Cobaloxime-Based Artificial Hydrogenases

被引：76

作者：

Bacchi, Marine ^{[1
]}

Berggren, Gustav ^{[1
]}

Niklas, Jens ^{[2
]}

Veinberg, Elias ^{[3
]}

Mara, Michael W. ^{[4
]}

Shelby, Megan L. ^{[4
]}

Poluektov, Oleg G. ^{[2
]}

Chen, Lin X. ^{[2
,4
]}

Tiede, David M. ^{[2
]}

Cavazza, Christine ^{[1
]}

Field, Martin J. ^{[3
]}

Fontecave, Marc ^{[1
,5
]}

Artero, Vincent ^{[1
]}

机构：

[1] Univ Grenoble Alpes, Lab Chem & Biol Met, CNRS, CEA, F-38000 Grenoble, France

[2] Argonne Natl Lab, Chem Sci & Engn Div, Argonne, IL 60439 USA

[3] Univ Grenoble Alpes, CEA 5075, UMR CNRS, DYNAMO,DYNAMOP,Inst Biol Struct, F-38000 Grenoble, France

[4] Northwestern Univ, Dept Chem, Evanston, IL 60208 USA

[5] Univ Paris 06, CNRS, Coll France, Lab Chim Proc Biol,UMR 8229, F-75005 Paris, France

来源：

INORGANIC CHEMISTRY | 2014年 / 53卷 / 15期

关键词：

PHOTOSYSTEM-I; MOLECULAR ELECTROCATALYSTS; FUNCTIONAL MODELS; OXYGEN CARRIERS; H-2; EVOLUTION; DESIGN; COBALT; COMPLEXES; CATALYST; MECHANISM;

D O I：

10.1021/ic501014c

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Cobaloximes are popular H-2 evolution molecular catalysts but have so far mainly been studied in nonaqueous conditions. We show here that they are also valuable for the design of artificial hydrogenases for application in neutral aqueous solutions and report on the preparation of two well-defined biohybrid species via the binding of two cobaloxime moieties, {Co(dmgH)(2)} and {Co(dmgBF(2))(2)} (dmgH(2) = dimethylglyoxime), to apo Sperm-whale myoglobin (SwMb). All spectroscopic data confirm that the cobaloxime moieties are inserted within the binding pocket of the SwMb protein and are coordinated to a histidine residue in the axial position of the cobalt complex, resulting in thermodynamically stable complexes. Quantum chemical/molecular mechanical docking calculations indicated a coordination preference for His93 over the other histidine residue (His64) present in the vicinity. Interestingly, the redox activity of the cobalt centers is retained in both biohybrids, which provides them with the catalytic activity for H-2 evolution near-neutral aqueous conditions. in

引用

页码：8071 / 8082

页数：12

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