Synthesis of poly(benzoxazole)s by direct polycondensation of dicarboxylic acids with 3,3′-dihydroxybenzidine dihydrochloride using phosphorus pentoxide/methanesulfonic acid as condensing agent and solvent

A convenient method for the synthesis of poly(benzoxazole)s of high molecular weights has been developed. These polymers were prepared readily by direct polycondensation of aromatic dicarboxylic acids containing phenyl either structure with 3,3′-dihydroxybenzidine dihydrochloride using phosphorus pentoxide/methanesulfonic acid (PPMA) as condensing agent and solvent. Polycondensations proceeded fast and was completed within 5 h at 140°C and produced poly(benzoxazole)s with inherent viscosities up to 4.6 dL/g. Model compound work was performed in detail to demonstrate the feasibility of the reaction for polymer formation. The thermogravimetry of the aromatic poly(benzoxazole)s showed 10% weight loss in air and nitrogen at 450–505°C and 465–535°C, respectively.     

Hydrothermal Synthesis of Mo-Based Oxide Catalysts and Selective Oxidation of Alkanes

Mo-V-M(=Al, Ga, Bi, Sb and Te)–O mixed oxide catalysts were synthesized hydrothermally for the first time, characterized structurally, and tested for ethane and propane oxidation after activation by various ways. These catalysts were black solids of rod-shaped (fiber like) crystals, which had a layer structure in the direction of fiber axis and a high dimensional arrangement of metal octahedra in the cross-section plane. These fresh crystalline materials became active for catalytic oxidation of alkanes after heat-treatment at 600 °C and subsequent grinding in order to increase exposed plane of the cross-section. The resulting catalysts were very active for an oxidative dehydrogenation of ethane with 80% of the ethylene selectivity in the reaction temperature range of 300 to 400 °C and also showed about 50% selectivity to acrylic acid in the propane oxidation. Multi-functional character which derived from the high dimensional structure of the catalysts and mechanism of the selective alkane oxidation were discussed.     

Fused silica capillary tube isotachophoresis using a multichannel photodiode array detector

Isotachophoresis carried out in a 0.25 mm i.d. fused-silica capillary tube yielded high resolution, compared with that in a fluorinated ethylene-propylene polymer tube. The use of an ultraviolet-visible multichannel spectrophotometer with photodiode array as detector together with a cross flow cell (volume 0.01 μl) was investigated. The system was successfully applied to the analysis of cationic dyes such as neutral red, bismarck brown, and basic fuchsine.     

Structural change of water by gelation of curdlan suspension

Phase transition of water restrained by curdlan suspension annealed at a temperature from 20 to 110°C was investigated by differential scanning calorimetry (DSC). The melting temperature of water restrained by annealed curdlan discontinuously decreased at around 60°C, while the amount of bound water calculated from enthalpy of melting increased at 60°C, regardless of water content. Using a highly sensitive DSC, curdlan suspension with various concentrations was studied. It was found that an endothermic transition was observed at ca. 58°C in a wide range of concentrations. The transition observed at 60°C is thermo-reversible and both temperature and transition enthalpy are constant even after gel formation. Well equilibrated suspension at a temperature lower than 60°C formed no gel.     

Fully automated micro- and nanoscale one- or two-dimensional high-performance liquid chromatography system for liquid chromatography-mass spectrometry compatible with non-volatile salts for ion exchange chromatography

A one- or two-dimensional high performance liquid chromatography system for electrospray ionization mass spectrometers has been developed that is optimized for ion exchange and reversed phase separations. A unique and simple valve configuration permits the use of a variety of non-volatile salts; ammonium sulfate was used in an example of strong cation exchange separations. The system was designed and evaluated for both micro- and nanoflow chromatography. The peptide detection limit was approximately 100 fmol for micro- and 20 fmol for nanoflow, demonstrating the concentration and mass sensitivity improvements expected with nanoelectrospray ionization. The 1D/2D-HPLC MS system is fully automated for routine peptide analyses, compatible with direct injection of proteolytic digests, and exhibits chromatographic reproducibility and sensitivity. Software permits operator selection of either a 1D or 2D configuration with corresponding system parameters as required for individual samples. The hardware elements and resulting performance are described in this paper.     

Analysis of oxidized epigallocatechin gallate by liquid chromatography/mass spectrometry

(-)-Epigallocatechin gallate (EGCG) of catechins changes from non-colored at around neutral pH to yellow at higher pH region in aqueous solution. The pH-dependent oxidation of EGCG was analyzed by liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS). LC/MS/MS analysis of EGCG and its related compounds, (-)-epicatechin gallate (ECG) and (-)-epigallocatechin (EGC), successfully elucidated the structure relationship of EGCG solution involving the color change reaction at different pH conditions. The oxidation species produced at alkaline pH was detected at a different retention time from EGCG in the chromatograms of the EGCG sample. The oxidation species was found to correspond to M+14 (where M is the molecular weight of EGCG), which has two hydrogen atoms removed and addition of one oxygen atom to the gallyl moiety in the B-ring of EGCG.     

Singlet Oxygen–mediated Hydroxyl Radical Production in the Presence of Phenols: Whether DMPO–·OH Formation Really Indicates Production of ·OH?¶

The reaction of singlet oxygen (1O2) generated by ultraviolet-A (UVA)-visible light (lambda > 330 nm) irradiation of air-saturated solutions of hematoporphyrin with phenolic compounds in the presence of a spin trap, 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), gave an electron spin resonance (ESR) spectrum characteristic of the DMPO-hydroxyl radical spin adduct (DMPO-*OH). In contrast, the ESR signal of 5,5-dimethyl-2-pyrrolidone-N-oxyl, an oxidative product of DMPO, was observed in the absence of phenolic compounds. The ESR signal of DMPO-*OH decreased in the presence of either a *OH scavenger or a quencher of *O2 and under anaerobic conditions, whereas it increased depending on the concentration of DMPO. These results indicate both 1O2- and DMPO-mediated formation of free *OH during the reaction. When DMPO was replaced with 5-(diethoxyphosphoryl)-5-methyl-1-pyrroline-N-oxide (DEPMPO), no DEPMPO adduct of oxygen radical species was obtained. This suggests that 1O2, as an oxidizing agent, reacts little with DEPMPO, in which a strong electron-withdrawing phosphoryl group increases the oxidation potential of DEPMPO compared with DMPO. A linear correlation between the amounts of DMPO-*OH generated and the oxidation potentials of phenolic compounds was observed, suggesting that the electron-donating properties of phenolic compounds contribute to the appearance of *OH. These observations indicate that 1O2 reacts first with DMPO, and the resulting DMPO-1O2 intermediate is immediately decomposed/reduced to give *OH. Phenolic compounds would participate in this reaction as electron donors but would not contribute to the direct conversion of 1O2 to *OH. Furthermore, DEPMPO did not cause the spin-trapping agent-mediated generation of *OH like DMPO did.