Lorenzo Zani – CNR ISOF – 11/06/2012
2002 «Laurea» in Chemistry – University of Florence (Italy)
2003-2006 Ph. D. in Chemistry – RWTH Aachen University (Germany) Supervisor Prof. C. Bolm Asymmetric Synthesis, Metal-catalyzed Reactions
2007-2008 Post-Doc – Stockholm University (Sweden) Supervisor Prof. H. Adolfsson Asymmetric Synthesis, Metal-catalyzed Reactions
2009-2010 Post-Doc – The Institute of Cancer Research (United Kingdom) Supervisor Prof. K. Jones Heterocyclic Synthesis, Medicinal Chemistry
2010-2011 Post-Doc – CNR-ICCOM (Italy) Supervisor Dr. G. Reginato Development of Photoelectrochemical Solar Cells (DSSC)
2011-present Researcher – CNR-ISOF (Italy) Development of DSSC, Synthetic Methodology
Lorenzo Zani – Brief CV and Research Interests
1/17
Asymmetric Addition of Organozinc Reagents to Aldehydes and Imines
Asymmetric Synthesis of Diarylmethanols
Lorenzo Zani – CNR ISOF – 11/06/2012
Precursors of active pharmaceutical
ingredients
Diarylmethanols
J. Org. Chem. 2006, 71, 2320
2/17
Asymmetric Addition of Organozinc Reagents to Aldehydes and Imines
One-pot Asymmetric Synthesis of Propargylamines
Lorenzo Zani – CNR ISOF – 11/06/2012
Extension of a known procedure to the preparation of new compounds
- Ligand optimization - Variation of the reaction conditions - Development of analytical methods
Chem. Eur. J. 2007, 13, 2587
3/17
Metal-catalyzed Reductions of Carbonyl Compounds
Enantioselective Transfer Hydrogenation (ETH) of Acetophenones
Lorenzo Zani – CNR ISOF – 11/06/2012
ETH of ketones is a well-established methodology to obtain enantiomerically enriched secondary alcohols:
Testing of new metal-ligand combinations:
[Ru] + chiral sulfinamides (stereogenic center on sulfur)
Use of a sulfonamide analogue (not having a stereogenic center
on sulfur) resulted in the formation of a racemic product!
Eur. J. Org. Chem. 2008, 4655
4/17
Metal-catalyzed Reductions of Carbonyl Compounds
Iron-catalyzed hydrosilylation of ketones
Lorenzo Zani – CNR ISOF – 11/06/2012
Use of silanes as reducing agents allows a mild and chemoselective conversion of ketones to alcohols:
- Use of abundant, cheap and non-toxic metal precursors
- In situ catalyst preparation, simple and mild procedure and work-up
Fe-NHC complexes
Appl. Organomet. Chem. 2011, 25, 748
5/17
Discovery of New Inhibitors of Chaperone Proteins
Lorenzo Zani – CNR ISOF – 11/06/2012
- Heat shock proteins (Hsp) are ubiquitous and highly conserved proteins, occurring in all cellular organisms.
- Hsp main role is to act as molecular chaperones which bind to unfolded proteins, either nascent polypeptides or denatured ones, facilitating their refolding to the native state.
- Hsp proteins are classified based on their molecular weight. Two of the main chaperone families are Hsp70 and Hsp90.
- Cancer cells are crucially dependent on chaperone protein function as they are a hot-house of protein synthesis and replication. Therefore, chaperones are promising molecular targets for cancer treatment.
Above: Structure of the Hsp90 molecular chaperone Below, right: Structure of the Hsp70 molecular chaperone Below, left: NVP AUY-922, an Hsp90-inhibitor currently in phase II clinical trials
In collaboration with:
6/17
Solar Energy and Photovoltaic Cells
PM.P04.012 – Design, sintesi e test di molecole e materiali per celle solari fotosensibilizzate Responsible: Dr. Filippo de Angelis (ISTM, Perugia)
Modulo: PM.P04.012.003 – Sintesi di nuovi sensibilizzatori con sistemi di ancoraggio ottimizzabili Responsible: Dr.ssa Gianna Reginato (ICCOM, Florence)
- Participation to an active CNR project
Lorenzo Zani – CNR ISOF – 11/06/2012 7/17
May 2010 – Nov 2011:
- FOTOSENSORG Project: «Design and synthesis of novel organic sensitizers for non-conventional photovoltaic cells» (research grant)
CNR-ICCOM
Supervisor: Dr.ssa Gianna Reginato
Università degli Studi di Siena Supervisor: Prof. Maurizio Taddei
Nov 2011 – present:
Solar Energy and Photovoltaic Cells
Lorenzo Zani – CNR ISOF – 11/06/2012
Photovoltaic Cell: a device able to convert light into electrical power
Main Classes of Photovoltaic Cells
1) Silicon Cells
a) Monocrystalline silicon cells
b) Polycrystalline silicon cells
2) Thin Film Solar Cells
a) GaAs
b) CdTe
c) CI(G)S – CuIn(Ga)Se2
d) Amorphous silicon (a-SiH)
3) Organic and Hybrid Photovoltaics
a) Bulk Heterojunction Solar Cells
b) Dye-Sensitized Solar Cells (DSSC)
8/17
Lorenzo Zani – CNR ISOF – 11/06/2012
Photovoltaic Cells: Hystorical Development
9/17
Cell efficiency: η = Pmax / Pin
Dye-Sensitized Solar Cells
Lorenzo Zani – CNR ISOF – 11/06/2012
Michael Grätzel G24i (UK)
Sony (Japan)
- Invented by Michael Grätzel at EPF in Lausanne (Switzerland) in 1991 (B. O’Regan, M. Grätzel, Nature 1991, 353, 737).
- High efficiency under optimized conditions: ηmax > 12% (lab scale).
- Readily available raw materials, simple and inexpensive production process.
- Relatively insensitive towards illumination conditions (angle, intensity, temperature).
- They can be built using flexible substrates.
- They can be transparent or opaque, and can be produced in different colours (important for BIPV).
10/17
Lorenzo Zani – CNR ISOF – 11/06/2012
Platinum
Electrolyte Solution (I-/I3
-)
TiO2 Dye
Transparent Conductive
Oxide
Glass
Glass
Components
1. Glass substrate
2. TCO (Transparent Conductive Oxide) layer
3. Nanocrystalline semiconductor (TiO2)
4. Dye (adsorbed on the semiconductor)
5. Electrolyte solution containing a redox couple
6. Counterelectrode (usually made of Pt)
7. Glass substrate
Dye-Sensitized Solar Cells
11/17
Lorenzo Zani – CNR ISOF – 11/06/2012
Mechanism
1. Light absorption
2. Photoexcitation
3. Injection
4. Charge collection
5. Regeneration
6. Electrolyte oxidation
Transition metal complexes
Organic Compounds
Porphirins
Dye
Dye-Sensitized Solar Cells
12/17
Development of New Organic Dyes for Dye-Sensitized Solar Cells
Lorenzo Zani – CNR ISOF – 11/06/2012
DONOR GROUP ACCEPTOR GROUP D-π-A structure:
Ideal Properties of a DSSC Dye:
a) Broad and efficient light absorption in the visible and near-infrared region.
b) Should have functional groups allowing a good anchoring on TiO2 (-COOH, -PO3H2, -SO3H).
c) Its energy levels should be correctly aligned to ease regeneration and electron injection.
d) It should not aggregate on the surface of the semiconductor.
e) It should be thermally, chemically and photochemically stable.
-SPACER π
13/17
Also responsible of anchoring
to TiO2
Gem-Silanediol Anchoring Group
Lorenzo Zani – CNR ISOF – 11/06/2012
- Form strong bonds with metal oxides
- Could be used to build long-lasting DSSCs
photovoltaic performances still unsatisfactory, must be
improved (stronger EWG group?)
UV-Vis absorption spectra of 8a-b and 9a-b in ethanol solution.
Cyclic voltammetry (semiderivative plot) of 8b and 9b in CH2Cl2 solution.
14/17
Fused-Thiazole Heterocycles as Conjugate Spacers
Lorenzo Zani – CNR ISOF – 11/06/2012
- Previously employed in OPV but not in DSSCs
- Oxidative and thermal stability
- High charge carrier mobility
- Good light absorption properties
- Thiazolothiazole unit weak EWG
TD-DFT calculations suggest that these compounds are suitable for employment in DSSCs.
15/17
Fused-Thiazole Heterocycles as Conjugate Spacers
Lorenzo Zani – CNR ISOF – 11/06/2012
UV-Vis absorption spectra of 13 in methanol (●) and CH2Cl2 (▼), and emission spectrum in methanol (○).
Cyclic (full) and Osteryoung square wave (dashed) voltammograms recorded of a CH2Cl2 solution of 13.
Under illumination (―)
Dark (---) J-V characteristic of a DSSC built using 13 as the sensitizer. Main photovoltaic parameters: Voc = 712 mV; Jsc = 7.0 mA/cm2; ff = 0.67; η = 2.5%.
16/17
Dye-Sensitized Solar Cells: Outlook
Lorenzo Zani – CNR ISOF – 11/06/2012
- Measurement and optimization of the photovoltaic performances of all new compounds (8, 9, 14, 15).
- Synthesis and application of new DSSC dyes having different anchoring/acceptor units.
- Exploration of alternative anchoring mechanisms (semiconductor functionalization).
- Start investigations on novel (metall)organic redox couples and electrolyte compositions.
17/17