Enantioselective addition Of diketene to aldehydes promoted by chiral schiff base—titanium alkoxide complex. Application to asymmetric synthesis of potential inhibitors of HMG coenzyme reductase

Highly enantioselective addition of diketene to aldehydes was achieved by using novel Schiff base—titanium alkoxide complexes. Up to 92% ee of 5-hydroxy-3-oxoesters was obtained. This procedure provides an efficient method for the asymmetric synthesis of potential inhibitors of HMG coenzyme reductase.     

Research and Development of the Coprecipitation Process for Lanthanum Germanate Oxyapatite

Although lanthanum germanate oxyapatite (La–Ge–O) has shown good potential for use as a solid electrolyte in energy storage applications, its synthesis has been challenging by either solid‐ or solution‐state methods. In this study, a new synthesis of La–Ge–O was developed through a coprecipitation technique, in which a highly concentrated homogeneous aqueous solution of La and Ge was prepared from aqueous ammonium germanate and lanthanum nitrate solutions with the addition of dilute nitric acid. Several precipitates were formed by pH manipulation, including an amorphous material obtained at pH > 3. Compared to the individual precipitation behaviors of the parent compounds, the amorphous precipitate was formed only from the aqueous two‐component mixture, and appeared to contain both metals. This material was transformed into crystalline mixtures upon heating at 1273 K. The crystalline phases were La₂Ge₃O₉ and hexagonal‐type GeO₂ when the precipitate was formed below pH 8, and the La–Ge–O and La₂Ge₂O₇ phases when the precipitate was formed around pH 8. Product formation from the coprecipitate was discussed based on X‐ray diffraction and thermal analyses. The improved availability of La–Ge–O will allow more extensive investigations of its useful properties.     

Synthesis of polychloroprene–silica composites by sol‐gel method in the presence of modified polychloroprene containing triethoxysilyl group

Triethoxysilyl‐modified polychloroprene (CR) latex was synthesized by the emulsion copolymerization of 2‐(3‐triethoxysilylpropyl)‐1,3‐butadiene with chloroprene. This latex was mixed with unmodified CR latex and tetraethoxysilane to obtain CR–silica composites by sol‐gel reaction in the latex. SEM observation showed that the silica particles in unvulcanized composites have various diameters ranging from 0.1 to 0.6 μ m, and their size became larger with the decrease of the silica content. Vulcanized CR–silica composites showed that the tensile modulus and tear strength improved with an increase of the amount of modified CR. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1545–1552, 2005     

Surface Orientation and Wetting Phenomena in Si/α-Alumina System at 1723 K

Wetting phenomena and the effect of alumina surface orientation on the wettability in Si/α-Al₂O₃ system were studied by an improved sessile drop method using     ,     , C(0001) faces of single crystals and polycrystals at 1723 K in a reducing Ar–3% H₂ atmosphere. The contact angles show a vibration behavior for all the single crystals but to a less extent for the polycrystals. The extent of the vibration correlates not only with the reaction intensity but also with the stability of the Si droplet on the alumina surfaces. The interfacial reaction leads to the formation of a series of reaction rings, which is more serious at the single crystal surfaces. More importantly, the wettability is dependent on the alumina surface orientation, with the intrinsic contact angles being about 98±2°, 101±1°, 69±1°, and 98±2°, respectively, for the     ,     , C(0001) and polycrystal α-Al₂O₃ substrates. The much smaller contact angle for molten Si on the C(0001) surface is explained by the favorable reduction in the Si/α-Al₂O₃ interfacial free energy by the terminated and enriched aluminum atoms at the reconstructed     surface. The importance of the aluminum presence at the Si/α-Al₂O₃ interface to the wettability of this system was further demonstrated by a substantial improvement in the wettability of the     α-Al₂O₃ substrates by Si–Al alloys.     

Preparation of micro-dot electrodes of LiCoO2 and Li4Ti5O12 for lithium micro-batteries

Fabrications of micro-dot electrodes of LiCoO₂ and Li₄Ti₅O₁₂ on Au substrates were demonstrated using a sol-gel process combined with a micro-injection technology. A typical size of prepared dots was about 100 μm in diameter, and the dot population on the substrate was 2400 dots cm⁻². The prepared LiCoO₂ and Li₄Ti₅O₁₂ micro-dot electrodes were characterized with scanning electron microscopy, X-ray diffraction, micro-Raman spectroscopy, and cyclic voltammetry. The prepared LiCoO₂ and Li₄Ti₅O₁₂ micro-dot electrodes were evaluated in an organic electrolyte as cathode and anode for lithium micro-battery, respectively. The LiCoO₂ micro-dot electrode exhibited reversible electrochemical behavior in a potential range from 3.8 to 4.2 V versus Li/Li⁺, and the Li₄Ti₅O₁₂ micro-dot electrode showed sharp redox peaks at 1.5 V.     

Relationship between electron sensitivity and chemical structures of polymers as electron beam resists. VI: Electron sensitivity of various acetalized poly(vinyl alcohol)s

Acetalized poly(vinyl alcohol)s which were synthesized from poly(vinyl alcohol) (PVA) and aldehyde or ketone were evaluated as electron beam (EB) resists, in order to investigate the relationship between EB sensitivity and chemical structures of the polymers. It was found that the acetalized PVAs were easily crosslinked by EB exposure. The main mechanism of crosslinking may be radical reaction at acetal group. The sensitivity of the acetalized PVA depended on the structure of the acetal group. Acetalized PVAs synthesized from benzaldehyde, in which the electron attracting group was substituted on the benzene ring and from linear aliphatic aldehyde having a long alkyl chain, had high sensitivity. A high sensitivity of 7.2 × 10⁻⁷ C/cm² was attained when the acetalized PVA synthesized from p-chloro-benzaldehyde was used. Acetalized PVAs synthesized from PVA and aldehyde having a cyclic structure had an excellent dry etching durability and were suitable as negative EB resists.     

Decomposition and regeneration of methane in the absence and the presence of a hydrogen-absorbing alloy CaNi5

Suitable catalysts for the decomposition of methane into carbon and hydrogen and for the regeneration of methane by hydrogenation of the carbon have been looked for in a series of transition metals and precious metals supported on various carriers. The most active catalyst for both reactions was Ni/SiO₂. The carbon formed on this catalyst was thermodynamically less stable than graphite. The different rate equations for the decomposition of methane obtained for the fresh and carbon deposited Ni/SiO₂ suggest that the rate-determining steps are different for the two catalysts. The highest number of carbon atoms deposited per one Ni atom was 31 at 773 K. However, the number of methane molecules recovered easily at 773 K was limited to 1.5 per Ni atom.

A physical mixture of Ni/SiO₂ and CaNi₅, a hydrogen-absorbing alloy, enhanced the decomposition rate of methane, enabling the complete conversion of methane at 773 K beyond the thermodynamic limitation. The presence of CaNi₅ at 273 K separated from the catalyst in a reaction system further enhanced the decomposition of methane due to an increased hydrogen-absorbing capacity of the CaNi₅ at low temperatures. The carbon deposited on Ni/SiO₂ in this case was reactive to be hydrogenated back to methane at 773 K, giving an average 7.5 CH₄ molecules per one Ni atom.     

Further Improvement in Mechanical Properties of Highly Anisotropic Silicon Nitride Ceramics

Si₃N₄ceramics were fabricated by tape casting of a raw-powder slurry seeded with three types of rodlike β-Si₃N₄particles. The effects of seed size on the microstructure and mechanical properties of the sintered specimens were investigated. All the seeded and tape-cast silicon nitrides presented an anisotropic microstructure, where the elongated grains grown from seeds were preferentially oriented parallel to the casting direction. The orientation degree of these grains, f ₀, was affected by seed size, and small-seed addition led to the highest f ₀value. This material exhibited high bending strength (∼1.4 GPa) and high fracture toughness (∼12 MPa^.m^1/2) in the direction normal to the grain alignment, which were attributed to the highly anisotropic and fine microstructure.     

Preparation and Properties of Carbon/Zeolite Composites with Corrugated Structure

Composites of carbon/zeolite with corrugated structures were prepared by carbonization, steam activation and/or hydrothermal treatment of corrugated paper. No zeolite formation resulted from conventional hydrothermal treatment of the carbonized and activated samples in NaOH solution but zeolite Na P1 was formed by addition of silica to the solution. By contrast, zeolites Na P1 and Na A were formed by the in-situ crystallization method (hydrothermal treatment of solid samples impregnated with NaOH solution). With higher impregnating NaOH concentrations, longer reaction times and higher reaction temperatures, the products changed to sodalite- and cancrinite-type compounds. Hydrothermal treatment was effective in increasing the specific surface area of the products by the formation of zeolite from amorphous calcium aluminosilicate, and also increased the mechanical strength by gluing together the carbon fibers in the samples. The resulting samples showed enhanced adsorption for polar molecules such as ammonia, water vapor and methanol due to the formation of composites of activated carbon with hydrophilic zeolites.     

Potato and soy peptides alter caecal fermentation and reduce serum non‐HDL cholesterol in rats fed cholesterol

We examined the effect of potato peptides (PPC) in rats fed a cholesterol‐enriched diet, in comparison with two cholesterol‐enriched diets containing soy peptides (SPC) or casein (CNC), and a cholesterol‐free diet containing casein (CN) for 4 weeks. The serum non‐high‐density lipoprotein (HDL) cholesterol level was lower in the PPC‐ (–18.39%) and SPC‐fed (–32.76%) groups (p <0.05) than in the CNC‐fed group at the end of the feeding period. The low‐density lipoprotein receptor mRNA level in the PPC‐fed group, and cholesterol 7α‐hydroxylase and scavenger receptor class B type 1 mRNA levels in the SPC‐fed group, were higher (p <0.05) than in the CN‐ and CNC‐fed groups. Faecal neutral sterol and caecal short‐chain fatty acid concentrations in the PPC‐ and SPC‐fed groups were higher (p <0.05) than in the CN‐ and CNC‐fed groups. The faecal total acidic sterol concentration was higher in the SPC‐fed group than in the CN‐ and PPC‐fed groups. Caecal anaerobe and Bifidobacterium populations were higher (p <0.05) in the PPC‐ and SPC‐fed groups than in the CN‐fed group. This study suggests that potato peptides, as soy peptides, alter caecal fermentation and steroid absorption and reduce the serum non‐HDL cholesterol level in rats fed cholesterol.