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首页> 外文期刊>Molecules >The Application of Transient-State Kinetic Isotope Effects to the Resolution of Mechanisms of Enzyme-Catalyzed Reactions
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The Application of Transient-State Kinetic Isotope Effects to the Resolution of Mechanisms of Enzyme-Catalyzed Reactions

机译：瞬态动力学同位素效应在酶催化反应机理解析中的应用

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摘要

Much of our understanding of the mechanisms of enzyme-catalyzed reactions is based on steady-state kinetic studies. Experimentally, this approach depends solely on the measurement of rates of free product appearance (d[P]/dt), a mechanistically and mathematically complex entity. Despite the ambiguity of this observed parameter, the method’s success is due in part to the elaborate rigorously derived algebraic theory on which it is based. Transient-state kinetics, on the other hand, despite its ability to observe the formation of intermediate steps in real time, has contributed relatively little to the subject due in, some measure, to the lack of such a solid mathematical basis. Here we discuss the current state of existing transient-state theory and the difficulties in its realistic application to experimental data. We describe a basic analytic theory of transient-state kinetic isotope effects in the form of three novel fundamental rules. These rules are adequate to define an extended mechanism, locating the isotope-sensitive step and identifying missing steps from experimental data. We demonstrate the application of these rules to resolved component time courses of the phenylalanine dehydrogenase reaction, extending the previously known reaction by one new prehydride transfer step and two new post hydride transfer steps. We conclude with an assessment of future directions in this area.
机译：我们对酶催化反应机理的大部分理解是基于稳态动力学研究。从实验上讲，这种方法仅取决于机械和数学上复杂的自由产品外观速率（d [P] / dt）的测量。尽管此观测参数含糊不清，但该方法的成功部分归因于它所基于的精心精心衍生的代数理论。另一方面，尽管瞬态动力学能够实时观察中间步骤的形成，但由于缺乏这种可靠的数学基础，因此它对受试者的贡献相对较小。在这里，我们讨论现有瞬态理论的现状以及将其实际应用于实验数据的困难。我们以三个新的基本规则的形式描述了瞬态动力学同位素效应的基本分析理论。这些规则足以定义扩展的机制，确定同位素敏感的步骤并从实验数据中识别出缺少的步骤。我们证明了这些规则对苯丙氨酸脱氢酶反应的组分时间进程的应用，通过一个新的预氢化物转移步骤和两个新的后氢化物转移步骤扩展了先前已知的反应。最后，我们评估了该领域的未来发展方向。

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