DFT calculations of the electronic structure of the paramagnetic states Ni-A, Ni-B and Ni-C of [NiFe] hydrogenase

被引：71

作者：

Stein, M ^{[1
]}

Lubitz, W ^{[1
]}

机构：

[1] Tech Univ Berlin, Inst Chem, Max Volmer Lab Biophys Chem, D-10623 Berlin, Germany

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2001年 / 3卷 / 13期

关键词：

D O I：

10.1039/b101508g

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Structural parameters and atomic spin densities of the active centre of [NiFe] hydrogenases in the paramagnetic states Ni-A, Ni-B and Ni-C are reported. The DFT (BLYP/DZVP) calculated spin density distribution is found to be in good agreement with experimental data when the bridging ligand is OH- in the Ni-B and O2- in the Ni-A states of the enzyme. For the reduced enzyme (Ni-C) it is postulated that a hydride ligand bridges the Ni and Fe atoms. The atomic spin densities for the proposed paramagnetic states are in good agreement with experimental electron magnetic resonance data. Based on the deduced composition of the states Ni-A, Ni-B and Ni-C a model for the reaction mechanism is proposed.

引用

页码：2668 / 2675

页数：8

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