Ring hydrogenation of naphthalene and 1-naphthol over supported metal catalysts in supercritical carbon dioxide solvent

Catalytic ring hydrogenations of naphthalene and 1-naphthol were studied over several supported metal catalysts in supercritical carbon dioxide solvent at low temperature. Higher concentration of hydrogen in supercritical carbon dioxide and lower reaction temperature were responsible for higher catalyst activity and selectivities to the desired partial ring hydrogenated products as compared with those observed in organic solvent for the same catalyst.     

Ethanol production from raw starch by a recombinant yeast having saccharification and fermentation activities

In order to develop a method for converting raw starch into ethanol efficiently, direct fermentation of ozonized raw starch using a recombinant yeast was investigated. Ozonolysis was carried out as a pretreatment to convert raw starch into ethanol rapidly and efficiently, and then the effect of the ozone degradation conditions on the degree of polymerization and the amount of amylose in a raw starch was determined. Since the degree of polymerization was low and the amount of amylose was high, raw starch treated with an ozone concentration of 40 gm^?3 and an ozonation time of 30 min was the material chosen for alcohol fermentation. Though the recombinant yeast could not convert the untreated raw starch, it converted the soluble starch and the ozonized raw starch at a comparatively high yield into ethanol. About 56% of the ozonized raw starch decomposed, and the ethanol concentration obtained from the ozonized raw starch was markedly greater than that obtained from untreated raw starch. The dynamic behavior of cell growth, substrate degradation, and ethanol production was examined in a continuous culture under various dilution rates, and the optimal dilution rate, ie 0.15 h^?1, was determined for maximizing the ethanol productivity (amount of ethanol produced per unit time). © 2002 Society of Chemical Industry     

Dehydration of Gels and Glasses in the Systems B2 O3-SiO2 and ZrO2-SiO2 Prepared by the Sol-Gel Process from Metal Alkoxides

Dehydration of gels prepared by the sol-gel process from metal alkoxides in the systems B₂O₃-SiO₂ and ZrO₂-SiO₂ was determined by measuring the shrinkage of the gel on heating. Dehydration was enhanced with increased ZrO₂ content, whereas it decreased with B₂O₃ content. Diffusion of water was also measured in the nonporous glasses obtained by heating the gels. The diffusion rate was independent of the composition of the glass.     

Role of tungsten in promoting selective reduction of NO with CO over Ir/WO3–SiO2 catalysts

Catalytic hydrogenation of naphthalene to decalin was studied over a carbon-supported rhodium catalyst in supercritical carbon dioxide solvent at 333 K, and the results were compared with those in an organic solvent. cis-, trans-Decalin and tetralin were formed from the beginning of the reaction in supercritical carbon dioxide. Higher concentration of hydrogen in carbon dioxide solvent and on the active site, and also the suppression of desorption of partially hydrogenated tetralin molecules from the active site would be responsible for higher selectivity to cis-decalin in supercritical carbon dioxide than that in an organic solvent.     

Thermal strain of high strength polyethylene fiber in low temperature

High strength polyethylene fiber (Toyobo, Dyneema® fiber: hereinafter abbreviated to DF) has a negative thermal expansion coefficient. Relation between fiber structure and thermal strain of DF used as reinforcement of DF reinforced plastic (DFRP) for cryogenic use was investigated. The crystallinities and orientation angles of several kinds of polyethylene fibers having different modulus from 15 to 134Gpa (herein after abbreviated to DFs) were measured by NMR and X‐ray. We obtained the parameters of the mechanical series‐parallel model composed of crystal and amorphous by crystallinity and modulus. Thermal expansion coefficients of DFs were estimated by mechanical series‐parallel model. All DFs having different modulus showed negative thermal expansion coefficients in the temperature range from 180 to 300K, and absolute values of those markedly increased by increasing tensile modulus of DF. The estimated thermal expansion coefficients showed negative values, and thermal strains showed a similar curve to observed ones mostly. Average thermal expansion coefficients in the temperature range from 180 to 300K estimated by mechanical model agreed with the observed ones. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2918–2925, 2004     

Alternative technologies for biotechnological fuel ethanol manufacturing

The challenges of implementing biorefineries on a global scale include socioeconomic, financial, and technological constraints. In particular, the development of biorefineries is tightly linked to the continued availability of fermentation raw materials. These constraints can be relaxed by the use of diverse raw materials, while advances that confer higher flexibility would enable biotechnological plant managers to swiftly react to volatile markets. In conventional processes, Saccharomyces cerevisiae grows on a relatively limited range of substrates, and produces only a single product—ethanol. Given the observed maturity of the S. cerevisiae fermentation technology, alternatives to baker's yeast may be needed to tip the economic balance in favour of biotechnological ethanol. These alternative fermentation technologies may allow a greater diversity of substrates to be used to produce an individually tailored mix of ethanol and other chemicals. Copyright © 2007 Society of Chemical Industry     

Prostaglandin-like substances formed during autoxidation of methyl linolenate

Prostaglandin-like substances other than 3-(2-ethyl-5-hydroxy-3-oxo)-cyclopentanyl-2-propenal (compound I), which upon reacting with amino acids form reddish pigments, were purified, and their chemical structures were determined. Three red pigment-forming substances (RPS) in autoxidized methyl linolenate were purified successively by gel chromatography on Sephadex LH-20, column chromatography and thin layer chromatography on Silica Gel 60, and by high performance liquid chromatography on μ-Porasil. IR spectra of the RPS showed the absorption of an ester group (νC=O 1730 cm⁻¹ in CHCl₃) and of a longer branched chain (νC-H 2800–3100 cm⁻¹), in addition to the absorption bands observed in compound I. Electron impact mass spectra of the trimethylsilyl ethers obtained after reduction with NaBH₄ and NaBD₄ were analyzed in detail and compared with those of compound I. The structures of the RPS were identified as stereoisomeric methyl 8-[2-(2-formylvinyl)-3-hydroxy-5-oxo-cyclopentanyl]-octanoates derived from methyl 12-hydroperoxy-linolenate. Presented at the general meeting of the Japanese Society of Scientific Fisheries, held at Tohoku University, Sendai, Japan, October 1984.     

Synthesis of tetramethyl-p-silphenylenesiloxanedimethylsiloxane triblock copolymer by employing living anionic polymerization

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 $\text{M}\text{?}{}_{\mathrm{v}}$ 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.     

Separation of surfactant mixtures and their homologs by high performance liquid chromatography

A technique for separating similar and diverse ionogenic mixtures into their individual homologs was studied by high performance liquid chromatography on an octadecyl-silica (TSK Gel LS-410) column. Conditions used for the separation were: column size, 6 mm id×200 mm; mobile phase, water/methanol (15:85, v/v) containing (a) 1.0 M sodium perchlorate and adjsting to pH 2.5 with phosphoric acid, (b) 0.1 M and pH 3.5; column temp., 50 C. By using 2 mobile phase conditions, various surfactant mixtures were separated into their individual homologs and simultaneously distinguished from each other, regardless of their ionogenic properties.     

Differential scanning calorimetric studies on the glass transition temperature of polyhydroxystyrene derivatives containing sorbed water

Poly(4-acetoxystyrene) (PAS) and poly(4-acetoxy-3-methoxystyrene) (PAMS), poly(4-hydroxystyrene) (PHS) and poly(4-hydroxy-3-methoxystyrene) (PHMS) have been prepared. The effects of hydrogen bonding on the glass transition temperatures (T_g) of these polymers have been studied by differential scanning calorimetry. The T_g′s of partially hydrolyzed PAS and PAMS increased with the degree of hydrolysis. Partially hydrolyzed PAS and PAMS are estimated to be random copolymers, judging from the correspondence between the calculated and observed T_g′s of these polymers. The effect of water on the glass transition was also studied, and it was clarified how water adsorbed on the polymers acts as a hydrogen-bond breaker. The ‘critical water content’ is calculated from the decrease of T_g by water absorption, and the relation between hydrogen bonding and T_g is discussed.