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.     

Modified Householder iterative method free from second derivatives for nonlinear equations

In this paper, we suggest and analyze a new two-step predictor–corrector type iterative method free from second derivatives for solving nonlinear equations of the type f(x)=0. This new method includes the two-step Newton method as a special case. We prove that the new iterative method is of fourth-order. Several examples are given to illustrate the efficiency of this new method and its comparison with other iterative methods. This method can be considered as a significant improvement of the Newton method and its variant forms.     

Allocating unfunded liability in pension valuation under uncertainty

This paper studied the cost allocation for the unfunded liability in a defined benefit pension scheme incorporating the stochastic phenomenon of its returns. In the recent literature represented by Cairns and Parker [Insurance: Mathematics and Economics 21 (1997) 43], Haberman [Insurance: Mathematics and Economics 11 (1992) 179; Insurance: Mathematics and Economics 13 (1993) 45; Insurance: Mathematics and Economics 14 (1994) 219; Insurance: Mathematics and Economics 14 (1997) 127], Owadally and Haberman [North American Actuarial Journal 3 (1999) 105], the fund level is modeled based on the plan dynamics and the returns are generated through several stochastic processes to reflect the current realistic economic perspective to see how the contribution changed as the cost allocation period increased. In this study, we generalize the previous constant value assumption in cost amortization by modeling the returns and valuation rates simultaneously. Taylor series expansion is employed to approximate the unconditional and conditional moments of the plan contribution and fund level. Hence the stability of the plan contribution and the fund size under different allocation periods could be estimated, which provide valuable information adding to the previous works.     

混合范数空间中函数的Taylor系数

本文研究了混合范数空间Ｈ（ｐ，ｑ，ａ）中解析函数ｆ的Ｔａｙｌｏｒ系数，对０＜ｐ≤２，０＜ｑ＜∞，ａ＞０和２≤ｐ＜∞，０＜ｑ＜∞，ａ＞０两种情形，分别给出了ｆ属于Ｈ（ｐ，ｑ，ａ）的必要条件和充分条件。用上述结果我们还得到了几个关于混合范数空间的乘子定理，这些结果也推广了Ｈａｒｄｙ和Ｌｉｔｔｌｅｗｏｏｄ关于Ｈ＾ｐ空间的相应结论。     

纯生跳跃扩散型交换期权定价公式

在假定标的资产价格服从纯生跳跃过程的条件下,研究一类多资产期权——资产权重不同的交换期权,并在风险中性的条件下建立相应的定价方程,运用条件期望等相关知识得出交换期权的解析公式。文中最后列出一些特殊纯生跳跃扩散型交换期权的定价的例子.     

第二类Fredholm积分方程的泰勒展开解法

本进一步发展了用Taylor公式求解第二类Fredholm积分方程的方法，并给出了近似解的误差精度分析．     

Multilayered Cu–Ti deposition on silicon substrates for chemiresistor applications

Abstract

On the perspective to develop CuO–TiO₂ MOS, multilayered Cu and Ti thin layers were alternatively deposited on silicon wafers using 25?keV Ar?+?ion beam sputtering and, subsequently, oxidized by thermal annealing in air at 400?°C for 24?h. The deposited films have variable ratios of the Cu and Ti % at. One of the main goal is to obtain such multilayers avoiding the presence of Cu–Ti–O compounds. The samples were characterized in terms of composition (by RBS and SIMS analyses) and morphology (by AFM and SEM investigations). In particular, SIMS maps allows to observe the spatial distribution and thickness of each phase of the Cu/Ti multilayers, and further to observe Cu diffusion and mixing with Ti, as well as phase separation of CuO and TiO₂ in the samples. The reasons of this effect represent an open issue that has to investigated, in order to improve the MOS fabrication.     

Reaction des lithiens avec les organophosphores. Reaction d'addition du t-butyllithium sur le noyau benzenique des sels de phenylphosphoniums

A new reaction of organolithium compounds with phosphonium salts is described; reaction of t-butyllithium with dibenzylaminophosphonium or tetraphenylphosphonium bromides takes place through addition of the t-butyl group on a benzene ring at the position para to the phosphorus atom, the ylid formed reacts in a characteristic Wittig reaction with p-tolylaldehyde.