Photocatalytic Property and Electronic Structure of Lanthanide-based Oxysulfides

Lanthanide-based oxysulfides and sulfide, LnTaO_3.5S_0.5, Ln₁₀OS₁₄ (Ln = La, Pr, Nd, Sm) and La₄In₅S₁₃, were successively synthesized by sulfurization in a flowing H₂S. The sulfurization decreased the band-gap energies from >4 eV to <3eV, because of the formation of occupied S3p orbitals on the top of valence band. In accordance with the small band gap, the H₂ evolution from a 0.01 M Na₂S and 0.01 M Na₂SO₃ solution system was observed under irradiation of light up to >500 nm. The rate of H₂ evolution under light irradiation of >500 nm increased in the order of Ni/LaTaO_3.5S_0.5 < Ru/La₁₀OS₁₄ < Pt/La₄In₅S₁₃.     

Crack opening displacement of a through-wall crack in a plate subjected to bending load

This study was performed in order to clarify crack opening displacement (COD) of through-wall cracks in a plate subjected to bending load. The former COD evaluation methods were mainly developed corresponding to tensile load, but there has been nothing that has been developed corresponding to bending load. Therefore, the authors evaluated CODs of the through-wall cracks in plates which were subjected to a bending load using finite element method (FEM) analyses, and proposed a simplified COD evaluation method accounting for both tensile and bending loads. The proposed method is useful for leakage evaluation at a crack opening of an elbow crown or in the vicinity of the coolant surface of a vessel in which the bending stress is relatively large.     

Magnetic breakdown phenomena in quasi-two dimensional organic conductors

Magneto-oscillation phenomena of the magnetization in low dimensional organic conductors (BEDT-TTF)₂X, are investigated theoretically, focusing on the magnetic breakdown (MB) occured in high fields. Our full quantum mechanical theory reproduces various oscillations, including the interference difference oscillation, which is prohibited in the so-called network model of semi-classical theory, and demonstrates a smooth crossover to the MB orbit oscillation, or MB phenomenon. This is interpreted in terms of the recursive band structures.     

Gas permeation property of polyaniline films

We examined the influence of polyaniline (PAn)'s unit sequence and doping with low molecular weight dopants or polymer dopants on permeation property. It was found that CO₂ permeability was increased by the formation of a quinonediimine unit in PAn with the oxidation. CO₂ sorption amount of PAn was decreased by oxidation. The increase of CO₂ permeability with oxidation, therefore, resulted from the increase of diffusivity, which was attributable to morphological variation by the increase of a quinonediimine unit. The permselectivity of PAn films was found to be remarkably improved by doping. In particular, the selectivity value of the PAn film doped with polyvinyl sulphonic acid as a polymer dopant went up to over 2,000. This remarkable increase of selectivity was found to result in the increase of selectivity, depending on diffusivity. It was also found that the permselectivity of the PAn film doped by polymer dopants was surpassed, as compared with that doped by low molecular dopants. © 1995 John Wiley & Sons, Inc.     

Plasma developable photoresist containing electronic excitation energy quenching system

A dry developable negative working resist composition comprised of poly(methyl isopropenyl ketone) (PMIPK) and 4-methyl-2,6-di(4′-azido-benzylidene) cyclohexanone-1 was examined. The main photochemical product formed in the resist pattern was found to be a secondary amine which crosslinks PMIPK. Post-annealing forms a hydrogen-bonded product which shows a powerful electronic excitation energy quenching effect. The quencher is more powerful than the aromatic compound arising from the azide by post-annealing only. The residual resist thickness of the negative pattern is about 80 percent of the initial thickness of the coating in spite of all the azide compound remaining in the resist coating. The obtained dry developed resist pattern has a high dry etch resistance. Etchings of Si and SiO₂ were performed by plasma and reactive ion etching, respectively.     

Promotion of hydrogen permeation on metal-dispersed alumina membranes and its application to a membrane reactor for methane steam reforming

A mesoporous membrane for selective separation of hydrogen was prepared usingthe sol-gel method. Some metal salts such as RuCl₃, Pd(NH₃)₄Cl₂, RhCl₃,, and H ₂PtCl₆, were added to the boehmite sol and coated on a porous alumina substrate before firing at 500°C. It was foundthat the permeability of hydrogen and the separation factor for a hydrogen-nitrogen gaseous mixture of these metaldispersed membranes exceeded the limitations of the Knudsen diffusion mechanism. Although the gas permeation through a neat alumina membrane is governed by the Knudsen diffusion, the metals dispersed in alumina membranes were effective in promoting hydrogen permeation. These metaldispersed alumina membranes were also used in a membrane reactor for methane steam reforming at low temperature. In the temperature range of 300 to 500°C, the membrane reactor attained a methane conversion twice as high as the equilibrium value of the packed bed catalytic reactor system as a result of the selective removal of hydrogen from the reaction system.     

Interdiffusion in Co-Mn alloys

Interdiffusion coefficient in cobalt-manganese alloys has been determined by Matano's method in the temperature range between 1133 and 1423 K on (pure Co)-(Co-30.28 at. pct Mn alloy) and (pure Co)-(Co-51.76 at. pct Mn alloy) couples. This, ∼D, has been found to increase with the increase of manganese content. However, the activation energy (∼Q) and frequency factor ( ₀) show a maximum at about 10 at. pct Mn. The concentration dependence of and has been discussed taking into account the thermodynamic properties of the alloy. The difference in between the ferro- and paramagnetic phases in Co-5 at. pct Mn alloy has been found to be 24 kJ/mol, which is larger, than that for the diffusion of Mn⁵⁴ in this alloy. Further it has been found that the Kirkendall marker moves toward manganese-rich side, showing that manganese atoms diffuse faster than cobalt atoms. From the marker shift, the intrinsic diffusion coefficients,D _Co andD _Mn, at 33 at. pct Mn have been determined as follows:D _Co=0.22×10⁻⁴ exp(−263 kJ mol⁻¹/RT) m²/s, andD _Mn=0.98×10⁻⁴ exp(−229 kJ mol⁻¹/RT) m²/s.     

Eudragit Coating of Chitosan-Prednisolone Conjugate Microspheres and In Vitro Evaluation of Coated Microspheres

Chitosan-prednisolone conjugate microspheres (Ch-SP-MS) were prepared, and Eudragit coating was applied in order to efficiently deliver the microspheres and drug to the intestinal disease sites. The Eudragit L100-coated microspheres (Ch-SP-MS/EuL100) were examined for particle characteristics and the release of drug and Ch-SP-MS in different pH media at 37°C. Ch‐SP-MS were spherical, with a mean size of 4.5 μm and prednisolone content of 3.3% (w/w). Ch-SP-MS/EuL100 were fairly spherical, with a mean size of 22. 5 μm and drug content of 0.32% (w/w). At pH 1.2, the release extent was less than 5% even at 48 h, and Eudragit coating tended to suppress the release. In contrast, at pH 6.8 and 7.4, Ch-SP-MS/EuL100 tended to show somewhat faster drug release than Ch-SP-MS. Ch-SP-MS/EuL100 displayed a release extent of 23 and 27% at pH 6.8 and 7.4, respectively. Ch-SP-MS aggregated at pH 1.2, but almost kept their initial size and shape at pH 6.8 and 7.4. Ch-SP-MS/EuL100 almost maintained their original shape and size at pH 1.2, and gradually released Ch-SP-MS at pH 6.8 and 7.4 due to dissolution of the Eudragit layer. Eudragit coating is suggested to be useful to efficiently deliver Ch-SP-MS to the intestinal disease sites.     

Production of Lacto-N-biose I Using Crude Extracts of Bifidobacterial Cells

Lacto-N-biose I (LNB) is supposed to represent the bifidus factor in human milk oligosaccharides, and can be practically produced from sucrose and GlcNAc using four bifidobacterial enzymes, 1,3-β-galactosyl-N-acetylhexosamine phosphorylase, sucrose phosphorylase, UDP-glucose-hexose 1-phosphate uridylyltransferase, and UDP-glucose 4-epimerase, recombinantly produced by Escherichia coli. Here the production of LNB by the same enzymatic method without using genetically modified enzymes to consider the use of LNB for a food ingredient was reported. All four enzymes were produced as the intracellular enzymes of Bifidobacterium strains. The mixture of the crude extracts contained all four enzymes, with other enzymes interfering with the LNB production, namely, phosphoglucomutase, fructose 6-phosphate phosphoketolase, and glycogen phosphorylase. The first two interfering enzymes were selectively inactivated by heat treatment at 47 °C for 1 h in the presence of pancreatin, and glycogen phosphorylase was disabled by hydrolyzing its possible acceptor molecules using glucoamylase. Finally, 91 % of GlcNAc was converted into LNB in the 100-mL reaction mixture containing 300 mM GlcNAc.     

Functional and Structural Insights into Human PPARα/δ/γ Subtype Selectivity of Bezafibrate,Fenofibric Acid,and Pemafibrate

Among the agonists against three peroxisome proliferator-activated receptor (PPAR) subtypes, those against PPARα (fibrates) and PPARγ (glitazones) are currently used to treat dyslipidemia and type 2 diabetes, respectively, whereas PPARδ agonists are expected to be the next-generation metabolic disease drug. In addition, some dual/pan PPAR agonists are currently being investigated via clinical trials as one of the first curative drugs against nonalcoholic fatty liver disease (NAFLD). Because PPARα/δ/γ share considerable amino acid identity and three-dimensional structures, especially in ligand-binding domains (LBDs), clinically approved fibrates, such as bezafibrate, fenofibric acid, and pemafibrate, could also act on PPARδ/γ when used as anti-NAFLD drugs. Therefore, this study examined their PPARα/δ/γ selectivity using three independent assays—a dual luciferase-based GAL4 transactivation assay for COS-7 cells, time-resolved fluorescence resonance energy transfer-based coactivator recruitment assay, and circular dichroism spectroscopy-based thermostability assay. Although the efficacy and efficiency highly varied between agonists, assay types, and PPAR subtypes, the three fibrates, except fenofibric acid that did not affect PPARδ-mediated transactivation and coactivator recruitment, activated all PPAR subtypes in those assays. Furthermore, we aimed to obtain cocrystal structures of PPARδ/γ-LBD and the three fibrates via X-ray diffraction and versatile crystallization methods, which we recently used to obtain 34 structures of PPARα-LBD cocrystallized with 17 ligands, including the fibrates. We herein reveal five novel high-resolution structures of PPARδ/γ–bezafibrate, PPARγ–fenofibric acid, and PPARδ/γ–pemafibrate, thereby providing the molecular basis for their application beyond dyslipidemia treatment.