Simple chemical syntheses of TAG monohydroperoxides

For the purpose of synthesizing standards to be used in the quantification of TAG hydroperoxides, three TAG (1,2-dioleoyl-3-palmitoylglycerol, 1-oleoyl-2-linoleoyl-3-palmitoylglycerol, and triolein) monohydroperoxides were chemically synthesized as authentic specimens. TAG were prepared by using a simple condensation in pyridine of glycerol and the corresponding acid chlorides. These TAG were then converted into monohydroperoxides by a photosensitized peroxidation. The synthesized monohydroperoxides were analyzed by normal-phase and RP-HPLC. The results of normal-phase HPLC analysis showed that monohydroperoxides from a corresponding TAG were a mixture of regioisomers. In RP-HPLC, however, the regioisomers of monohydroperoxides were not separated and gave a single peak, which may improve the sensitivity for the detection of TAG monohydroperoxides. In this study TAG monohydroperoxide standards were synthesized; these will be useful for the study of yet unknown biological and pathological roles of TAG hydroperoxides.     

Preparation of modified poly(vinyl chloride) containing N,N-di(β-hydroxyethyl)dithiocarbamate and its reaction with metal ions

Reaction of N,N-di(β-hydroxyethyl)dithiocarbamate ion with poly(vinyl chloride) (PVC) was undertaken, and the reaction with metal ions of the polymer obtained was investigated. The effect of γ-irradiation on the reaction with metal ion was also studied. The modified PVC (PHDC) obtained from the reaction with N,N-di(β-hydroxyethyl)dithiocarbamate ion is pale yellow even after reaction at 100°C for 5 hr in dimethylformamide (DMF); it is soluble in dipolar solvents and its chlorine content is decreased considerably. This polymer reacted well with acetate salts of copper(II), nickel(II), zinc(II), and silver(I) heterogeneously in aqueous solution because of the introduction of hydrophilic groups (two hydroxy groups). The reactivity of the metal ions toward the polymer was of the order Ag(I) ? Cu(II) > Ni(II) > Zn(II). From the result of the reaction of γ-irradiated polymer with cupric ion, the polymer was judged to have fairly good antiradiation property.     

Isotachophoretic analysis of surfactants

The qualitative and quantitative determination of anionic surfactants (sodium and lithium alkylsulfate, sodium dodecylbenzenesulfonate, sodium di-2-ethylhexyl sulfosuccinate, sodium and lithium perfluoroalkylcarboxylate, and lithium perfluorooctanesulfonate) were investigated by a capillary tube isotachophoresis using a potential gradient detector. The leading electrolyte solution was the mixture of acetonitrile and aqueous solution of histidine buffer containing calcium chloride. The terminating electrolyte solution was the aqueous solution of sodium octanoate. These electrolytes were effective for the analysis of the mixtures of strongly acidic surfactants.     

Studies on phase separation rate in porous polyimide membrane formation by immersion precipitation

Phase separation rate during porous membrane formation by immersion precipitation was investigated by light scattering in a polyimide/N‐Methylpyrrolidone (NMP)/water system. In the light scattering measurement, plots of scattered intensity against scattered angle showed maxima in all cases, which indicated that phase separation occurred by a spinodal decomposition (SD). Characteristic properties of the early stage of SD, such as an apparent diffusion coefficient D_app and an interphase periodic distance Λ, were obtained. The growth process of Λ was also followed by light scattering. The growth rate had the same tendency as D_app when water content in the nonsolvent bath and the polymer concentration in the cast solution were changed. The pore size of the final membrane increased with decreasing water content, which was opposite to the tendency of Λ growth rate. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 292–296, 2003     

Sintering of the Mechanochemically Activated Powders of Hexagonal Boron Nitride

Pressureless sintering of hexagonal boron nitride (BN) was performed using a powder activated by mechano-chemical treatments. Physical properties of the sintered BN bodies depend on the type of starting powder and the conditions of the treatments. The BN body, which was obtained at 2000°C using an appropriate activated powder, was 99 wt% pure and was excellent in mechanical and physical properties, in spite of its low density (1.64 g/cm³).     

The effect of the N-linked glycans on structural features and physicochemical functions of soybean β-conglycinin homotrimers

β-Conglycinin is a trimeric protein consisting of three subunits, α,α′,and β, which are N-glycosylated. The α and α′ subunits contain extension regions in addition to core regions common to all subunits. We purified homogeneous trimers consisting of only α, α′, or β from mutant soybean cultivars containing β-conglycinin lacking one or two subunits: α homotrimers from an α′-lacking mutant, α′ homotrimers from an α-lacking mutant, and β homotrimers from an α-and α′-lacking mutant. Structural features and physicochemical functions of the three homotrimers were examined and compared with those of recombinant homotrimers having no N-linked glycans. The native homotrimers have secondary structures very similar to those of the recombinant ones. In analogy with the recombinant homotrimers, the native ones exhibit different thermal stabilities from one another (β>α′>α), and the native α and α′ homotrimers exhibit better solubility, emulsifying ability, and heat-induced association than the native β homotrimer. Further, the N-linked glycans contribute to solubilities of the three subunits at low ionic strength (μ=0.08) and to the emulsifying ability of the native β homotrimer. N-Linked glycans also prevent heat-induced associations of the native α and α′ homotrimers but do not contribute to the secondary structure and the thermal stability of β-conglycinin.     

High-strength–high-modulus polyimide fibers II. Spinning and properties of fibers

The polyimides based on 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) described in Part I of this series were dissolved in p-chlorophenol and spun into fibers using a coagulating bath of ethanol. The fibers as spun had in general low tenacities and low moduli, but a heat treatment at 300–500°C under tension produced a remarkable increase in strength and modulus, and fibers with a tensile strength of 26 g/den (3.1 GPa) and an initial modulus higher than 1,000 g/den (120 GPa) could be obtained. Thus, the annealed fibers of polyimides are comparable to aramid fibers in mechanical properties. To heating in air and in the saturated steam, the polyimide fibers showed higher resistance than the aramid fibers. The polyimide fibers surpassed the aramid fibers in resistance to acid treatment and ultraviolet (UV) irradiation, but were inferior in resistance to alkali treatment. The annealed fibers of polyimides displayed distinct X-ray diffraction patterns. The chain repeat distance of 20.5 Å determined on the fibers of polyimide prepared from BPDA and o-tolidine, and 20.6 Å determined on the fibers of polyimide derived from BPDA and 3,4′-diaminodiphenyl ether are reasonable when the dimensions of monomeric units and the shapes of the molecular chains are considered. The X-ray reflections of both polyimide fibers were indexed satisfactorily on the basis of postulated unit cells.     

Effect of pressure on phase transition and morphology of bulk poly(trans-1,4-butadiene)

The effect of pressure on the melting, solid-solid transition, and crystallization of poly(trans-1,4-butadiene) (PTBD) was investigated using the pressure range of 1–3000 kg/cm². D.t.a. measurements showed that, the melting and transition temperatures increase with increasing pressure, whose pressure coefficients are 38°C per 1000 kg/cm² and 22°C per 1000 kg/cm², respectively. These values were in fairly close agreement with those calculated from the Clausius-Clapeyron equation. Morphological studies using electron microscope and small-angle X-ray scattering method revealed that, the samples crystallized with relatively small supercoolings under normal or high pressure, are formed of distinct lamellae 400–800 Å thick. The lamellar thickness was inappreciably dependent on crystallization pressure. The significant effect of pressure on crystallization was recognized in a tendency of the crystallinity to increase, with increasing crystallization pressure. This pressure effect was explained by the mechanism that, the increased pressure might make the packing of molecular chains in liquid, more dense and that the secondary crystallization might be accelerated, to increase the lateral dimensions of lamellae.     

Novel CO2 Absorbents Using Lithium-Containing Oxide

We have discovered a series of lithium-containing oxides that immediately react with ambient carbon dioxide (CO₂) up to 700°C. The products react and return reversibly to the oxides at a temperatures higher than about 700°C. The absorption capacity surpasses that of other CO₂ absorbents by a factor of 10. Utilizing these absorbents, the possibility of a CO₂ separation system that operates at around 500°C is proposed. It is generally believed that a CO₂ separation process operable at temperatures higher than 500°C has the special benefit of a small energy penalty. Moreover, the absorption also proceeds at ambient temperature in the atmospheric environment. This property offers the possibility of many other applications, such as air cleaners or cartridges. Therefore, we think these materials have the potential to make a valuable contribution to the realization of CO₂ emission control.     

Nonlinear effects on spin waves in3He-4He dilute solutions

Spin dynamics of³He-⁴He dilute solution have been studied in the collisionless regime by NMR methods. In cw NMR experiments, we observed spin waves in a magnetic field gradient. The frequency difference between the first mode and the others obeyed a two-thirds power law in the strength of the field gradient. By using a pulsed NMR method, nonlinear spin dynamics were studied. We observed the large amplitude spin waves after an rf pulse. The frequency of each spin-wave mode depended on the tipping angle. By using the parameter determined in the present experiment, the numerical calculated results based on Leggett-Rice theory are in good agreement with the results of the pulsed NMR experiments.