光系统II的水氧化化学
Water oxidation chemistry of photosystem II.
作者信息
Vrettos John S, Brudvig Gary W
机构信息
Department of Chemistry, Yale University, PO Box 208107, New Haven, CT 06520-8107, USA.
出版信息
Philos Trans R Soc Lond B Biol Sci. 2002 Oct 29;357(1426):1395-404; discussion 1404-5, 1419-20. doi: 10.1098/rstb.2002.1136.
Abstract
The O(2)-evolving complex of photosystem II catalyses the light-driven four-electron oxidation of water to dioxygen in photosynthesis. In this article, the steps leading to photosynthetic O(2) evolution are discussed. Emphasis is given to the proton-coupled electron-transfer steps involved in oxidation of the manganese cluster by oxidized tyrosine Z (Y(*)(Z)), the function of Ca(2+) and the mechanism by which water is activated for formation of an O-O bond. Based on a consideration of the biophysical studies of photosystem II and inorganic manganese model chemistry, a mechanism for photosynthetic O(2) evolution is presented in which the O-O bond-forming step occurs via nucleophilic attack on an electron-deficient Mn(V)=O species by a calcium-bound water molecule. The proposed mechanism includes specific roles for the tetranuclear manganese cluster, calcium, chloride, Y(Z) and His190 of the D1 polypeptide. Recent studies of the ion selectivity of the calcium site in the O(2)-evolving complex and of a functional inorganic manganese model system that test key aspects of this mechanism are also discussed.
摘要
光系统II的放氧复合体在光合作用中催化光驱动的水向二氧的四电子氧化反应。本文讨论了光合放氧的步骤。重点关注了氧化型酪氨酸Z（Y(*)(Z)）氧化锰簇所涉及的质子耦合电子转移步骤、Ca(2+)的功能以及水被激活以形成O-O键的机制。基于对光系统II的生物物理研究和无机锰模型化学的考虑，提出了一种光合放氧机制，其中O-O键形成步骤是通过钙结合的水分子对缺电子的Mn(V)=O物种进行亲核攻击而发生的。所提出的机制包括四核锰簇、钙、氯、Y(Z)和D1多肽的His190的特定作用。还讨论了对放氧复合体中钙位点的离子选择性以及测试该机制关键方面的功能性无机锰模型系统的最新研究。
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