Modifying ability of Ql-free coal-tar pitch to develop optical anisotropy in co-carbonizations

Carbonization properties of a Ql-free coal-tar pitch (CTP-ASM) prepared by selective precipitation were studied to evaluate it as a source for needle-coke. Its modifying ability for production of needlecoke in co-carbonizations with principal carbonizing substances which gave cokes of mozaic texture in single carbonizations was estimated by changing mixing ratios. The shape and size of the anisotropic optical texture in the co-carbonized coke were measured by point counting. CTP-ASM and Ashland A240, of eight additives, had the highest modifying ability in the co-carbonizations with Khafji vacuum residue. Both contained ca. 6% benzene-insolubles (Bl), and had f_a values of ≈0.9. Other additives of either lower or higher Bl or f_a showed less modifying ability. The modifying susceptibility of principal carbonizing substances varies with their structure and properties. Based on a systematic investigation of co-carbonizations the compatibility between a principal carbonizing substance and an additive is discussed from a viewpoint of their structural parameters.     

Structure and Properties of Endosperm Starch and Water Soluble Polysaccharides from Sugary Mutant of Rice (Oryza sativa L.)

Structure and properties of starch and water soluble polysaccharides (WSP) from sugary (su) endosperm of rice were examined. The su starch contained more amylose and had a somewhat higher ratio of the short chains to the long chains of amylopectin than normal starch. The WSP consisted of short α-1, 4-chains and their average degree of polymerization was 8.6 glucose units. Susceptibility of the su starch to crude Rh. glucoamylase was higher than that of the normal. The initial and final temperatures and heat of gelatinization of the su starch granules were much lower than those of the normal ones.     

A fast method for the determination of the efficiency coefficient of bare CR-39 detector

A fast and simple method for the determination of the efficiency coefficient (η) of bare CR-39 detector is presented and discussed. The efficiency coefficient of bare CR-39 detector is then calculated by different ways and the obtained values are found to be comparable to each other. The average value of η of bare CR-39 is found to be 0.20 ± 0.01 tracks cm⁻² day⁻¹ per Bq m⁻³.     

Computer simulation of CAICISS spectra of clean Cu(1 0 0) surface and Cu(1 0 0) surface by Pt deposition

The clean Cu(1 0 0) surface and Pt/Cu(1 0 0) surface by Pt deposition at room temperature have been investigated using the computer simulation of coaxial impact-collision ion scattering spectroscopy (CAICISS). The computer simulations employing the ACOCT program code, which treats the atomic collisions three-dimensionally and is based on the binary collision approximation (BCA), were carried out for the case of 3 keV He⁺ ions incident along the 〈1 0 0〉 and 〈1 1 0〉 azimuths of the clean Cu(1 0 0) and Pt/Cu(1 0 0) surfaces. The comparisons between ACOCT results and experimental CAICISS data show that the experimental results on the clean Cu(1 0 0) surface are relatively well reproduced by the ACOCT simulations including the inward relaxation of 1.2% in the first interlayer spacing and the outward relaxation of 1.6% in the second interlayer spacing, and that the ACOCT simulations for the Pt deposition with coverages of 2.35 ML and 2.75 ML on the Cu(1 0 0) surface appear the concentrations of 0.24 ML of Pt sitting 2.3 Å and 0.25 ML of Pt sitting 2.5 Å above the outermost atomic layer, respectively.     

[FeII(MeCN)4]2+(ClO4−)2 and [FeIIICl33] as Mimics for the Catalytic Centers of Peroxidase,Catalase and Cvtochrome P-450

Addition of [Fe^II(MeCN)²₄⁺(ClO⁻₄)₂ to solutions of hydrogen peroxide in dry acetonitrile (MeCN) catalyzes a rapid disproportionation of H₂O₂ via the initial formation of an adduct, [Fe^II(HOOH)↔Fe(O)(OH₂)]²⁺, which oxidizes a second H₂O₂ to dioxygen. This intermediate also cleanly oxidizes substituted hydrazines, alcohols, aldehydes, and thioethers by a two-electron process. The products for these H₂O₂ oxidations are consistent with those that result from catalase- and some peroxidase-catalyzed processes. In the same aprotic medium (MeCN) anhydrous Fe^IIICl₃ catalyzes the demethylation of N,N-dimethylaniline, the epoxidation of olefins, and the oxidative cleavage of 1-phenyl-1,2-ethanediol (and other 1,2-diols) by hydrogen peroxide. A mechanism is proposed in which an initial Lewis acid-base interaction of Fe^IIICl₃ with H₂O₂ generates a highly electrophilic Fe^III-oxene species as the reactive intermediate. For each class of substrate the products closely parallel those that result from their enzymatic oxidation by cytochrome P-450. Because of (a) the close congruence of products, (b) the catalytic nature of the Fe^IIICl₃/H₂O₂ reaction mimic, and (c) the similarity of the dipolar aprotic solvent (acetonitrile) to the proteinaceous lipid matrix of the biomembrane, the form of the reactive intermediate may be the same in each case. This is in contrast to the prevailing view that cytochrome P-450 acts as a redox catalyst to generate an Fe(V)-oxo species or an Fe(IV)-oxo cation radical as the reactive intermediate.     

Short- and long-term strength characteristics of particulate-filled cast epoxy resin

Particulate-filled thermosetting composites are widely used, yet little systematic work has been done on their long-term strength characteristics. In this study short-term tensile, flexural, and impact tests as well as tensile creep-rupture tests were made for unfilled and filled epoxy to clarify the effects of filler size, filler content, and temperature. Fillers used were silica, alumina particles, and glass beads. Test temperatures were varied from 25 to 110°C. As a result of short-term testing, it was found that the Petch relation held between strength and filler size if brittle fracture occurred, while a strength and filler size if brittle fracture occurred, while a strengthening effect existed when ductile fracture occurred. On creeprupture testing, a strengthening is observed with filler size and content for silica and glass beads. The Arrhenius plot of rupture time for various filler sizes and contents converges to a characteristic point corresponding to the glass transition temperature of the material. Using this relation, a modified Larson-Miller master rupture curve is proposed which can predict the long-term strength of particulate-filled thermosetting composites as functions of rupture time, temperature, filler size, and content.     

Novel anion exchange membranes having fluorocarbon backbone: Preparation and stability

Anion exchange membranes with excellent durability were prepared by chemical modification of Nafion. The modification was achieved by transformation of the sulfonic acid group into quaternary ammonium group. Namely, Nafion membrane was first converted into an amide-type membrane. Reduction of the carbonxyl group to methylene followed by quaternarization with alkyl iodide resulted in the formation of an anion exchange membrane. The electric resistance of the resulting membranes depends on the equivalent weight of the starting membranes (4.4–6.0 Ω cm² in 0.5N NaCl). The characteristics of the membranes are the excellent stability toward chemical substances such as organic solvents, oxidizing agents, acids, etc. For example, the membranes are stable in aqueous saturated chlorine solution at 60°C for 1000 hr.     

Steric Effect on the Catalytic Performance of the Selective Oxidation of Alcohols Over Novel Crystalline Mo–V–O Oxide

The Mo–V–O crystalline oxide with novel pore structure and consisting uniform six- and seven-member rings on the a–b plane is investigated for the selective oxidation of alcohols of different steric hindrance in liquid phase. The research target is to correlate catalytic activity with the pore structure of the crystal. Specially, substituted pyridines are employed as probe molecules to study poison effect which is closely related to the steric hindrance. As a result, the oxidation of benzyl alcohol, 1-hexanol and cyclohexanol produces aldehydes or ketones as main products. The oxidation of substrates with methyl groups on the carbon next to alcohol group mainly affords dehydrated products as olefins. The catalytic results with adding substituted pyridines in the oxidation of benzyl alcohol, 1-hexanol and 2-hexanol suggest that the active sites are located around the pore area, and are reachable by pyridine, not by substituted pyridines, such as 2-methylpyridine, 2-ethylpyridine and 2, 6-dimethylpyridine. Competitive adsorption on active sites between pyridine and benzyl alcohol remarkably decreases catalytic activity, which 2, 6-dimethylpyridine affects slightly. We have discussed that the adsorption-activation model of substrate is greatly dependent on its steric hindrance.     

Quantitation of vitamin K in human milk

A quantitative method was developed for the assay of vitamin K in human colostrum and milk. The procedure combines preparative and analytical chromatography on silica gel in a nitrogen atmosphere followed by reversed phase high performance liquid chromatography (HPLC). Two HPLC steps were used: gradient separation with ultraviolet (UV) detection followed by isocratic separation detected electrochemically. Due to co-migrating impurities, UV detection alone is insufficient for identification of vitamin K. Exogenous vitamin K was shown to equilibrate with endogenous vitamin K in the samples. A statistical method was incorporated to control for experimental variability. Vitamin K₁ was analyzed in 16 pooled milk samples from 7 donors and in individual samples from 15 donors at 1 month post-partrum. Vitamin K₁ was present at 2.94±1.94 and 3.15±2.87 ng/mL in pools and in individuals, respectively. Menaquinones, the bacterial form of the vitamin, were not detected. The significance of experimental variation to studies of vitamin K in individuals is discussed.     

Glycoconjugated polymer 6. Synthesis of poly[styrene-<Emphasis Type="Italic">block</Emphasis>-(styrene-<Emphasis Type="Italic">graft</Emphasis>-amylose)] via potato phosphorylase-catalyzed polymerization

Summary The potato phosphorylase-catalyzed polymerization of α-D-glucose-1-phosphate (G-1-P) onto poly[styrene-block-(4-vinylbenzyl maltohexaoside)] (1) was performed at the molar ratios of [G-l-P]₀ and [maltohexaose]₀ of 35, 80, and 250. The product was found to be soluble in dimethyl sulfoxide, which was a good solvent for amylose, and showed the complex-formation with iodine, indicating that the product was assignable to poly[styrene-block-(styrene-graft-amylose)] (2). The quantitative analysis of the liberated phosphoric acid gave the average degree of polymerization o f the glucose unit (n) as 27, 5 1, and 180 for 2-I, 2-II, and 2-III, respectively. Received: 29 November 2002/Accepted: 22 December 2002 Correspondence to Toyoji Kakuchi