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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.
H. Akimune T. Yamagata S. Nakayama M. Fujiwara K. Fushimi K. Hara K. Y. Hara K. Ichihara K. Kawase K. Matsui K. Nakanishi A. Shiokawa M. Tanaka H. Utsunomiya M. Yosoi 《Physics of Atomic Nuclei》2004,67(9):1721-1725
Trinucleon molecular structures in 6He and 6Be were investigated by using the 6Li(7Li, 7Be)6He reaction at 455 MeV and 6Li(3He, t)6Be reaction at 450 MeV, respectively. Binary decays into t + t from a broad state at E x =18.0±1.0 MeV in 6He and into 3He + 3He from one at E x =18.0±1.2 MeV in 6Be, respectively, were observed by measuring trinucleon cluster decays in coincidence with reaction particles. The branching ratios for binary decay were estimated to be about 0.7 for 6He and 6Be. These large branching ratios show that a trinucleon cluster state exists as an isobaric partner around E x =18 MeV in 6He and 6Be. 相似文献
3.
Atsuhiro Fujimori Mikako Ishitsuka Hiroo Nakahara Eisuke Ito Masahiko Hara Kaname Kanai Hisao Ishii Yukio Ouchi Kazuhiko Seki 《Journal of Polymer Science.Polymer Physics》2004,42(12):2329-2336
Photopolymerization of cadmium 10,12-pentacosadiynoate (CdDA) in Langmuir–Blodgett (LB) films, with the molecular packing well arranged by moderate preannealing, was investigated with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Greenish films of polydiacetylene with an absorption wavelength of 705 nm were obtained through the photopolymerization of preannealed monomer LB films, and this resulted in an extended π-conjugate system based on the well-ordered monomer in a two-dimensional arrangement. The electronic structures of the polydiacetylenes were found to be correlated to the variation of the molecular arrangements in the films from the changes in the NEXAFS spectra through photopolymerization in the LB films. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2329–2336, 2004 相似文献
4.
Takayuki Nakai Yoshiko Murakami Yoshiaki Sasaki Isamu Fujiwara Shoji Tagashira 《Analytical sciences》2004,20(1):235-237
The extraction and separation of copper(II), zinc(II), cobalt(II), and cadmium(II) were investigated. Both copper(II) and zinc(II) formed ammine-complexes, while cadmium(II) and cobalt(II) formed hydroxide precipitates in an ammonia medium. By the addition of sodium dodecylsulfate (SDS), a copper(II) complex formed an ion-pair (copper-ammine-DS), which was extracted into the SDS phase. However, a zinc(II) complex did not form an ion-pair, and was soluble in water. Copper(II) ion was recovered by stripping (back-extraction) after the addition of hydrochloric acid. This method was applied to the separation of copper(II) in a brass alloy. 相似文献
5.
A large-volume (100 microl) injection-ETAAS with W-treated PG furnace combined with a phosphate modifier was applied to the determination of unpolluted levels of Cd in tap, snow and river-water samples. The limit of detection of 1.1 ng l(-1) was observed for a 4 w/v% NH4H2PO4 modifer. Matrix interference studies were tested for major ion species well found in fresh water. The direct determination of Cd in certified river water (12 +/- 2 ng l(-1)) was carried out and the observed value was in agreement with the certified one. The good recoveries of Cd added to real environmental water samples were also observed. This method was applied to the determination of Cd in unpolluted environmental water samples. 相似文献
6.
7.
Selective oxidation of an AlInAs layer was investigated for enhancement of magneto-optic effect in an optical isolator. Twelve times nonreciprocal phase shift enhancement was estimated from a measured AlInAs-oxide refractive index. 相似文献
8.
Mat Rasol Awang Hassan Hamdani Mutaat Mohd. Shukri Mahmud Wan Badrin Wan Husain Tajuddin Osman Khomsaton Abu Bakar Asmahwati Kassim Zal U''yun Wan Mahmud Ishak ManafTamikazu Kume Shoji Hashimoto 《Radiation Physics and Chemistry》1993,42(4-6):611-616
In solid state fermentation, Pleurotus sajor-caju has been found to be able to degrade at least 30% oil palm empty Fruit Bunch (EFB) fibre leaving 70 % useful materials. Conditions under which fermentation carried out were investigated. It was found that, in the temperature range between 25– 28 °C, relative ph between 6–8, moisture between 60–70 % and medium composition of CaCO3: rice bran 2 %: 5 % were the optimum conditions. The results showed in fermented products that, there were substantial reduction in cellulosic component such as Crude Fiber (CF, 18 %); Acid Detergent Fibre (ADF, 45 %), Neutral Detergent Fibre (NDF, 61 %) and Acid Detergent Lignin (ADL, 14 %). However, Crude Protein (CP, 10%) increased resulted from single cell protein enrichment of mycelial microbial mass. The mass reductions of substrate in fermentation process corresponds to the CO2 released during fermentation. Hence, attributable to the decreased in content of CF, ADF, NDF, and ADL. The digestibility study has also been carried out to determine the useful level of this product to ruminant. Aflatoxin content was detected low in both the initial substrates and products. Based on nutritional value and low content of aflatoxin, the product is useful as a source of roughage to ruminant. 相似文献
9.
The environmental radioactivity caused by the reactor accident at Chernobyl' was investigated from May 7 to May 31 of 1986 in Toyama. Measurement of radioactivities in airborne particles, rain water, drinking water, milk, and mugwort are carried out by gamma-ray spectrometry (pure Ge detector; ORTEC GMX-23195). Ten different nuclides (103Ru, 106Ru, 131I, 132Te-I, 134Cs, 136Cs, 137Cs, 140Ba-La) are identified from samples of airborne particles. In the air samples, a maximum radioactivity concentration of each nuclide is observed on 13th May 1986. The time of the reactor shut-down and the flux of thermal neutron at the reactor were calculated from 131I/132I and 137Cs/134Cs ratio. The exposure dose in Toyama by this accident is given as follows: internal exposure; [thyroid] adult-59 microSv, child-140 microSv, baby-130 microSv, [total body] adult-0.2 microSv, child, baby-0.4 microSv, external exposure; 7 microSv, effective dose equivalent; adult-9 microSv, child-12 Sv, baby-11 microSv. 相似文献
10.