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.     

电磁场中带电粒子束运动的力学模拟

研究以不同初速度进入互相垂直的匀强磁场和均强电场中的带电粒子束的运动情形，并同相似的力学运动相比拟，建立了直观的力学模型。     

Synthesis of coumarins by Pt-catalyzed hydroarylation of propiolic acids with phenols

Synthesis of coumarins from phenols and propiolic acids was examined by using a Pt catalyst such as PtCl₂/AgOTf, K₂PtCl₄/AgOTf, and K₂PtCl₄/AgOAc. Propiolic acid reacted even with less reactive phenols in trifluoroacetic acid to give coumarins and dihydrocoumarins. In the case of substituted propiolic acids, phenylpropiolic acid and 2-octynoic acid, the reactions proceeded selectively to afford coumarins in good to high yields.     

Stress-Strain State in the Zone of Load Transfer in a Composite Specimen under Uniaxial Tension

The stress-strain state in the zone of load transfer in a uniaxially stretched specimen made of a unidirectional epoxy carbon-fiber-reinforced plastic (CFRP) is investigated. A parametric analysis of the influence of geometric and mechanical characteristics of the specimen on its stress-strain state is performed by means of finite-element modeling. The parameters allowing us to significantly reduce the dangerous concentration of transverse and tangential stresses are revealed. The mechanical tensile characteristics of a high-strength pultruded unidirectional CFRP are determined experimentally, and the size effect of its strength is estimated.     

On the hysteresis of vortex shedding in a periodically-varying flow

Efforts are made to explore the hysteresis characteristics of vortex shedding in a pipe flow, whose velocity varies periodically in time. Results obtained show that during acceleration of the flow, the vortex strength tends to be stronger, whereas during deceleration of the flow, the situation is reversed. As reconstructed from the velocity signals measured at a point in the flow field, the shed vortex arrays appear to possess uneven vortex strengths in response to periodically-varying incoming flows. Furthermore, in the hysteresis range, the streamwise spacings between the vortices appear to be unequal.     

Non-protein amino acids in peptide design

An overview of the use of non-protein amino acids in the design of conformationally well-defined peptides, based on work from the author’s laboratory, is discussed. The crystal structures of several designed oligopeptides illustrate the useα-aminoisobutyric acid (Aib) in the construction of helices, D-amino acids in the design of helix termination segments and^DPro-Xxx segments for nucleating ofβ-hairpin structures.β- andγ-amino acid residues have been used to expand the range of designed polypeptide structures. Dedicated to Professor C N R Rao on his 70th birthday     

Influence of SiO2 in SiCp on the microstructure and impact strength of Al/SiCp composites fabricated by pressureless infiltration

The effect of SiO₂ in SiC_p and the following processing parameters on the microstructure and impact strength of Al/SiC_p composites fabricated by pressureless infiltration was investigated: Mg content in the aluminum alloy, SiC particle size, and holding time. Preforms of SiC_p in the form of rectangular bars (10 × 1 × 1 cm) were infiltrated at 1150°C in an argon→nitrogen atmosphere for 45 and 60 min by utilizing two aluminum alloys (Al-6 Mg-11 Si and Al-9 Mg-11 Si, wt.%). The results obtained show that the presence of SiO₂ in SiC affects the microstructure and impact strength of the composites significantly. When Al₄C₃ is formed, the impact strength decreases. However, a high proportion of SiC to SiO₂ limits the formation of the unwanted Al₄C₃ phase in the composites. Also, a higher content of Mg in the Al alloy lowers the residual porosity and, consequently, increases the composite strength. The impact strength grows with decrease in SiC particle size and increases considerably when the residual porosity is less than 1%. Russian translation published in Mekhanika Kompozitnykh Materialov, Vol. 42, No. 3, pp. 401–418, May–June, 2006.     

某库岸滑坡稳定分析及治理措施研究

从地质条件出发,详细分析了滑坡的成因,以大型的岩土工程数值分析软件(ADINA)为研究手段,建立有限元计算模型,用强度折减的方法分析了滑坡体在初始工况、蓄水工况、暴雨工况、水位骤降工况和地震工况下的稳定情况,根据滑坡的失稳情况,在综合考虑的基础上,提出了削坡减载和地表排水相结合的治理措施,计算结果表明,治理措施是可行的,研究结果对设计和施工具有较大的参考价值.     

Interpretation of the polyelectrolyte and antipolyelectrolyte effects of poly(N‐vinylimidazole‐co‐sodium styrenesulfonate) hydrogels

Hydrogels of N‐vinylimidazole (VI) and sodium styrenesulfonate (SSS) were synthesized in aqueous solution by radical crosslinking copolymerization with N,N′‐methylene‐bis(acrylamide) as crosslinker. Swelling in several saline solutions was measured for hydrogel samples synthesized with different comonomer concentrations (C_T = 10, 25, or 40%) and with SSS mole fractions covering a broad range (f_SSS = 0–0.7), while the crosslinker ratio was 2 wt % in all cases. The degree of swelling in aqueous solution with a specific ionic strength (μ), plotted versus the SSS composition of the feed, shows a minimum for any set of samples synthesized with a fixed C_T. The dependence of swelling on μ shows both polyelectrolyte (f_SSS beyond the minimum) and antipolyelectrolyte behaviors (in the low f_SSS limit). It was found that the nonGaussian factor of the crosslinking density and the polymer‐solvent interaction parameter increase with f_SSS for any C_T. Moreover, in the low f_SSS limit, the osmotic swelling pressure is governed not only by the ionic contribution, but also by the polymer‐solvent mixing and, the concentration of mobile counterions inside the gel is not proportional to the net fixed charge but to the addition of cationic and anionic side groups, what discards the formation of ionic pairs. The antipolyelectrolyte effect is interpreted as due to the increasing protonation of VI as μ goes up. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1683–1693, 2007