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活性位点的氧化状态依赖的结合性质在含有Mo的格式中脱酶

William E Robinson¹, Arnau Bassegoda², Erwin Reisner¹

¹Department of Chemistry, University of Cambridge , Lensfield Road, Cambridge CB2 1EW, U.K.

Journal of the American Chemical Society

|June 22, 2017

概括

酸盐脱酶H (EcFDH-H) 使用氧化状态依赖的抑制剂结合来揭示其催化机制. 这项研究证明了基质直接与结合,澄清了二氧化碳减少和成型氧化途径.

科学领域:

生物化学和酶学生物化学和酶学
生物有机化学生物有机化学
电触媒溶解是一种电触媒.

背景情况:

来自大肠杆菌的含有的甲酸脱酶H (EcFDH-H) 是研究可逆CO2降解成甲酸的关键酶.
关于FDH的精确催化机制,特别是协调在基质结合过程中的作用,仍在讨论中.

研究的目的:

通过检查活性部位的变化如何影响抑制剂结合性质来研究 EcFDH-H 催化机制.
阐明氧化状态在酸盐氧化和二氧化碳减少过程中的基质和抑制剂相互作用中的作用.

主要方法:

用蛋白膜电化学研究 EcFDH-H. 的电化学行为.
时光度测量用于分析不同潜力的基质和抑制剂度效应.
应用了动态建模来解释电化学数据并确定结合机制.

主要成果:

由 EcFDH-H 进行的甲酸盐氧化被各种离子 (N3-, OCN-, SCN-, NO2-, NO3-) 强烈和有竞争力的抑制,而二氧化碳的减少则显示出弱的,非竞争性的抑制.
在催化周期期间,选择性地观察到Mo(VI) =S状态的抑制剂结合,这涉及Mo(VI) =S和Mo(IV) -SH状态之间的循环.
抑制剂结合亲和力强烈依赖于氧化状态和抑制剂的电子捐赠强度,这表明直接与Mo中心结合.

结论:

这项研究提出,在单半氨酸连接体解离后,抑制剂和基质直接与中心结合,从而为催化产生空位.
这些发现为EcFDH-H的甲酸盐氧化和二氧化碳减排的催化机制提供了关键的见解,解决了机制上的模两可.

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