FeFe hydrogenases catalyze H2 oxidation and formation at an inorganic active site (the "H-cluster"), which consists of a [Fe2(CO)3(CN)2(dithiomethylamine)] subcluster covalently attached to a Fe4S4 subcluster. This active site is photosensitive: visible light has been shown to induce the release of exogenous CO (a reversible inhibitor of the enzyme), shuffle the intrinsic CO ligands, and even destroy the H-cluster. These reactions must be understood because they may negatively impact the use of hydrogenase for the photoproduction of H2. Here, we explore in great detail the reactivity of the excited states of the H-cluster under catalytic conditions by examining, both experimentally and using TDDFT calculations, the simplest photochemical reaction: the binding and release of exogenous CO. A simple dyad model can be used to predict which excitations are active. This strategy could be used for probing other aspects of the photoreactivity of the H-cluster.

Sensi, M., Baffert, C., Greco, C., Caserta, G., Gauquelin, C., Saujet, L., et al. (2016). Reactivity of the Excited States of the H-Cluster of FeFe Hydrogenases. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 138(41), 13612-13618 [10.1021/jacs.6b06603].

Reactivity of the Excited States of the H-Cluster of FeFe Hydrogenases

SENSI, MATTEO
Primo
;
GRECO, CLAUDIO;DE GIOIA, LUCA;BERTINI, LUCA
Ultimo
2016

Abstract

FeFe hydrogenases catalyze H2 oxidation and formation at an inorganic active site (the "H-cluster"), which consists of a [Fe2(CO)3(CN)2(dithiomethylamine)] subcluster covalently attached to a Fe4S4 subcluster. This active site is photosensitive: visible light has been shown to induce the release of exogenous CO (a reversible inhibitor of the enzyme), shuffle the intrinsic CO ligands, and even destroy the H-cluster. These reactions must be understood because they may negatively impact the use of hydrogenase for the photoproduction of H2. Here, we explore in great detail the reactivity of the excited states of the H-cluster under catalytic conditions by examining, both experimentally and using TDDFT calculations, the simplest photochemical reaction: the binding and release of exogenous CO. A simple dyad model can be used to predict which excitations are active. This strategy could be used for probing other aspects of the photoreactivity of the H-cluster.
Si
Articolo in rivista - Articolo scientifico
Scientifica
Hydrogen, hydrogenase
English
Sensi, M., Baffert, C., Greco, C., Caserta, G., Gauquelin, C., Saujet, L., et al. (2016). Reactivity of the Excited States of the H-Cluster of FeFe Hydrogenases. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 138(41), 13612-13618 [10.1021/jacs.6b06603].
Sensi, M; Baffert, C; Greco, C; Caserta, G; Gauquelin, C; Saujet, L; Fontecave, M; Roy, S; Artero, V; Soucaille, P; Meynial Salles, I; Bottin, H; DE GIOIA, L; Fourmond, V; Léger, C; Bertini, L
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/10281/132740
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