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.     

光突发交换网络中最长队列优先调度组装机制

提出了光突发交换网络中的最长队列优先调度（LQF-SA）机制，将边缘节点的突发组装和突发调度两种技术紧密结合在一起.在现实网络中，业务通常是非均匀分布的，即在某些源宿对之间存在更大的业务流量.仿真结果表明，LQF-SA机制可以很好地完成非均匀分布业务流的组装.即使在均匀分布业务流输入下，LQF-SA机制在突发大小分布、组装效率和突发丢失率等方面也优于已提出的轮询调度组装（RR-SA）机制.     

光突发交换的交换控制策略和光缓存配置

光突发交换是面向下一代互联网的光交换模式.讨论了异步光突发交换系统的交换控制策略以及相应光缓存的优化配置策略.除了传统预约模式的交换策略,还研究了非预约和改进型预约模式,它们的性能评估由计算机仿真给出.结果表明:在条件相当情况下,改进型预约模式具有最低的丢包率.同时光缓存的配置对上述几类交换控制策略的性能都有很大影响,仿真结果指出:光缓存的粒度对系统性能具有重要影响,所讨论的几类交换模式都存在最佳时延粒度,研究结果对光交换矩阵的设计有指导意义.     

强流束晕-混沌的外部磁场开关控制

研究了强流离子束在周期聚焦磁场通道中束晕-混沌的外部磁场开关参数控制方法. 将该方法应用在多粒子模型中，实现了对5种不同初始分布质子束的束晕-混沌的有效控制，得到了消除束晕及其再生现象的理想结果.在强流加速器系统中，由于外部磁场是可测和可调 的物理量，因此该控制方法有利于实验研究，可为强流质子加速器中周期聚焦磁场的设计和实验提供参考. 关键词： 强流离子束 周期聚焦磁场通道 束晕_混沌 混沌控制 开 关控制     

L-Fuzzy拟序集的理想完备化

建立[4]中定义的L-fuzzy拟序集的一种理想完备化,即证明了L-fuzzy拟序集上的所有L-fuzzy理想组成的集合,赋以合适的程度映射构成L-fuzzydomain,任意从L-fuzzy拟序集到L-fuzzydomain的L-fuzzy单调映射都可以扩张成为一个L-fuzzyScott连续映射。     

In situ observations of domain wall motion in Mn–Zn and Ni–Zn ferrites by Lorentz microscopy and electron holography

Domain wall motion in Mn–Zn and Ni–Zn ferrites with applied magnetic fields is investigated by in situ observations with Lorentz microscopy and electron holography. It is found that both Mn–Zn and Ni–Zn ferrites have a mean grain size of approximately 10 μm and several pores with sizes ranging from 0.2 to 1.1 μm. In situ observations by Lorentz microscopy with an applied magnetic field reveals that in Mn–Zn ferrite, the domain walls move easily across the grain boundary, while in Ni–Zn ferrite, the domain walls move along the grain boundary but are pinned at the grain boundary and pores. From in situ observations of Ni–Zn ferrite by electron holography, it is clarified that domain wall pinning at the grain boundary retards a sensitive increase in magnetic flux parallel to the applied field direction, which is considered to result in high hysteresis loss.     

Shape Optimization for Semi-Linear Elliptic Equations Based on an Embedding Domain Method

We study a class of shape optimization problems for semi-linear elliptic equations with Dirichlet boundary conditions in smooth domains in ℝ². A part of the boundary of the domain is variable as the graph of a smooth function. The problem is equivalently reformulated on a fixed domain. Continuity of the solution to the state equation with respect to domain variations is shown. This is used to obtain differentiability in the general case, and moreover a useful formula for the gradient of the cost functional in the case where the principal part of the differential operator is the Laplacian. Online publication 23 January 2004.     

背景光光伏效应对屏蔽-光伏空间孤子的影响

在光伏晶体两端外加一恒定的直流偏压，背景光的光伏效应对形成屏蔽-光伏孤子的空间电荷场没有影响，但对晶体中的电流有影响.如果外电源的电动势是恒定的，则背景光的光伏效应与外电路的电阻协同起作用，可以通过晶体两端的电压降影响晶体中的空间电荷场，进而影响空间孤子的宽度.在一定的条件下甚至可以实现亮、暗孤子的转换. 关键词： 屏蔽-光伏 空间孤子 孤子宽度 亮暗孤子转换     

Domain decomposition for an asymptotic geological fault modeling

We present in this paper a domain decomposition method to treat faults in geological basin modeling. The particularity of this model is that the faults whose widths are very small in comparison with the basin size, are not characterized as subdomains any more but as interfaces between sedimentary blocks. The originality of this work lies in the formulation of this new fault model and in the definition and the computation of the interface conditions between the subdomains. To cite this article: E. Flauraud et al., C. R. Mecanique 331 (2003).     

光子晶体中四能级系统的量子相干效应

研究了处于光子带隙材料中的四能级原子系统的电磁感应透明、自发辐射和光子开关效应，分析了其稳态与瞬态特性, 发现特殊的模密度能够导致反常的吸收、色散、自发辐射及瞬态无反转增益, 并可以通过外加调制场进行控制.详细讨论了特殊频率处模密度的变化对透明窗口和光子开关效应的影响. 关键词： 光子带隙材料 电磁感应透明 模密度 光子开关