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71.
We have studied the adsorption of benzenethiol molecules on the Au(111) surface by using first principles total energy calculations. A single thiolate molecule is adsorbed at the bridge site slightly shifted toward the fcc-hollow site, and is tilted by 61 degrees from the surface normal. As for the self-assembled monolayer (SAM) structures, the (2 square root of 3 x square root of 3)R30 degrees herringbone structure is stabilized against the (square root 3 x square root 3)R30 degrees structure by large steric relaxation. In the most stable (2 square root 3 x square root 3)R30 degrees SAM structure, the molecule is adsorbed at the bridge site with the tilting angle of 21 degrees, which is much smaller compared with the single molecule adsorption. The van der Waals interaction plays an important role in forming the SAM structure. The adsorption of benzenethiolates induces the repulsive interaction between surface Au atoms, which facilitates the formation of surface Au vacancy. 相似文献
72.
A new method for installation of aryl and alkenyl groups onto a cyclopentene ring and synthesis of prostaglandins 总被引:1,自引:0,他引:1
Kobayashi Y Murugesh MG Nakano M Takahisa E Usmani SB Ainai T 《The Journal of organic chemistry》2002,67(20):7110-7123
To construct a new strategy for synthesis of cyclopentanoids, the transition metal-catalyzed coupling reaction of cis 4-cyclopentene-1,3-diol monoacetate 1 with hard nucleophiles, R(T)-m, was investigated (eq 1 in Chart 1). Although preliminary experiments using PhZnCl, PhSnMe(3), [Ph-B(Me)(OCH(Me)CH(Me)O)]-Li(+) (6a) (derived from boronate ester 4a (R(T) = Ph) and MeLi) in the presence of a palladium or a nickel catalyst resulted in production of unidentified compounds, enone 16, and/or ketone 17 or recovery of 1, a new borate 5a (derived from 4a and n-BuLi) in the presence of a nickel catalyst (NiCl(2)(PPh(3))(2)) in THF at room temperature furnished the trans coupling products 2a (R(T) = Ph) and 3a (R(T) = Ph) in high combined yield, but with a low product ratio of 0.9:1. The ratio was improved to 13:1 by addition of t-BuCN and NaI into the reaction mixture. This is the first successful example of the reaction of 1 with a hard nucleophile, and the increase in the ratio, realized with the additives, is unprecedented. This reagent system (borate 5 (1.2-1.8 equiv), NiCl(2)(PPh(3))(2) (5-10 mol %), t-BuCN (2-5 equiv), NaI (0.5-1 equiv), THF, room temp) was further investigated with aryl borates 5b-g and alkenyl borates 5h-n to afford 2b-n in moderate to good yields (52-89%) with practically acceptable levels of the regioselectivity (5 approximately 21:1), thus establishing the generality of the reaction (Table 2, eqs 6 and 7). Starting with the products of the coupling reaction, syntheses of the prostaglandin intermediates 13 and 14 (for 11-deoxy-PGE(2) and PGA(2)) and Delta(7)-PGA(1) methyl ester (15) were accomplished efficiently. During these investigations, LDA, LiCA, and LHMDS were found to be equally efficient bases for aldol reaction at the alpha' (alpha prime) position of cyclopentenones 39, 40, and 41 (Table 3). 相似文献
73.
Takakazu Yamamoto Yukiko Muramatsu Takahisa Shimizu Wataru Yamada 《Macromolecular rapid communications》1998,19(5):263-266
π-Conjugated polymers bearing nitro substituent(s), e.g., poly(aryleneethynylene) (PAE) type polymers and poly(4,8-dinitroanthraquinone-1,5-diyl) P(4,8-NO2-1,5-AQ), show semiconducting properties with electrical conductivities of an order of 10−7 to 10−6 S · cm−1 at room temperature without special oxidation and reduction of the polymer. P(4,8-NO2-1,5-AQ) shows a large shift of phase in alternating current (ac) measurements and a unique magnetism at low temperature. 相似文献
74.
Takahisa Iida Toshio Sugizaki Toshifumi Kageyama Osamu Moriya 《Journal of polymer science. Part A, Polymer chemistry》1998,36(4):655-663
Tributylstannylated silicic acid (TBSA), which was regarded as a protected polymeric silanol against self-condensation to give silica gel, was newly prepared from the reaction of water glass (WG) and bis(tributyltin) oxide (TBO). The ratios of Si/Sn contained in TBSA were determined by gravimetric analysis to be in the range of 2–3. The gelation of TBSA in usual organic solvents such as hexane, benzene, and dichloromethane was not observed over 3 weeks. In addition, TBSA was shown to be a convenient precursor for the preparations of silica gel modified with organofunctional groups. From the reaction of TBSA with trimethoxysilanes and aromatic alcohols, the silica gels havingorganofunctional groups were obtained with the elimination of a tributyltin group. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 655–663, 1998 相似文献
75.
Manabu Tsumura Takahisa Iwahara Toshifumi Hirose 《Journal of polymer science. Part A, Polymer chemistry》1996,34(15):3155-3161
The polycarbosilanes (PCS) with meta-linkage bending unit ((SINGLE BOND)Me2Si(SINGLE BOND)m(SINGLE BOND)C6H4(SINGLE BOND)Me2Si(SINGLE BOND)CH2CH2(SINGLE BOND)) were successfully synthesized in mild conditions by hydrosilylation in the presence of [Pt{(CH2(DOUBLE BOND)CHSiMe2)2O}2]. The PCS obtained were soluble in various solvents owing to the lowering of the crystallinity. These properties are well compared with those of the PCS [(SINGLE BOND)Me2Si(SINGLE BOND)p(SINGLE BOND)C6H4(SINGLE BOND)Me2Si(SINGLE BOND)CH2CH2(SINGLE BOND)]n. © 1996 John Wiley & Sons, Inc. 相似文献
76.
Stefan Machill Takahisa Shodai Yoji Sakurai Jun-ichi Yamaki 《Journal of Solid State Electrochemistry》1999,3(2):97-103
Tin-based composite oxide materials have received considerable attention as potential anode materials for rechargeable lithium
batteries. In this contribution we present the results of our investigations of the SnOB2O3P2O5 system. We have investigated its electrochemical properties and especially its cycling performance. A focus of our interest
was to explain the structural changes which occur during lithium cycling and their strong dependence on the preparation method.
A part of the SnO component was converted into a very stable metallic phase. In addition, a decrease was observed in capacity
owing to the formation of isolated and inactive tin grains. We also report on structural changes in the B2O3P2O5 matrix.
Received: 2 October 1997 / Accepted: 3 July 1998 相似文献
77.
Yoshihiro Koide Kei Fujisawa Michiharu Nakane 《Colloids and surfaces. A, Physicochemical and engineering aspects》2008,330(2-3):108-111
A thin metallic bilayer consists of fused hollow hemispheres of 930 nm in diameter is fabricated by sputter deposition of Ti and Fe at 50 and 5 nm of thickness, respectively, onto an array of spherical polystyrene colloidal particles. The fused metal hemispheres are utilized to assemble polystyrene colloidal particles of smaller diameters (800 nm) into non-contact two-dimensional periodic array by trapping them in the metallic wells. 相似文献
78.
Katsuhiro Nose Takahisa Omata Shinya Otsuka-Yao-Matsuo Hideaki Maeda 《Journal of luminescence》2007,126(1):21-26
The role of organic amines in the colloidal synthesis of CdSe quantum dots (QDs) has been studied. CdSe QDs were synthesized from the source solutions containing 5 vol% of amines having various alkyl chain lengths, stereochemical sizes and electron donation abilities. The role of the additional amines was evaluated on the basis of the photoluminescence (PL) properties such as PL wavelength and intensity of the obtained CdSe QDs. The observed PL spectra were explained by the fact that the amines behaved as capping ligands on the surface of the QDs in the product colloidal solution and complex ligands for cadmium in the source solutions. It was shown that the particle size was controlled by the diffusion process depending on the mass and stereochemical shape of the amines, and the luminescence intensity increased with the increasing electron donation ability and capping density of the amines. 相似文献
79.
Oikawa M Saito T Takahisa K Suga Y Kino K Nakagawa T Tohei T Abe K Ueno H 《Physical review letters》2000,84(11):2338-2341
Out of plane measurements of the angular correlations for the 12C(e, e(')n) reaction have been performed for the first time in the giant resonance region. The cross sections were directly separated into the longitudinal and transverse, longitudinal-transverse, and transverse-transverse components. The cross section at the peak of the giant resonance ( omega = 22.5 MeV) has been found to be almost all longitudinal. It was reproduced by the multipole expansion with E0 and E2 components besides E1. The longitudinal-transverse component might have a maximum around 24 MeV. The transverse-transverse component is very small over the giant resonance. 相似文献
80.
K. Oda Y. Imasaka K. Tsukahara T. Yamauchi Y. Nakane Y. Yamaguchi 《Radiation measurements》2003,36(1-6):119-124
The effect of radiators supplying charged particles to plastic nuclear track detectors has been investigated both experimentally and theoretically in order to apply them to personal dosimeters for high-energy neutrons. Performance of four types of radiator materials, CH2, CD2 (deuterized hydrocarbon), LiF (lithium fluoride) and C (graphite), was checked in a quasi-monoenergetic neutron field generated by p-Li reactions. The efficiency has been numerically calculated based on a model with a special attention to the angular dependence of cross sections and data of characteristic response to light ions. The effect of respective radiator candidates has been evaluated as a function of the neutron energy. A two-layer radiator has also been proposed to adjust the energy dependence of the relative sensitivity to conversion factor for dose-equivalent. 相似文献