朝向功能性 Ni-SOD 仿生：实现结构/电子相关性与氧化还原动力学。

Toward functional Ni-SOD biomimetics: achieving a structural/electronic correlation with redox dynamics.

机构信息

Department of Chemistry and Center for Computational Chemistry, The University of Georgia, 1001 Cedar Street, Athens, Georgia 30602, United States.

出版信息

Inorg Chem. 2011 Oct 3;50(19):9216-8. doi: 10.1021/ic201822f. Epub 2011 Sep 2.

DOI:10.1021/ic201822f

PMID:21888395

Abstract

We have prepared and characterized a Ni complex with an N(3)S(2) ligand set (1) that represents the first isolable synthetic model of the reduced form of the Ni-SOD (SOD = superoxide dismutase) active site featuring all relevant donor functionality in the proper spatial distribution. As revealed by X-ray crystallography, the axial py-N donor of 1 does not bind Ni(II) in the solid state or in solution like SOD. Oxidation of 1 provides a disulfide-linked dinuclear species, [{Ni(N(3)S(2))}(2)] (2), which we have isolated and characterized. Moreover, the 1 → 2 conversion is reversible, much like redox cycling in the enzyme.

摘要

我们制备并表征了一种具有 N(3)S(2)配体的 Ni 配合物（1），它代表了 Ni-SOD（SOD=超氧化物歧化酶）活性位点的还原形式的第一个可分离的合成模型，具有适当空间分布的所有相关供体功能。正如 X 射线晶体学所揭示的那样，1 的轴向 py-N 供体在固态或溶液中不与 Ni(II)结合，就像 SOD 一样。1 的氧化提供了一个二硫键连接的双核物种，[{Ni(N(3)S(2))}(2)]（2），我们已经对其进行了分离和表征。此外，1→2 的转化是可逆的，很像酶中的氧化还原循环。