le giornate di chimica organica a pavia · self-assembly of molecular materials via halogen bonding...
TRANSCRIPT
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 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. (1) Komarova, N. L.; Boland, C. R. Nature 2013, 499, 291. (2) Sortino, S. J. Mater. Chem. 2012, 22, 301. (3) Sortino, S. Chem. Soc. Rev. 2010, 39, 2903.
1O2
•NO1O2
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 multi-branched 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 open- and 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) Irie, M; Mohri, M. J. Org. Chem., 1988, 53, 803. (2) Irie, M. Chem. Rev. 2000, 100, 1685. (3) Irie, M.; Fukaminato, T.; Sasaki, T.; Tamai, N.; Kawai, T. Nature, 2002, 420, 759. (4) Uno, K.; Niikura, H.; Morimoto, M.; Ishibashi, Y.; Miyasaka, H.; Irie, M. J. Am. Chem. Soc., 2011, 133, 13558. (5) Irie, M.; Kobatake, S.; Horichi, M. Science, 2001, 291, 1769. (6) Kobatake, S.; Takami, S.; Muto, H.; Ishikawa, T.; Irie, M. Nature, 2007, 446, 778. (7) Morimoto, M.; Irie, M. J. Am. Chem. Soc., 2010, 132, 14172. (8) 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
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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anno 1462 - Biblioteca Universitaria - Pavia