Department of Chemistry, University of Pavia
LE GIORNATE DI CHIMICA ORGANICA A PAVIA
Aula Magna, Palazzo Centrale dell’Università
Wednesday, 15th October 2014
Under the auspices of:
Sponsored by:
Program
9.30
Opening Remarks
9.45
Shedding Light on Nanomedicine: Photoactivated Nanoconstructs
with Multiple Imaging and Therapeutic Modalities
Salvatore Sortino (University of Catania, Italy)
10.35
Organic and organometallic materials for new generation photovoltaic cells
Alessandro Abbotto (University Milano-Bicocca, Italy)
(11.25-11.50 break)
11.50
Photochromism of Diarylethene Molecules and Crystals
Masahiro Irie (Rikkyo University, Tokyo, Japan)
(lunch break)
14.30
Photoredox catalysis in Organic Synthesis
David MacMillan (Princeton University, USA)
Shedding Light on Nanomedicine: Photoactivated Nanoconstructs
with Multiple Imaging and Therapeutic Modalities
Salvatore Sortino
Laboratory of Photochemistry, Department of Drug Sciences, University of Catania,
Viale A. Doria 95125, Catania, Italy;
[email protected]
The achievement of molecular nanoconstructs able to release multiple therapeutic
species in a controlled fashion is a major challenge in the burgeoning field of
nanomedicine (1). Light is a powerful tool for the introduction of bio-active agents
in a cellular environment, mimicking an “optical microsyringe” with an exquisite
control of three main factors, site, timing and dosage, which are determining for
the therapeutic outcome (2). Moreover light-triggering is biofriendly and offers the
additional advantages of not affecting important physiological parameters such as
temperature, pH and ionic strength. In this context, the use of photoactive
compounds having intrinsic fluorescence properties or their integration with
suitable fluorogenic units is a fundamental requisite for an imaging-guided
phototherapy. This allows indeed the visualization of the phototherapeutic agent
in cells through fluorescence techniques and can provide a highly localized “burst”
precisely at the desired sites. Singlet
oxygen (1O2) and nitric oxide radical (NO)
are able to attack biological substrates of
O
•NO
different nature (i.e., lipids, proteins, and
DNA)
representing
multitarget
therapeutic agents and avoiding Multiple
Drug Resistance problems encountered
with several conventional drugs often
target-specific. Due to their short half-life
and lack of charge, both 1O2 and NO
radical
diffuse
in
the
cellular
environment over short distances
without inflicting systemic side effects
common to general anticancer drugs. For all these reasons, the combination of 1O2
with NO has received growing attention in the last few years (3) with the exciting
prospect to tackle cancer and bacterial diseases.
In our laboratories, we have been working on the design and fabrication of a
number of nanoplatforms merging multicolor fluorescence imaging and
multimodal therapeutic photofunctionalities. This contribution illustrates some of
the most recent and representative examples including molecular and
supramolecular conjugates, polymer nanoparticles, hydrogels and quantum dots,
highlighting the rationale design and their potential relevance in biomedical
research.
1O2
1
(1)
(2)
(3)
2
Komarova, N. L.; Boland, C. R. Nature 2013, 499, 291.
Sortino, S. J. Mater. Chem. 2012, 22, 301.
Sortino, S. Chem. Soc. Rev. 2010, 39, 2903.
Organic and organometallic materials for new generation
photovoltaics (and solar fuels)
Alessandro Abbotto
Department of Materials Science and Solar Energy Center MIB-SOLAR,
University of Milano-Bicocca, Via Cozzi 55, Milano (I)
[email protected]
Energy from Sun in modern society implies both electricity and fuels. With this
target in mind we have developed in the last years a multidimensional approach,
from molecular design to device, based on hybrid and organic materials. Our
studies on organometallic and organic sensitizers, (1-3) iodine-free and quasi-solid
electrolytes, (4) nanostructured TiO2 (5) will be presented. In particular we have
introduced in the last years a new design approach for metal-free sensitizers, now
widely used in the DSSC community, based on a multi-branched geometry, for
improved light harvesting and enhanced stability compared to the conventional
linear D--A sensitizers. (1) We will also present our most recent results on multibranched dyes for solar-induced hydrogen production from water.
In the last part of the lecture a few slides will be dedicated to the introduction of
EnerCHEM, the recently established group of the Italian Chemical Society on
Chemistry of Renewable Energies, whose members come for the diverse areas of
research on renewable energy materials and devices in Italy. (6)
(1)
Reviews: Manfredi, N.; Cecconi, B.; Abbotto, A. Eur. J. Org. Chem. 2014, DOI:
10.1002/ejoc.201402422; Abbotto, A.; Manfredi, N. Dalton Trans. 2011, 40, 12421.
(2)
Abbotto, A.; Coluccini, C.; Dell'Orto, E.; Manfredi, N.; Trifiletti, V.; Salamone,
M. M.; Ruffo, R.; Acciarri, M.; Colombo, A.; Dragonetti, C.; Ordanini, S.; Roberto, D.;
Valore, A. Dalton Trans. 2012, 41, 11731; Coluccini, C.; Manfredi, N.; Salamone, M.
M.; Ruffo, R.; Lobello, M. G.; De Angelis, F.; Abbotto, A. J. Org. Chem. 2012, 77, 7945;
Lobello, M. G.; Fantacci, S.; Manfredi, N.; Coluccini, C.; Abbotto, A.; Nazeeruddin, M.
K.; De Angelis, F. Thin Solid Films 2014, 560, 86.
(3)
Abbotto, A.; Leandri, V.; Manfredi, N.; De Angelis, F.; Pastore, M.; Yum, J.-H.;
Nazeeruddin, M. K.; Grätzel, M. Eur. J. Org. Chem. 2011, 2011, 6195; Leandri, V.;
Ruffo, R.; Trifiletti, V.; Abbotto, A. Eur. J. Org. Chem. 2013, 2013, 6793; Di Carlo, G.;
Biroli, A. O.; Pizzotti, M.; Tessore, F.; Trifiletti, V.; Ruffo, R.; Abbotto, A.; Amat, A.; De
Angelis, F.; Mussini, P. R. Chem. Eur. J. 2013, 19, 10723.
(4)
Manfredi, N.; Bianchi, A.; Causin, V.; Ruffo, R.; Simonutti, R.; Abbotto, A. J.
Polym. Sci. Part A 2014, 52, 719.
(5)
Trifiletti, V.; Ruffo, R.; Turrini, C.; Tassetti, D.; Brescia, R.; Di Fonzo, F.;
Riccardi, C.; Abbotto, A. J. Mater. Chem. A 2013, 1, 11665; Dell'Orto, E.; Raimondo,
L.; Sassella, A.; Abbotto, A. J. Mater. Chem. 2012, 22, 11364.
(6)
http://www.soc.chim.it/it/gruppi/enerchem/home.
Photochromism of Diarylethene Molecules and Crystals
Masahiro Irie
Research Center for Smart Molecules, Rikkyo University, Tokyo, Japan
[email protected]
Photochromism is defined as a reversible transformation of a chemical species
between two isomers having different absorption spectra induced in one or both
directions by photoirradiation. Although vast numbers of photochromic molecules
have been so far reported, molecules which exhibit thermally irreversible
photochromic reactivity are limited. A new class of thermally irreversible
photochromic molecules is a “diarylethene” family. (1,2) The diarylethenes are
derivatives of stilbene. When the phenyl rings of stilbene are replaced with five
membered heterocyclic rings with low aromatic stabilization energy, both openand closed-ring isomers become thermally stable. Diarylethenes undergo
reversible cyclization and cycloreversion reactions in a picosecond time region
upon alternate irradiation with UV and visible light and the
coloration/decoloration cycles can be repeated more than 10,000 times. The
chemical bond rearrangement induces electronic as well as geometrical structure
changes. The electronic structure changes can be potentially applied to ultrahigh
density (Pbits/inch2) optical memory media, (3), various photoswitching devices
and super-resolution fluorescence imaging. (4) The geometrical structure changes
can be applied to light-driven actuators and others (5-8). In this lecture,
fundamental properties of diarylethene molecules and crystals, and their
applications to photoswitchable fluorescence imaging and light-driven actuators
will be presented.
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
Irie, M; Mohri, M. J. Org. Chem., 1988, 53, 803.
Irie, M. Chem. Rev. 2000, 100, 1685.
Irie, M.; Fukaminato, T.; Sasaki, T.; Tamai, N.; Kawai, T. Nature, 2002, 420,
759.
Uno, K.; Niikura, H.; Morimoto, M.; Ishibashi, Y.; Miyasaka, H.; Irie, M. J. Am.
Chem. Soc., 2011, 133, 13558.
Irie, M.; Kobatake, S.; Horichi, M. Science, 2001, 291, 1769.
Kobatake, S.; Takami, S.; Muto, H.; Ishikawa, T.; Irie, M. Nature, 2007, 446,
778.
Morimoto, M.; Irie, M. J. Am. Chem. Soc., 2010, 132, 14172.
Terao, F.; Morimoto, M.; Irie, M. Ang. Chem. Int. Ed., 2012, 51, 901.
Photoredox Catalysis: A Molecule Activation Strategy to Enable
New Chemical Reactions
David W. C. MacMillan
Merck Center for Catalysis, Princeton University, Princeton, NJ 08544
[email protected]
This lecture will discuss the advent and development of new concepts in chemical
synthesis, specifically the combination of photoredox catalysis with organic
catalysis. This new approach to “synergistic catalysis” will demonstrate that
multiple yet separate catalytic cycles can be aligned to generate activated
intermediates that rapidly combine with each other, thereby allowing new
approaches to enantioselective C-C and C-heteroatom bond formation.
We will also introduce an approach to the discovery of new chemical reactions that
we term accelerated serendipity. Accidental or ‘serendipitous’ discoveries have led
to some of the most important breakthroughs in scientific history, many of which
have directly affected human life. Given our overarching goal of developing
fundamentally new and useful chemical transformations using catalysis and by
acknowledging the tremendous impact of serendipity in scientific discovery, we
questioned whether this phenomenon could be forced or simulated and therefore
employed as a tool for reaction discovery.
In this presentation, we will describe several new transformations that have been
discovered in our laboratory that we expect will find widespread adoption
throughout the field of chemical synthesis. Moreover, we will further describe how
mechanistic understanding of these processes has led to the design of new yet
fundamental chemical transformations. In particular: (i) a new catalysis activation
mode that allows for the direct functionalization of ketones and aldehydes at the carbon position, (ii) a new synergistic catalysis approach to C-H bond
functionalization, and (iii) the development of decarboxylative coupling reactions.
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Da “ARS SIVE DOCTRINA DE TRASMUTATIONE METALLORUM”
anno 1462 - Biblioteca Universitaria - Pavia