Supervisor
Prof. Marcella Bonchio
e-mail: [email protected] http://www.chimica.unipd.it/NanoMolCat/
tel.: +39 049 827 5670
Title project
Artificial Synzimes in the Oxygen Cycle
1. Objectives, methods & expected results Nature deals with severe kinetic challenges by
adopting very efficient nano-catalytic strategies. The formidable complexity of these processes is
catalyzed by key metallo-enzymes, enabling a cascade of redox transformations while coupling
electron and proton transfers with bond cleavage and forming
reactions. One prominent case is the four electron H2O / O2
cycle, powering our aerobic life on earth, by oxygenic
photosynthesis and its alter-ego found in the mitochondrial
respiration chain. These transformations have therefore a
primary impact in fields of enormous importance for Mankind,
such as the search for renewable solar fuels and the
prevention of neurodegenerative diseases.
This project deals with a bioinspired strategy for the development of new artificial catalysts,
together with the comprehension of their reaction mechanism, for the key transformations of the
H2O / O2 cycle, namely superoxide dismutase (SOD, eq. 1), hydrogen peroxide dismutation
(catalase, CAT eq. 2), water oxidation (WO, eq. 3).
2 O2- + 2 H+ → O2 + H2O2 (SOD, eq. 1)
2 H2O2 → O2 + 2 H2O
(CAT, eq. 2)
2 H2O → O2 + 4 H+ + 4 e- (WO, eq. 3)
The project will consist of (i) synthesis and characterization of metal based complexes, (ii)
investigation of their catalytic activity, (iii) pinpoint of mechanistic outcomes, by taking advantage of
classical physical organic chemistry techniques.
2. Relevant references
Al-Oweini, R.; Sartorel, A.; Bassil, B. S.; Natali, M.; Berardi, S.; Scandola, F.; Kortz, U.; Bonchio,
M. Angew. Chem. Int. Ed., 2014, 126,11364.
Grau, M.; Rigodanza, F.; White, A.J.P.; Sorarù, A.; Carraro, M.; Bonchio, M.; Britovsek, G. Chem.
Commun., 2014, 50, 4607.
Piccinin, S.; Sartorel, A.; Aquilanti, G.; Goldoni, A.; Bonchio, M.; Fabris, S. Proc. Natl. Acad. Sci. U.
S. A. 2013, 110, 4917.
EU COST Action http://www.cost.eu/COST_Actions/cmst/Actions/CM1205