Oxomanganese complexes for natural and artificial photosynthesis.
Oxomanganese complexes for natural and artificial photosynthesis.
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DOI：
10.1016/j.cbpa.2012.03.003
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发表时间：
2012-04
影响因子：
7.8
通讯作者：
Batista, Victor S.
中科院分区：
文献类型：
--
作者：
Rivalta, Ivan;Brudvig, Gary W.;Batista, Victor S.
光系统II（PSII）的放氧复合物（OEC）是一种氧锰复合物，催化水分解为O2，质子和电子。最近在X射线晶体学的突破解决了立方OEC结构在1.9纳米分辨率，激发了显着的兴趣，在结构/功能关系的研究。本文综述了近年来OEC的研究进展，并沿着合成了用于人工光合作用的氧锰配合物。量子力学/分子力学混合方法已经能够模拟OEC的S1状态，包括最近的X射线数据提出的连接，其中D170桥接CaMn 3核心外的Ca和Mn中心。分子动力学和蒙特卡罗模拟已经探索了氯化物的结构/功能作用，表明它调节D 61和K317之间的静电相互作用，这可能对质子提取至关重要。此外，合成的氧锰配合物，包括[H2O（terpy）MnIII（μ-O）2 MnIV（terpy）OH 2]3+（1，terpy= 2，2 ′：6′，2 ″-terpyridine）配合物的结构研究，提供了在析氧过程中与Mn催化剂紧密接触的羧酸基团的机理影响的有价值的见解。1到TiO 2的共价连接已经通过直接沉积和通过使用有机发色团连接子实现。通过可见光激发，1与TiO 2的（III，IV）氧化态可以提前到（IV，IV），导致光诱导界面电子转移。这些研究与基于廉价材料的人工光合装置的开发特别相关。
The oxygen-evolving complex (OEC) of Photosystem II (PSII), is an oxomanganese complex that catalyzes water-splitting into O2, protons and electrons. Recent breakthroughs in X-ray crystallography have resolved the cuboidal OEC structure at 1.9 Å resolution, stimulating significant interest in studies of structure/function relations. This article summarizes recent advances on studies of the OEC along with studies of synthetic oxomanganese complexes for artificial photosynthesis. Quantum mechanics/molecular mechanics hybrid methods have enabled modeling the S1 state of the OEC, including the ligation proposed by the most recent X-ray data where D170 is bridging Ca and the Mn center outside the CaMn3 core. Molecular dynamics and Monte Carlo simulations have explored the structural/functional roles of chloride, suggesting that it regulates the electrostatic interactions between D61 and K317 that might be critical for proton abstraction. Furthermore, structural studies of synthetic oxomanganese complexes, including the [H2O(terpy)MnIII(μ-O)2MnIV(terpy)OH2]3+ (1, terpy=2,2′:6′,2″-terpyridine) complex, provided valuable insights on the mechanistic influence of carboxylate moieties in close contact with the Mn catalyst during oxygen evolution. Covalent attachment of 1 to TiO2 has been achieved via direct deposition and by using organic chromophoric linkers. The (III,IV) oxidation state of 1 attached to TiO2 can be advanced to (IV,IV) by visible-light photoexcitation, leading to photoinduced interfacial electron transfer. These studies are particularly relevant to the development of artificial photosynthetic devices based on inexpensive materials.
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影响因子：
2.9
作者：
Luber, Sandra;Rivalta, Ivan;Umena, Yasufumi;Kawakami, Keisuke;Shen, Jian-Ren;Kamiya, Nobuo;Brudvig, Gary W.;Batista, Victor S.
通讯作者：
Batista, Victor S.
影响因子：
3.3
作者：
KOK, B;FORBUSH, B;MCGLOIN, M
通讯作者：
MCGLOIN, M
影响因子：
32.5
作者：
Li, Gonghu;Sproviero, Eduardo M.;Batista, Victor S.
通讯作者：
Batista, Victor S.
影响因子：
16.8
作者：
Guskov, Albert;Kern, Jan;Saenger, Wolfram
通讯作者：
Saenger, Wolfram
影响因子：
3.3
作者：
Dau, H;Liebisch, P;Haumann, M
通讯作者：
Haumann, M