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.     

Sobolev-Hardy不等式与临界双重调和问题

该文讨论一类带有奇异系数的双重调和方程{△^2u-μu/|x|^s=f(x,u),x∈Ω,u=δu/δv=0,x∈δΩ，这里Ω包含R^N是包含0的有界光滑区域，u∈H0^2(Ω），μ∈R是参数，0≤s≤2,△^2=△△表示双重拉普拉斯算子，当f(x,u)=u^p,p=2N/N-4时，上述问题就是一个临界双重调和问题，该文运用Sobolev-Hardy不等式和变分方法，得到它的解的存在性的一些结果。     

An inner product lemma

Given the operator product BA in which both A and B are symmetric positive‐definite operators, for which symmetric positive‐definite operators C is BA symmetric positive‐definite in the C inner product 〈x, y〉C? This question arises naturally in preconditioned iterative solution methods, and will be answered completely here. Copyright © 2004 John Wiley & Sons, Ltd.     

环面上具有间断梯度的势函数的模拟退火

本文证明了环面上具有间断梯度的势函数的模拟退火过程：dXt=-VU(Xt)dt √2dWt概率收敛到势函数的全局极小集附近。     

Sobolev-Type Classes of Functions with Values in a Metric Space. II

We prove equivalence of the definitions by the author and by Korevaar and Schoen of the Sobolev classes of mappings of a domain of an arithmetic n-dimensional space to a metric space.     

Fifty years of the Siberian Division of the Russian Academy of Sciences

This is a write-up on the foundation of the Sobolev Institute of Mathematics in 1957.     

Sobolev空间H~s(R~n)上矩阵伸缩的多尺度分析特征刻画

本文对高维Sobolev空间Hs(Rn)上具有矩阵伸缩的多尺度分析特征进行了 刻划,特别给出了稠密性特征的一个充分必要条件,从而解决了文献[4]中提出的一个 问题.所得结果覆盖了这方面的已知结论.     

Nonlinear Schrödinger equations with symmetric multi-polar potentials

This paper deals with a class of nonlinear elliptic equations involving a critical power-nonlinearity as well as a potential featuring multiple inverse square singularities. When the poles form a symmetric structure, it is natural we wonder how the symmetry affects such mutual interaction. The present paper means to study this aspect from the point of view of the existence of solutions inheriting the same symmetry properties as the set of singularities. Mathematics Subject Classification (2000) 35J60, 35J20, 35B33