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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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.     

Temperature and field dependences of photo-induced changes in the magnetization in yttrium iron garnet

The changes in the magnetization of yttrium iron garnet (YIG) when irradiated by a pulsed neodymium laser beam with wavelength λ=1.06 μm are investigated. Measurements are performed in the temperature range from 100 K to 600 K in various external magnetic fields. YIG single crystals grown along the crystallographic (100), (110), and (111) directions are chosen so that the external anisotropy of the indicated processes can be determined. Characteristic temperature intervals dominated by different mechanisms of variation of the magnetization under the influence of a laser pulse are discussed. Fiz. Tverd. Tela (St. Petersburg) 39, 1263–1266 (July 1997)     

Temperature and frequency dependence of the spin-lattice relaxation times of E′1 centers in neutron-irradiated quartz glass

Results are reported for measurements of the spin-lattice relaxation times of E′₁ centers in quartz glass, produced by neutron irradiation, with the measurements made at two frequencies 9.25 and 24.0 GHz over a wide temperature interval 1.5–300 K. The experimental data are interpreted on the basis of interaction mechanisms of the spins with two-level systems with excitation energies ∼6, ∼26, and ∼420 cm⁻¹. A small modification of the existing theory allows us to explain a number of features of the observed temperature and frequency dependence of the relaxation rate. The results are compared with the data available in the literature on spin-lattice relaxation of irradiation centers in crystalline quartz and quartz glass. Fiz. Tverd. Tela (St. Petersburg) 39, 1335–1337 (August 1997)     

Quantum-well states and resonances in thin single-crystal layers of noble metals on W(110) substrates

This paper reports on the first experimental observation of quantum-well states and sp-type resonances in thin single-crystal gold, silver, and copper layers formed on single-crystal W(110) surfaces, which result from spatial localization of Bloch-type electronic wave functions in a quantum well with potential barriers at the vacuum/metal and metal/W(110) interfaces. The quantization of the valence-band electronic structure in Au/W(110), Ag/W(110), and Cu/W(110) systems was studied experimentally using angle-resolved photoelectron spectroscopy.     

To the problem of the vector and axial-vector dominance of weak interactions

The problem of the vector and axial-vector dominance of weak interactions within the framework of the quark model of superconductivity type is discussed.     

Characterization of low molecular weight hydrocarbon oligomers by laser desorption/ionization time-of-flight mass spectrometry using a solvent-free sample preparation method.

A new solvent-free sample preparation method using silver trifluoroacetate (AgTFA) was developed for the analysis of low molecular weight paraffins and microcrystalline waxes by laser desorption/ionization time-of-flight mass spectrometry (LDI-TOFMS). Experiments show that spectral quality can be enhanced by dispersing AgTFA directly in liquid paraffins without the use of additional solvents. This preparation mixture is applied directly to the MALDI probe. Solid waxes could be examined by melting prior to analysis. The method also provides sufficiently reproducible spectra that peak area ratios between mono- and bicyclic alkane peaks indicated variations in the cycloalkane content of paraffin samples. Dehydrogenation of hydrocarbons observed during the desorption/ionization process was studied by analysis of alkane standards.