A Large-Area Patterned TiO2/SnO2 Bilayer Type Photocatalyst Prepared by Gravure Printing

Anatase TiO₂ films (thickness = 50 nm) were formed in shape of stripes (width = 1.6 mm, interval = 0.4 mm) by gravure printing on commercially available SnO₂ coated soda-lime glass substrates (dimension = 300 × 300 mm). Its photocatalytic activity was examined for the gas-phase oxidation of CH₃CHO in comparison with a simple TiO₂ photocatalyst formed on a silica glass. The patterned TiO₂/SnO₂ bilayer type photocatalyst showed a high photocatalytic activity in an H₂O bearing atmosphere. On the other hand, neither the patterning nor stacking effect was observed for the same reaction under dry conditions. These results could be explained in terms of the reducing potential of the electrons in the conduction band of the SnO₂ layer.     

Distribution pattern of rare earth ions between water and montmorillonite and its relation to the sorbed species of the ions.

REE (rare earth element) distribution coefficients (Kd) between the aqueous phase and montmorillonite surface were obtained to investigate the relation between the REE distribution patterns and the species of REE sorbed on the solid-water interface. It was shown that the features in the REE patterns, such as the slope of the REE patterns, the tetrad effect, and the Y/Ho ratio, were closely related to the REE species at the montmorillonite-water interface. In a binary system (REE-montmorillonite) below pH 5, three features (a larger Kd value for a lighter REE, the absence of the tetrad effect, and the Y/Ho ratio being unchanged from its initial value) suggest that hydrated REE are directly sorbed as an outer-sphere complex at the montmorillonite-water interface. Above pH 5.5, the features in the REE patterns, the larger Kd value for heavier REE, the M-type tetrad effect, and the reduced Y/Ho ratio, showed the formation of an inner-sphere complex of REE with -OH group at the montmorillonite surface. In addition, the REE patterns in the presence of humic acid at pH 5.9 were also studied, where the REE patterns became flat, suggesting that the humate complex is dominant as both dissolved and sorbed species of REE in the ternary system. All of these results were consistent with the spectroscopic data (laser-induced fluorescence spectroscopy) showing the local structure of Eu(III) conducted in the same experimental system. The present results suggest that the features in the REE distribution patterns include information on the REE species at the solid-water interface.     

Chiral self-dimerization of vanadium complexes on a SiO2 surface: the first heterogeneous catalyst for asymmetric 2-naphthol coupling

The self-dimerized chiral assembly of vanadium-Schiff-base complexes was found to occur on a SiO2 surface and to be the first heterogeneous catalyst for the asymmetric oxidative coupling of 2-naphthol with 100% selectivity and 90% enantioselectivity.     

Correlation between the structure of water in the vicinity of carboxybetaine polymers and their blood-compatibility

The structure and hydrogen bonding of water in the vicinity of carboxybetaine homopolymer (poly[1-carboxy-N,N-dimethyl-N-(2'-methacryloyloxyethyl)methanaminium inner salt] (PolyCMB), and a random copolymer of CMB and n-butyl methacrylate, Poly(CMB-r-BMA), with various molecular weights were analyzed in their aqueous solutions and thin film with contours of O-H stretching of Raman and attenuated total reflection infrared (ATR-IR) spectra, respectively. The relative intensity of the collective band (C value) corresponding to a long-range coupling of O-H stretchings of the Raman spectra for aqueous solution of Poly(CMB-r-BMA) was very close to that for pure water, which is in contrast with the smaller C value in aqueous solution of ordinary polyelectrolytes. The number of hydrogen bonds collapsed by the presence of one monomer residue (N(corr) value) of PolyCMB and Poly(CMB-r-BMA) (CMB, 45 mol %) (M(w), 1.14 x 10(4) and 1.78 x 10(4), respectively) could be calculated from the C value. The N(corr) values were much smaller than those for ordinary polyelectrolytes and close to those for nonionic water-soluble polymers such as poly(ethylene glycol) and poly(N-vinylpyrrolidone). Furthermore, a water-insoluble Poly(CMB-r-BMA) with a large BMA content (M(w) = 347 kD, CMB 27 mol %) could be cast as a thin film (thickness, ca. 10 microm) on a ZnSe crystal for the ATR-IR analyses. At an early stage of sorption of water into the Poly(CMB-r-BMA) film, the O-H stretching band of IR spectra for the water incorporated in the film was similar to that for free water, which is in contrast with the drastic change in the O-H stretching band of water incorporated in polymer films such as poly(methyl methacrylate) (PMMA) and poly(n-butyl methacrylate) (PBMA). The theoretical vibrational frequency for water molecules hydrating a betaine molecule calculated by using a density functional method supported the experimental results. The adhesion of human platelets to Poly(CMB-r-BMA) films was much less than that to PMMA and PBMA. With an increase in the content of CMB residue, the number of platelets adhered to the Poly(CMB-r-BMA) film drastically decreased and then gradually increased, probably due to the increase in the roughness of the film surface. These results suggest that the carboxybetaine monomer residues with a zwitterionic structure do not significantly disturb the hydrogen bonding between water molecules in both aqueous solution and thin film systems, resulting in the excellent blood-compatibility of the carboxybetaine polymers.     

Further studies on the reaction of amines and proteins with 4-fluoro-7-nitrobenzo-2-oxa-1,3-diazole

The reaction of glycine with NBD-F (4-fluoro-7-nitrobenzo-2-oxa-1,3-diazole) is investigated to establish conditions that provide a high formation rate of NBD-glycine and a low hydrolysis rate of the reagent. The reaction rate increases with higher temperature, larger contents of organic solvent and a sodium borate buffer. The use of borate buffer decreases ther ate of hydrolysis of the reagent. For low-molecular-weight amines, condition for a suitable liquid chromatographic postcolumn reactor include a high content of acetonitrile and 0.1 M sodium borate (pH 8.0–8.5). For proteins, separated by molecular-exclusion chromatography, water is needed for sensitive reactions. Suitable postcolumn reactor conditions include borate buffer (pH 7.9) containing 0.1 M potassium chloride, a 0.02% (w/v) NBD-F solution in acetonitrile with reaction at 50°C for about 45 s. The detection limits for human serum albumin, β-lactoglobulin and myoglobin are 6.6 pmol, 8.4 pmol and 11 pmol, respectively.     

A new synthesis of 1,3-dienes from allyl sulfides and allyl sulfones using tri-n-butylstannylmethyl iodide

Allyl 2-pyridyl sulfide $\text{6}$ or allyl phenyl sulfone $\text{7}$ on treatment with n-butyllithium in tetrahyrofuran followed by tri-n-butylstannylmethyl iodide ($\text{4}$) afforded directly the 1,3-diene $\text{8}$ in good yield.     

Silica sol-gel/organic hybrid material for protein encapsulated column of capillary electrochromatography

A new-type of sol-gel/organic hybrid composite material using gelatin or chitosan with tetramethoxysilane was developed for the bovine serum albumin (BSA)-encapsulated monolithic column for capillary electrochromatography (CEC). The composite monolith was used to immobilize BSA in a fused-silica capillary. The addition of gelatin and chitosan to the alkoxysilane enabled the enantioseparation of Trp. A very small amount of these polymers were effective for the enantioseparation. Especially, the monolithic column prepared from chitosan with tetramethoxysilane showed a high enantioselectivity for Trp enantiomers and the value (alpha' = t2/t1, t1: fast eluted enantiomer, t2: second eluted enantiomer) reached 1.15 on CEC mode. Furthermore, the composite materials exhibited a higher stability compared to the silica sol-gel column. These results showed that the sol-gel/organic hybrid composite was useful as a monolithic matrix for the BSA-encapsulated column for CEC.     

Synthesis, characterization and FET properties of novel dithiazolylbenzothiadiazole derivatives

Dithiazolylbenzothiadiazoles easily obtained have high electron affinity and the FET device of a trifluoromethylphenyl derivative exhibited a good n-type performance with high electron mobility.     

Optical microscopy and in situ Raman scattering of single crystalline ethylene hydrate and binary methane-ethylene hydrate at high pressures

Visual observations through a microscope and in situ Raman measurements have been made for single crystalline ethylene hydrate (EH) and binary methane-ethylene hydrate (MEH) at pressures up to 3.7 GPa and room temperature. Both hydrates showed pressure-induced phase transitions at 1.6, 2.0, and 3.0 GPa for EH and at 1.7, 2.1, and 3.3 GPa for MEH. The cubic sI phase of EH and MEH remains stable up to 1.6 and 1.7 GPa, respectively, which are more widely ranging values than the values for the methane hydrate sI phase. In this sI phase of binary MEH, the cage occupancies by methane and ethylene molecules are investigated from Raman spectra. Above P = 3.0 GPa for EH and 3.3 GPa for MEH, they decomposed by associating with the formation of the polyethylene.