1 protein that accelerates progression to AIDS and
enhances the infectivity of progeny viruses. Nef binding to Hck leads to kinase activation which is
important in AIDS pathogenesis.
For these reasons, Hck represents an interesting therapeutic target for the treatment of both
specific cancers and HIV infection [5].
On this bases, a new family of compounds was designed and synthesized in order to explore
structure-activity relationships. As a result, most of the selected compounds were found active
against Hck, with Ki values ranging from 0.14 to 18.4 µM, showing an interesting anti
hyperproliferative activity. Furthermore hit compound 7 is able to block HIV-1 at micromolar
concentration.
[1] G. Manning, D. B. Whyte, R. Martinez, T. Hunter and S. Sudarsanam, Science 298 (2002) 1912-1934.
[2] C. L. Willman, C. C. Steward, T. L. Longacre, D. R. Head, R. Habbersett, S. F. Ziegler and R. M.
Perlmutter, Blood 77 (1991) 726-734.
[3] T. Pene-Dumitrescu and T. E. Smithgall, J. Biol. Chem. 285 (2010) 21446-21457.
[4] L. A. Emert-Sed-Lad, P. Narute, S. T. Shu, J. J. Alovarado, J. S. Lazo, J. I. Yeh and P. A. Smithgall,
Chem. Biol. 20 (2013) 82-91.
[5] F. Musumeci, S. Schenone, C. Brullo, A. Degosus, L. Botta and C. Tintori, Curr. Med. Chem. 22 (2015)
1540-1564.
145
POS-43
Improvement of analytical procedures for screening
of cutting agents in street drugs
Emanuele Morganti,a Marcello D’Elia,b Marco Zanella,b and Maria Augusta
Raggia
a
Dipartimento di Farmacia e Biotecnologie, Università di Bologna, Via Belmeloro 6, 40126Bologna, Italy
b
Gabinetto Regionale di Polizia Scientifica per l’Emilia Romagna, Via Volto Santo 3, 40123Bologna, Italy
E-mail: [email protected]
Fast and cheap analysis of cutting agents in illicit drugs powders and tablets is crucial
considering the implications in medical, legal and crime investigation field. Many analytical
methods have been used so far for the analysis of adulterants [1] by different approaches:
separation techniques such as liquid chromatography (HPLC) and gas-chromatography (GC)
and bulk techniques such as infrared spectroscopy (FT/IR). Separation methods are sensitive
and selective, but the analysis are laborious and time consuming (sample pre-treatment
and/or derivatization is often required). On the other hand, the IR spectrum produces a pattern
that is unique as it bounds to the chemical structure (functional groups) of the drug and can be
easily compared with massive archive of reference spectra. This method has, however,
limitations: to obtain a significant spectrum, samples must be almost pure and free of wet
debris. In recent times, special software algorithms have introduced the possibility to resolve
and identify multi-components mixtures. Nevertheless, this mathematical approach can, at
most, reveal two-three of major components present in comparable percentage. The related
technique FT/IR-ATR is a very useful, fast and non-destructive method, that enables to
analyze samples directly in the solid or liquid (non aqueous) state without further preparation,
but it suffers of low sensitivity (generally, analyte concentration must be >5% of total mass).
For the analysis of street drugs, capillary electrophoresis (CE) is a good alternative as it offers
important advantages over HPLC, GC/MS and FT/IR, including high separation efficiency of
complex samples, rapid analysis, a reduced consumption of samples and organic solvents.
Moreover, CE can be used for the analysis of a large number of compounds: polar substances,
heat-labile, and non-volatile compounds. The aim of this investigation is the optimization of a
capillary electrophoresis method that is suitable for the fast analysis of cutting agents with
different charge, lipophilicity and pKa. The proposed method uses a background electrolyte
(BGE) containing sodium dodecyl sulphate (SDS) in basic buffer and a photodiode array
(PDA) detector set at 218 nm, 233 nm, 274 nm. It resulted capable of discriminating several
compounds with different chemical properties, such as alkaloids, acid and basic drugs. This
method is very fast, cheap and simple and seems to be suitable for forensic purposes.
[1] A. Brancaccio, P. Maresca, S. Albrizio, M. Fattore, M. Cozzolino and S. Seccia, Anal. Methods 5
(2013) 2584-2590.
146
POS-44
First-principles design strategy towards triple conductor oxides
from mixed ion-electron conductors: Ba-doping and beyond
Ana B. Muñoz-García and Michele Pavone
Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia 26, 80126Napoli, Italy
E-mail: [email protected]
Electrolyzer and fuel cells based on proton-conducting oxides (PC-SOEC/FCs) are gaining
grounds in the energy conversion scenario thanks to the high proton conductivity of protons at
intermediate temperatures. Major advances on PC-electrolytes (e.g. BaCeO3 and LaNbO4
derivatives) have not been sufficient to bring PC-SOEC/FCs to an applicative stage because
of the severe limitations of electrodes, which must comply a list of requirements: high
catalytic activity, high electron and proton conductivity. Current electrodes are mostly
composites, made of mixed ionic and electronic conductor (MIEC) oxides and the PCelectrolyte [1]. Only recently, triple (e-/O2-/H+) conducting oxides (TCOs), i.e. MIEC with
enhanced proton transport capability, have been proposed as single-phase electrodes instead
of composites [2].
In this work, we evaluated the TCO properties of the double perovskite Sr2Fe1.5Mo0.5O6-δ
(SFMO) with state-of-the-art DFT+U calculations. SFMO has been proposed as anode and
cathode material for symmetric oxide-conducting SOFCs because it pairs good catalytic
activity, excellent MIEC properties and remarkable stability in both oxidizing and reducing
environment. SFMO is inherently non-stoichiometric [3], which turns this MIEC into a good
candidate for proton conduction provided that oxygen vacancies allow the incorporation of
protons via water dissociative incorporation into the lattice. Thus, we analyzed hydration
properties and proton migration barrier heights in SFMO and in two derivatives, namely
Sr0.875Ba0.125Fe1.5Mo0.5O6-δ and Sr0.875K0.125Fe1.5Mo0.5O6-δ.
Ba and K substitutions at the A-site of SFMO perovskite affect both the structural and
electronic features, boosting the proton transport of SFMO. In particular, aliovalent K doping
results in a higher concentration of oxygen vacancies and in a lower migration barrier. From
analysis of our ab initio results, we identified key structural parameters that promote the
proton transport between oxygen sites and we designed new promising TCO candidates for
PC-SOEC/FC electrodes.
[1] L. Bi, S. Boulfrad and E. Traversa, Chem. Soc. Rev. 43 (2014) 8255-8270.
[2] J. Kim, S. Sengodan, G. Kwon, D. Ding, J. Shin, M. Liu and G. Kim, ChemSusChem 7 (2014)
2811-2815.
[3] A. B. Muñoz-García, D. E. Bugaris, M. Pavone, J. P. Hodges, A. Huq, F. Chen, H.-C. zur Loye
and E. A. Carter, J. Am. Chem. Soc. 134 (2012) 6826-6833.
147
POS-45
Inhibition of Acinetobacter derived cephalosporinases by boronic
acids: exploring the carboxylate recognition pocket through click
chemistry
Alexandra Neagu-Chivu, Chiara Romagnoli, Emilia Caselli, and Fabio Prati
Dipartimento di Scienze della Vita, Università degli Studi di Modena e Reggio Emilia, Via G.
Campi 103, 41125-Modena, Italy
E-mail: [email protected]
The Gram-negative bacterium Acinetobacter baumannii is an opportunistic pathogen in
humans and infections caused by this bacteria are poorly treated by current therapy. Recent
emergence of β-Lactam resistance in Acinetobacter baumannii presents one of the greatest
challenges to contemporary antimicrobial chemotherapy. Much of this resistance to
cephalosporins derives from the expression of the class C β-lactamase enzymes, known as
Acinetobacter-derived cephalosporinases (ADCs). Since currently available β-lactamase
inhibitors (i.e. clavulanic acid) are not effective against ADC, new molecules are urgently
needed, and amongst others, a promising class of inhibitors are boronic acid transition-state
inhibitors (BATSIs). In previous studies, our research group has identified a very potent
ADC-7 inhibitor, compound S02030, designed to mimic the natural substrate cephalothin.
The crystal structure of S02030 in complex with ADC-7 highlighted the importance of the R1
amide side chain typical of cephalothin in enzyme-BATSI recognition, and the critical role of
the R2 carboxylate [1]. The latter group is inserted in the structure through a click chemistry
reaction between the (+)-pinanediol (1R)-2-azido-1-(2-thienylacetylamino)ethaneboronate
and propiolic acid, catalyzed by Cu(I). Here I describe the design, synthesis and activity of
five derivatives of S02030 where the carboxylate is modified in order to explore and improve
the interactions between the inhibitor and the enzyme. From a synthetic point of view, the
application of CuAAC is a crucial tool for the synthesis of new ADC-7 inhibitors, giving a
clear opportunity to easily insert a wide range of R2 groups [2].
[1] R. A. Powers, H. C. Swanson, M. A. Taracila, N. W. Florek, C. Romagnoli, E. Caselli, F. Prati, R.
A. Bonomo and B. J. Wallar, Biochemistry 53 (2014) 7670-7679.
[2] E. Caselli, C. Romagnoli, R. Vahabi, M. A. Taracila, R. A. Bonomo and F. Prati, J. Med. Chem. 58
(2015) 5445-5458.
148
POS-46
Self-assembling peptide-polymer conjugates as promising
candidates for drug delivery
Federica Novelli,a Serena De Santis,a Cesare Giordano,b Pasqualina Punzi,a
Giancarlo Masci,a Anita Scipioni.a
a
Dipartimento di Chimica, Sapienza - Università di Roma, Piazzale A. Moro 5, 00185-Roma,
Italy
b
Istituto di Chimica Biomolecolare, Consiglio Nazionale delle Ricerche, Piazzale A. Moro 5,
00185-Roma, Italy
E-mail: [email protected]
Soft biomaterials based on peptide-polymer conjugates open new horizons for nanomedicine.
They are able to self-assemble into nanostructures useful for drug delivery, the properties of
which can be finely tuned at nanometer scale. Among the strategies developed for peptide
engineering, those characterized by regularly alternating enantiomeric sequences are
particularly attractive, since they provide low-pitch helices that self-assemble in stacks
directed and stabilized by hydrogen bonds where the peripheral side chains, are available to
be functionalized with various molecules, such as polymers. When the peptide and polymer
are suitably chosen in order to achieve core-shell morphology, these conjugates are able to
self-assemble in water in stable nanoparticles (NPs) with enhanced circulation half-life.
Here the synthesis and structural characterization of the hybrid conjugates Cbz-(L-Ala-DVal)4-NH-(CH2-CH2-O)45-CH3 (I) and Cbz-(L-Ala-D-Val)2-NH-(CH2-CH2-O)45-CH3 (II). A
comparison between the conformational properties of the conjugates and their self-assembling
capability were investigated by NMR, CD and fluorescence spectroscopies, DLS, SEM, AFM
and TEM microscopies, testing their stability and sensitivity. TEM micrographs (Fig. A)
revealed the ability of the conjugate I to self-assemble in nanotubes with a rod-like structure
while SEM and AFM images of the conjugate II (Fig. B) show spherical nanoparticles whose
dimensions are compatible with the hydrophobic peptide region irregularly embedded in PEG
chains. The assessed thermodynamic stability along with biocompatibility makes these
nanoparticles promising candidates for drug delivery applications.
Figure 1: A) TEM images of Cbz-(L-Ala-D-Val)4-NH-(CH2-CH2-O)45-CH3 (I), B) SEM and
AFM images of Cbz-(L-Ala-D-Val)2-NH-(CH2-CH2-O)45-CH3 (II).
[1] I. W. Hamley, Biomacromolecules 15 (2014) 1543-1559
149
POS-47
Use of room temperature ionic liquids (RTIL) to accomplish
efficient electroanalytical determinations of olive oil acidity
Paolo Oliveri,a Maria Antonietta Baldo,b Remo Simonetti,a and Salvatore
Danieleb
a
Dipartimento di Farmacia, Università degli Studi di Genova, Via Brigata Salerno 13,
16147-Genova, Italy
b
Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca’ Foscari Venezia, Calle
Larga Santa Marta, 30123-Venezia, Italy
E-mail: [email protected]
Free acidity – expressed as mass percentage of free oleic acid – is a key parameter routinely
determined to classify and/or assess the quality, the freshness, and the economic value of
commercial olive oils. The official method, suggested by ECC Regulation, for the
quantification of olive oil acidity, is a classical acid/base volumetric titration, performed in
non-aqueous solvents [1]. The procedure is simple, but very slow, laborious and organic
solvent consuming. Considering the large number of routine measurements necessary for
marketing purposes, the development of fast, simple, low-cost, solvent-free and reliable
instrumental analytical methodologies for quantifying olive oil acidity is a task of great
interest.
To this purpose, in the present study an electroanalytical strategy for the evaluation of
acidity directly in small amounts (< 1 mL) of olive oils is presented. The experimental
conditions for exploiting the reduction process of the acidic species present in this food matrix
were studied both under deoxygenated and under oxygenated conditions, taking as an acid
probe oleic acid (OA), which is the prevailing long-chain fatty acid component of olive oil.
Oil samples were prepared by adding, as a supporting electrolyte, the room temperature ionic
liquid (RTIL) tri-hexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl) imide
([P14,6,6,6]+[NTf2]-), which is soluble in vegetable oils and enhances their conductivity [2,3].
The measurements were performed in a 2 mL glass vial as the electrochemical cell, using a
12.5 m radius Pt microdisk as the working electrode. By applying suitable voltammetric and
chronoamperometric setup, reliable correlations between the currents measured and oil acidity
(evaluated by the official method) were found in several olive oils of different commercial
categories. The results obtained indicate that the electrochemical procedure developed can be
advantageously exploited as a fast, low-cost and solvent-saving analytical tool for the
determination of olive oil acidity.
Financial support from PRIN 2010-11 prot. 2010AXENJ8, is acknowledged.
[1] ECC Regulation n° 2568/91.
[2] P. Oliveri, M. A. Baldo, S. Daniele and M. Forina, Anal. Bioanal. Chem. 395 (2009) 1135-1143.
[3] M. A. Baldo, P. Oliveri, R. Simonetti and S. Daniele, J. Electroanal. Chem. 731 (2014) 43-48.
150
POS-48
Synthesis and biological evaluation of novel macrocyclic
antifungals
Francesco Orofino,a Davide Deodato,a Alexandru Casian,a and Maurizio
Bottaa,b,c
a
Dipartimento di Biotecnologie, Chimica e Farmacia, Università degli Studi di Siena, Via A. Moro, 2,
53100-Siena, Italy
b
Sbarro Institute for Cancer Research and Molecular Medicine, Center for Biotechnology, College of
Science and Technology, Temple University, BioLife Science Bldg., Suite 333, 1900 N 12th Street,
19122-Philadelphia, USA
c
Lead Discovery Siena s.r.l, Via Vittorio Alfieri 31, 53019-Castelnuovo Berardenga, Italy.
E-mail: [email protected]
Invasive fungal infections constitute an important problem in immunocompromised patients
and, nowadays, even for healthy patients, due to resistance to one or more antifungal agents
[1]. The search for new classes of antifungals is, as a consequence, of crucial importance, to
deal with systemic (and sometimes life-threatening) infections.
Our research group reported in the last years the discovery and synthesis of a new class of
antifungals, namely the amidinoureas [2][3], whose generic structure is reported in figure 1.
Figure 1: Generic structure of the synthesized compounds
In order to investigate structure-activity relationship, these compounds have been tested
against the most clinically important strains of Candida, including fluconazole-resistant ones.
With the aim to explore even deeper the SARs, a new series of compounds has been
prepared, in which the long alkyl chain in the macrocycle has been replaced with an aromatic
ring. The results of the biological and enzymatic tests performed on this new series are of
great importance to better understand the mechanism of action of these new antifungals.
[1] Z. A. Kanafani and J. R. Perfect, Clin. Infect. Dis. 46 (2008) 120-128.
[2] D. Castagnolo, F. Raffi, G. Giorgi and M. Botta, Eur. J. Org. Chem. 3 (2009) 334-337.
[3] M. Sanguinetti, S. Sanfilippo, D. Castagnolo, D. Sanglard, B. Posteraro, G. Donzellini and M.
Botta, ACS Med. Chem. Lett. 4 (2013) 852-857.
151
POS-49
Synthesis of glycomimetics of N-acetylglucosamine as inhibitor of
hexosamine biosynthesis pathway
Alice Paiotta and Barbara La Ferla
Dipartimento di Biotecnologie e Bioscienze, Università degli Studi di Milano-Bicocca, Piazza
della Scienza 2, 20126-Milano, Italy
E-mail: [email protected]
Carbohydrates are crucial in the regulation of many biological processes as the regulation of
the function of several proteins and enzymes in important biosynthetic pathways. Their key
role in biological, physiological and patological process has stimulated the study of
glycomimetics, which mimic the carbohydrate shapes and structures, thus can be recognized
by carbohydrate processing enzyme and interfere in their biological functions.
One of the pathway essential in human body for the cell growth and survival is the
Hexosamine Biosynthesis Pathway (HBP), used by the pancreatic cancer cells to proliferate
and migrate. The HBP pathway requires nutrients such as glutamine and glucose for the
synthesis of UDP-N-acetyl-D-glucosamine, the substrate for N/O-protein GlcNAc
glycosylation.
The aim of our research project is to interfere with the HBP through the inhibition of Nacetylglucosaminephosphate mutase (AGM1), a key enzyme of the pathway, which catalyzes
the conversion of N-acetylglucosamine-6-phosphate into N-acetylglucosamine-1-phosphate:
we have synthesized GlcNAc analogues modified on the functional groups directly involved
in the catalytic process, the C1-OH and the C6-OH.
The glycomimetics could be new nanotools which can help us to get a better
comprehension of the molecular bases of the role of the HBP and the inhibition of HBP may
represent a fundamental basic research tool to further define its role in pancreatic cancer
biology as well as a new promising therapeutic route for PDCA.
Figure 1: Conversion of N-acetylglucosamine-6-phosphate into N-acetylglucosamine-1phosphate and GlcNAc analogues modified.
152
POS-50
New metal-free catalysts for the oxidation of toluene to
benzaldehyde
Emanuele Paris, Veronica Santacroce, Giovanni Maestri, Raimondo Maggi, and
Franca Bigi
Dipartimento di Chimica, Università degli Studi di Parma, Parco Area delle Scienze, 17/A,
43124-Parma, Italy
E-mail: [email protected]
We report here the effective and efficient heterogenization of polymeric perfluorosulfonic
acid (PFSA) Aquivion® resin into a silica network. The material proved to be an active
organocatalyst for redox processes, allowing selective oxidation of toluene to benzaldehyde
with hydrogen peroxide under solvent- and metal-free conditions.
Remarkably, the oxidation of benzylic C-H bonds with an organocatalyst was not
previously reported.
Preliminary results with the perfluorinated resin delivered good selectivity but low
conversions. Therefore, we decided to heterogeneize Aquivion®
on silica. The Aquivion®-silica composites (10wt% of
Aquivion®) were prepared by Sol-Gel method [1,2] with the aid
of different types of surfactants, obtaining materials with either
mesoporous structure or as nanoparticles.
Under optimized conditions, the hybrid materials Aquivion®silica showed good catalytic activity and excellent selectivity.
The nanoparticle catalyst is fully reusable, maintaining stable
performances for up several consecutive cycles without any
intermediate treatment.
The complex catalytic cycle likely involves -SO3H groups and the morphology of the
support can influence the activity and selectivity of this radical reaction. Ongoing studies are
focused on the scope of these novel catalytic methods, screening a variety of substrates
containing benzylic and allylic methylene groups as substrates.
[1] M. Fujiwa, K. Shiokawa and Y. Zhu, J. Mol. Catal. A. Chem. 124 (2007) 153-161.
[2] J. Hotz and W. Meier, Langmuir 14 (1998) 1031-1036.
153
POS-51
α,α-dialkyl aldehydes in Mannich-type addition reactions
on N-protected fluorinated aldimines
Luca Parise, Stefania Fioravanti, and Lucio Pellacani
Dipartimento di Chimica, Sapienza - Università di Roma, Piazzale A. Moro 5, 00185-Roma,
Italy
E-mail: [email protected]
Among the carbon−carbon bond forming reactions, the Mannich reaction is one of the most
powerful methodologies. Imines can be used as preformed starting materials to obtain a direct
access to nitrogen functionalized compounds. While several examples of Mannich-type
reactions have been reported, there are only a few cases involving fluorinated compounds,
although the relevance of these molecules is evidenced by the growing interest in the
organofluorine chemistry and its practical applications [1].
Recently, different trifluoromethyl aldimines were considered both in the ZrCl4-catalyzed
aza-Henry additions of nitro alkanes [2] and in the organocatalyzed Mannich-type reactions
with linear aldehydes [3,4].
Continuing our studies, we here report the reactions of N-protected fluorinated aldimines 1
with suitable cyclic or acyclic α,α-dialkyl aldehydes 2 that lead, after reduction reaction, to
fluorinated γ-amino alcohols 3 bearing a quaternary chiral center.
The reactions were performed without catalyst and solvent, following a green chemistry
approach. After a few hours, the expected products were obtained in good yields and with a
selectivity from low to very high, depending on R’.
Surprisingly, the same Mannich-type reaction performed by using ZrCl4 as catalyst gave
interesting 1,3-diaminic compounds as major products, due to a condensation between the
unisolable Mannich adduct and the nucleophilic primary amine, generated in situ by a Lewis
acid promoted imine hydrolysis [5].
[1] K. Mikami, Y. Itoh and M. Yamanaka, Chem. Rev. 104 (2004) 1-16.
[2] S. Fioravanti, L. Pellacani and M. C. Vergari, Org. Biomol. Chem. 10 (2012) 8207-8210.
[3] S. Fioravanti, L. Parise, A. Pelagalli, L. Pellacani and L. Trulli, RSC Adv. 5 (2015) 29312-29318.
[4] L. Parise, A. Pelagalli, L. Trulli, M. C. Vergari, S. Fioravanti and L. Pellacani, Chirality 27 (2015)
571-575.
[5] G. Smitha, S. Chandrasekhar and S. Sanjeeva, Synthesis 6 (2008) 829-855.
154
POS-52
Synthesis and fluorescein labeling of polyaminoalkylguanidine
endowed with antibacterial activity
Carolina Pasero,a Davide Deodato,a Francesco Orofino,a and Maurizio
Bottaa,b,c
a
Dipartimento di Biotecnologie, Chimica e Farmacia, Università degli Studi di Siena, Via
Aldo Moro 2, 53100-Siena, Italy
b
Sbarro Institute for Cancer Research and Molecular Medicine, Center for Biotechnology,
College of Science and Technology, Temple University, BioLife Science Building, 1900 N
12th Street, 19122-Philadelphia, USA
c
Lead Discovery Siena s.r.l, Via Vittorio Alfieri 31, 53019-Castelnuovo Berardenga, Italy
E-mail: [email protected]
The antibiotic resistence represent today a serious threat for the public health and it reached
alarming level in many clinically-relevant human pathogens, both Gram+ and Gram-. For this
reason there is an increasing clinical need for new antibiotics, active on drug-resistant pathogens.
In the last years, our research group has been involved in the synthesis of
polyaminoalkylguanidine compounds as antibacterial agents [1]. The potential antibacterial
properties of a series of compounds was evaluated with a panel of different bacteria, including
both type strains, allowing the identification of some active molecules.
The general structure of the synthesized compounds is reported in Fig. 1 and is characterized
by a symmetrical triamine, biguanylated at the two ends. The synthesized compounds have been
obtained by the insertion of various substituents on one of the two guanidine moiety and by the
variation of the length of the alkyl chains, in order to analyze the structure-activity relationship.
Figure 1: General structure of the synthesized compounds
Compounds 1 (R1=cyclopropylmethyl, R2=H, R3=H) showed potent and broad-spectrum
antibacterial activity, being active against representatives of both Gram+ and Gram- bacteria.
Presently, we do not know neither the mechanism of action of these compounds, nor their
molecular target.
Aiming at finding out more about the mechanism of action of these compounds, the lead
compound 1 has been chosen to study which is the target at the molecular level. For this purpose,
a fluorescein labeled compound 1 was sinthesized.
The compound will be tested for its antibacterial activity to ascertain that its biological activity
was not altered by the introduction of fluorescein and subsequently will be studied by means of
confocal microscopy to asses whether the cojugate interacts with the membrane or not. These
information will be crucial to unveil the mechanism of action of this new class of antibacterial
compunds.
[1] G. Maccari, S. Sanfilippo, F. De Luca, D. Deodato, A. Casian, M.C. Dasso Lang, C. Zamperini, E.
Dreassi, G. M. Rossolini, J. D. Docquier and M. Botta, Bioorg. Med. Chem. Lett. 24 (2014) 55255529.
155
POS-53
Structural characterisation of B. mori silk fibroin fibres grafted
with methacrylamide and their stability towards alkaline
hydrolysis
Eleonora Pavoni,a Paola Taddei,a and Masuhiro Tsukadab
a
Dipartimento di Scienze Biomediche e Neuromotorie, Università di Bologna, Via Belmeloro
8/2, 40126-Bologna, Italy
b
Division of Applied Biology, Faculty of Textile Science and Technology, Shinshu University,
3-15-1, Tokida, Ueda City, Nagano Prefecture 386-8567, Japan
E-mail: [email protected]
B. mori silk fibroin fibres grafted with methacrylamide (MAA) were characterized by Raman
and IR spectroscopy before and after alkaline hydrolysis.
Upon grafting, the fibres underwent conformational rearrangements towards a more
unordered state, while at weight gains higher than 60% they lost also the orientation.
Upon hydrolysis, silk fibroin resulted enriched in β-sheet conformation, due to the
preferential removal of the unordered domains, more prone to the alkaline attack. As a result
of the interactions with the silk fibroin, the polymer increased its stability towards alkaline
hydrolysis; in the presence of the fibres, the complete solubilization of the polymer is
avoided.
The A731/A1004 Raman ratio proved to be a suitable parameter to evaluate the composition
of the grafted samples; its value linearly increases with weight gain (R2 = 0.998). Vibrational
spectroscopy resulted a valid technique to investigate the mechanism and the effects of the
hydrolytic attack, both fundamental for the designing of new-generation silk-based materials.
Figure 1: Raman spectra of B. mori silk fibroin fibres grafted with polyMAA (right).
Evaluation of the composition using the A731/A1004 Raman ratio as a function of the weight
gain (center). Weight loss results after alkaline hydrolysis treatment (left).
156
POS-54
Modelling halogen bonding in protein-ligand complexes
Stefano Pieraccinia,b, Stefano Rendinec, Alessandra Fornib, Federico Dapiaggia,
and Maurizio Sironia,b
a
Dipartimento di Chimica, Università degli Studi di Milano, Via Golgi 19, 20133-Milano,
Italy
b
Istituto di Scienze e Tecnologie Molecolari, Consiglio Nazionale delle Ricerche, Via Golgi
19, 20133-Milano, Italy.
c
Syngenta Crop Protection Münchwilen AG, Schaffhauserstrasse, Postfach, 4332-Stein,
Switzerland
E-mail: [email protected]
The halogen bond is an important non covalent interaction that is currently receiving
increased attention in the study of protein−ligand complexes [1]. A growing number of crystal
structures of proteins in complex with halogenated ligands have appeared in the last years [2],
where the presence of halogen bonding was confirmed by observing interatomic distances
below the sum of the van der Waals radii of the interacting atoms. Due to their high
directionality and specificity, halogen bonds can effectively be used in drug design to direct
the binding of ligands to the target site. Nonetheless, their correct modeling in silico is
currently impossible, since existing molecular dynamics force fields do not account for the
anisotropy of the charge density around the halogen atoms, and, in particular, for the positive
‘-hole’ which is responsible of their interaction with Lewis bases.
We have recently proposed a new approach aimed at obtaining an accurate Molecular
Mechanics modelling of halogen bonds [3]. The method is based on a modification of the
AMBER force field through the introduction of appositely parametrized pseudo-atoms. We
show that, unlike the original force field, the modification introduced allows the correct
simulation of ligand-protein complexes involving halogen bonds, reproducing both
crystallographic data and the results of Quantum Mechanical/Molecular Mechanics
calculations. We thus believe our work would be a significant improvement in the modeling
of halogen bonds for drug design.
[1] S. Sirimulla, J. B. Bailey, R. Vegesna and M. Narayan, J. Chem. Inf. Model. 53 (2013) 2781-2791.
[2] Y. Lu, T. Shi, Y. Wang, H. Yang, X. Yan, X. Luo, H. Jiang and W. Zhu, J. Med. Chem. 52 (2009)
2854-2862.
[3] S. Rendine, S. Pieraccini, A. Forni and M. Sironi, Phys. Chem. Chem. Phys. 13 (2011) 1950819516.
157
POS-55
New chemosensors for metal ions based on a benzoxazole
derivative as signaling unit
Luca Piersanti,a Gianluca Ambrosi,a Mauro Formica,a Vieri Fusi,a Luca Giorgi,a
and Mauro Michelonia
Dipartimento di Scienze di Base e Fondamenti, Università degli Studi di Urbino "Carlo Bo",
Via della Stazione 4, 61029-Urbino, Italy
E-mail: [email protected]
The development of molecular sensors for the detection of specific targets represents an area
of current interest in supramolecular chemistry due to their relevance to the development of
analytical tools for the detection and monitoring in biological, environmental and industrial,
waste samples. Here we developed a series of functionalised ligands obtained by coupling
several amine fragments with the [2-(2’-hydroxy-3’-naphthyl)-4-metylbenzoxazole] (HNBO)
signalling unit. The series of new chemosensors gave different and selective response
exploring their interaction with target species (metal ions).
The synthesis, coordination properties and fluorescent response towards several metal ions
of L1, L2, L3 will be reported in aqueous as well as in organic media. The role of the sensing
HNBO unit in metal ion coordination as well as to cause the detectable change in the physical
properties of ligands have been explored.
158
POS-56
Master course and permanent training course in forensic
chemistry
Maria Augusta Raggia and Stefano Girottib
a
Dipartimento di Farmacia e Biotecnologie, Università di Bologna, Via Belmeloro 6, 40126Bologna, Italy
b
Dipartimento di Farmacia e Biotecnologie, Università di Bologna, Via San Donato 15,
40126-Bologna, Italy
E-mail: [email protected]
In the Academic Year 2012/2013, a second level Master course in "Chemical Analysis and
Chemical Toxicological Forensic Analysis” was activated at the Alma Mater Studiorum University of Bologna under the direction of prof. M.A. Raggi. The first three editions of the
course were successful, with a large number of participants. Currently, the fourth edition of
the Master course is starting under the direction of prof. S. Girotti and the supervision of a
Scientific Council and a Proponent Committee.
This Master course aims to train professional forensic experts as consultants of the Police
Forces in the chemical and chemical-toxicological field. The course is open to chemistry and
biotechnology graduates.
At the end of the course (60 credits) the students will be able to:
 perform high specialization forensic analysis in the field of drugs, food and
environment,
 prepare, and discuss a forensic expert report.
In the Academic Year 2015/2016, a new course entitled "The Doping Substances in Sport"
will be held (12 credits). This course will deepen increasingly relevant issues that are related
to the abuse of prohibited substances among athletes and will consider the spread of this
phenomenon in gyms.
At the end of the course the trainees will be able to provide correct, scientifically valid and
up to date information on doping substances and on their toxic effects.
In addition the trainees will be able to collaborate with the Judicial Authorities, public and
private organizations, sports clubs and schools, for various activities, in the field of antidoping.
159
POS-57
Enantioselective BINOL-phosphoric acid organocatalyzed
vinylogous Mannich-type reaction involving isatin
Giulia Rainoldi,a Giordano Lesma,a Alessandro Sacchetti,b Alessandra Silvani,a
and Mattia Stucchia
a
Dipartimento di Chimica, Università degli Studi di Milano, Via Golgi 19, 20133-Milano,
Italy
b
Dipartimento di Chimica, Materiali e Ingegneria Chimica "Giulio Natta", Politecnico di
Milano, Via Mancinelli 7, 20131-Milano, Italy
E-mail: [email protected]
Substituted oxindoles continue to be recognized as important compounds of interest for drug
discovery. 2-Oxindoles, especially 3,3-disubstituted or spiro-fused, feature in a large number
of natural and non-natural pharmaceutically relevant compounds [1].
Going on with our interest in the asymmetric synthesis of 3,3-disubstituted oxindoles [2],
we are developing an asymmetric BINOL-derived phosphoric acid catalyzed vinylogous
Mannich-type reaction [3]. Using isatin as carbonyl moiety, we are going to obtain
enantiomerically enriched 3-aminooxindole butenolide derivatives. The application of such
reaction to ketimines remains to date largely unexplored due to the steric challenge inherent in
the stereocontrolled formation of a quaternary stereocenter consecutive with a bulky tertiary
one. Reaction of trimethylsilyloxyfurans with various preformed isatin-derived imines
allowed us to access a small family of highly functionalized compounds in high yields and
enantiomeric excesses. To demonstrate the synthetic utility of such Mannich-type adducts,
increasing the number of achievable compounds, post-transformation reactions are presently
in progress. The assignment of the absolute and relative configuration through X-ray
diffraction is currently underway on selected compounds, as well as computational studies
aimed to explain the stereochemical outcome of this organocatalyzed process.
[1] G. S. Singh and Z. Y. Desta, Chem. Rev. 112 (2012) 6104-6155.
[2] G. Lesma, F. Meneghetti, A. Sacchetti, M. Stucchi and A. Silvani, Belstein J. Org. Chem. 10
(2014) 1383-1389.
[3] a) M. Mahalau and B. List, Angew. Chem. Int. Ed. 52 (2013) 518-533; b) V. U. B. Rao, A. P.
Jadhav, D. Garad and R. P. Singh, Org. Lett. 16 (2014) 648-651; c) M. Hayashi, M. Sano, Y.
Funahashi and S. Nakamura, Angew. Chem. Int. Ed. 52 (2013) 5557-5560; d) Y. H. Shi, Z. Wang, Y.
Shi and W. P. Deng, Tetrahedron 68 (2012) 3649-3653.
160
POS-58
Hydrogel supported chiral imidazolidinone for organocatalytic
enantioselective reduction of olefins in water
Arianna Rossetti, Emanuele Mauri, Roberto Pesa, Alessandro Sacchetti, and
Filippo Rossi
Dipartimento di Chimica, Materiali e Ingegneria Chimica "Giulio Natta", Politecnico di
Milano, Via Mancinelli 7, 20131-Milano, Italy
E-mail: [email protected]
In the last decades chiral products have been recognized as a powerful tool in the field of
medicinal chemistry, where it is known that enantiomers often display different biological
properties and effect according to the targeted application. One of the leading methods to
obtain a product as single enantiomer is asymmetric catalysis.
Organocatalysis, i.e. the use of small organic molecules to catalyze enantioselective
transformations, has recently emerged as a prominent field in asymmetric synthesis [1,2].
In this work we report the first use of hydrogel as support for a chiral imidazolidinone
organocatalyst (MacMillan catalyst) and its application in the reduction of activated olefins
mediated by the Hantzsch ester [3,4]. Results showed a good activity of the hydrogels both in
yield and enantioselection.
Figure 1: The polymer supported catalysts.
[1] I. Atodiresei, C. Vila and M. Rueping, ACS Catal. 5 (2015) 1972-1985.
[2] P. I. Dalko and L. Moisan, Angew. Chem. Int. Ed. 40 (2001) 3726-3748.
[3] S. Itsuno and M. M. Hassan, RSC Adv. 4 (2014) 52023-52043.
[4] N. Annabi, A. Tamayol, J. A. Uquillas, M. Akbari, L. E. Bertassoni, C. Cha, G. Camci-Unal,
M. R. Dokmeci, N. A. Peppas and A. Khademhosseini, Adv. Mater. 26 (2014) 85-124.
161
POS-59
Aptasensors development for marine water monitoring
Marianna Rossetti, Alessandro Porchetta, Francesco Ricci, and Giuseppe
Palleschi
Dipartimento di Scienze e Tecnologie Chimiche, Università degli Studi di Roma Tor Vergata,
Via della Ricerca Scientifica 1, 00173-Roma, Italy
E-mail: [email protected]
Some marine algae can produce harmful toxins that accumulated in vectors have impact
human health through the consumption of contaminated shellfish and finfish or through water
or aerosol exposure. Therefore, early detection of algal toxins is an important aspect for
public safety and natural environment [1]. For this purpose, we are developing biosensors that
can be used in a novel automated networked system that will enable real-time in-situ
monitoring of marine water chemical and ecological status in coastal areas.
The challenging purpose is the development of a multi-aptasensors system which can in
principle detect simultaneously several toxins in the same box, functionalizing aptamers with
different fluorophores/quencher emitting at different wavelengths in order to distinguish
simultaneously the different toxins. By introducing organic fluorophores into
conformationally labile regions of the aptamers, it is possible transduce ligand binding into a
change in the chemical environment of the fluorophore and hence to a change in fluorescence
intensity [2].
The authors would like to acknowledge the financial support from the European Union’s
Seventh Framework Programme for research, technological development and demonstration
under grant agreement no 613844.
[1] F. M. Van Dolah, Environ. Health Persp. 108 (2000) 133-141.
[2] E. J. Cho, J. W. Lee and A. D. Ellington, Annu. Rev. Anal. Chem. 2 (2009) 241-264.
162
POS-60
Synthesis and biological evaluation of novel N-acylhydrazone
lactate dehydrogenase-A inhibitors
Sebastiano Rupiani,a Rosa Buonfiglio,b Marina Vettraino,c Giuseppina Di
Stefano,c Marinella Roberti,a and Maurizio Recanatinia
a
Dipartimento di Farmacia e Biotecnologie, Università di Bologna, Via Belmeloro 6, 40126Bologna, Italy
b
Dipartimento di Medicina Specialistica Diagnostica e Sperimentale, Università di Bologna,
Via Zamboni 33, 40126-Bologna, Italy
c
Chemistry Innovation Centre, Discovery Sciences, AstraZeneca R&D. Pepparedsleden 1,
43183-Mölndal, Sweden
E-mail: [email protected]
Alteration in glucose metabolism is the best-known example of metabolic reprogramming in
cancer cells [1]. Anaerobic glycolysis is drastically increased in tumors and it is the main
route to energy production with a minor use of oxidative phosphorylation (Warburg effect)
[2]. Among the key enzymes in the glycolytic process, LDH is emerging as one of the most
interesting targets for the development of new inhibitors. The isoform LDH-A catalyzes the
interconversion of pyruvate to lactate using NADH as a co-factor. This last step of the
glycolysis is not active in healthy cells, in conditions of normal functional activity and
sufficient oxygen supply. Anticancer effects obtained through LDH-A inhibition are thus
under active investigation.
In this context, in continuation of our research on
innovative anticancer lead candidates, we carried out a
virtual screening procedure followed by a biological
evaluation that permitted to define four active compounds
which were able to inhibit LDH-A at μM concentration.
The biological profile of these molecules was
subsequently optimized according to a “hit-to-lead”
process generating a library of analogs (Figure 1), the
synthesis of which has been tuned in his key steps to be carried out with Microwave Assisted
Organic Synthesis methods.
The effects of the new molecules were preliminary probed against purified human LDH-A
and the compounds found to be active in the low micromolar range were additionally tested
on a Raji human cell line to highlight their activity inhibiting the key metabolic processes in
which LDH-A is involved, thus inducing death of cancer cells.
[1] H. Pelicano, D. S. Martin, R. H. Xu and P. Huang, Oncogene 25 (2006) 4633-4646.
[2] W. H. Koppenol, P. L. Bounds and C. V. Dang, Nat. Rev. Cancer 11 (2011) 325-337.
163
POS-61
A simple heterogeneous catalyst for phosphite addition on
carbonyl groups
Veronica Santacroce, Giovanni Maestri, Daniele Cauzzi, and Raimondo Maggi
Dipartimento di Chimica, Università degli Studi di Parma, Parco Area delle Scienze 17/A,
43124-Parma, Italy
E-mail: [email protected]
Hydroxyphosphonic acids and their derivatives represent an important class of compounds
which occur in nature; in the last decades they became more and more interesting thanks to
their role in biological processes [1].
Here we propose a novel method for the synthesis of α–hydroxyphosphonates by
exploiting a cheap and commercially available hydrotalcite as catalyst under mild and
solvent-free conditions.
Figure 1: Reactivity of hydrotalcites as catalyst for the synthesis of α-hydroxyphosphonates.
Reasoning on the structure of these material and on literature studies [2], we propose that
basic sites of hydrotalcites could act as a catalyst and promote a shift in the tautomeric
equilibrium of a proximal diorganophosphite molecule.
The basicity of the catalyst ensures almost quantitative yields of desired products and no
traces of condensation products are detected, allowing the use of aliphatic, enolizable
aldehydes in these reactions.
Furthermore, the catalyst can be retrieved by simple filtration and reused without any
treatment maintaining its efficiency fully preserved at least for the first six cycles.
[1] (a) F. R. Hartly, in The Chemistry of Organo Phosphorous Compounds, John Wiley and Sons,
New York, USA, 1990; (b) O. I. Kolodiazhnyi, Tetrahedron: Asymmetry 16 (2005) 3295-3340.
[2] J. C. A. A. Roelofs, D. J. Lensveld, A. J. van Dillen and K. P. de Jong, J. Catal. 203 (2001) 184191.
164
POS-62
A new chiral catalyst for the enantioselective addition of
diethylzinc to aldehydes
Carla Sappino,a Paolo Bovicelli,b Agnese Mantineo,a Giuliana Righi,b and
Chiara Tatangeloa
a
Dipartimento di Chimica, Sapienza - Università di Roma, Piazzale A. Moro 5, 00185-Roma,
Italy
b
Istituto di Biologia e Patologia Molecolari, Consiglio Nazionale delle Ricerche, P.le Aldo
Moro 5, 00185-Roma, Italy
E-mail: [email protected]
β-amino alcohol motif is typical of numerous chiral catalysts used in asymmetric synthesis
[1], and they are the first choice when considering the addition of diethyl zinc to aldehydes, a
classical reaction test for new ligands employable in asymmetric catalysis [2].
Recently, the use of functionalized magnetic nanoparticles led to new catalysts that
combine advantages of both homogeneous and heterogeneous catalysis [3]. In the past years
we were involved in the development of a novel versatile, magnetically recoverable β-amino
alcohol ‘nanocatalyst’. We focused on the design and synthesis of ligands bearing, in addition
to a fine-tunable catalytic site, a functionality (an alkoxysilane group) for their covalent
anchoring to magnetite nanoparticles (Fig 1-A).
Before the immobilization of the catalyst on the nanoparticles we dealt with the design and
the optimization of the ligands, and after an extensive fine-tuning process we selected the
structure 1 (Fig 1-B) as an excellent chiral ligand in the addition of diethylzinc to
benzaldehyde (yields: >95%, ee: >95%). We finally confirmed the validity of the optimization
process employing the selected ligand in the addition of diethylzinc to a family of aldehydes
leading to outstanding results (Fig 1-C).
Figure 1: A) Structure of amino alcohol catalysts supported on magnetic nanoparticles; B)
Optimized ligand; C) Addition of diethylzinc to a family of aldehydes employing 1.
[1] J. L. Vicario, D. Badia, L. Carrillo, E. Reyes and J. Etxebarria, Curr. Org. Chem. 9 (2005) 219235.
[2] L. Pu and H. B. Yu, Chem. Rev. 101 (2001) 757-824.
[3] S. Shylesh, V. Schuneman and W. R. Thiel, Angew. Chem. Int. Ed. 49 (2010) 3428-3459.
165
POS-63
Ab initio study of hybrid organic-inorganic materials for energy
conversion devices
Eduardo Schiavo, Ana B. Muñoz-García, and Michele Pavone
Dipartimento di Scienze Chimiche, Università degli Studi di Napoli Federico II, Via Cintia
26, 80126-Napoli, Italy
E-mail: [email protected]
Hybrid organic-inorganic systems are widely applied in different technological devices thanks
to the peculiar combination of molecular functions (e.g., molecular recognition) and solidstate inorganic features (e.g., fast charge and heat transport) [1,2]. Graphene nanostructures
(GNS), for example, can be easily combined with inorganic substrates for designing new
energy conversion devices [3]. The objective is to find an effective and cheap alternative to
the expensive platinum-based cathodes for oxygen reduction reaction (ORR) in low
temperature fuel cells.
In this contribution we report the application of a modified DFT-D approach (DFT-DM)
[4] to study a layered hybrid material based on GNS and doped-GNS on a metallic substrate.
Experiments support the idea that dopants and a metal surface can enhance GNS catalytic
activity [5,6]. Therefore, with ab initio methods we aim at understanding how the structural,
electronic and catalytic properties of GNS are tuned by dopants and by direct interaction with
a noble metal surface. First, we discuss minimum-energy geometries, binding energies and
electronic structure features of pristine and doped graphene on the hexagonal Ag(111) surface
slab. Then, we address the ORR catalysis at the surface of the hybrid electrode. We focus on
the reaction intermediates and the minimum energy pathway for the ORR in order to
understand the effects of the metal substrate on the physical and chemical properties of GNS.
Furthermore, we target the design of new and effective GNS-silver hybrid cathode for low
temperature fuel cells by identifying the dopants and/or defects that boost ORR catalysis
without weakening the excellent electronic features of graphene.
[1] C. De Rosa, F. Auriemma, R. Di Girolamo, G.P. Pepe, T. Napolitano and R. Scaldaferri, Adv.
Mater. 22 (2010) 5414-5419.
[2] A. Hagfeldt, G. Boschloo, L. Sun, L. Kloo and H. Pettersson, Chem. Rev. 110 (2010) 6595-6663.
[3] A. K. Geim and I. V. Grigorieva, Nature 499 (2013) 419-425.
[4] E. Schiavo, A. B. Muñoz-García and M. Pavone, manuscript in preparation.
[5] F. Sedona, M. Di Marino, D. Forrer, A. Vittadini, M. Casarin, A. Cossaro, L. Floreano, A. Verdini
and M. Sambi, Nat. Mater. 11 (2012) 970-977.
[6] T. Xing, Y. Zheng, L. H. Li, B. C. Cowie, D. Gunzelmann, S. Z. Qiao, S. Huang and Y. Chen, ACS
Nano 8 (2014) 6856-6862.
166
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Synthesis and biological evaluation of novel potent dual acting
ribose modified N6-substitued adenosine derivatives
Mirko Scortichini,a Riccardo Petrelli,a Yara Angeloni,a Livio Luongo,b Sabatino
Maione,b Antonio Lavecchia,c Karl-Norbert Klotz,d and Loredana Cappellaccia
a
Scuola di Scienze del farmaco e dei Prodotti della Salute, Università di Camerino, Via S.
Agostino 1, 62032-Camerino, Italy
b
Dipartimento di Medicina Sperimentale, Seconda Università degli Studi di Napoli, Via
Costantinopoli 16, 80138-Napoli, Italy
c
Dipartimento di Farmacia, Università di Napoli Federico II, Via D. Montesano 49, 80131Napoli, Italy
d
Institut für Pharmakologie and Toxikologie, Universität Würzburg, Sanderring 2, 97078Würzburg, Germany
E-mail: [email protected]
Adenosine receptors (ARs) belong to the G protein-coupled receptor (GPCR) family, and can
be subdivided into four subtypes A1, A2A, A2B and A3. A1 and A3 receptor subtypes couple to
Gi-proteins, mediating the inhibition of adenylyl cyclase and a decrease in cAMP levels,
whereas A2A and A2B receptors activate adenylyl cyclase and increase cAMP levels via the
stimulatory Gs-proteins [1]. In the last two decades many selective ligands for a certain AR
subtype have been developed and some are in clinical use. More recently the concept of
multitarget drugs has emerged as strategy to potentiate efficacy (either additively or
synergistically) and/or to reduce side effects. The dual-acting ligands of ARs may have
considerable promise as novel approaches to treat pathological conditions e.g. ischemic
conditions, asthma, inflammatory diseases and glaucoma. Our recent work discovered the first
dual A1AR agonists and A3AR antagonists [2] by combining a 5’-C-ethyl-tetrazolyl moiety
and an appropriate N6-substitution in adenosine derivatives. In order to better understand the
role of the substituent in N6 position, a series of novel 5’-C-2-ethyl-tetrazolyl-N6-substituted
adenosine derivatives were synthesized and assayed at all human adenosine receptor subtypes.
The results of this study will be discussed.
[1] B. B. Fredholm, A. P. IJzerman, K. A. Jacobson, J. Linden and C. Muller, Pharmacol. Rev. 63
(2011) 1-34.
[2] R. Petrelli, I. Torquati, S. Kachler, L. Luongo, S. Maione, P. Franchetti, M. Grifantini, E.
Novellino, A. Lavecchia, K. N. Klotz and L. Cappellacci, J. Med. Chem. 58 (2015) 2560-2566.
167
POS-65
Marine-inspired antiplasmodial thiazinoquinones: synthesis, in
vitro activity and electrochemical studies
Maria Senese,a Anna Aiello,a Paolo Luciano,a Caterina Fattorusso,a Concetta
Imperatore,a Marco Persico,a Donatella Taramelli,b Gerardo Cebrián-Torrejón,c
Antonio Doménech-Carbó,c and Marialuisa Mennaa
a
Dipartimento di Farmacia, Università di Napoli Federico II, Via D. Montesano 49, 80131Napoli, Italy
b
Dipartimento di Scienze Farmacologiche e Biomolecolari, Università degli Studi di Milano,
Via Pascal 36, 20133-Milano, Italy
c
Departament de Química Analítica, Universitat de València, Dr. Moliner 50, 46100Burjassot, Spain
E-mail: [email protected]
A number of quinones have been shown to be effective antimalarials; the antiplasmodial activity of
quinone structures is most likely related to the most prominent chemical feature of these kind of
molecules, that is their ability to undergo redox cycling. Several marine-derived quinone compounds
exhibited antiplasmodial activity and, interestingly, it has been demonstrated that a dioxothiazine ring
fused to the quinone moiety to give the thiazinoquinone scaffold enhances the activity. Having thus
identified the thiazinoquinone as a possible chemotype active against Plasmodium falciparum, we
have synthesized a series of analogues (1-12) of marine natural thiazinoquinones, aplidinones A and
B, isolated from the Mediterranean ascidian Aplidium conicum [1-3]. Most of synthetic derivatives,
with different substituents and simplified alkyl chains, have shown a significant pharmacological
activity in vitro against two strains (CQ-S, D10 and CQ-R, W2) of Plasmodium falciparum; the
toxicity of the active compounds has been evaluated against human microvascular endothelial cells
(HMEC-1) [2]. The redox properties of compounds (1-12) have been investigated by computational
studies and electrochemical assays [3,4]. This study evidenced important structural requirements for
the pharmacological effects of the synthetic thiazinoquinones and, thus, further analogues (13-19)
have been synthesized to explore and/or confirm them.
[1] A. Aiello, E. Fattorusso, P. Luciano, A. Mangoni and M. Menna, Eur. J. Org. Chem 23 (2005) 50245030.
[2] A. Aiello, E. Fattorusso, P. Luciano, M. Menna, M. A. Calzado, E. Munoz, F. Bonadies, M. Guiso, M.
F. Sanasi, G. Cocco and R. Nicoletti, Bioorg. Med. Chem. 18 (2010) 719-727.
[3] C. Imperatore, M. Persico, A. Aiello, P. Luciano, M, Guiso, M. F. Sanasi, D. Taramelli, S. Parapini, G.
Cebrián-Torrejón, A. Doménech-Carbó, C. Fattorusso and M. Menna, RSC Adv. 5 (2015) 70689-70702.
[4] A. Doménech-Carbó, A. Maciuk, B. Figadère, E. Popuon and. G. Cebrián-Torrejón, Anal. Chem. 85
(2013) 4014-4021.
168
POS-66
Design and synthesis of reversine-like molecules as Aurora B
kinase inhibitors
Denise Sighel,a Bartolomeo Bosco,a Andrea Defant,b Simona Casarosa,a and
Ines Mancini b
a
Centro di Biologia Integrata, Università degli Studi di Trento, Via delle Regole 101, 38123Mattarello (Trento), Italy
b
Dipartimento di Fisica, Università degli Studi di Trento, Via Sommarive 14, 38123-Povo
(Trento), Italia
E-mail: [email protected]
First synthesized in 2004 by the group of Peter G. Schultz [1], reversine is a 2,6-diamino
substituted purine showing a potent inhibition on Aurora B, a protein kinase overexpressed in
a variety of solid tumors. Due to its relevance in the cell cycle regulation, Aurora B represents
a good target for anti-cancer drug development, so that reversine can be used as a promising
lead compound for new potential antitumor agents[2].
Recently we have designed a series of reversine analogs by docking calculation having
Aurora B kinase as specific target (Figure 1). The synthesis of new selected molecules
bearing structural modifications in 2 and 6 positions has been carried out, focusing on the
improvement of both the synthetic strategy (also using microwave-assisted reactions) and the
products purification.
The presence of different tautomeric forms for each analog is also under investigation.
Figure 1: Molecular structure of reversine and 2D-view of its interactions with Aurora kinase
B (2VGO pdb file) by AutoDock Vina calculation.
[1] S. Chen, Q. Zhang, X. Wu, P. G. Schultz and S. Ding, J.Am.Chem.Soc. 126 (2004) 410-411.
[2] A. M. D’Alise, G. Amabile, M. Iovino, F. P. Di Giorgio, M. Bartiromo, F. Sessa, F. Villa, A.
Musacchio and R. Cortese, Mol. Cancer Ther. 7 (2008) 1140-1149.
169
POS-67
Effective bioconjugation strategies for optical biosensors
Alberto Sinibaldi,a Rona Chandrawati,b Subinoy Rana,b Norbert Danz,c Frank
Sonntag,d and Francesco Michelottia
a
Dipartimento di Scienze di Base e Applicate per l'Ingegneria, Sapienza - Università di
Roma, Via A. Scarpa 14-16, 00161-Rome, Italy
b
Department of Materials, Imperial College London, South Kensington Campus, SW72AZLondon, UK
c
Fraunhofer Institute for Applied Optics and Precision Engineering IOF, Albert-EinsteinStraße 7, 07745-Jena, Germany
d
Fraunhofer Institute for Applied Optics and Precision Engineering IOF, Winterbergstr. 28,
01277-Dresden, Germany
E-mail: [email protected]
In this study, we present a research conducted on two alternative chemical immobilization
strategies used to conjugate biomolecules with dielectric optical biochips. The biochips are
constituted by an engineered dielectric stack deposited on a glass substrate. Such multilayer
has the intrinsic capacity to sustain evanescent surface electromagnetic waves ideal for labelfree optical biosensing. The biochips surface was bioconjugated with capturing antibodies
using alternative immobilization chemistries, either through a protein G (PtG) orienting layer
or via covalently immobilized EDC-activated capture antibodies [1]. The two strategies build
upon an initial surface activation treatment using the convenient wet deposition of an aminofunctional silane and incorporate passivation schemes and biomolecular immobilization
techniques. An angularly resolved optical sensing apparatus was assembled to carry out the
sensing studies [2].
A practical application was demonstrated by detecting a specific glycoprotein, Angiopoietin
2 (Ang-2), involved in angiogenesis and inflammation processes. In this particular case, the
results show that the measured limit of detection (LoD) can be estimated for the two
immobilization routes.
Figure 1: Sensorgram after injection of increasing Angiopoietin-2 solutions.
[1] S. K. Vashist, C. K. Dixit, B. D. MacCraith and R. O'Kennedy, Analyst 136 (2011) 4431-4436.
[2] A. Sinibaldi, N. Danz, A. Anopchenko, P. Munzert, S. Schmieder, R. Chandrawati, R. Rizzo, S. Rana, F.
Sonntag, A. Occhicone, L. Napione, S. De Panfilis, M.M. Stevens and F. Michelotti, J. Lightwave Technol. 33
(2015) 3385-3393.
170
POS-68
On the interactions of nicotine with metal(II) in aqueous solutions
Ilaria Sorrentino, Carla Manfredi, and Marco Trifuoggi
Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia 26, 80126Napoli, Italy
E-mail: [email protected]
Neurodegenerative diseases like Alzheimers and Parkinsons disease are associated with
elevated levels of metals, such as iron, copper, and zinc and consequentially high levels of
oxidative stress [1]. Metal-chelating agents provide one such function as an intervention for
ameliorating metal-associated damage in degenerative diseases. In this perspective, we focus
our attention on nicotine of which several uses have been made in most of the fields of
Applied Sciences (Pharmacology, Medicine, Biology). Some of its effects on the human body
are well known since its discovery: changes in respiration, heart rate, blood pressure,
constriction of arteries and increased alertness [1a,2]. Nowadays, it is evident that they are not
the only ones. In fact, there is more awareness than in the past toward the use of nicotine in
numerous biological processes as apoptosis, cell proliferation and oxidative stress [3]. These
apparently contradictory effects seem to be explained by the result that the nicotine induces
oxidative stress at more high concentrations than of those that induce its inhibition. Our
interest is to highlight some of the mechanisms in which nicotine can be involved in the
presence of metal ions. As suggested by its structure, it can behave, in fact, as a good ligand.
In this work we propose a chemical investigation on the interaction mechanisms of nicotine
with metals of biological interest,such as Pb2+, Fe2+, Cu2+. The study has been conducted at
25.00 ± 0.02°C, in constant ionic medium (sodium perchlorate or sodium chloride), by UVVis spectrophotometric and potentiometric methods. The pH investigated spans between 3
and 10. The results of the graphical and numerical methods indicated the formation of a
predominating Me(II)-nicotine, mononuclear complexes.
[1] a) R. Jain and K. Mukherjee, Indian J. Pharmacol. 35 (2003) 281-289; b) Z. Z. Guan, W. F. Yu
and A. Nordberg, Neurochem. Int. 43 (2003) 243-249; c) R. Soto-Otero, E. Mendez-Alvarez, A.
Hermida-Ameijeiras, A. M. Lopez-Real and J. L. Labandeira-Garcia, Biochem. Pharmacol. 64 (2002)
125-135.
[2] D. Yildiz, Toxicon 43 (2004) 619-632.
[3] a) K. Aoshiba, A. Nagai, S. Yasui and K. Konno, J. Lab. Clin. Med. 127 (1996) 186194; b) S.
Konno, B. T. Oronsky, A. R. Semproni and J. M. Wu, Biochem. Int. 25 (1991) 7-17.
171
POS-69
Design, synthesis, and pharmacological characterization of 2,N6disubstituted adenosine analogues as adenosine receptor ligands
Andrea Spinaci, Michela Buccioni, Diego Dal Ben, Catia Lambertucci, Claudia
Santinelli, Ajiroghene Thomas, Gabriella Marucci, and Rosaria Volpini
School of Pharmacy, Medicinal Chemistry Unit, Università di Camerino, Via S. Agostino 1,
62032-Camerino, Italy
E-mail: [email protected]
Thanks to the crystallographic structures of the A2A adenosine receptor (A2AAR), that presents
structural features typical of G protein-coupled receptors, it is possible to acquire very
important information about the interaction of the receptor with the co-crystallized ligands
[1]. In particular, the residues Asn253 and Glu169 form polar interactions with the 6-amino
group of adenosine, while Phe168 forms π-stacking bonding with the aromatic scaffold of the
same molecule (Figure 1). Furthermore, water molecules are distributed in a network of
reciprocal interaction and they play a role as a “bridge” in the ligand-receptor contact [2].
Comparative sequence analysis between the A2A and A3 AR subtypes shows that, among the
residues mentioned above, only Phe168 and Asn253 are conserved in these receptors. In
contrast, the Glu169 of A2AAR is replaced by Val169 in the A3AR [3].
Figure 1: Some interactions of adenosine with the A2AAR binding site and synthesized
molecules.
Based on these observations, known A2A ligands modified through the introduction of an
N -amino or N6-alkylamino group were designed and synthesized, to enhance the A2A
selectivity versus the A3 receptor subtype. These new analogues were tested in binding and
functional studies at human A1, A2A, A2B, and A3 ARs cloned and transfected in CHO cells.
Surprisingly, preliminary results show that the synthesized derivatives present higher affinity
at the A3AR respect to the A2AAR, behaving as A2AAR agonists but showing an antagonist
profile at the A3AR.
6
[1] K A. Jacobson, In Silico Pharm. 1 (2013) 22.
[2] G. Lebon, T. Warne, P. C. Edwards, K. Bennett, C. J. Langmead, A. G. W. Leslie and C. G. Tate,
Nature 474 (2011) 521-525.
[3] D. Dal Ben, C. Lambertucci, G. Marucci, R. Volpini and G. Cristalli, Curr. Top. Med. Chem. 10
(2010) 993-1018.
172
POS-70
Synthesis of poly-imidazole β-strand minimalist peptidomimetics
through an iterative Van Leusen multicomponent reaction
Mattia Stucchi,a Giovanni Grazioso,b Giordano Lesma,a and Alessandra Silvania
a
Dipartimento di Chimica, Università degli Studi di Milano, Via Golgi 19, 20133-Milano,
Italy
b
Dipartimento di Scienze Farmaceutiche, Università degli Studi di Milano, Via Mangiagalli
25, 20133-Milano, Italy
E-mail: [email protected]
Statistical analyses of structurally characterized protein-protein interfaces have shown sidechain substituents to account for about 80% of the interactions; the polyamide backbone
accounts for much less [1]. Compounds that present only selected side-chains to resemble
peptide secondary structures are referred as minimalist mimics by Burgess in 2011 [2]. They
can disrupt protein-protein interactions (PPIs) by mimicking the key interaction residues of
the main recognition motifs (α-helix, β-turn and β-strand). Although substantial progress has
been made in the mimicry of α-helix and β-turn structures, less work has been done toward
the development of β-strand mimetics [3].
Following our interest in the isocyanide-based multicomponent reactions (IMCRs) for the
synthesis of conformationally constrained peptidomimetics [4], we designed a poly-imidazole
β-strand minimalist peptidomimetic scaffold, by means of an iterative approach involving the
Van Leusen multicomponent reaction [5]. The ability to mimic a β-strand structure was
assessed through NMR and computational studies.
[1] I. S. Moreira, P. A. Fernandes and M. J. Ramos, Proteins: Struct., Funct., Bioinf. 68 (2007) 803812.
[2] a) E. Ko, J. Liu and K. Burgess, Chem. Soc. Rev. 40 (2011) 4411-4421; b) E. Ko, J. Liu, L. M.
Perez, G. Lu, A. Schaefer and K. Burgess, J. Am. Chem. Soc. 133 (2011) 462-477.
[3] a) W. A. Loughlin, J. D. A. Tyndall, M. P. Glenn, T. A. Hill and D. P. Fairlie, Chem. Rev. 110
(2010) PR32-PR69; b) P. N. Wyrembak and A. D. Hamilton, J. Am. Chem. Soc. 131 (2009) 45664567.
[4] M. Stucchi, S. Cairati, R. Cetin-Atalay, M. S. Christodoulou, G. Grazioso, G. Pescitelli, A. Silvani,
D. C. Yildirim and G. Lesma, Org. Biomol. Chem. 13 (2015) 4993-5005.
[5] A. M. Van Leusen, J. Wildeman and O. H. Oldenziel, J. Org. Chem. 42 (1977) 1153-1159.
173
POS-71
Mechanism of oxygen evolution reaction on Fe-based perovskite
oxides: towards effective electrocatalysis of water splitting
Bernardino Tirri, Ana B. Muñoz-García, and Michele Pavone
Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia 26, 80126Napoli, Italy
E-mail: [email protected]
In this work, we report an ab initio study of the oxygen evolution reaction (OER) catalysis on
the surface of a transition-metal oxide with perovskite structure. Perovskite oxides are object
of extensive investigations, especially those that show property of mixed ion-electron
conductors (MIEC) [1] and can be used as air-electrode in intermediate-temperature solid
oxide fuel/electrolyzer cells (SOFC/ECs) [2]. Currently, Fe-based MIEC perovskites are
extensively used in SOFC/ECs, but there are still very few studies on the OER mechanism at
its surfaces.
Here, we address a Fe-based perovskite oxide, LaFeO3, and our objective is to understand
from an atomistic perspective the mechanism and the rate limiting steps of the OER at its
surface. We apply the density functional theory +U method (DFT+U) to obtain the minimumenergy geometries and of OER reactants, intermediates and products on the FeO2-terminated
LaFeO3 (001) surface. We evaluate the effectiveness of different reaction pathways by
considering the proton-coupled electron transfer steps, according to the approach proposed by
Nørskov and co-workers [3]. From our results, we find a reaction mechanism with a low
overpotential, which is very close to the reported value for gas-phase OER on hematite [4].
Moreover, we identify three reaction paths that do present no overpotential: our ab initio
results show that the co-adsorption of water molecules at the catalytic active surface sites is
crucial in lowering the thermodynamic barrier for the advancement of the OER. In
conclusion, the present study paves the route toward the development and rational design of
new electrocatalysts for the air-electrode in SOFC/EC devices.
[1] A. B. Muñoz-García, A. M. Ritzmann, M. Pavone, J. A. Keith and E. A. Carter, Acc. Chem. Res.
47 (2014) 3340-3348.
[2] L. Bi, S. Boulfrad and E. Traversa. Chem. Soc. Rev. 43 (2014) 8225-8270.
[3] J. Rossmeisl, A. Logadottir and J. K. Nørskov, Chem. Phys. 319 (2005) 178-184.
[4] M. C. Toroker, J. Phys. Chem. 118 (2014) 23162-23167.
174
POS-72
Ab-initio investigation of amine adsorption on TiO2 nanorods
Leonardo Triggiani,a,b,c Ana Belén Muñoz-García,a Angela Agostiano,b,c and
Michele Pavonea
a
Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia 26, 80126Napoli, Italy
b
Dipartimento di Chimica, Università degli Studi di Bari "Aldo Moro", Via E. Orabona 4,
70125-Bari, Italy
c
Istituto per i Processi Chimico-Fisici, Consiglio Nazionale delle Ricerhce, Via Orabona 4,
70125-Bari, Italy
E-mail: [email protected]
TiO2 nanomaterials are widely applied in numerous energy-related technologies because of
their peculiar optoelectronic and physicochemical properties. Specifically, rod-shaped anatase
nanocrystals were demonstrated to provide better performances than spherical crystals for
photocatalytic applications [1].
The behavior of amines as adsorbates on TiO2 nanosystems has recently attracted
considerable interest: they are widely used for nitrogen doping [2]; polymers containing
amino groups and TiO2 nanoparticles are used together in novel nanocomposite materials [3];
a new class of heterojunction solar cells relying on titania nanoparticles and hybrid perovskite
materials composed of alkylammonium, lead (both cations) and halides (anions) has recently
been enthusiastically proposed [4].
Nevertheless the fundamental interactions between amino compounds and TiO2 surfaces
are quite unexplored, so we performed a first-principles study of the adsorption of a model
tertiary amine (trimethylamine, TMA) and water on the three most exposed surfaces of TiO2
anatase nanorods, i.e. (100), (001) and (101) [5]. The TMA effectively adsorbs on all the three
surfaces without any marked selectivity, while water showed a major affinity for the (001)
surface. We found evidence of a coordinative bond between the adsorbates and the
undercoordinated titanium ions at the surfaces. Dispersion forces were shown to play an
important role in stabilizing TMA adsorption on all the surfaces. Moreover, the TMA
molecular adsorption led to the appearance of new high densely populated nitrogen states in
the system valence band top.
Overall, the results reported in our contribution will offer new insights on the adsorption
behavior of tertiary amine derivatives on anatase nanorod surfaces. We believe that our
conclusions could help to understand and design new synthetic strategies for N-doped TiO2
nanorods and for new titania-based composite materials.
[1] P. D. Cozzoli, R. Comparelli, E. Fanizza, M. L. Curri and A. Agostiano, Mater. Sci. Eng., C 23
(2003) 707-713.
[2] C. Burda, Y. Lou, X. Chen, A. C. S. Samia, J. Stout and J. L. Gole, Nano Lett. 3 (2003) 10491051.
[3] J. C. Shearer, M. J. Fisher, D. Hoogeland and E. R. Fisher, Appl. Surf. Sci. 256 (2010) 2081-2091.
[4] L. Etgar, P. Gao, Z. Xue, Q. Peng, A. K. Chandiran, B. Liu, M. K. Nazeeruddin and M. Grätzel, J.
Am. Chem. Soc. 134 (2012) 17396-17399.
[5] L. Triggiani, A. B. Muñoz-García, A. Agostiano and M. Pavone, Theor. Chem. Acc. 134 (2015)
51-61.
175
POS-73
Enantiomeric molecular recognition of -amino acid derivatives by
chiral uranyl-salen hosts
Giuseppe Trusso Sfrazzetto, Francesco P. Ballistreri, Andrea Pappalardo,
Gaetano A. Tomaselli, and Rosa Maria Toscano
Dipartimento di Scienze Chimiche, Università degli Studi di Catania, Viale A. Doria 6,
95125-Catania, Italy
E-mail: [email protected]
The development of chiral receptors able to efficiently discriminate enantiomers is an
important target because of their applications in the drug synthesis, analysis, sensing, and
catalysis [1]. In this context, chiral uranyl–salen complexes have emerged as artificial hosts
able to exploit a Lewis metal center to strongly bind carboxylate anions (Figure 1) [2]. In this
contribution, the recognition abilities of two new chiral uranyl–salen hosts towards –amino
acid derivatives are reported. The 1H NMR titrations showed high efficiency to enantiodiscriminate amino acidic ion pairs.
Furthermore, due to the importance of a signaling event after the recognition process, we
design and synthesized the first fluorescent chiral uranyl–polymer, able to give a turn–on
fluorescence response in the presence of guests. Also this receptor showed good
enantioselectivity for the chiral guests tested.
Figure 1 Chiral uranyl–salen complexes as artificial hosts able to exploit a Lewis metal center
to strongly bind carboxylate anion.
[1] a) B. He and Y. Shi, Am. Pharm. Rev. 11 (2008) 47-52; b) W. Tang and S. Ng, Nat. Protoc. 3
(2008) 691-697; c) Y. Shoji, K. Tashiro and T. Aida, J. Am. Chem. Soc. 125 (2006) 10690-10691; d)
Zhao, Q.–F. Sun, W. M. Hart-Cooper, A. G. Di Pasquale, F. D. Toste, R. G. Bergman and K. N.
Raymond, J. Am. Chem. Soc. 135 (2013) 18802-18805.
[2] a) F. P. Ballistreri, A. Pappalardo, R. M. Toscano, G. A. Tomaselli and G. Trusso Sfrazzetto, Eur.
J. Org. Chem. 20 (2010) 3806-3810; b) M. E. Amato, F. P. Ballistreri, S. D’Agata, A. Pappalardo, G.
A. Tomaselli, R. M. Toscano and G. Trusso Sfrazzetto, Eur. J. Org. Chem. 2011 (2011) 5674-5680; c)
A. Pappalardo, M. E. Amato, F. P. Ballistreri, G. A. Tomaselli, R. M. Toscano and G. Trusso
Sfrazzetto, J. Org. Chem. 77 (2012) 7684-7687; d) G. Forte, A. D’Urso, F. P. Ballistreri, R. M.
Toscano, G. A. Tomaselli, G. Trusso Sfrazzetto and A. Pappalardo, Tetrahedron Lett. 56 (2015) 29222926.
176
POS-74
Cytotoxicity study on luminescent nanocrystals containing
phospholipid micelles in primary cultures of rat astrocytes
Gianpiero Valente,ab Tiziana Latronico,c Nicoletta Depalo,b Elisabetta Fanizza,a
Valentino Laquintana,d Nunzio Denora,d Anna Fasano,c Marinella Striccoli,b
Matilde Colella,c Angela Agostiano,ab Maria Lucia Curri,b and Grazia Maria
Liuzzic
a
Dipartimento di Chimica, Università degli Studi di Bari "Aldo Moro", Via E. Orabona 4,
70125-Bari, Italy
b
Istituto per i Processi Chimico-Fisici, Consiglio Nazionale delle Ricerhce, Via Orabona 4,
70125-Bari, Italy
c
Dipartimento di Bioscienze, Biotecnologie e Scienze Farmacologiche, Università degli Studi
di Bari "Aldo Moro", Via E. Orabona 4, 70125-Bari, Italy
d
Dipartimento di Farmacia - Scienze del Farmaco, Università degli Studi di Bari "Aldo
Moro", Via E. Orabona 4, 70125-Bari, Italy
E-mail: [email protected]
Luminescent colloidal nanocrystals (NCs) are emerging as a new tool in cellular imaging and
medical diagnosis, offering a powerful tool for diagnosis of neurological disorders. Due to
their size and advanced optical properties, fluorescent NCs can be suitably designed to
interact with neuronal and glial cells of Central Nervous System, at cellular and subcellular
levels [1]. Properly functionalized and bioconjugated NC-based systems may provide
powerful nanoplatforms for investigating the effects of drugs or other biologically relevant
molecules for the care and treatment of neurological diseases [2]. Since astrocytes activation
is one of the key components of the cellular responses to stress and brain injuries, here a
comprehensive and systematic investigation on the in vitro toxicological effect of luminescent
core-shell CdSe@ZnS NCs on primary cultures of rat astrocytes is presented. Cytotoxicity
response of empty PEG based phospholipid micelles has been compared to that of those
containing NCs [3], studying also the effect of surface charge and terminal groups on cell
interaction and toxicity in order to investigate the effect on cell viability. The ability of NC
containing PEG-lipid micelles to be internalized into the cells has been assessed by confocal
laser scanning fluorescence microscopy and photoluminescence assay.
Figure 1 Evaluation of cellular uptake of
CdSe@ZnS NCs containing PEG functionalized
phospholipid micelles by confocal fluorescence
microscopy. Scale bar 25 µm.
[1] S. Pathak, E. Cao, M. C. Davidson, S. Jin and G. A. Silva, J. Neurosci. 26 (2006) 1893-1895.
[2] S. Hanada, K. Fujioka, Y. Inoue, F. Kanaya, Y. Manome and K. Yamamoto, Int. J. Mol. Sci. 15
(2014) 1812-1825.
[3] N. Depalo, A. Mallardi, R. Comparelli, M. Striccoli, A. Agostiano and M. L. Curri, J. Colloid
Interface Sci. 325 (2008) 558-566.
177
POS-75
Bottom-up approach to highly functionalized sulfur-bearing fourmembered heterocycles: easy access to neglected chemical motifs
Marina Zenzola,a Flavio Fanelli,a,b Laura Carroccia,a Giovanna Parisi,a,d Luisa
Pisano,c Vittorio Pace,d Leonardo Degennaro,a and Renzo Luisia
a
Dipartimento di Farmacia - Scienze del Farmaco, Università degli Studi di Bari "Aldo
Moro", Via E. Orabona 4, 70125-Bari, Italy
b
Istituto di Cristallografia, Consiglio Nazionale delle Ricerche, Via E. Orabona 127/A,
70125-Bari, Italy
c
Dipartimento di Chimica e Farmacia, Università degli Studi di Sassari, Via Vienna 2,
07100-Sassari, Italy
d
Department of Pharmaceutical Chemistry, University of Vienna, Althanstrasse 14, 1090Vienna, Austria
E-mail: [email protected]
Four-membered heterocycles (4-MHs) with one or two heteroatoms are of great importance in
medicinal chemistry and synthetic organic chemistry [1] and attracted our attention in recent
years [2]. Our recent research efforts have been focused on the stereoselective synthesis and
functionalization of sulfur-bearing 4-MHs such as thietane 1,1-dioxide, thietane 1-dioxide and
thietane sulfoximine [3]. Our interest for this kind of heterocycles arises from the evidence
that there are few reports concerning their stereoselective preparation and functionalization by
using the corresponding polar organometallic intermediates. We have developed synthetic
strategies for the preparation of new chemical motifs by a regio- and stereoselective
decoration of 4-membered sulfurated heterocycles.
[1] a) F. Couty, B. Drouillat, G. Evano and O. David, Eur. J. Org. Chem. 2013 (2013) 2045-2056; b)
C. Guérot, B. H. Tchitchanov, H. Knust and E. M. Carreira, Org. Lett. 13 (2011) 780-783; c) A.
Brandi, S. Cicchi and F. M. Cordero, Chem. Rev. 108 (2008) 3988-4035.
[2] a) M. Zenzola, L. Degennaro, P. Trinchera, L. Carroccia, A. Giovine, G. Romanazzi, P.
Mastrorilli, R. Rizzi, L. Pisano and R. Luisi, Chem. Eur. J. 20 (2014) 12190; b) L. Degennaro, M.
Zenzola, P. Trinchera, L. Carroccia, A. Giovine, G. Romanazzi, A. Falcicchio and R. Luisi, Chem.
Commun. 50 (2014) 1698-1700; c) G. Parisi, E. Capitanelli, A. Pierro, G. Romanazzi, G. J. Clarkson,
L. Degennaro and R. Luisi, Chem. Commun. 51 (2015) DOI: 10.1039/C5CC06323J.
[3] a) L. Carroccia, L. Degennaro, G. Romanazzi, C. Cuocci, L. Pisano and R. Luisi, Org. Biomol.
Chem. 12 (2014) 2180; b) M. Zenzola, R. Doran, R. Luisi and J. A. Bull, J. Org. Chem. 80 (2015)
6391-6399.
178
List of participants
SURNAME
ALFANO
ALLETTO
ANDRONICO
ARCUDI
ARNABOLDI
BARSOTTI
BELLA
BERGFELT
CANTI
CAPONE
CAPPELLI
CARETTO
CASAMASSA
CASO
CASSOTTA
NAME
E-MAIL
INSTITUTE
GAETANO
[email protected]
UniNA
FRANCESCO
[email protected]
UniMORE
LUCA ALFIO
[email protected]
UniBO
FRANCESCA
[email protected]
UniTS
SERENA
[email protected]
UniMI
FRANCESCO
[email protected]
UniTO
FEDERICO
[email protected]
PoliTO
ANDREAS
[email protected]
Uppsala Univ
LORENZO
[email protected]
UniUPO
DARIA
[email protected]
UniNA
CHIARA
[email protected]
SNS
ALESSIO
[email protected]
HELIV
ENRICO
[email protected]
UniTO
ALESSIA
[email protected]
UniNA
PIETRO
[email protected]
UniBO
MARIA
CATAPANO
[email protected]
UniBO
CARMEN
CATTELAN
LISA
[email protected]
UniVE
CAUDA
VALENTINA
[email protected]
IIT
CAVALLO
CARMEN
[email protected]
UniROMA-1
CECCONI
BIANCA
[email protected]
UniMIB
CHIMINAZZO
ANDREA
[email protected]
UniVE
CHUGUNOVA
ELENA
[email protected]
RAS
CHUGUNOVA
SVETLANA
[email protected]
Accompanying
CINO
SILVIA
[email protected]
UniBO
CIOCE
CLAUDIA
[email protected]
UniNA
CIPPITELLI
MARTA
[email protected]
UniMC
COLO'
FRANCESCA
[email protected]
PoliTO
COMPAGNONI
MATTEO
[email protected]
UniMI
CORINTI
DAVIDE
[email protected]
UniROMA-1
GIUSEPPINA
CORRENTE
[email protected] UniSALENTO
ANNA
CORRICELLI
MICHELA
[email protected]
UniBA
COSCONATI
SANDRO
[email protected]
UniNA-2
CRISCUOLO
VALERIA
[email protected]
UniNA
CRISTALDI
ANDREA
[email protected]
UniCT
CUFFARO
DORETTA
[email protected]
UniPI
MASSIMO
D'ALTERIO
[email protected]
UniNA
CHRISTIAN
D'URSO
ALESSANDRO
[email protected]
UniCT
DA PIAN
MARTA
[email protected]
UniVE
DAPIAGGI
FEDERICO
[email protected]
UniMI
DASSO LANG
CHIARA
[email protected]
UniSI
DE COLA
LUISA
[email protected]
UniSTRA
DE MARCO
ROSSELLA
[email protected]
UniBO
DI DATO
ANTONIO
[email protected]
UniNA
DI FOGGIA
MICHELE
[email protected]
UniBO
DI GIOSIA
MATTEO
[email protected]
UniBO
DI MARTINO
RITA M. C.
[email protected]
UniBO
DI MAURO
A. EVELYN
[email protected]
CNR
DIAFERIA
CARLO
[email protected]
UniNA
DORDEVIC
LUKA
[email protected]
UniTS
EMENDATO ALESSANDRO
[email protected]
UniNA
FAROLDI
FEDERICA
[email protected]
UniPR
179
FERRARO
GIUSEPPE
FERRARO
LUCA
FERRAZZANO
LUCIA
FINAMORE
CLAUDIA
FIORILLO
GAETANO
FOGLIA
ANTONIO
FORTE
LUCIA
FRANCESCONI
OSCAR
FRANCHI
DANIELE
FREZZA
CLAUDIO
FUMAGALLI
GAIA
GADO
FRANCESCA
GALLIANO
SIMONE
GANGEMI
CHIARA
GASPA
SILVIA
GENTILE
GIANFRANCO
GIACONA
GIULIA
GRAZIADIO ALESSANDRA
GRILLO
GIORGIO
GUALANDI
LORENZO
GUIDI
SANDRO
HAGFELDT
ANDERS
IDILI
ANDREA
IOVENITTI
GIULIA
ISMAIL
OMAR
JESCHULL
FABIAN
LA ROSA
MARCELLO
LAMBERTI
ANDREA
LEHN
JEAN-MARIE
LENCI
ELENA
MAGNABOSCO
GIULIA
MAGNI
MIRKO
MANDRIOLI
ROBERTO
MANFRIN
SILVIA
MANZI
JESSICA
MARGARI
PIERO
MARIANETTI
GIULIA
MARIOTTINI
DAVIDE
MARRA
ANNAMARIA
MARTELLI
GIULIA
MARTINO
EMANUELA
MARUCCI
CRISTINA
MASSARO
ARIANNA
MASULLO
DARIO
MATTEUCCI
ELIA
MATULLI
THOMAS
CAVEDAGNA
MAZZONE
GLORIA
MERCOLINI
LAURA
MERLINO
FRANCESCO
MEZZETTA
ANDREA
MICHELETTI
GABRIELE
MINNITI
ELIROSA
MIRABELLA
STEFANIA
MOLINARI
ALESSIO
MONTRONI
DEVIS
MORGANTI
EMANUELE
MUNOZANA BELEN
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
IIT
UniBO
UniBO
UniNA
Naxospharma
UniSA
UniBO
UniFI
UniFI
UniROMA-1
UniMI
UniPI
UniTO
UniCT
UniSS
Vishay
UniTO
UniBO
UniTO
UniBO
UnIVE
EPFL
UniROMA-2
UniSI
UniROMA-1
Uppsala Univ
UniBO
PoliTO
UniSTRA
UniFI
UniBO
UniMI
UniBO
UniTO
UniBAS
UniPI
SNS
UniROMA-2
UniPV
UniBO
UniPV
UniMI
UniNA
UniNA
UniBO
[email protected]
UniBO
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
UniCAL
UniBO
UniNA
UniPI
UniBO
UniBO
UniFI
UniSI
UniBO
UniBO
UniNA
180
GARCIA
NASTI
RITA
NEAGU CHIVU ALEXANDRA
NEWTON
SARAH
NOVELLI
FEDERICA
OLIVERI
PAOLO
OLSZÓWKA
MARTA
OROFINO
FRANCESCO
PAIOTTA
ALICE
PALUMBO
CHIARA
PARIS
EMANUELE
PARISE
LUCA
PASERO
CAROLINA
PAVONE
MICHELE
PAVONI
ELEONORA
PERRINO
DAVIDE
PIAZZETTA
PAOLO
PIERACCINI
STEFANO
PIERSANTI
LUCA
PIFFERI
VALENTINA
PONTREMOLI
CARLOTTA
PORCARELLI
LUCA
PRATI
LUCA
PROTTI
MICHELE
PULEO
FABRIZIO
MARIA
RAGGI
AUGUSTA
RAINOLDI
GIULIA
RANDAZZO
ROSALBA
RICCIO
RAFFAELE
RODRIGUEZ
ANTONIO
GARCIA
ROSSETTI
ARIANNA
ROSSETTI
MARIANNA
ROTOLO
LAURA
ROVIELLO
GIOVANNI
RUGGERI
IRENE
RUI
MARTA
RUPIANI
SEBASTIANO
RUSCONI
SELINA
SABUZI
FEDERICA
SAMPAOLESI
SUSANNA
SANTACROCE
VERONICA
SAPPINO
CARLA
SCARANO
PIERPAOLO
SCARCELLA
VINCENZO
SCHIAVO
EDUARDO
SCORTICHINI
MIRKO
SEMENTA
DEBORAH
SENESE
MARIA
SIGHEL
DENISE
SILVESTRINI
PAOLO
SIMONETTI
REMO
SINIBALDI
ALBERTO
SORRENTINO
ILARIA
SPINACI
ANDREA
SPINELLI
DOMENICO
STUCCHI
MATTIA
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
UniPV
UniMORE
EYCN
UniROMA-1
UniGE
UniPI
UniSI
UniMIB
CNR
UniPR
UniROMA-1
UniSI
UniNA
UniBO
UniMI
UniCAL
UniMI
UniURB
UniMI
UniTO
PoliTO
UniBO
UniBO
CNR
[email protected]
UniBO
[email protected]
[email protected]
[email protected]
UniMI
UniCT
UniSA
[email protected]
UniNA
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
PoliMI
UniROMA-2
UniTO
UniNA
UniBO
UniPV
UniBO
UniPV
UniROMA-2
UniCAM
UniPR
UniROMA-1
UniNA
UniTO
UniNA
UniCAM
UniNA
UniNA
UniTN
UniMC
UniGE
UniROMA-1
UniNA
UniCAM
UniBO
UniMI
181
TAFUR
MARINOS
THOMAS
TIRRI
TORTI
TOVAR
RODRIGUEZ
TRIGGIANI
TRUSSO
VALENTE
VALENTONI
VIGORITO
VOLPI
VOLPI
YOUSIF
ZANNA
ZEGARRA
ZENZOLA
JANETH
[email protected]
UniTO
AJIROGHENE
BERNARDINO
EDOARDO
[email protected]
[email protected]
[email protected]
UniCAM
UniNA
UniPV
JORGE
[email protected]
UniFI
LEONARDO
GIUSEPPE
GIAMPIERO
ANTONIO
ANNALISA
GIORGIO
STEFANO
ALI MUNAIM
NICOLA
MARCOS
MARINA
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
UniBA
UniCT
UniBA
UnISS
UniBO
UniTO
UniPR
UniNA
UniBO
Accompanying
UniBA
182
Società Chimica Italiana
The Italian Chemical Society (Società Chimica
Italiana, SCI), founded in 1909 and erected as a
Legal Institution with R.D. n. 480/1926, is a
scientific association that includes more than
3000 members. SCI members carry out their
activities in universities and research institutes, schools, industries, public
and private research and control laboratories, or as freelancers. They are
joined not only by the interest in chemical sciences, but also by the desire
to contribute to the cultural and economic growth of the national
community, improving the quality of human life and the protection of the
environment.
For new members
All SAYCS participants are (or have just become) SCI members.
Those who, before reaching Rimini, were not yet SCI members will be
contacted shortly (by e-mail) to complete the membership procedure and
indicate the preferred SCI division.
Those who have chosen to become members for a year will be enrolled
until 31/12/2016; those who chose the two-year membership will be SCI
members up to the end of 2017.
183
SCI Giovani / SCI Young
All SCI members with less than 35 years are part
of the Young Group. It is an interdisciplinary group
that proposes several initiatives to its members:
SAYCS, Levi and Reaxys Award, Y-RICh workshops
for the preparation of EU projects, the creation of
collaborative networks, and much more.
Delegates of the various Divisions form the Board of SCI Young, which
is responsible for the planning and organization of the activities of the
Young Group:
 Michele Pavone – Physical Chemistry, Coordinator
 Sandro Cosconati - Pharmaceutical Chemistry, Vice-Coordinator
 Oscar Francesconi - Organic Chemistry, Treasurer
 Davide Rosestolato – Electrochemistry, Secretary
 Federico Bella - Industrial Chemistry
 Julien Bloino - Theoretical and Computational Chemistry
 Alessandro D’Urso - Chemistry of Biological Systems
 Paolo Oliveri - Analytical Chemistry
 Luca Rocchigiani - Inorganic Chemistry
 Giorgia Sciutto – Chemistry of Environment and Cultural Heritage
SCI Giovani
SCI Giovani
Assemblea Ordinaria dei Soci del Gruppo Giovani
Mercoledì 28 Ottobre 2015 – h 18.45 – Hotel Ambasciatori (Rimini)
1.
2.
3.
4.
5.
6.
Ordine del giorno
Comunicazioni
Relazione annuale del direttivo
Consuntivo amministrativo e preventivi di spesa
Programmazione delle attività del Gruppo Giovani
Rinnovo Direttivo Gruppo Giovani
Varie ed eventuali
184
European Young Chemists’ Network
SCI Young members are invited to follow the activities of the European
Young Chemists’ Network (EYCN), i.e. the young group of the European
Association for Chemical and Molecular Sciences (EuCheMS), that brings
together chemistry-related organisations throughout Europe to provide a
single voice on key science and policy issues, based on expert scientific
knowledge.
In this SAYCS event we host Sarah Newton, board member of EYCN,
who will show you the activities of EYCN (events, conferences, prizes,
etc.). You are invited to like the Facebook webpage of EYCN:
EYCN
EYCN will also award the two best posters presented during this
conference.
National delegates at the 10th Delegates Assembly in Berlin (April 2015).
185
EYCN: 10 years connecting European Young Chemists
Sarah L. Newton,a,d Camille Oger,b,d and Fernando Gomollón-Belc,d
a
Centre for Doctoral Training in Physical Sciences of Imaging in the Biomedical Sciences,
School of Chemistry, University of Birmingham, University Rd W, B152TT-Birmingham, UK
b
Institute of Biomolecules Max Mousseron, Unité Mixte de Recherche 5247 - Centre National
de la Recherche Scientifique, Faculty of Pharmacy, Université de Montpellier, Ecole
Nationale Supérieure de Chimie, 15 Av. C. Flahault, 34093-Montpellier, France
c
Instituto de Síntesis Química y Catálisis Homogénea, Universidad de Zaragoza, Pedro
Cerbuna 12, 50009-Zaragoza, Spain
d
European Young Chemists’ Network, 62 Rue du Trône, 1050-Brussels, Belgium
E-mail: [email protected]
The European Young Chemists’ Network (EYCN) is the younger members’ division of
EuCheMS. It was created back in 2006 and has grown to represent 26 different societies from
22 European countries [1].
The EYCN organizes different activities throughout Europe: several poster prizes in
younger chemists’ conferences; the European Young Chemist Award (EYCA) [2]; career
days for young students; and since 2011, the Young Chemists Crossing Borders exchange
programs in collaboration with the Younger Chemists Committee of the American Chemical
Society [3].
In April 2016, EYCN will host the first European Young Chemists’ Conference in
Guimarães, Portugal. This will give young chemists around Europe a unique opportunity to
meet, create new connections and develop their soft-skills thanks to the training courses and
seminars.
If you wish to get in touch with the EYCN, visit our website (http://www.eycn.eu) or
contact us using our social media profiles in Facebook, Twitter and LinkedIn. We look
forward to collaborating with you!
Figure 1: EYCN logo.
[1] F. Gomollón-Bel, C. Oger and C. Todasca. Chem. Views 10.1002/chemv.201500500
[2] The EYCA Award is organized in collaboration with the Italian Chemical Society and the Italian
Consiglio Nazionale dei Chimici.
[3] U. I. Zakai, N. LaFranzo, C. Dunne and J. Breffke. Chem. Views 10.1002/chemv.201500051
186
187