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41.
This article reviews the enantio-differentiating hydrogenation of prochiral ketones over a asymmetrically modified catalyst, focusing on the hydrogenation of simple prochiral alkanones. The parameters affecting catalytic activity and enantiodifferentiating ability are considerable in number, and each parameter should be optimized in order to attain a highperformance enantio-differentiating catalyst. Optimization of the parameters and the mode of enantio-differentiation are discussed and compared with the enantio-differentiating hydrogenation of β-ketoesters. 相似文献
42.
Dimethylsiloxane-tetramethyl-p-silphenylenesiloxane-dimethylsiloxane (DMS-TMPS-DMS) triblock copolymer was synthesized by employing living anionic polymerization of hexamethylcyclotrisiloxane (D3). Two synthetic methods were carried out for the polymerization. One of those methods was the anionic polymerization of D3 initiated at the silanolate anion which was prepared from the terminal hydroxyl group of silanol-terminated TMPS prepolymer by reaction with n-butyllithium (method 1). The other was the coupling reaction of vinyl-terminated TMPS prepolymer with hydrosilyl-terminated DMS prepolymer obtained from the anionic polymerization of D3 by using diphenylmethylsilanolate anion as initiator (method 2). In method 1, DMS contents of the copolymers ranged from 25.8 to 72.5 wt% and the values agreed with the ratio of D3 to TMPS prepolymer. The weight-average molecular weights ranged from 1.36×104 to 19.4×104 and were close to the predicted values calculated from the of the TMPS prepolymer and the amount of D3 added. In the case of method 2, weight-average molecular weights ranged from 19.5×104 to 24.2×104. The high molecular weight copolymer could thus be obtained by method 2. Intrinsic viscosity values of the triblock copolymers agreed with calculated values obtained by considering the copolymer as a binary mixture of these homopolymers. Differential scanning calorimetry and thermogravimetry were carried out on the triblock copolymers. The equilibrium melting temperatures of each of the copolymers were very close to that of poly-TMPS (160°C). The glass transition temperature and heat of fusion were decreased as the DMS content was increased. The thermogravimetric curves for the copolymers indicated that the thermal stability of the triblock copolymer was intermediate between the DMS and TMPS homopolymers. 相似文献
43.
As previously reported, high surface area microporous carbons with long-range order can be synthesized by using zeolite Y as a template. In this work, an attempt is made to synthesize porous carbon using several other types of zeolites (zeolite β, ZSM-5, mordenite and zeolite L). Special attention is paid to whether the structural regularity of each zeolite can be transferred to the carbon structure as well as with the case of zeolite Y. The carbon filling method was then examined to see which gives the highest regularity to the carbon structure. It has been found that the optimum carbon filling method for zeolite Y is not an optimum one for the other zeolites and the degree of the regularity of long-range ordering in the carbons strongly depends on zeolite type. The order of the regularity in the resultant carbons is zeolite β>>zeolite L>mordenite>ZSM-5. The effect of zeolite type on the regularity is discussed in relation to the size and the shape of the zeolite channels. 相似文献
44.
Momoji Kubo Tsuguo Kubota Changho Jung Minako Ando Satoshi Sakahara Kenji Yajima Kotaro Seki Rodion Belosludov Akira Endou Seiichi Takami Akira Miyamoto 《Catalysis Today》2004,89(4):479-493
Recently, we introduced a concept of combinatorial chemistry to computational chemistry and proposed a new method called “combinatorial computational chemistry”, which enables us to perform a theoretical high-throughput screening of catalysts. In the present paper, we reviewed our recent application of our combinatorial computational chemistry approach to the design of new catalysts for high-quality transportation fuels. By using our combinatorial computational chemistry techniques, we succeeded to predict new catalysts for methanol synthesis and Fischer–Tropsch synthesis. Moreover, we have succeeded in the development of chemical reaction dynamics simulator based on our original tight-binding quantum chemical molecular dynamics method. This program realizes more than 5000 times acceleration compared to the regular first-principles molecular dynamics method. Electronic- and atomic-level information on the catalytic reaction dynamics at reaction temperatures significantly contributes the catalyst design and development. Hence, we also summarized our recent applications of the above quantum chemical molecular dynamics method to the clarification of the methanol synthesis dynamics in this review. 相似文献
45.
Changho Jung Hideyuki Tsuboi Michihisa Koyama Momoji Kubo Ewa Broclawik Akira Miyamoto 《Catalysis Today》2006,111(3-4):322-327
CO adsorption over Pd4 and Pt4 cluster supported by c-ZrO2(1 1 1) and CeO2(1 1 1) catalyst systems was investigated using periodic density functional method in order to clarify the support effect on CO activation. We found that the support increases the CO activation for bridge and three-fold sites but decreases for the atop site. Moreover, it was found that the support changes the site preference for the CO adsorption. Bridge site on both the Pt4/c-ZrO2 and Pt4/CeO2 show larger CO adsorption energies than those on the other sites while the atop site is energetically preferable on isolated Pt4 cluster. c-ZrO2 supported Pd shows the largest CO activation with large charge transfer from the catalyst to the CO molecule. This reveals that ZrO2 supported Pd can be a good catalyst for CO activation because of its higher probability to the three-fold site CO adsorption. We also found that positively charged M4 clusters on the support keep their strong electron-donating properties and have enough charge density to contribute to the activation of an adsorbed CO molecule by a charge transfer. 相似文献
46.
47.
Free primary alcohols in oils and waxes from germs,kernels and other components of nuts,seeds, fruits and cereals 总被引:2,自引:0,他引:2
Kazuko Kawanishi Kumlko Aoki Yohei Hashimoto Akira Matsunobu 《Journal of the American Oil Chemists' Society》1991,68(11):869-872
The composition of free primary alcohols in oils and waxes obtained from the germ, kernel, seed coat, shell and skin (peel)
of various nuts, seeds, fruits and cereals and from the chrysalis of silkworm was examined. These alcohols are usually present
in small amounts, along with large quantities of hydrocarbons, esters and glycerides in oils and waxes. Thus, it is necessary
to remove hydrocarbons, esters and glycerides to analyze the alcohols. We found that preparative reverse-phase thin-layer
chromatography (TLC) was the best way to isolate alcohols from oils and waxes. Gas liquid chromatography (GLC) then detected
hexacosanol, octacosanol and triacontanol in the oils and waxes. Octacosanol usually was the predominant alcohol. Relationships
between the organs from nuts, seeds, fruits and cereals and the contents of octacosanol are suggested. For example, degermed
kernels contained two times more octacosanol than the germ, and the skin coat and shell contained one-half and one-fortieth
the octacosanol of the germ, respectively. 相似文献
48.
The local disturbances ahead of a running crack front in a viscoelastic solid were measured through noncontact electro-optical tools. It was observed that the very high local strain rate up to 200/sec exists even in the present quasistatic loading case. It may be concluded that the running crack propagation velocities, not the conventional average strain rates ranging from about 10?4/sec to 10?2/sec, govern the local disturbances, as the crack propagation velocities always exceed 200m/sec for both average strain rates, while the local strain rates observed do not show much differences between both average strain rate cases. 相似文献
49.
Keiji Mimura Susumu Yukawa Yoshio Mori Kazuya Okada Masatoshi Mune Osamu Nishikawa Akira Hibino Miyahiko Sonobe Tetuya Goto Hiroshi Nomoto 《Lipids》1991,26(12):1102-1107
We investigated the effect of platelet-activating factor (PAF) and of the PAF specific antagonist CV-6209 on plasma lipid
metabolism, and particularly on post-heparin plasma lipolytic activity in male Wistar rats. Lipoprotein lipase (LPL) activity
was enhanced by intravenous injection of PAF before intravenous injection of heparin when the PAF dose was low (0.2 μg/kg).
PAF activated hepatic triacylglycerol lipase (HTGL) activity dose-dependently. Plasma triacylglycerols (TG) significantly
decreased with the activation of LPL and/or HTGL. Plasma total cholesterol (TC) and phospholipid (PL) levels decreased at
a low dose of PAF (0.2 μg/kg), but increased when higher doses were used. The PAF antagonist CV-6209 partially reversed the
PAF induced effects on HTGL, TC and PL.
Based on a paper presented at the Third International Conference on Platelet-Activating Factor and Structurally Related Alkyl
Ether Lipids, Tokyo, Japan, May 1989. 相似文献
50.
Effects of dietary lipids on daunomycin-induced nephropathy in mice: comparison between cod liver oil and soybean oil 总被引:3,自引:0,他引:3
Although it is well known that dietary lipids affect the course of glomerulonephritis in rats and humans, the precise mechanisms
involved have not been fully elucidated. The aim of this study was to investigate the effects of different types of dietary
lipids (fish oil and vegetable oil) on daunomycin (DM)-induced nephropathy in mice fed on soybean oil (SO) or cod liver oil
(CLO). Urinary protein excretion, serum albumin, creatinine, total cholesterol, and TG were measured, and glomerular histological
changes were evaluated. Antioxidant enzymes were also measured, along with the levels of lipid peroxide, GSH, thromboxane
(Tx) B2′ and 6-keto prostaglandin F1α in renal cortical tissue. Dietary CLO significantly reduced urinary albumin excretion and ameliorated the histological changes
induced by DM. The increase of tissue lipid peroxide levels seen in SO-fed mice was suppressed in CLO-fed mice, whereas CLO-fed
mice showed higher GSH levels than SO-fed mice throughout the experiment. In addition, renal tissue GSH peroxidase activity
was significantly higher at 72 h after DM injection in CLO-DM mice than in SO-DM mice. Both renal cortical TxB2 and 6-keto PGF1α levels were significantly lower in CLO-DM mice than in SO-DM mice. These results suggest that inhibition of oxidative damage
by dietary CLO played an important role in the prevention of DM nephropathy in this mouse model. The effect of CLO was closely
associated with the inhibition of Tx synthesis. 相似文献