Theory of chemical bonds in metalloenzymes XXII: a concerted bond-switching mechanism for the oxygen–oxygen bond formation coupled with one electron transfer for water oxidation in the oxygen-evolving complex of photosystem II

ABSTRACT

QM(UB3LYP)/MM(AMBER) calculations were performed for the locations of the transition structure (TS) of the oxygen–oxygen (O–O) bond formation in the S₄ state of the oxygen-evolving complex (OEC) of photosystem II (PSII). The natural orbital (NO) analysis of the broken-symmetry (BS) solutions was also performed to elucidate the nature of the chemical bonds at TS on the basis of several chemical indices defined by the occupation numbers of NO. The computational results revealed a concerted bond switching (CBS) mechanism for the oxygen–oxygen bond formation coupled with the one-electron transfer (OET) for water oxidation in OEC of PSII. The orbital interaction between the σ-HOMO of the Mn(IV)₄–O₍₅₎ bond and the π*-LUMO of the Mn(V)₁=O₍₆₎ bond plays an important role for the concerted O–O bond formation for water oxidation in the CaMn₄O₆ cluster of OEC of PSII. One electron transfer (OET) from the π-HOMO of the Mn(V)₁=O₍₆₎ bond to the σ*-LUMO of the Mn(IV)₄–O₍₅₎ bond occurs for the formation of electron transfer diradical, where the generated anion radical [Mn(IV)₄–O₍₅₎]^-? part is relaxed to the ?Mn(III)₄?…?O₍₅₎^- structure and the cation radical [O₍₆₎=Mn(V)₁]⁺ ? part is relaxed to the ⁺O₍₆₎–Mn(IV)₁? structure because of the charge-spin separation for the electron-and hole-doped Mn–oxo bonds. Therefore, the local spins are responsible for the one-electron reductions of Mn(IV)₄->Mn(III)₄ and Mn(V)₁->Mn(IV)₁. On the other hand, the O₍₅₎^- and O₍₆₎⁺ sites generated undergo the O–O bond formation in the CaMn₄O₆ cluster. The Ca(II) ion in the cubane- skeleton of the CaMn₄O₆ cluster assists the above orbital interactions by the lowering of the orbital energy levels of π*-LUMO of Mn(V)₁=O₍₆₎ and σ*-LUMO of Mn(IV)₄–O₍₅₎, indicating an important role of its Lewis acidity. Present CBS mechanism for the O–O bond formation coupled with one electron reductions of the high-valent Mn ions is different from the conventional radical coupling (RC) and acid-base (AB) mechanisms for water oxidation in artificial and native photosynthesis systems. The proton-coupled electron transfer (PC-OET) mechanism for the O–O bond formation is also touched in relation to the CBS-OET mechanism.     

Azobenzene‐Functionalized Cage Silsesquioxanes as Inorganic–Organic Hybrid,Photoresponsive, Nanoscale,Building Blocks

Mono‐ and octa‐azobenzene‐functionalized cage silsesquioxanes were easily synthesized by the reaction of 4‐bromoazobenzene with monovinyl‐substituted octasilsesquioxane and cubic octavinylsilsesquioxane through the Heck coupling reaction. Excited‐state energies obtained from time‐dependent density functional theory (TDDFT) and the CAM‐B3LYP functional correlate very well with experimental trans–cis photoisomerization results from UV/Vis spectroscopy. These azobenzene‐functionalized cages exhibit good thermal stability and are fluorescent with maximum emission at approximately 400 nm, making them potential materials for blue‐light emission.     

两个DEA的逆问题的解法的探讨

文[1]提出了两个DEA的逆问题，并用搜索法来解．而本文根据所证的定理，对每个问题一般只要解二、三个线性规划问题就能得到答案．     

用DDM实现分布式三维虚拟环境

介绍了HLA中数据分发管理(DDM)的过滤原理;研究分析了目前几种实现DDM过滤机制的方法及其存在的问题,并提出一种简单易行的DDM实现策略,以实现三维虚拟环境的分布式,来提高它的响应速度.     

N-烯丙基-N''''-(对苯磺酸钠)硫脲的合成及分析应用进展

本文评述了一种新的硫脲试剂N-烯丙基-N'-(对苯磺酸钠)硫脲的合成、性质及其在定性分析、光度分析、电化学分析中的应用进展,展望了今后的研究方向.引用文献20篇.     

数字电视机顶盒综述

在介绍数字电视机项盒的定义、功能及分类的基础上，着重探讨了数字电视机顶盒的软、硬件结构以及该产品的市场前景等问题。     

集成电路设计产业产品创新趋势研究——国际片上系统（SOC）IP核发展现状及对策分析

基于国际集成电路设计产业的分析，系统阐述了国际SOCIP核的发展状况，指出SOC设计将是集成电路设计企业技术创新的发展方向。提出了一些国际SOCIP核发展的对策，包括口核标准化、SOC技术平台开发及加强与Foundry的合作。     

Rigidity and flexibility of virtual polytopes

All 3-dimensional convex polytopes are known to be rigid. Still their Minkowski differences (virtual polytopes) can be flexible with any finite freedom degree. We derive some sufficient rigidity conditions for virtual polytopes and present some examples of flexible ones. For example, Bricard's first and second flexible octahedra can be supplied by the structure of a virtual polytope.     

乙酰胆碱对人胃粘膜上皮细胞和胃腺癌细胞内Ca2+、Mg2+浓度的影响

目的:探讨乙酰胆碱对人胃粘膜上皮细胞和胃腺癌细胞内Ca2 、Mg2 浓度的影响。方法:利用大型生化分析仪,检测了乙酰胆碱作用后培养的人胃粘膜上皮细胞和胃腺癌细胞内Ca2 、Mg2 的浓度。结果:与正常胃粘膜上皮细胞比较,胃腺癌细胞内Ca2 、Mg2 浓度偏低(P>0 01)。在乙酰胆碱作用下,胃粘膜上皮细胞内Ca2 浓度升高(P<0 01),Mg2 浓度降低(P<0 01);胃腺癌细胞仅有Ca2 浓度升高(P<0 05),Mg2 浓度无变化。阿托品能阻断乙酰胆碱的作用(P<0 05)。结论:乙酰胆碱对胃粘膜上皮细胞和胃腺癌细胞的作用是通过毒蕈碱受体实现的。     

关于图的第二特征标R2(G)

对任意图G，h(G，x)表示图G的伴随多项式，R2(G)表示图G的第二特征标，本文刻画了R2(G)=-2，-1，0，1，2的全部连通图。