Diimide reduction of cis-1,4-polyisoprene with p-toluenesulphonylhydrazide

The hydrogenation of cis-1,4-polyisoprene with diimide generated in situ from p-toluenesulphonylhydrazide (TSH), was investigated under various conditions. In aromatic solvents at 100–140°C, the rate of hydrogenation was increased with increase in concentration of polyisoprene and of TSH. Part of the polymer was depolymerized and cyclized during the reaction. Increasing the hydrogenation tended to decrease the rate of sulphur vulcanization, of the compounded rubber and the physical properties of vulcanizates were poor. The reaction of polyisoprene rubber with TSH, was also carried out in a solid state at 140°C for 20–60 min. It was found that by using a large amount of TSH hydrogenation and cyclization of rubber occurred. The quantity of TSH used as a blowing agent, for rubber in the manufacture of sponge rubber, i.e. 5–10 phr, did not cause hydrogenation.     

Molecular weights and molecular weight distributions of irradiated cellulose fibers by gel permeation chromatography

Radiation degradation of cellulose fibers was investigated by gel permeation chromatography (GPC). Scoured cotton of Mexican variety (cellulose I), Polynosic rayon (cellulose II), and their microcrystalline celluloses obtained by hydrolysis of the original fibers were irradiated by Co-60 γ-rays under vacuum or humid conditions. The irradiated samples were then nitrated under nondegradative conditions. The molecular weights and molecular weight distributions were measured by GPC using tetrahydrofran as solvent. The relationship between molecular weight and elution count was obtained with cellulose trinitrate standards fractionated by preparative GPC. The degree of polymerization of the fibers decreased with increasing irradiation dose, but their microcystalline celluloses were only slightly degraded by irradiation, especially in microcrystalline cellulose from cellulose I. Degradation of the fibers irradiated under humid conditions was less than that irradiated under vacuum. It was found that the G-values for main-chain scission for the irradiated cellulose I, cellulose II, microcrystalline cellulose I, and microcrystalline cellulose II were 2.8, 2.9, less than 1, and 2.9, respectively, but the G-value for main-chain scission for the irradiated cellulose II was increased to 11.2 at irradiation doses above 3 Mrad. Consequently, it is inferred that cellulose molecules in the amorphous regions are degraded more readily, and the well-aligned molecules in crystalline regions are not as easily degraded by irradiation.     

Oxidative stability of sardine and mackerel lipids with reference to synergism between phospholipids and α-tocopherol

Relationships between oxidative stability and the compositions of sardine and mackerel lipids were investigated in view of possible synergism between phospholipids andα-tocopherol (α-Toc). The total lipids extracted from viscera were highly susceptible to autoxidation, compared with lipids of white and red muscles and of skin. This seemed to be due to lower concentrations ofα-Toc and phosphatidylethanolamine (PE) in the tissue, but not to the level of polyunsaturated fatty acids. The synergistic effect of PE withα-Toc seemed to be slightly affected by the degree of unsaturation of its fatty acyl chains. The synergistic ability ofO-phosphoethanolamine, the base moiety of PE, was higher than that ofO-phosphoserine.O-Phosphocholine was only slightly effective. During the induction period of autoxidation, theα-Toc level decreased rapidly, and rapid lipid oxidation began only afterα-Toc was almost exhausted.     

Mesophase structure discovered through in-situ X-ray measurement in drawing process of poly(ethylene 2,6-naphthalene dicarboxylate) fiber

The structure development in the continuous laser-heated drawing process of poly(ethylene 2,6-naphthalene dicarboxylate) (PEN) fiber was analyzed by in-situ X-ray diffraction measurement. Because of the rapid and uniform laser heating, and the resultant steady-state nature of the necking-drawing, the structure development after the on-set of necking could be measured in the time resolution of several hundred microseconds. We found for the first time the temporal appearance of meridional (001′) diffraction at several milliseconds after the on-set of necking indicating that the mesophase structure similar to the one reported for poly(ethylene terephthalate) was also formed in the initial stage of fiber structure development of PEN. The d-spacing of the (001′) diffraction 1.230 ± 0.003 nm was shorter than the c-axis lengths of both α and β crystals.     

High performance liquid chromatographic separation of stereoisomeric bile acids as their UV-sensitive esters

High performance liquid chromatographic separation of a series of mono-, di- and trihydroxylated 5β-cholanic acids which differ only in position and configuration of hydroxyl groups at positions C-3, C-7 and/or C-12, is reported. The C-24 free acids were derivatized to four different classes of UV-sensitive esters, i.e.,p-bromophenacyl (BP),m-methoxyphenacyl (MP), 4-nitrophthalimidemethyl (NPM) and 9-anthrylmethyl (AM) esters, and chromatographed on two, variants of C₁₈ reversed-phase columns (Nova-Pak C₁₈ and Zorbax ODS) with methanol-water systems as mobile phase. Separation efficiency and elution order of some isomeric pairs were influenced by both the structure of the C-24 ester groups and the nature of the columns used. Excellent chromatographic properties were found for those derivatives, particularly for the NPM esters.     

Reactive carbon black having isocyanate or acyl azide group

Summary Introduction of isocyanate (NCO) group onto carbon black surface was achieved by the treatment of carbon black with toluene-2,4-diisocyanate. In addition, carbon black having acyl azide (CON₃) group, a precursor of NCO group, was prepared by the reaction of COCl or COOCOOC₂H₅ group on carbon black with NaN₃. The CON₃ group on carbon black was relatively stable at below 20°C but readily decomposed to NCO group by heating (Curtius rearrangement). By the reation of NCO group on carbon black with hydroxyl group of polymers, such as polypropylene glycol, polyethylene glycol, and polyvinyl alcohol, these polymers were found to be grafted onto carbon black.     

Construction of hydrogen fermentation from garbage slurry using the membrane free bioelectrochemical system

The aim of this study was to show the effectiveness of the membrane free bioelectrochemical system (BES) using three electrodes on inhibition of methanogenesis and construction of hydrogen fermentation from the artificial garbage slurry. The electrical redox-potential on the working electrode was adjusted to -1.0V (vs. Ag/AgCl) that has positive effect on methanogenesis. The redox-potential on the counter electrode was measured to be 1.6V. The pH in the effluents was 5.5-6.4. Hydrogen production rate at the cathode side was similar to that at the anode side and much higher than that calculated from current, and reached a maximum of 2445±815 (average±standard deviation) mL?L(-1)?d(-1) at an organic loading rate of 58.7g dichromate chemical oxygen demand per L d(-1). Methane production was negligible throughout the experiment. Acetate and butyrate were the main products of the fermentation using a BES; these offered favorable conditions for hydrogen production. The bacterial community in the bioelectrochemical hydrogen fermentor differed from that in the methanogenic seed sludge and included hitherto unknown species. These results show that high redox-potential on the anodic electrode and acidic pH in the membrane free BES can be utilized for hydrogen fermentation from the artificial garbage slurry by avoiding methanogenesis.     

Automated single nucleotide polymorphism typing using bead array in capillary tube

A low-cost and simple on-site technique for genotyping single nucleotide polymorphisms (SNPs) was developed. The technique is based on allele-specific primer PCR and the recently developed bead arrays in a single tip technique. The performance of the method was verified by genotyping four SNPs that correlate with cardiovascular diseases.