Application of the second rule of transient-state kinetic isotope effects to an enzymatic mechanism.
Application of the second rule of transient-state kinetic isotope effects to an enzymatic mechanism.
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瞬态动力学同位素效应的第二条规则在酶促机制中的应用。
DOI：
10.1021/bi901514h
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发表时间：
2009
期刊：
影响因子：
2.9
通讯作者：
Tabanor,Kayann
中科院分区：
文献类型：
--
作者：
Fisher,HarveyF;Maniscalco,StevenJ;Tally,Jon;Tabanor,Kayann
瞬态动力学方法实时地揭示了中间体的形成和随后的相互转化。然而，与不太直接但基于稳定状态的代数算法相比，它在酶和其他复杂化学机制的机制解决方面的潜力受到了严重限制，因为缺乏严格和适用的理论基础。最近建立了三个严格推导的适用于实际多步反应的瞬态动力学基本“规则”，我们在这里提出了非常违反直觉的“第二规则”的成功应用，以解决苯丙氨酸脱氢酶催化反应的机制。
The transient-state kinetic approach reveals the formation and subsequent interconversions of intermediates in real time. Its potential for the mechanistic resolution of enzymatic and other complex chemical mechanisms has been severely limited however by the lack of a rigorous and applicable theoretical basis in contrast to that of the less direct but soundly based algebraic algorithms of the steady-state approach. Having recently established three rigorously derived fundamental “rules” of transient-state kinetics applicable to realistic multiple step reactions, we present here the successful application of the very counterintuitive “second rule” to the resolution of the mechanism of thel-phenylalanine dehydrogenase catalyzed reaction.