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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.
Monika Goikoetxea María J. Barandiaran José M. Asua 《Journal of polymer science. Part A, Polymer chemistry》2007,45(24):5838-5846
The mechanisms involved in the formation of n‐butanol during the synthesis of butyl acrylate containing latices were investigated. The experimental results showed that neither the hydrolysis of butyl acrylate nor of the ester bond in the butyl acrylate segments of the polymer played a major role in the formation of n‐butanol, which was mainly generated from the polymer backbone, by transfer reactions to polymer chain followed by cyclization. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5838–5846, 2007 相似文献
3.
The association of complex formation with static quenching in CT systems was investigated. Evaluation of the data made evident
that the inner filter effect must be allowed for. Time-resolved and temperature-dependent stationary measurements of fluorescence
led to the separation of dynamic and static quenching components. The static quenching constant is discussed with respect
to the equilibrium constant of complex formation determined by absorption spectroscopy. 相似文献
4.
E. Hatta H. Hosoi H. Akiyama T. Ishii K. Mukasa 《The European Physical Journal B - Condensed Matter and Complex Systems》1998,2(3):347-349
We have observed a remarkable two-armed spiral in the collapse process of a floating monolayer at the air-water interface
by phase contrast microscopy. This demonstrates that the floating monolayer as a form of soft condensed matter reorganizes
itself due to a certain kind of macroscopic or collective behavior of molecules as it collapses. This pattern formation is
caused by the breakdown of a critical dynamical balance between the deformation of solid domain and the applied surface pressure.
The fragility as well as the flexibility of the floating monolayer can be associated with the observed pattern growth. There
are also observed interesting, periodically arranged collections of molecules in numerous collapsed regions.
Received: 8 July 1997 / Accepted: 4 November 1997 相似文献
5.
We have investigated the free energy of formation for AgxIn1-x and AgxSn1-x liquid binary alloys at temperatures 1173 and 1250 K, respectively. A microscopic theory based on the first order perturbation has been applied. The interionic interaction and a reference liquid are the fundamental components of the theory. The interionic interaction is described by a local pseudopotential. A liquid of hard spheres (HS) of two different effective diametres and charges is used to describe the reference system. The results of the calculations for energy of formation agree very well with the available experimental data. Our calculations also reveal that a simple perturbative approach along with appropriate effective pair potentials can produce nearly quantitative results for the concerned alloys. 相似文献
6.
Martin A. Bos Bertus Dunnewind Ton van Vliet 《Colloids and surfaces. B, Biointerfaces》2003,31(1-4):95-105
Interfacial rheological properties and their suitability for foam production and stability of two vegetable proteins were studied and compared to β-casein. Proteins used ranged from flexible to rigid/globular in the order of β-casein, gliadin and soy glycinin. Experiments were performed at pH 6.7. Network forming properties were characterised by the surface dilational modulus (determined with the ring trough) and the critical falling film length (Lstill) at which a stagnant protein film will break. Gliadin had the highest dilational modulus, followed by glycinin and β-casein, whereas glycinin formed the strongest film against fracture in the overflowing cylinder. The rate of decrease in the surface tension was studied at the air–water (Wilhelmy plate method) and the oil–water interface (bursting membrane) and the dynamic surface tension during compression and expansion in the caterpillar. Gliadin had the lowest equilibrium interfacial tensions and β-casein the lowest dynamic surface tension during expansion. Hardly any foam could be formed at a concentration of 0.1 g/l by shaking. At a concentration of 1.4 g/l most foam was formed by β-casein, followed by gliadin and glycinin. It seems that in the first place the rate of adsorption is important for foam formation. For the vegetable proteins, adsorption was slow. This resulted in lower foamability, especially for glycinin. 相似文献
7.
Eugene Savov 《Complexity》2007,12(3):61-76
The solar wind makes the magnetosphere to expand and contract as indicated by the expansions and contractions of the auroral oval due to balancing of the dynamic pressure of the ambient space plasma at inner and outer magnetic lines. This self‐similar magnetospheric behavior elucidates the controversial magnetic storm‐substorm relationship and reveals the 3D‐spiral structure of magnetic interaction. The found self‐similarly evolving structure of one seen as fundamental interaction suggests dynamic fractal unifying interaction that builds a firework universe having 3D‐spiral code. The unifying interaction is described with equation drawn in new fundamental dynamic fractal framework. The equation of unifying interaction converges to the inverse square laws and the principle of uncertainty at laboratory scales. The dynamic fractal fundamental framework is made of one 3D‐spirally‐faster‐inward contracting and expanding, oscillating, basic matter. It simply accounts for observed constant speed of light and for the creation of bright and dark bands on a screen behind a tiny slit. The dynamic fractal framework is quantitatively confirmed with the orbital data for the Milky Way Galaxy, the Sun, the Earth, and the triple asteroid system 87 Sylvia. Many testable predictions are also made. The presented new fundamental dynamic fractal framework allows qualitative and quantitative modeling and simplification. © 2007 Wiley Periodicals, Inc. Complexity 12: 61–76, 2007 相似文献
8.
The change of the superstructure of different polyethylenes during uniaxial deformation is investigated. The method used is small-angle scattering with synchrotron radiation. For branched polyethylene (Lupolen 1840D) the whole deformation range is analyzed. Beginning with superstructure of the lamellar cluster type, the superstructure partly disappears on a time scale of a few minutes and the fibrillar structure is built up. The degree of destruction and rebuilding depends on the drawing temperature. For very high molecular weight polyethylene (GUR) a reversible change of the superstructure at higher deformation ratios and at different temperatures is observed. The superstructure of (ethylene—hexene) copolymers (TIPELIN) at high draw ratios depends on the drawing temperature and is almost independent of the side group content. Interfibrillar microcracks parallel to the draw direction are produced in samples with a low side group content for draw ratios λ ≥ 1.5. 相似文献
9.
Hiroki Shigehisa 《Tetrahedron letters》2006,47(41):7301-7306
The first total synthesis of a spiro-isoquinoline alkaloid, (±)-annosqualine, was established by employing an enamide-phenol coupling of a 1-methylene-1,2,3,4-tetrahydroisoquinoline derivative with a hypervalent iodine reagent, where the formation of the phenoxide was recognized to be an essential step for the reaction of the phenolic hydroxyl group with the hypervalent iodine reagent leading to the formation of the desired product. 相似文献
10.
T. Hayashita T. Kurosawa T. Miyata K. Tanaka M. Igawa 《Colloid and polymer science》1994,272(12):1611-1619
The cationic azo-surfactants possessing different spacers and tail alkyl chain lengths have been synthesized by azocoupling ofp-alkylaniline orop-ethoxyaniline with phenol, followed by alkylation and quaternalization with dibromoalkane and trimethylamine, respectively. These surfactants showed a good solubility in water. A reversibletrans-cis isomerization of the azosurfactants by photoirradiation was assessed by UV-Vis absorption spectra. Due to a difference in HLB between thetrans- andcis-surfactants, the observed critical micelle concentration (CMC) values and the electric conductivity of the surfactant solution at above the CMC were significantly affected by the photoinducedtrans-cis isomerization. The azo-surfactants bearing moderate alkyl chain lengths such as surfactants 6 (R2=C2H4, R3=C4H9) and 9 (R2=C4H8, R3=C2H5) were found to be effective to achieve large CMC changes (3.6 mmol/L for 6 and 5.9 mmol/L for 9) by UV-light irradiation. The replacement of the tail chain species also affected the photoresponsive function. The surfactant 12, possessingp-ethoxy group as the tail chain, was found to form a stable micelle aggregation as compared with the structurally related surfactant 10 having ethyl unit as its tail group, but it exhibited a large CMC change (5.3 mmol/L) by UV-light irradiation. 相似文献