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11.
A relativistic Green function formalism has been applied to calculate layer-projected densities of states on Pd(110). In particular, we obtained unoccupied surface states and their dispersion relations along two directions in the surface Brillouin zone. Good agreement with recent inverse photoemission data is reached by using an energy-dependent dynamical surface potential barrier, which is based on a simple electron-plasmon interaction model, instead of a static surface barrier. 相似文献
12.
Tadao Seguchi Naoyuki Tamura 《Journal of polymer science. Part A, Polymer chemistry》1974,12(9):1953-1964
The regions trapping allyl radicals in irradiated polyethylene and the reactivity of the radicals with various monomers have been studied by electron spin resonance. Most of the allyl radicals are trapped in defects or surfaces of the crystallite, and only 10% of the radicals are trapped inside the crystallites. Since the reactivity of the allyl radicals depends on whether they come in contact with reactive monomers, the rate of reaction is related to the concentration of the monomers. When grafting reactions are initiated by allyl radicals, the rate of initiation is rapid and the rate of termination at the initial stage is also very fast. Consequently the yield of grafting increases at the initial stage but soon levels off, which is in contrast to the grafting behavior with alkyl radicals. 相似文献
13.
An interesting transformation occurs during acylation of 4(R)-hydroxymethyl-3-methyl-1,3-thiazolidine when 4(R)-acylthiomethyl-3-methyl-1,3-oxazolidines are yielded: the reaction competing with O-acylation is controlled by the bulkiness of the acyl group. 相似文献
14.
Y. Sakaiguchi T. Shikata H. Urakami A. Tamura H. Hirata 《Colloid and polymer science》1987,265(8):750-753
Some cationic surfactants such as cetyltrimethylammonium bromide (CTAB) show a very spectacular viscoelasticity in solution, in even very diluted states, with some aromatic substances added, such as salicylic acid. Formerly, the authors established that the remarkable solution behaviour was the result of the entanglement of such enormously elongated giant micelles, based on recognition of the existence of large aggregates, through direct observation of them as substantial images under the electron microscope.In this report, we further confirm the relation between micelle length and solution viscoelasticity after arbitrarily obtaining different size aggregates by altering the media pH, or by admixing shorter chain length surfactants than CTAB, which alone did not induce viscoelasticity. 相似文献
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Exciton charge separation in photosynthetic reaction centers from purple bacteria (PbRC) and photosystem II (PSII) occurs exclusively along one of the two pseudo-symmetric branches (active branch) of pigment–protein complexes. The microscopic origin of unidirectional charge separation in photosynthesis remains controversial. Here we elucidate the essential factors leading to unidirectional charge separation in PbRC and PSII, using nonadiabatic quantum dynamics calculations in conjunction with time-dependent density functional theory (TDDFT) with the quantum mechanics/molecular mechanics/polarizable continuum model (QM/MM/PCM) method. This approach accounts for energetics, electronic coupling, and vibronic coupling of the pigment excited states under electrostatic interactions and polarization of whole protein environments. The calculated time constants of charge separation along the active branches of PbRC and PSII are similar to those observed in time-resolved spectroscopic experiments. In PbRC, Tyr-M210 near the accessary bacteriochlorophyll reduces the energy of the intermediate state and drastically accelerates charge separation overcoming the electron–hole interaction. Remarkably, even though both the active and inactive branches in PSII can accept excitons from light-harvesting complexes, charge separation in the inactive branch is prevented by a weak electronic coupling due to symmetry-breaking of the chlorophyll configurations. The exciton in the inactive branch in PSII can be transferred to the active branch via direct and indirect pathways. Subsequently, the ultrafast electron transfer to pheophytin in the active branch prevents exciton back transfer to the inactive branch, thereby achieving unidirectional charge separation.Essential factors leading to unidirectional charge separation in photosynthetic reaction centers are clarified via nonadiabatic quantum dynamics calculations. 相似文献
20.
(+)-Biotin (1) was synthesized in 25% overall yield over 11 steps from L-cysteine. The contiguous asymmetric centers at C-3a and C-6a were formed through a novel and highly stereoselective Lewis base-catalyzed cyanosilylation of alpha-amino aldehyde 3 to provide anti-O-TMS-cyanohydrin 4 with high stereoselectivity and in high yield (anti/syn = 92:8, 96%). Treatment of 4 with a di-Grignard reagent, 1,4-bis(bromomagnesio)butane, followed by carbon dioxide, efficiently installed the 4-carboxybutyl chain at C-4 to give keto acid 5. The final cyclization to bicyclic compound 7b, a precursor to 1, was realized by a palladium-catalyzed intramolecular allylic amination of cis-allylic carbonate 6b that was elaborated from 5. 相似文献