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.     

Stability of O3 + N2, O3 + O2 and O3 + CO2 double hydrates: DFT study

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<Emphasis Type="Italic">FCC/BCC</Emphasis> competition and enhancement of saturation magnetization in nanocrystalline Co-Ni-Fe films

The structure, chemical composition, and magnetic properties of electrochemically deposited nanocrystalline Co-Ni-Fe films were investigated using a number of techniques. A high saturation magnetic induction up to B _s = 21 kG was attained. An enhancement of the saturation magnetization compared to the ideal anticipated one was revealed, which correlated with the nonlinear behavior of the structural phase composition and lattice parameters with the change of the composition. The text was submitted by the authors in English.     

Gas adsorption in mcm-41 porous silicas dynamic measurements using sans

The European Physical Journal E - The isothermal gas adsorption of two hexane isomers (n-hexane and cyclohexane) in the mesopores of MCM-41 silica have been investigated by small angle neutron...     

Effect of phonon scattering from neutral and charged impurity centers on the lattice heat conductivity of PbTe:(Tl, Na)

Experimental data on the effect of thallium and sodium impurities on the lattice heat conductivity of PbTe at room temperature are reported. Because the lattice of lead chalcogenides is strongly polarized near charged impurities, the effect of impurities on the lattice heat conductivity depends substantially on their charge state. This property of the material has been used to determine the charge state of the thallium impurity in PbTe. The results obtained argue for a model of quasi-local thallium-impurity states which assumes low electron-correlation energy at an impurity center. Fiz. Tverd. Tela (St. Petersburg) 40, 1206–1208 (July 1998)     

Loss and non-linearity saturation effects on the bistability of non-linear distributed feedback structures

We investigate theoretically the effects of optical absorption and saturation of the non-linear index of refraction on the bistability of non-linear distributed feedback structures (NLDFBs). By assuming that the Kerr non-linearity saturates in an exponential fashion, we obtain for the first time closed-form expressions for the so-called self-phase and cross-phase modulation terms. Our investigation shows that both absorption and, in particular, saturation significantly affect the bistable properties of this structure and in many cases eliminate this response completely. In some cases, however, saturation alters the NLDFB's transfer characteristics in a potentially useful manner. We find that weak levels of saturation may increase the contrast ratio between the intensities of the high and low bistable states. At increasing levels of saturation, where bistability is no longer observed, we find regimes where the NLDFB structure could possibly be used for optical amplification. This revised version was published online in November 2006 with corrections to the Cover Date.     

Mössbauer study of Martian regolith analogues

Terrestrial basalt rocks considered to be a good analogues of the Martian regolith were studied by using the Mössbauer spectroscopy and X-ray diffraction. The weathering of basalts was followed by the changes of the Fe²⁺/Fe³⁺ ratio. The basalt rock undergoes alteration from primary mineral composition (olivine+pyroxene+plagioclase) through smectite to kaolinite clay with oxides and hydroxides with the increase of the Fe²⁺/Fe³⁺ ratio.     

Hydroxyl ion conduction in ytterbium-doped strontium cerate at T<580 K in H2O/air atmosphere

Open circuit voltage (OCV) measurements in H₂O/air concentration cells at T<580 K using Yb-doped SrCeO₃ electrolyte indicate that under these conditions, protons are transported through the electrolyte as -ve ions, possibly as hydroxyl (OH⁻) ions. The H⁺ ionic transport, which is generally reported, becomes the dominant mode for H₂O/air concentration cells at temperatures greater than 750 K or when H₂O/air electrodes are replaced by H₂/Ar, and the anomalous OCV sign disappears. The combination of low temperature and the presence of hydrogen and oxygen as provided by the H₂O/air system appears to be necessary for the postulated hydroxyl ion electrode reactions to take place. In addition to OCV measurements, results from impedance spectroscopy are used to provide evidence in support of the suggested hydroxyl ion mode of protonic transport under the specified conditions. These findings are directly relevant in the development of novel humidity sensors in the temperature range 450–580K and is reported in a separate paper in this conference. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Normalization and averaging on compact lie groups in nonlinear mechanics

We consider the method of normal forms, the Bogolyubov averaging method, and the method of asymptotic decomposition proposed by Yu. A. Mitropol’skii and the author of this paper. Under certain assumptions about group-theoretic properties of a system of zero approximation, the results obtained by the method of asymptotic decomposition coincide with the results obtained by the method of normal forms or the Bogolyubov averaging method. We develop a new algorithm of asymptotic decomposition by a part of the variables and its partial case — the algorithm of averaging on a compact Lie group. For the first time, it became possible to consider asymptotic expansions of solutions of differential equations on noncommutative compact groups.     

On Series of Ordinals and Combinatorics

This paper deals mainly with generalizations of results in finitary combinatorics to infinite ordinals. It is well-known that for finite ordinals ∑_bT<αβ is the number of 2-element subsets of an α-element set. It is shown here that for any well-ordered set of arbitrary infinite order type α, ∑_bT<αβ is the ordinal of the set M of 2-element subsets, where M is ordered in some natural way. The result is then extended to evaluating the ordinal of the set of all n-element subsets for each natural number n ≥ 2. Moreover, series ∑_β<αf(β) are investigated and evaluated, where α is a limit ordinal and the function f belongs to a certain class of functions containing polynomials with natural number coefficients. The tools developed for this result can be extended to cover all infinite α, but the case of finite α appears to be quite problematic.