PTCR Characteristics in Barium Titanate Ceramics with Curie Points Between 60° and 360°C

PTCR characteristics in porous semiconducting barium titanate ceramics with Curie points from 60° to 360°C were investigated. The magnitude of the PTCR effect in these cerumics decreases self-onsistently with increasing Curie point within this temperature range. A PTCR efSect of more than 4 orders of magnitude was ahserved, for a Ba_0.44Pb_0.6TiO₃ ceramic with a Curie point of 360°C .     

Functional monomers and polymers, 64. Synthesis of poly-β-alanine from β-alanine, β-alanyl-β-alanine,and β-alanyl-β-alanyl-β-alanine 4-dodecanoyl-2-nitrophenyl esters

Active 4-dodecanoyl-2-nitrophenyl esters of β-alanine, β-alanyl-β-alanine, and β-alanyl-β-alanyl-β-alanine were prepared, and tried to polymerize in various solvents. Nonpolar solvents were found to be convenient for the polycondensation reaction. The yield of the polycondensation was high for the monopeptide ester, and less for the dipeptide and tripeptide esters. The effect of temperature on the polycondensation reaction was also studied.     

Strain-induced ordering of microdomain structures in polystyrene-block-polybutadiene-block-polystyrene triblock copolymers cross-linked in the disordered state

Strain-induced ordering of microdomain structures in cross-linked polystyrene-block-polybutadiene-block-polystyrene (SBS) triblock copolymers was examined by the small-angle X-ray scattering technique. To stretch the SBS samples at elevated temperature above the glass transition temperature of polystyrene, polybutadiene blocks were chemically cross-linked in the disordered state. The initial morphology was disorder-like or bicontinuous due to incompletion of microphase separation in the presence of the chemical cross-links. When the cross-linked SBS samples were mechanically stretched at 130 °C and were further annealed for 24 h under a stretched state, the random domain structures ordered gradually and lamellar-like regularity was finally attained. It was found that the ordering proceeded more for the case of the higher strain.     

Oxidative coupling of methane over LaCoO3−δ-based mixed oxides

The catalytic activity of LaCoO_3–-based mixed oxides for the oxidative coupling of methane has been tested by TPR and cyclic reaction. Characterization has been done by XRD, TGA and Mössbauer spectrometry. It is likely that the perovskite-crystal structure containing hypervalent metal ions has an important role and that unique structural oxygen species in the perovskite contribute to the partial oxidation of methane.     

Sintering of Ceria-Doped Tetragonal Zirconia Crystallized in Organic Solvents, Water, and Air

Amorphous CeO₂–ZrO₂ gels were prepared by coprecipitation in ammonia solutions. The onset of crystallization of the gels, from calcining in air, was 420°C, while 200° to 250°C in the presence of water and organic solvents such as methanol and ethanol. The sintering behaviors of CeO₂–ZrO₂ powders were sensitive to the crystallizing conditions, since hard agglomerates formed when the precipitated gels were crystallized by normal calcination in air, whereas soft agglomerates formed when they were crystallized in water or organic solvents. CeO₂–ZrO₂ powders crystallized in methanol and water at 250°C were sintered to full theoretical density at 1150° and 1400°C, respectively, whereas that crystallized by calcination in air at 450°C was sintered to only 95.2% of theoretical density, even at 1500°C.     

Preparation of poly(p-phenylene terephthalamide)/poly(vinyl chloride) molecular composite and its thermal and mechanical properties

Poly(p-phenylene terephthalamide) (PPTA) was blended with poly(vinyl chloride) (PVC) by solution-blending method. PPTA was metalated for dissolving in dimethyl sulfoxide. Dimethyl sulfoxide was used as a common solvent. In PPTA/PVC composite, PPTA accelerated the thermal degradation of PVC. PPTA molecules are aggregated as microfibrillar form in PVC matrix. Such microfibrils are dispersed homogeneously in PVC matrix, according to polarizing microscopic observation. The average diameter of the microfibrils becomes smaller in the composite with lower content of PPTA. In the surface region of PPTA microfibrils the intermolecular hydrogen bonds between C? Cl of PVC and N? H of PPTA are formed. Young's modulus and the yield stress at room temperature were higher in the composites than those in PVC. The modulus of the composites was higher, especially at the high temperatures above their glass transition temperatures, than that in PVC. The temperature dependence of modulus can be calculated by using the mechanical model equivalent to the quasi-3-dimensional microfibrillar model which will be approximately applied to the composite structure. It becomes apparent that the modulus of the PPTA microfibrils evaluated by using the mechanical model is higher in the higher molecular weight PPTA.     

Antitumor activity of synthetic alkylphospholipids with or without PAF activity

1-O-Octadecyl-2-O-methyl-sn-glycero-3-phosphocholine (ET-18-OMe) has been reported to possess definite antitumor activity in vivo. Twenty-two alkyl lysophospholipid analogs were chemically synthesized, and their antitumor activity against mouse experimental tumors (Sarcoma 180, MM46, P388) was examined. Among them, 1-O-octadecyl-2-O-acetoacetyl-rac-glycerol-3-phosphocholine was found to show antitumor activity similar to ET-18-OMe with less acute toxicity. Intravenous injection of the ET-18-OMe withsn-3 configuration retarded the subcutaneous growth of Sarcoma 180 cells effectively, while the growth inhibition by thesn-1 isomer was much less effective. This stereospecificity was similar to that observed in their activities as platelet-activating factor (PAF) agonists. The acetoacetyl compound, another PAF agonist, showed similar stereospecific antitumor action in vivo. These findings suggest that some alkyl lysophospholipids may activate host cells to a cytostatic stage against tumor cells in vivo through binding to a PAF receptor. Our preliminary results indicated that the responsible cells under these conditions might be primarily immature macrophages present in the bone marrow. No appreciable or even adverse stereospecificity was observed in the different sets of experiments where the activity of ET-18-OMe against MM46 tumor cells in vivo or the direct cytotoxicity against human promyelocytic leukemia HL-60 cells in vitro was examined. Under, some conditions, the antitumor activity of ET-18-OMe in vivo may be revealed through direct cytotoxicity and/or modulation of the host defense system by “nonspecific” mechanisms. Some alkylphospholipids without PAF activity may also show antitumor activity through similar, “nonspecific” mechanisms.     

Carbon molecular sieve membranes derived from trimethylsilyl substituted poly(phenylene oxide) for gas separation

Carbon molecular sieve membranes for gas separation prepared using poly(phenylene oxide) (PPO) as precursor have been examined. The PPO precursor was modified by introducing a trimethylsilyl (TMS) substituent and its effect on the gas transport property of the resulting carbon membrane was examined. TMS-substituted PPO (TMSPPO) was prepared in a high yield by a simple one-step reaction, and its carbon membrane was successfully fabricated. The modification improved the gas permeability of the resulting membrane which also exhibited excellent O₂/N₂ and CO₂/CH₄ separation performance comparable to those of polyimide-derived carbon membranes. From the analysis of the microstructure of the TMSPPO carbon membranes, it is believed that the TMS groups improve gas diffusivity by increasing the micropore volume.     

E.s.r. study of annealing and melting effects on the molecular motion of spin trapped chain-end radicals located on the polyethylene surface

E.s.r. spectra of chain-end spin labels on the surface of polyethylene powder were obtained for high and low density polyethylene samples at various stages of heat treatment process. The subsequent crystalline structures of the samples were examined with wide angle and small angle X-ray diffraction spectra. The effects of annealing on the motion of the labels were dependent on annealing temperature and the type of the samples. Higher temperature annealing decreased the rotational correlation times (τ_c) and their activation energy in high density polyethylene but did not affect those of low density polyethylene. Melting decreases the values of τ_c and ΔE for both high an low density polyethylene samples. The cause of these decreases were attributed to the changing of the sites of the chain-end labels. The motion of the labels appeared to be influenced by the local segmental motion of the polymer main chains.     

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.