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.     

Design of new catalysts for ecological high-quality transportation fuels by combinatorial computational chemistry and tight-binding quantum chemical molecular dynamics approaches

Recently, we introduced a concept of combinatorial chemistry to computational chemistry and proposed a new method called “combinatorial computational chemistry”, which enables us to perform a theoretical high-throughput screening of catalysts. In the present paper, we reviewed our recent application of our combinatorial computational chemistry approach to the design of new catalysts for high-quality transportation fuels. By using our combinatorial computational chemistry techniques, we succeeded to predict new catalysts for methanol synthesis and Fischer–Tropsch synthesis. Moreover, we have succeeded in the development of chemical reaction dynamics simulator based on our original tight-binding quantum chemical molecular dynamics method. This program realizes more than 5000 times acceleration compared to the regular first-principles molecular dynamics method. Electronic- and atomic-level information on the catalytic reaction dynamics at reaction temperatures significantly contributes the catalyst design and development. Hence, we also summarized our recent applications of the above quantum chemical molecular dynamics method to the clarification of the methanol synthesis dynamics in this review.     

Allelopathic Effects of Volatile Monoterpenoids Produced by <Emphasis Type="Italic">Salvia leucophylla</Emphasis>: Inhibition of Cell Proliferation and DNA Synthesis in the Root Apical Meristem of <Emphasis Type="Italic">Brassica campestris</Emphasis> Seedlings

Salvia leucophylla, a shrub observed in coastal south California, produces several volatile monoterpenoids (camphor, 1,8-cineole, -pinene, -pinene, and camphene) that potentially act as allelochemicals. The effects of these were examined using Brassica campestris as the test plant. Camphor, 1,8-cineole, and -pinene inhibited germination of B. campestris seeds at high concentrations, whereas -pinene and camphene did not. Root growth was inhibited by all five monoterpenoids in a dose-dependent manner, but hypocotyl growth was largely unaffected. The monoterpenoids did not alter the sizes of matured cells in either hypocotyls or roots, indicating that cell expansion is relatively insensitive to these compounds. They did not decrease the mitotic index in the shoot apical region, but specifically lowered mitotic index in the root apical meristem. Moreover, morphological and biochemical analyses on the incorporation of 5-bromo-2-deoxyuridine into DNA demonstrated that the monoterpenoids inhibit both cell-nuclear and organelle DNA synthesis in the root apical meristem. These results suggest that the monoterpenoids produced by S. leucophylla could interfere with the growth of other plants in its vicinity through inhibition of cell proliferation in the root apical meristem.     

Intrinsic Elastic, Dielectric, and Piezoelectric Losses in Lead Zirconate Titanate Ceramics Determined by an Immittance-Fitting Method

The material coefficients of "soft" and "hard" lead zirconate titanate (PZT) ceramics were determined as complex values by the nonlinear least-squares-fitting of immittance data measured for length-extensional bar resonators. The piezoelectric d -constant should be a complex value to obtain a best fitting between observed and calculated results. Because the elastic, dielectric, and piezoelectric losses determined in this process were not "intrinsic" losses, a calculation process to evaluate the "intrinsic" losses was proposed. It was confirmed that the intrinsic losses were smaller than the corresponding extrinsic losses. The intrinsic piezoelectric loss existed in both soft and hard PZTs; ∼50% of the loss of piezoelectric d -constant was derived from the elastic and dielectric losses. The most notable difference between the soft and hard PZTs was observed in their elastic losses.     

New multicolor and rewritable holographic polymer film for three‐dimensional holographic display

We have developed a new multicolor holographic polymer film. Our holographic polymer film contains 3‐[(2,4,6‐trichloro)azo]‐9H‐carbazole‐9‐ethanol (A‐1) and poly(methyl methacrylate). The holographic polymer film can be recorded with a holographic image without applying an external electric field. The diffraction efficiency was 57% at A‐1 with a 20 wt% of dope ratio. The writable holographic image writing for the holographic polymer film step used the silver halide photographic emulsion master plate 532‐nm laser beam under the nonelectric field. After the copy hologram is formed, our holographic polymer film can be displayed in red and green holographic images. Even though our holographic polymer film is rewritten over 200 times, the diffraction efficiency does not fall. As the holographic polymer film is manufactured using roll‐to‐roll techniques, although still in a laboratory scale in this study, it has a strong possibility of being manufactured in larger sizes with lower cost.     

The effect of sputter etching on the surface characteristics of dyed aramid fabrics

Three kinds of aramid fabrics, Technora (modified p-aramid), Conex (m-aramid) and Kevlar (p-aramid), were subjected to sputter etching and argon low-temperature plasma treatments after dyeing in black with disperse dyes. The depth of shade increased considerably on Technora and Kevlar with the sputter etching treatment, but not on Conex fabrics. Argon low-temperature plasma treatment had virtually no effect on the depth of shade on the aramid fabrics.     

High oleic acid oil suppresses lung tumorigenesis in mice through the modulation of extracellular signal-regulated kinase cascade

This study was undertaken to estimate the effect of dietary high oleic acid oil (OA) on 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK)-induced lung tumorigenesis in mice. Diet containing 10% oil was fed to mice through experimental periods. On day 30 after NNK injection (100 mg/kg body weight, i.p.), the treatment increased the level of prostaglandin E₂ (PGE₂) as well as proliferating cell nuclear antigen, a marker of cell proliferation in a high linoleic acid oil (LA)-fed group but not in an OA-fed group. The NNK treatment also induced the activation of an extracellular signal-regulated kinase (Erk) cascade (Erk, Mek and Raf-1) in an LA-fed group. On the other hand, OA feeding abolished the NNK-induced activation of the Erk cascade. In conjugation with these events, OA feeding reduced lung tumor incidence and tumor multiplicity (percentage of mice with tumors) in mice compared with LA feeding at the 20th experimental week. These results suggest that OA suppresses lung tumorigenesis and that this suppression is correlated with the inhibition of PGE₂ production and inactivation of the Erk cascade.     

Synthesis of Super-Microporous Aluminosilicate Having Excellent Water Vapor Adsorption Property as an Adsorbent for an Adsorption Heat-Pump

The synthesis of super-microporous aluminosilicate with a pore diameter of 14.6 Å has been achieved, by means of synthesis under specified conditions with a skeletal material comprising TMOS and a small quantity of sodium aluminate, and a conventional alkyl-trimethylammonium halide (C₁₀TMABr) as a template. This super-microporous aluminosilicate has an adsorption capacity of 0.2 ml/g at a relative water vapor pressure of 0.2, and thus is promising as an adsorbent for an adsorption heat-pump.     

Microstructure and Thermal Shock Resistance of Molten Glass-Coated Carbon Materials Fabricated by Interfacial Control

Carbon substrates were coated completely with a molten silicate glass, where the wettability of carbon to glass was improved by infiltration and pyrolysis of perhydropolysilazane. Microstructures of the carbon–glass interface were dependent on P n ₂ during coating. Coating at lower P n ₂ induced the formation of cristobalite at the carbon–glass interface. When the coating was performed at higher P n ₂, the glass and carbon were strongly adhered, without the formation of cristobalite. Coating at higher P n ₂ improved the thermal shock resistance of the glass layer, because crack initiation was not induced by the phase transformation of cristobalite during the cooling process. In the case of coating at higher P n ₂, an oxynitride glass layer was formed at the glass subsurface by dissolution of N₂. A porous glass subsurface layer with uniform spherical micro-pores could be produced by soaking near the glass transition temperature in a steam environment. The porous layer with fine and homogeneous microstructure acts as a thermal shock absorbing layer, so that glass-coated carbon with a porous glass layer has excellent thermal shock resistance in addition to steam oxidation resistance.     

Striped‐pattern deterioration and morphological analysis of injection moldings comprising polypropylene/ethylene α‐olefin rubber blends. I. Influence of ultraviolet irradiation

Unique deterioration with a periodical striped pattern on the injection moldings of polypropylene/rubber blends is reported. After exposure to ultraviolet irradiation with a sunshine fade meter, striped patterns appeared on the injection moldings along the flow direction of the molten resin during the filling process of injection molding, even though the initial specimen showed no sign of any stripe pattern on its surface. The stripe was carefully observed with ultrasonic echo imaging, scanning electron microscopy, transmission electron microscopy, and Fourier transform infrared spectroscopy. As a result, a number of microvoids were observed inside the injected body at a depth of 50–100 μm from the surface. It became clear that the difference in the number of voids along the flow direction formed the stripe pattern. Surprisingly, these voids occurred in domains comprising a rubber phase. The distribution of voids in depth indicated the existence of a trace of a snakelike flow caused inside the injected body during the injection‐molding process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007