New technology for selective catalytic oxidation of ammonia to nitrogen

The selective catalytic oxidation (SCO) of ammonia to N₂ was studied by using a series of noble metal-V₂O₅-WO₃ catalysts supported on titania-silica (TS) prepared by coprecipitation method. In the V₂O₅-WO₃ catalyst system, the use of TS as a support was very effective to enhance catalytic activity compared with TiO₂ or SiO₂ alone. The addition of a slight amount of Pd and Ir to V₂O₅-WO₃/TS catalyst caused also remarkable enhancement of the catalytic activity without decreasing the selectivity to N₂. The present catalysts provide remarkably high catalytic performance for SCO of ammonia to N₂ under the practical reaction conditions for an industrial application.     

Regioselective synthesis and properties of novel [60]fullerene bisadducts containing a dibenzocrown ether moiety

The reactions of [60]fullerene with bis-o-quinodimethane precursors 3, 4, and 5 containing a dibenzo-18-crown-6, 24-crown-8 and 30-crown-10 moiety, respectively, were investigated. Both 3 and 4 provided trans-4 bisadducts 6a and 7a, respectively, as major product, though the selectivity in the latter was lower than that in the former. As minor product, 6b (cis-2) was produced from 3, while 7c (e) as well as 7b (cis-2) were produced from 4. Precursor 5 exclusively afforded e bisadduct 8 without any other regioisomers. These bisadducts showed different ionophoric properties from one another; for instance, 6a and 7b exhibited a high complexing ability toward the K+ ion, while 6b hardly showed complexation with any alkali metal ions. The selectivity coefficients (K(Na,K)(pot)) of 6a and 7b toward K+ over Na+ ion, determined with an ion-selective electrode, were much higher than that of dibenzo-18-crown-6.     

Photophysical properties of oligo(2,3-thienyleneethynylene)s

Photophysical properties of oligo(2,3-thienyleneethynylene)s (nTE, n denotes the number of thiophene rings, n = 2, 3) in benzene were investigated using steady-state, time-resolved fluorescence, and transient absorption spectroscopies. For 2TE, generation of the radiative S2 and nonradiative S1 states was confirmed. Upon excitation, the S2 state was initially generated and deactivated to the S1 state within 10 ps. The S1 state exhibited the transient absorption band at 470 nm, of which the lifetime was estimated to be 5.3 ns. In the case of 3TE, on the other hand, it was revealed that the radiative S1 state with a transient absorption peak at 650 nm was generated upon excitation. The T1 states of nTE were generated from the S1 states. The quantum yields were estimated to be 0.52 and 0.54 for 2TE and 3TE, respectively. Extremely fast reactions in the higher triplet excited state were indicated for both 2TE and 3TE.     

Bromination by means of sodium monobromoisocyanurate (SMBI)

A variety of aromatic compounds with both activating and deactivating substituents were brominated with sodium monobromoisocyanurate (SMBI) 1, diethyl ether, diethyl ether-methanesulfonic acid, trifluoroacetic acid, or sulfuric acid were employed as solvents. Thus nitrobenzene was conveniently brominated in sulfuric acid, benzene was readily monobrominated in diethyl ether-methanesulfonic acid, and phenol was selectively brominated at the ortho position under mild conditions in refluxing diethyl ether. With substituents that are easily protonated, trifluoroacetic acid may be employed as solvent in the reaction with 1, in contrast NBS was ineffective in trifluoroacetic acid. This renders 1 a superior reagent relative to NBS. In addition to aromatics, alkenes, ketones and esters were also brominated with 1. Diethyl malonate was brominated with 1 and then subjected to a Bingel reaction with NaH to afford the desired methanofullerene in reasonable yield.     

Effects of electrolytes on the configuration change of cobalt(II)-halide complexes in chloroform/water reverse micelle systems.

The effects of various salts and HClO4 on the configuration change of cobalt(II)-halide complexes in CHCl3/CTAC or CTAB/H2O reverse micelle systems were examined at 25 degrees C by means of spectrophotometry, where CTAC and CTAB represent cetyltrimethylammonium chloride and bromide, respectively. The formation of the [CoCl4]> or [CoBr4]2- species of the tetrahedral configuration from [Co(H2O)6]2+ of the octahedral configuration in the reverse micelles was greatly promoted not only by a decrease in the W value (W = [H2O]/[surfactant]), but also, at a constant W value (e.g., W = 2.0), by the addition of relatively low concentrations of salts or the acid (e.g., 4.0 mol dm(-3) in the aqueous phase or 4.0 x 10(-2) mol dm(-3) in the whole reverse micelle system). The effects of perchlorate salts increased as Na+ < or = Li+ approximately H+ < Sr2+ < Ca2+ < Mg2+. Non-metallic salts, various tetraalkylammonium (R4N+) salts at lower concentrations, gave minor effects. The enhanced effects of metal salts on the configuration change of the cobalt(II)-halide complexes were interpreted by a further distortion of the hydrogen-bonded structure of the water in a "water pool" in the presence of salts of even relatively low concentrations. A conformation change with increasing temperature was also attributed to a further distortion of the water structure. An almost completed formation of [CoBr4]2- as well as [CoCl4]2- was attained in the reverse micelles at a low W value of 0.69 containing LiClO4 or HClO4. A partial transfer of the [CoX4]2- species from a "water pool" into the CHCl3 phase by the addition of the metal salts may be suspected. An examination of cobalt(II)-bromide complexes in dichloromethane/CTAB/H2O at W = 1.3 - 5.55 justified all the arguments concerning the chloroform systems. The Raman spectra of D2O containing concentrated LiBr and LiClO4 have supplied conclusive evidence that the hydrogen-bonded structure of the bulk water is completely distorted by extremely concentrated salts.     

Solvent effect on protein binding by polymer brush grafted onto porous membranes

An epoxy-group-containing polymer chain was grafted onto the hollow-fiber form of a porous polyethylene membrane by the immersion of the electron beam-irradiated trunk polymer in glycidyl methacrylate diluted with methanol and 1-butanol. The epoxy group density ranged from 8.5 to 13.4 mol per kg of the trunk polymer. Subsequently, the epoxy groups produced were converted into sulfonic acid and diethylamino groups. The density of -SOH and -N(C2H5), groups was 0.40 and 2.2 mol per kg of the product. respectively. The polymer brush, defined as a polymer chain extending from the surface of a pore toward the interior of the pore, was evaluated from the determination of an equilibrium binding capacity of hen egg lysozyme (HEL) and bovine serum albumin (BSA). The polymer brush prepared in 1-butanol was found to be longer than that prepared in methanol from the determinations of liquid permeability and protein adsorptivity. The proteins were bound to the polymer brush prepared in 1-butanol, followed by the functionalization, at higher degrees of multilayer binding: about 30 for HEL and 6 for BSA.     

Synthesis of Ultrafine SiC Powders from Carbon-Silica Hybridized Precursors with Carbothermic Reduction

Inorganic-organic hybrid gels were prepared by simultaneous condensation of the liquid mixture of ethyl silicate, ethyl borate and water soluble phenol resin with low molecular weight. The liquid mixtures were changed into lightly colored transparent gels after a catalyst addition and stirring. The obtained gels were crushed, dried and fired in controlled conditions to yield the inorganic precursors. Since the tailored inorganic precursors mainly consisted of SiO2 and carbon, silicon carbide was formed with the heat treatments in an Ar atmosphere beyond 1773 K with carbothermic reduction. The properties and morphology of the formed silicon carbide powders in terms of the starting precursor compositions and the conditions of the carbothermic reduction were investigated with SEM, XRD and TG-DTA analysis.