Template synthesis of novel porous carbons using various types of zeolites

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.     

Design of new catalysts for ecological high-quality transportation fuels by combinatorial computational chemistry and tight-binding quantum chemical molecular dynamics approaches

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.     

Different support effect of M/ZrO2 and M/CeO2 (M = Pd and Pt) catalysts on CO adsorption: A periodic density functional study

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.     

Free primary alcohols in oils and waxes from germs,kernels and other components of nuts,seeds, fruits and cereals

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.     

Local disturbances preceding a running crack front in a viscoelastic solid

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.     

Aging and availability of binocular disparity and pictorial depth cues in 3D graphics contents

Some stereoblind observers do not perceive depth of 3D stimuli that depends on binocular disparity. These individuals, who have no disabilities, comprise over 5% of the general population. In addition, 17–30% of nonstereoblind young and young–middle people do not use disparity information in certain 3D environments, a phenomenon known as pseudo‐stereoblindness. This study aimed to investigate the relationship between aging and the proportion of pseudo‐stereoblindness in the general population. In an experiment, 134 nonstereoblind participants, ranging in age from 17 to 83 years, judged subjective depth of 3D stimuli containing binocular disparity and pictorial depth cues. Results showed that the proportion of pseudo‐stereoblindness among young (17–24 years old) and young–middle aged observers (25–39 years old) was 29%, in both cases. However, the proportion of pseudo‐stereoblind observers increased in older populations: 65% and 82% in the middle (40–54 years old) and senior (55–83 years old) age groups, respectively. These results suggest that a number of people, especially in elderly populations, have trouble perceiving depth from binocular disparity in 3D graphic contents despite their essential ability to use disparity information.     

Effect of platelet-activating factor on lipoprotein lipase and blood lipids

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.     

Effects of dietary lipids on daunomycin-induced nephropathy in mice: comparison between cod liver oil and soybean oil

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) B_2′ and 6-keto prostaglandin F_1α 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 PGF_1α 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.     

Plasma developable photoresist containing electronic excitation energy quenching system

A dry developable negative working resist composition comprised of poly(methyl isopropenyl ketone) (PMIPK) and 4-methyl-2,6-di(4′-azido-benzylidene) cyclohexanone-1 was examined. The main photochemical product formed in the resist pattern was found to be a secondary amine which crosslinks PMIPK. Post-annealing forms a hydrogen-bonded product which shows a powerful electronic excitation energy quenching effect. The quencher is more powerful than the aromatic compound arising from the azide by post-annealing only. The residual resist thickness of the negative pattern is about 80 percent of the initial thickness of the coating in spite of all the azide compound remaining in the resist coating. The obtained dry developed resist pattern has a high dry etch resistance. Etchings of Si and SiO₂ were performed by plasma and reactive ion etching, respectively.