Proton-coupled electron flow in protein redox machines.

Proton-coupled electron flow in protein redox machines.
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DOI:
10.1021/cr100182b
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发表时间:
2010-12-08
期刊:
影响因子:
62.1
通讯作者:
Gray, Harry B.
Gray, Harry B.
中科院分区:
化学1区
文献类型:
--
作者:
Dempsey, Jillian L.;Winkler, Jay R.;Gray, Harry B.

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电子转移(ET)反应是生物氧化还原过程中的基本步骤。呼吸是一个恰当的例子:至少需要15个ET反应才能从NADH中提取还原当量,将它们存款在O2中,并产生驱动ATP合成的电化学质子梯度。1-10这些反应中的大多数涉及嵌入折叠蛋白质内部的弱耦合氧化还原辅因子(ET距离> 10 μ m)之间的量子隧穿。在这里,我们回顾实验结果,揭示了控制这些遥远的ET事件的因素。我们还回顾了敏化剂修饰的铜蛋白光系统的工作,其中多步电子隧穿(跳跃)通过干预色氨酸是数量级快于相应的单步ET reaction.If质子转移耦合到ET事件,我们指的过程作为质子耦合ET,或PCET,一个由Huynh和Meyer在1981年引入的术语。11在这里,我们专注于两个蛋白质氧化还原机器,光系统II和核糖核苷酸还原酶,其中涉及酪氨酸的PCET过程被认为是功能的关键。相关的酪氨酸模型系统也将进行讨论。
Electron transfer (ET) reactions are fundamental steps in biological redox processes. Respiration is a case in point: at least 15 ET reactions are required to take reducing equivalents from NADH, deposit them in O2, and generate the electrochemical proton gradient that drives ATP synthesis. 1-10 Most of these reactions involve quantum tunneling between weakly coupled redox cofactors (ET distances> 10 Å) embedded in the interiors of folded proteins. Here we review experimental findings that have shed light on the factors controlling these distant ET events. We also review work on a sensitizer-modified copper protein photosystem in which multistep electron tunneling (hopping) through an intervening tryptophan is orders of magnitude faster than the corresponding single-step ET reaction.If proton transfers are coupled to ET events, we refer to the processes as proton coupled ET, or PCET, a term introduced by Huynh and Meyer in 1981. 11 Here we focus on two protein redox machines, photosystem II and ribonucleotide reductase, where PCET processes involving tyrosines are believed to be critical for function. Relevant tyrosine model systems also will be discussed.
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影响因子: 56.9
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影响因子: 15
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