在酶催化醇和胺氧化的机理研究中结合溶剂同位素效应与底物同位素效应。
Combining solvent isotope effects with substrate isotope effects in mechanistic studies of alcohol and amine oxidation by enzymes.
作者信息
Fitzpatrick Paul F
机构信息
Department of Biochemistry, University of Texas Health Science Center, San Antonio, TX 78212, USA.
出版信息
Biochim Biophys Acta. 2015 Nov;1854(11):1746-55. doi: 10.1016/j.bbapap.2014.10.020. Epub 2014 Oct 30.
Abstract
Oxidation of alcohols and amines is catalyzed by multiple families of flavin- and pyridine nucleotide-dependent enzymes. Measurement of solvent isotope effects provides a unique mechanistic probe of the timing of the cleavage of the OH and NH bonds, necessary information for a complete description of the catalytic mechanism. The inherent ambiguities in interpretation of solvent isotope effects can be significantly decreased if isotope effects arising from isotopically labeled substrates are measured in combination with solvent isotope effects. The application of combined solvent and substrate (mainly deuterium) isotope effects to multiple enzymes is described here to illustrate the range of mechanistic insights that such an approach can provide. This article is part of a Special Issue entitled: Enzyme Transition States from Theory and Experiment.
摘要
醇类和胺类的氧化由多个黄素和吡啶核苷酸依赖性酶家族催化。溶剂同位素效应的测量为OH键和NH键断裂的时间提供了独特的机理探针，这是完整描述催化机制所需的信息。如果将同位素标记底物产生的同位素效应与溶剂同位素效应结合起来测量，那么在解释溶剂同位素效应时固有的模糊性就会显著降低。本文描述了溶剂和底物（主要是氘）同位素效应的组合在多种酶中的应用，以说明这种方法所能提供的一系列机理见解。本文是名为“理论与实验中的酶过渡态”的特刊的一部分。
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