Chemically gated electron transfer. A means of accelerating and regulating rates of biological electron transfer.
Chemically gated electron transfer. A means of accelerating and regulating rates of biological electron transfer.
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化学门控电子转移。
DOI：
10.1021/bi026812k
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发表时间：
2002
期刊：
影响因子：
2.9
通讯作者：
Davidson,VictorL
中科院分区：
文献类型：
--
作者：
Davidson,VictorL
由于 ET 距离长且驱动力低，长程蛋白质电子转移 [ET] 反应可能相对较慢。通过使用绝热化学反应来激活系统以实现快速 ET，可以显着提高此类非绝热反应的速率。讨论了三个这样的例子；固氮酶、丙酮酸：铁氧还蛋白氧化还原酶和甲胺脱氢酶-氨基蓝蛋白复合物。在每个示例中，更快激活的 ET 反应受到化学反应的门控（即速率限制）。然而，在没有化学活化的情况下，反应速率仍然比非门控真正的 ET 反应高几个数量级。提出了模型来描述 ET 理论背景下的激活机制，并讨论了这种化学门控 ET 与代谢调节的相关性。
Long-range protein electron transfer [ET] reactions may be relatively slow because of long ET distance and low driving force. It is possible to dramatically increase the rate of such nonadiabatic reactions by using an adiabatic chemical reaction to activate the system for rapid ET. Three such examples are discussed; nitrogenase, pyruvate:ferredoxin oxidoreductase, and the methylamine dehydrogenase−amicyanin complex. In each example, the faster activated ET reaction is gated (i.e., rate-limited) by the chemical reaction. However, the reaction rate is still orders of magnitude greater than that of the ungated true ET reaction in the absence of chemical activation. Models are presented to describe the mechanisms of activation in the context of ET theory, and the relevance of such chemically gated ET to the regulation of metabolism is discussed.