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.     

Void formation in a filled SBR rubber determined by small-angle X-ray scattering

Two commercial styrene-butadiene (SBR) latexes were used to prepare a model filled material consisting of glassy SBR filler particles about 1000 Å in diameter embedded in a rubbery SBR matrix crosslinked by γ-radiation. When transparent specimens of this material were extended, voiding occurred, as evidenced by stress whitening and greatly enhanced X-ray scattering intensity. More voids were formed at higher rates of extension, but voids disappeared when specimens were relaxed. The effects of filler content and cure time of the matrix on the size and number of voids formed were determined by low-angle X-ray scattering for a constant extension rate and a constant extension ratio λ = 1.6. The number of voids measured by X-ray scattering intensity decreased rapidly with time over the 3-h period of measurement. The number of voids remaining 1 h after extension increased about 40 times as filler content was increased from 15% to 50%. Increasing the cure time from 24 to 96 h increased the number of voids about four times. In contrast, the radius of gyration of the voids formed (250–350 Å) did not depend strongly on time, nor did it depend strongly on the filler content or the cure time of the matrix. Stress relaxation measurements made under the same conditions as X-ray scattering measurements showed effects typical of filled materials. However, the relaxation of stress (which followed a power law decay) was much slower than the decay of the number of voids as measured by X-ray scattering intensity.     

Polymorphic behavior of gondoic acid and phase behavior of its binary mixtures with asclepic acid and oleic acid

Molecular properties of polymorphic forms of gondoic acid [cis-C_20:1Δ11ω9 (GOA)] have been studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC), optical microscopy, and Raman scattering, in comparison to those of six principal unsaturated fatty acids: oleic acid [cis-C_18:1Δ9ω9 (OA)], erucic acid [cis-C_22:1Δ13ω9 (ERA)], petroselinic acid [cis-C_18:1Δ6ω12 (PSA)], asclepic acid [cis-C_18:1Δ11ω7 (APA)], palmitoleic acid [cis-C_16:1Δ9ω7 (POA)], and elaidic acid [trans-C_18:1Δ9ω9 (ELA)]. In addition, phase behavior of binary mixtures of GOA and APA and OA was examined by XRD and DSC. The polymorphic structures of GOA are quite similar to those of APA, ERA, POA, and partly to OA. In particular, DSC and Raman scattering studies have shown that gondoic acid exhibits conformational disordering on heating at the ω-chain, a chain segment between the double bond and CH₃ group, as a transition from all-trans (γ form) to gauche-rich (α form) conformations. A miscible mixing phase was observed in the mixture of GOA and APA, yet eutectic phases were observed in the GOA and OA mixtures. This is a remarkable contrast because the binary mixture systems of varying combinations of cis-unsaturated fatty acids examined so far exhibited either eutectic nature or molecular compound formation. It is expected that specific molecular interactions between GOA and APA that originate from the equivalence of the length of the Δ-chain, the chain segment between the cis-double bond and COOH group, and also from the presence of the γ-α order-disorder transformation would be operating to form the miscible mixing phase.     

Photocatalysts using hexa- and octa-titanates with different tunnel space for water decomposition

Photocatalytic activities for water decomposition were examined for photocatalysts using hexa- and octa-titanates and TiO2(B) with different tunnel space in the structure. Using RuO2 as promoter, M2Ti6O13 (M = Li, Na, K, Rb) showed the stoichiometric production of Hz and O₂ except for Li, whereas H₂Ti₈O₁₇ and TiO₂(B) had very low activity producing only hydrogen as a product. The effects of promoters on Na₂Ti₆O₁₃ showed that the activity increased in the order of RuO₂ > RuO₂ + IrO₂ > IrO₂ > RuO₂ + Pt > MnO₂. These effects along with other related ones are discussed: it emerges that the presence of the tunnels is important for the achievement of high photocatalytic activity.     

Upper and lower critical solution temperatures in poly (ethylene glycol) solutions

Upper and lower critical solution temperatures have been determined for solutions of poly(ethylene glycol) in t-butyl acetate and water over the molecular weight range of M_η = 2.18 × 10³ to ～1020 × 10³. The phase diagram for solutions of poly(ethylene glycol) (M_η = 719 × 10³) in t-butyl acetate was expressed as the ‘hour glass’ type, while the phase diagram for solution of poly(ethylene glycol) (M_η = 2.18 × 10³ to ～2.29 × 10³) in water was expressed as the ‘closed loop’ type. The value of the pressure dependence of the lower critical solution temperature $\text{(}\text{d}\text{T}\text{d}\text{P}\text{)}{}_{\mathrm{c}}$ in the poly(ethylene glycol) (M_η = 1020 × 10³)/water system over the pressure range of 0 to ～50 atm was negligibly small and positive.     

Synthesis of functional π-conjugated polymers from aromatic acetylenes

Because of their unique structures and properties, π-conjugated polymers have attracted the attention of scientists and engineers. The authors have studied the synthesis of two kinds of π-conjugated poly(aromatic acetylene)s, i.e. poly(arylacetylene)s and poly(aryleneethynylene)s with the aim of obtaining new polymers having novel functions or higher performances. This review mainly concerns the authors' results, as follows: first, we describe the synthesis and properties of achiral poly(arylacetylene)s, containing trimethylsilyl groups, oligodimethylsiloxanyl groups, dendritic groups, and glavinoxyl groups, for application as oxygen permselective membrane materials. Their self-membrane-forming abilities and high oxygen permeabilities are presented. Second, the synthesis by asymmetric-induced polymerization of chiral poly(arylacetylene)s having both a main-chain chirality and chiral pendant groups and their application as optical resolution membranes are described. Third, two new synthetic methods for preparing chiral helical poly(phenylacetylene)s without the coexistence of any other chiral moieties are presented. One is helix-sense-selective addition polymerization and the other is in situ removal of chiral pendant groups from membranes of poly(arylacetylene)s that also contain a main-chain chirality. The chiral helical poly(arylacetylene)s were tested as optical resolution membranes. The chiral and achiral poly(arylacetylene)s were synthesized by addition polymerization using metathesis catalysts or rhodium complexes. Finally, the synthesis of regiospecific poly(aryleneethynylene)s bearing stable radicals by the polycondensation of bromoethynylanthracene derivatives using a Pd(0) complex is described. The magnetization and the static magnetic susceptibility of the polyradicals are explained.     

Glass transition behavior of emulsion-polymerized polymer films containing a surface-active agent

The glass transition behavior of emulsion-polymerized poly(methyl methacrylate) and polystyrene films containing sodium laurylsulfate as emulsifier was studied by measurements of dynamic mechanical properties and thermal depolarization current. The film specimens of the emulsion-polymerized polymers were prepared by casting from their benzene solutions. The glass transition temperatures of the emulsion-polymerized films are higher than those of the bulk-polymerized films. The higher glass transition temperature of the emulsion-polymerized films is attributed to the colloidal properties of sodium laurylsulfate in the process of the film formation. The restriction of the molecular chains in the emulsion-polymerized films is attributed to the interaction between the hydrophobic groups of sodium laurylsulfate and the polymer molecules.     

Toughening of cycloaliphatic epoxy resins by poly(ethylene phthalate) and related copolyesters

Poly(ethylene phthalate) (PEP) and poly(ethylene phthalate–co‐ethylene terephthalate) were used to improve the brittleness of the cycloaliphatic epoxy resin 3,4‐epoxycyclohexylmethyl 3,4‐epoxycyclohexane carboxylate (Celoxide 2021?), cured with methyl hexahydrophthalic anhydride. The aromatic polyesters used were soluble in the epoxy resin without solvents and effective as modifiers for toughening the cured epoxy resin. For example, the inclusion of 20 wt % PEP (MW, 7400) led to a 130% increase in the fracture toughness (K_IC) of the cured resin with no loss of mechanical and thermal properties. The toughening mechanism is discussed in terms of the morphological and dynamic viscoelastic behaviors of the modified epoxy resin system. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 388–399, 2002; DOI 10.1002/app.10363     

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.