脉冲 EPR 光谱和 DFT 计算对“困难”核的亚硫酸氧化酶机制的启示。
Implications for the mechanism of sulfite oxidizing enzymes from pulsed EPR spectroscopy and DFT calculations for "difficult" nuclei.
机构信息
Department of Chemistry and Biochemistry, University of Arizona, Tucson, Arizona 85721-0041, USA.
出版信息
Faraday Discuss. 2011;148:249-67; discussion 299-314. doi: 10.1039/c004404k.
Abstract
The catalytic mechanisms of sulfite oxidizing enzymes (SOEs) have been investigated by multi-frequency pulsed EPR measurements of "difficult" magnetic nuclei (35.37Cl, 33S, 17O) associated with the Mo(v) center. Extensive DFT calculations have been used to relate the experimental magnetic resonance parameters of these nuclei to specific active site structures. This combined spectroscopic and computational approach has provided new insights concerning the structure/function relationships of the active sites of SOEs, including: (i) the exchange of oxo ligands; (ii) the nature of the blocked forms; and (iii) the role of Cl- in low pH forms.
摘要
通过对与 Mo(v) 中心相关的“困难”磁性核（35.37Cl、33S、17O）的多频脉冲 EPR 测量，研究了亚硫酸盐氧化酶（SOE）的催化机制。广泛的 DFT 计算被用于将这些核的实验磁共振参数与特定的活性位点结构联系起来。这种组合的光谱和计算方法为 SOE 的活性位点的结构/功能关系提供了新的见解，包括：（i）氧配体的交换；（ii）受阻形式的性质；和（iii）Cl-在低 pH 形式中的作用。
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