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1.
ABSTRACTQM(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. 相似文献
2.
Prof. Dr. Junfeng Yang Yuto Mori Prof. Masahiro Yamanaka Prof. Naohiko Yoshikai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(37):8302-8307
A simple cobalt-diphosphine catalyst has been found to efficiently promote intramolecular cyclization of ortho-cyclopropylvinyl- and cyclopropylidenemethyl-substituted benzaldehydes into benzocyclooctadienone and benzocycloheptadienone derivatives, respectively. This ring-opening hydroacylation likely involves aldehyde C−H oxidative addition, olefin insertion, cyclopropane cleavage by β-carbon elimination, and C−C bond-forming reductive elimination, as was supported by mechanistic experiments and DFT calculations. 相似文献
3.
Ryohei Yoshisaki Dr. Shinya Kimura Dr. Masashi Yokoya Prof. Dr. Masamichi Yamanaka 《化学:亚洲杂志》2021,16(14):1937-1941
Maltose is a ubiquitous disaccharide produced by the hydrolysis of starch. Amphiphilic ureas bearing hydrophilic maltose moiety were synthesized via the following three steps: I) construction of urea derivatives by the condensation of 4-nitrophenyl isocyanate and alkylamines, II) reduction of the nitro group by hydrogenation, and III) an aminoglycosylation reaction of the amino group and the unprotected maltose. These amphiphilic ureas functioned as low molecular weight hydrogelators, and the mixtures of the amphipathic ureas and water formed supramolecular hydrogels. The gelation ability largely depended on the chain length of the alkyl group of the amphiphilic urea; amphipathic urea having a decyl group had the highest gelation ability (minimum gelation concentration=0.4 mM). The physical properties of the supramolecular hydrogels were evaluated by measuring their thermal stability and dynamic viscoelasticity. These supramolecular hydrogels underwent gel-to-sol phase transition upon the addition of α-glucosidase as a result of the α-glucosidase-catalyzed hydrolysis of the maltose moiety of the amphipathic urea. 相似文献
4.
Frontispiece: Entropy‐Driven 1,2‐Type Friedel–Crafts Reaction of Phenols with N‐tert‐Butoxycarbonyl Aldimines 下载免费PDF全文
5.
Back Cover: CH Activation Generates Period‐Shortening Molecules That Target Cryptochrome in the Mammalian Circadian Clock (Angew. Chem. Int. Ed. 24/2015) 下载免费PDF全文
Tsuyoshi Oshima Dr. Iori Yamanaka Dr. Anupriya Kumar Dr. Junichiro Yamaguchi Dr. Taeko Nishiwaki‐Ohkawa Kei Muto Rika Kawamura Dr. Tsuyoshi Hirota Prof. Dr. Kazuhiro Yagita Prof. Dr. Stephan Irle Prof. Dr. Steve A. Kay Prof. Dr. Takashi Yoshimura Prof. Dr. Kenichiro Itami 《Angewandte Chemie (International ed. in English)》2015,54(24):7200-7200
6.
M. Saka T. Shoji H. Takahashi H. Abé 《Journal of the mechanics and physics of solids》1982,30(4):209-224
A finite element analysis was performed to simulate crack tip blunting and the development of the intense strain region in a small compact tension specimen (0.4 T CT) of SA533B-1 under plane strain large-scale yielding, with the condition of large-geometry change around the crack tip taken into consideration. The region where the equivalent plastic strain g3p is greater than 0.15 was defined as the intense strain region, which corresponded to the recrystallized-etched zone delineated experimentally around the blunting crack tip. The development of the intense strain region was discussed as a function of the J-integral and the crack opening displacement. A linear relationship was obtained between the plastic work Wp dissipated within the intense strain region and (J/σy)2 or b2, where b is the crack opening displacement, defined as the separation of the two points at which the boundary of the intense strain region surrounding the crack tip intersects with the free surfaces of the crack. 相似文献
7.
A Cu-TiC alloy, with nanoscale TiC particles highly dispersed in the submicron-grained Cu matrix, was manufactured by a self-developed two-step ball-milling process on Cu, Ti and C powders. The thermostability of the composite was evaluated by high-temperature isothermal annealing treatments, with temperatures ranging from 727 to 1273 K. The semicoherent nanoscale TiC particles with Cu matrix, mainly located along the grain boundaries, were found to exhibit the promising trait of blocking grain boundary migrations, which leads to a super-stabilized microstructures up to approximately the melting point of copper (1223 K). Furthermore, the Cu-TiC alloys after annealing at 1323 K showed a slight decrease in Vickers hardness as well as the duplex microstructure due to selective grain growth, which were discussed in terms of hardness contributions from various mechanisms. 相似文献
8.
9.
Positive radial solutions to the semilinear elliptic equation \(\Delta u + K(|x|)u^p = 0\) inR n are studied, wherep > 1,n > 2 andK ≧ 0. It is shown that, under a general condition onK(r) andp, the structure of positive radial solutions becomes one of three types. We give sharp criteria to classify the type of the structure, and apply the result to the conformal scalar curvature equation. 相似文献
10.
The nondestructive testing technique is applied to evaluate the temper embrittlement of normalized and tempered
steel; it is based on the anodic polarization behavior in calcium nitrate solution. The steel specimen is aged at a stress of 210 MPa at 450°C for up to 8800 h in order to examine the effect of applied stress on the enhancement of intergranular segregation of phosphorus. The secondary peak observed in the polarization curve for the material aged under stress was compared with that for the non-stressed. It can be quantified with the degree of intergranular segregation of phosphorus. The data suggest that the enhancement of phosphorus segregation due to the applied stress is only recognized after 3000 h of aging. This effect diminishes with increasing aging time. 相似文献