当同位素阿仑尼乌斯前因子（A(H)/A(D)）为1时氢隧穿的实验证据。
Experimental evidence for hydrogen tunneling when the isotopic arrhenius prefactor (A(H)/A(D)) is unity.
作者信息
Sharma Sudhir C, Klinman Judith P
机构信息
Department of Chemistry and Molecular and Cell Biology, University of California, Berkeley, California 94720-1460, USA.
出版信息
J Am Chem Soc. 2008 Dec 31;130(52):17632-3. doi: 10.1021/ja806354w.
Abstract
The temperature dependence of the kinetic isotope effect (KIE) is one of the major tools used for the investigation of hydrogen tunneling in condensed phase. Hydrogen transfer reactions displaying isotopic Arrhenius prefactor ratios (A(H)/A(D)) of unity are generally ascribed to a semiclassical mechanism. Here, we have identified a double mutant of soybean lipoxygenase (SLO-1, an enzyme previously shown to follow quantum mechanical hydrogen tunneling), that displays an A(H)/A(D) of unity and highly elevated (nonclassical) KIEs. This observation highlights the shortcoming of assigning a hydrogen transfer reaction to a semiclassical model based solely on an Arrhenius prefactor ratio.
摘要
动力学同位素效应（KIE）的温度依赖性是研究凝聚相中氢隧穿的主要工具之一。显示同位素阿仑尼乌斯前因子比（A(H)/A(D)）为1的氢转移反应通常被归因于半经典机制。在这里，我们鉴定出一种大豆脂氧合酶（SLO-1，一种先前已证明遵循量子力学氢隧穿的酶）的双突变体，其显示出A(H)/A(D)为1且具有高度升高的（非经典）KIEs。这一观察结果突出了仅基于阿仑尼乌斯前因子比将氢转移反应归为半经典模型的缺点。
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