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

被引：21

作者：

Sensi, Matteo ^{[1
,7
]}

Baffert, Carole ^{[1
]}

Greco, Claudio ^{[2
]}

Caserta, Giorgio ^{[3
]}

Gauquelin, Charles ^{[4
]}

Saujet, Laure ^{[5
]}

Fontecave, Marc ^{[3
]}

Roy, Souvik ^{[6
]}

Artero, Vincent ^{[6
]}

Soucaille, Philippe ^{[4
]}

Meynial-Salles, Isabelle ^{[4
]}

Bottin, Herve ^{[5
]}

de Gioia, Luca ^{[7
]}

Fourmond, Vincent ^{[1
]}

Leger, Christophe ^{[1
]}

Bertini, Luca ^{[7
]}

机构：

[1] Aix Marseille Univ, CNRS, UMR 7281, BIP, Marseille, France

[2] Milano Bicocca Univ, Dept Earth & Environm Sci, Piazza Sci 1, I-20126 Milan, Italy

[3] Univ Paris 06, Coll France, Lab Chim Proc Biol, UMR 8229,CNRS, 11 Pl Marcelin Berthelot, F-75231 Paris 05, France

[4] Univ Toulouse, INSA, UPS, INP,LISBP,INRA,UMR792,135 CNRS,UMR 5504, Ave Rangueil, F-31077 Toulouse, France

[5] Univ Paris 11, Inst Biol & Technol Saclay IBITECS, Inst Biol Integrat Cellule I2BC SB2SM, UMR 9198,CEA,CNRS, F-91191 Gif Sur Yvette, France

[6] Univ Grenoble Alpes, Lab Chim & Biol Met, CNRS, CEA, 17 Rue Martyrs, F-38054 Grenoble, France

[7] Univ Milano Bicocca, Dept Biotechnol & Biosci, Piazza Sci 2, I-20126 Milan, Italy

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2016年 / 138卷 / 41期

关键词：

ACTIVE-SITE; ONLY HYDROGENASE; DESULFOVIBRIO-DESULFURICANS; LIGHT SENSITIVITY; CLOSTRIDIUM-PASTEURIANUM; NIFE HYDROGENASE; CARBON-MONOXIDE; INHIBITED FORM; INACTIVATION; COORDINATION;

D O I：

10.1021/jacs.6b06603

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

FeFe hydrogenases catalyze H-2 oxidation and formation at an inorganic active site (the "H-cluster"), which consists of a [Fe-2(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 H-2. Here, we explore in great detail the reactivity of the excited states of the H-duster 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 could be used for probing other, aspects of the photoreactivity of the H-cluster.

引用

页码：13612 / 13618

页数：7

共 52 条

[1] ELECTRONIC-STRUCTURE CALCULATIONS ON WORKSTATION COMPUTERS - THE PROGRAM SYSTEM TURBOMOLE [J].

AHLRICHS, R ;

BAR, M ;

HASER, M ;

HORN, H ;

KOLMEL, C .

CHEMICAL PHYSICS LETTERS, 1989, 162 (03) :165-169

[2] The active site of the [FeFe]-hydrogenase from Desulfovibrio desulfuricans.: 1.: Light sensitivity and magnetic hyperfine interactions as observed by electron paramagnetic resonance [J].

Albracht, SPJ ;

Roseboom, W ;

Hatchikian, EC .

JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY, 2006, 11 (01) :88-101

[3] Covalent Attachment of FeFe Hydrogenases to Carbon Electrodes for Direct Electron Transfer [J].

Baffert, Carole ;

Sybirna, Kateryna ;

Ezanno, Pierre ;

Lautier, Thomas ;

Hajj, Viviane ;

Meynial-Salles, Isabelle ;

Soucaille, Philippe ;

Bottin, Herve ;

Leger, Christophe .

ANALYTICAL CHEMISTRY, 2012, 84 (18) :7999-8005

[4] CO Disrupts the Reduced H-Cluster of FeFe Hydrogenase. A Combined DFT and Protein Film Voltammetry Study [J].

Baffert, Carole ;

Bertini, Luca ;

Lautier, Thomas ;

Greco, Claudio ;

Sybirna, Kateryna ;

Ezanno, Pierre ;

Etienne, Emilien ;

Soucaille, Philippe ;

Bertrand, Patrick ;

Bottin, Herve ;

Meynial-Salles, Isabelle ;

De Gioia, Luca ;

Leger, Christophe .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (07) :2096-2099

[5] Biomimetic assembly and activation of [FeFe]-hydrogenases [J].

Berggren, G. ;

Adamska, A. ;

Lambertz, C. ;

Simmons, T. R. ;

Esselborn, J. ;

Atta, M. ;

Gambarelli, S. ;

Mouesca, J. -M. ;

Reijerse, E. ;

Lubitz, W. ;

Happe, T. ;

Artero, V. ;

Fontecave, M. .

NATURE, 2013, 499 (7456) :66-+

[6] TDDFT Modeling of the CO-Photolysis of Fe2(S2C3H6)(CO)6' a Model of the [FeFe]-Hydrogenase Catalytic Site [J].

Bertini, Luca ;

Greco, Claudio ;

Fantucci, Piercarlo ;

De Gioia, Luca .

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 2014, 114 (13) :851-861

[7] Excited State Properties of Diiron Dithiolate Hydrides: Implications in the Unsensitized Photocatalysis of H2 Evolution [J].

Bertini, Luca ;

Fantucci, Piercarlo ;

De Gioia, Luca ;

Zampella, Giuseppe .

INORGANIC CHEMISTRY, 2013, 52 (17) :9826-9841

[8] CO Affinity and Bonding Properties of [FeFe] Hydrogenase Active Site Models. A DFT Study [J].

Bertini, Luca ;

Greco, Claudio ;

Bruschi, Maurizio ;

Fantucci, Piercarlo ;

De Gioia, Luca .

ORGANOMETALLICS, 2010, 29 (09) :2013-2025

[9] Structural and electronic properties of the [FeFe] hydrogenase H-cluster in different redox and protonation states. A DFT investigation [J].

Bruschi, Maurizio ;

Greco, Claudio ;

Fantucci, Piercarlo ;

De Gioia, Luca .

INORGANIC CHEMISTRY, 2008, 47 (13) :6056-6071

[10] Functionally Relevant Interplay between the Fe4S4 Cluster and CN- Ligands in the Active Site of [FeFe]-Hydrogenases [J].

Bruschi, Maurizio ;

Greco, Claudio ;

Bertini, Luca ;

Fantucci, Piercarlo ;

Ryde, Ulf ;

De Gioia, Luca .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (14) :4992-+

← 1 2 3 4 5 6 →