Implications for the mechanism of sulfite oxidizing enzymes from pulsed EPR spectroscopy and DFT calculations for "difficult'' nuclei
Implications for the mechanism of sulfite oxidizing enzymes from pulsed EPR spectroscopy and DFT calculations for "difficult'' nuclei
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DOI：
10.1039/c004404k
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发表时间：
2011-01-01
影响因子：
3.4
通讯作者：
Klein, Eric L.
中科院分区：
文献类型：
--
作者：
Enemark, John H.;Raitsimring, Arnold M.;Klein, Eric L.
通过对与钼（V）中心相关的“难测”磁性核（氯 - 35、氯 - 37、硫 - 33、氧 - 17）进行多频脉冲电子顺磁共振测量，研究了亚硫酸盐氧化酶（SOEs）的催化机制。广泛的密度泛函理论（DFT）计算已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相关联。这种光谱学和计算相结合的方法为亚硫酸盐氧化酶活性位点的结构/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；以及（iii）氯 - 1在低pH形式中的作用。
The catalytic mechanisms of sulfite oxidizing enzymes (SOEs) have been investigated by multi-frequency pulsed EPR measurements of "difficult'' magnetic nuclei (Cl-35,Cl-37, S-33, O-17) 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-1 in low pH forms.