Cytochrome P450: The Active Oxidant and Its Spectrum
Cytochrome P450: The Active Oxidant and Its Spectrum
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DOI：
10.1021/ic902062d
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发表时间：
2010-04-19
影响因子：
4.6
通讯作者：
Green, Michael T.
中科院分区：
文献类型：
--
作者：
Rittle, Jonathan;Younker, Jarod M.;Green, Michael T.
本次论坛重点讨论 P450 催化中难以捉摸的氧化中间体的性质。这个物种的身份再次成为有争议的话题。最近有报道称，激光闪光光解（LFP）可用于定量生成P450化合物I（P450-I）。 LFP 生成的中间体与底物反应的动力学分析表明化合物 I 不是 P450 催化中的活性氧化剂。我们通过分析 LFP 生成的中间体的紫外/可见光谱来评估这些说法。采用奇异值分解和目标测试技术，以模型无关的方式从P450与间氯过苯甲酸反应的停流数据中获得P450-I的光谱。结果表明，LFP 生成的光谱与 P450-I 光谱没有相似之处。人们可能会得出这样的结论：LFP 生成的中间体不是 P450-I。
This Forum focuses on the nature of the elusive oxidizing intermediate in P450 catalysis. The identity of this species has reemerged as a topic of contentious debate. It was recently reported that laser flash photolysis (LFP) can be used to generate P450 compound I (P450-I) quantitatively. Kinetic analyses of the reaction of the LFP-generated intermediate with substrates have been suggested to indicate that compound I is not the active oxidant in P450 catalysis. We evaluate these claims via an analysis of the UV/visible spectrum of the LFP-generated intermediate. The techniques of singular value decomposition and target testing are used to obtain the spectrum of P450-I in a model-independent manner from stopped-flow data of the reaction of P450 with m-chloroperbenzoic acid. It is shown that the LFP-generated spectrum bears no similarity to the P450-I spectrum. One may conclude that the LFP-generated intermediate is not P450-I.