DFT calculations of the electronic structure of the paramagnetic states Ni-A, Ni-B and Ni-C of [NiFe] hydrogenase
DFT calculations of the electronic structure of the paramagnetic states Ni-A, Ni-B and Ni-C of [NiFe] hydrogenase
复制标题
[NiFe]氢化酶顺磁态Ni-A、Ni-B和Ni-C电子结构的DFT计算
DOI：
10.1039/b101508g
复制
发表时间：
2001
影响因子：
3.3
通讯作者：
W. Lubitz
中科院分区：
文献类型：
--
作者：
M. Stein;W. Lubitz
结构
[NiFe]氢化酶活性中心的顺磁性参数和原子自旋密度
报道了Ni-A、Ni-B和Ni-C状态。DFT（BLYP/DZVP）计算的自旋密度分布为：
发现在良好的协议与实验数据时，桥接配体是OH-在Ni-B和O2-
在
酶的Ni-A状态。对于还原的酶（Ni-C），假设氢化物配体桥接还原的酶（Ni-C）。
Ni和Fe原子。所提出的顺磁态的原子自旋密度符合得很好
与实验电子磁共振数据。根据推断的成分，
状态Ni-A，
Ni-B和Ni-C模型
提出了反应机理。
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.