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.     

Surfaces of Constant Mean Curvature Bounded by Two Planar Curves

In this paper we study constant mean curvature compact surfaces with two Jordan curves in parallel planes as boundary and we investigate the point at which the surface inherits the symmetries of its boundary.     

Carathéodory's method for a class of dynamic games

The method of equivalent variational methods, originally due to Carathéodory for free problems in the calculus of variations is extended to investigate feedback Nash equilibria for a class of n-person differential games. Both the finite-horizon and infinite-horizon cases are considered. Examples are given to illustrate the presented results.     

Method of lines with boundary elements for 1‐D transient diffusion‐reaction problems

Time‐dependent differential equations can be solved using the concept of method of lines (MOL) together with the boundary element (BE) representation for the spatial linear part of the equation. The BE method alleviates the need for spatial discretization and casts the problem in an integral format. Hence errors associated with the numerical approximation of the spatial derivatives are totally eliminated. An element level local cubic approximation is used for the variable at each time step to facilitate the time marching and the nonlinear terms are represented in a semi‐implicit manner by a local linearization at each time step. The accuracy of the method has been illustrated on a number of test problems of engineering significance. © 2005 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 2006     

Numerical solutions of the shallow water equations with discontinuous bed topography

A simple scheme is developed for treatment of vertical bed topography in shallow water flows. The effect of the vertical step on flows is modelled with the shallow water equations including local energy loss terms. The bed elevation is denoted with z_b^‐ for the left and z_b⁺ for the right values at each grid point, hence exactly representing a discontinuity in the bed topography. The surface gradient method (SGM) is generalized to reconstruct water depths at cell interfaces involving a vertical step so that the fluxes at the cell interfaces can accurately be calculated with a Riemann solver. The scheme is verified by predicting a surge crossing a step, a tidal flow over a step and dam‐break flows on wet/dry beds. The results have shown good agreements compared with analytical solutions and available experimental data. The scheme is efficient, robust, and may be used for practical flow calculations. Copyright © 2002 John Wiley & Sons, Ltd.     

A modified predictor–corrector scheme for the two-dimensional sine-Gordon equation

A three-time level finite-difference scheme based on a fourth order in time and second order in space approximation has been proposed for the numerical solution of the nonlinear two-dimensional sine-Gordon equation. The method, which is analysed for local truncation error and stability, leads to the solution of a nonlinear system. To avoid solving it, a predictor–corrector scheme using as predictor a second-order explicit scheme is proposed. The procedure of the corrector has been modified by considering as known the already evaluated corrected values instead of the predictor ones. This modified scheme has been tested on the line and circular ring soliton and the numerical experiments have proved that there is an improvement in the accuracy over the standard predictor–corrector implementation. This research was co-funded by E.U. (75%) and by the Greek Government (25%).     

Instabilities in the Chapman-Enskog Expansion and Hyperbolic Burnett Equations

It is well-known that the classical Chapman-Enskog procedure does not work at the level of Burnett equations (the next step after the Navier-Stokes equations). Roughly speaking, the reason is that the solutions of higher equations of hydrodynamics (Burnett's, etc.) become unstable with respect to short-wave perturbations. This problem was recently attacked by several authors who proposed different ways to deal with it. We present in this paper one of possible alternatives. First we deduce a criterion for hyperbolicity of Burnett equations for the general molecular model and show that this criterion is not fulfilled in most typical cases. Then we discuss in more detail the problem of truncation of the Chapman-Enskog expansion and show that the way of truncation is not unique. The general idea of changes of coordinates (based on analogy with the theory of dynamical systems) leads finally to nonlinear Hyperbolic Burnett Equations (HBEs) without using any information beyond the classical Burnett equations. It is proved that HBEs satisfy the linearized H-theorem. The linear version of the problem is studied in more detail, the complete Chapman-Enskog expansion is given for the linear case. A simplified proof of the Slemrod identity for Burnett coefficients is also given.     

两种拔尿管方法对膀胱功能损伤的临床观察

为观察两种不同的拔尿管方法对膀胱功能损伤的差异,将80例患者随机分成两组,分别采用改良法(40例)和常规法(40例)拔除留置尿管,分析比较了两组患者排尿顺利率、逼尿肌功能恢复率及尿道刺激症、尿失禁、尿潴留。结果表明,两组患者拔管后上述指标与情况有显著性差异,P<0.05。提示改良组膀胱功能损伤明显低于对照组。改良的拔管方法是一种值得护理推广应用的好方法。     

Multilevel preconditioners for a quadrature Galerkin solution of a biharmonic problem

Efficient multilevel preconditioners are developed and analyzed for the quadrature finite element Galerkin approximation of the biharmonic Dirichlet problem. The quadrature scheme is formulated using the Bogner–Fox–Schmit rectangular element and the product two‐point Gaussian quadrature. The proposed additive and multiplicative preconditioners are uniformly spectrally equivalent to the operator of the quadrature scheme. The preconditioners are implemented by optimal algorithms, and they are used to accelerate convergence of the preconditioned conjugate gradient method. Numerical results are presented demonstrating efficiency of the preconditioners. © 2005 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 2006