Integrated electrochemical-chemical oxidation mediated by alkoxysulfonium ions

Generation of carbocations by the "cation pool" method followed by reaction with dimethyl sulfoxide (DMSO) gave the corresponding alkoxysulfonium ions. Alkoxysulfonium ions could also be generated by in situ DMSO trapping of electrochemically generated carbocations. The resulting alkoxysulfonium ions were transformed into carbonyl compounds by treatment with triethylamine. The present integrated electrochemical-chemical oxidation can be applied to the oxidation of diarylmethanes to diaryl ketones, toluenes to benzaldehydes, and aryl-substituted alkenes to 1,2-diketones. Moreover, the oxidation of unsaturated compounds bearing a nucleophilic group in an appropriate position gives cyclized carbonyl compounds.     

Generation of nitrile oxides from oximes using t-BuOI and their cycloaddition

tert-Butyl hypoiodite (t-BuOI) was found to be a powerful reagent for the cycloaddition of oximes and alkenes/alkynes, leading to the formation of a variety of isoxazolines or isoxazoles under mild conditions.     

Physicochemical properties and plastic crystal structures of phosphonium fluorohydrogenate salts

Fluorohydrogenate salts of quaternary phosphonium cations with alkyl and methoxy groups (tetraethylphosphonium (P(2222)(+)), triethyl-n-pentylphosphonium (P(2225)(+)), triethyl-n-octylphosphonium (P(2228)(+)), and triethylmethoxymethylphosphonium (P(222(101))(+))) have been synthesized by the metatheses of anhydrous hydrogen fluoride and the corresponding phosphonium bromide or chloride precursors. The three salts with asymmetric cations, P(222m)(FH)(2.1)F (m = 5, 8, and 101), are room temperature ionic liquids (ILs) and are characterized by differential scanning calorimetry, density, viscosity, and conductivity measurements. Linear sweep voltammetry using a glassy carbon working electrode shows these phosphonium fluorohydrogenate ILs have wide electrochemical windows (>4.9 V) with the lowest viscosity and highest conductivity in the known phosphonium-based ILs. Thermogravimetry shows their thermal stabilities are also improved compared to previously reported alkylammonium cation-based fluorohydrogenate salts. Differential scanning calorimetry and X-ray diffraction revealed that tetraethylphosphonium fluorohydrogenate salt, P(2222)(FH)(2)F, exhibits two plastic crystal phases. The high temperature phase has a hexagonal lattice, which is the first example of a plastic crystal phase with an inverse nickel arsenide-type structure, and the low-temperature phase has an orthorhombic lattice. The high-temperature plastic crystal phase exhibits a conductivity of 5 mS cm(-1) at 50 °C, which is the highest value for the neat plastic crystals.     

Effects of sub-millimeter-bubble injection on transition to turbulence in natural convection boundary layer along a vertical plate in water

Temperature and velocity measurements are performed to clarify the effects of sub-millimeter-bubble injection on the transition to turbulence in the natural convection boundary layer along a vertical plate in water. In particular, we focus on the relationship between the bubble injection position L and the transition to turbulence in the natural convection boundary layer. The bubble injection positions used in our experiments are L = 1.6 and 3.6 mm. Bubble injection at L = 1.6 mm delays the transition to turbulence in the natural convection boundary layer, while that at L = 3.6 mm accelerates the transition to turbulence in the boundary layer. In the case of L = 1.6 mm, the appearance region of the liquid velocity fluctuation in the bubble-induced upward flow in the upstream unheated section is restricted to near the wall, although the peak of the liquid velocity fluctuation is high. In contrast, in the case of L = 3.6 mm, the relatively large liquid velocity fluctuation is distributed widely over the laminar boundary layer width. These results suggest that the effect of the liquid velocity fluctuation on the laminar boundary layer is quite different between L = 1.6 and 3.6 mm. It is therefore expected that the transition to turbulence in the natural convection boundary layer for the case with bubble injection is dependent on the magnitude and appearance region of the liquid velocity fluctuation in the bubble-induced upward flow in the upstream unheated section.     

Preparation of telechelic oligomers by thermal degradation of propylene copolymers

The reactive end groups of nonvolatile oligomers obtained by controlled thermal degradation of poly(propylene-ran-ethylene) and poly(propylene-ran-1-butene) were determined by ¹H and ¹³C NMR spectroscopy. The molar ratio of unsaturated to saturated end groups was found to be about 9:1. The average number of unsaturated end groups per molecule was between 1.6 and 1.8, indicating that 60–80 mol% of the oligomer molecules were telechelic, having two terminal unsaturated end groups. These oligomers had a lower polydispersity than the raw material, despite their lower molecular weight and melting temperature. Although the end groups resulting from each monomer unit could be detected by ¹³C NMR, the end group composition differed from that of the main chains of the raw materials. The end group composition was satisfactorily explained by the differences in bond dissociation energy and activation energy of elementary reactions that occurred during thermal degradation, based on the monomer composition of the raw materials.     

Studies on thermal degradation of acrylonitrile–butadiene–styrene copolymer (ABS-Br) containing brominated flame retardant

The thermal degradation of acrylonitrile-butadiene-styrene copolymer (ABS-Br; 10 g) containing brominated flame retardant (Br: 9.59 wt.%) was carried out at 450 °C using a semi batch operation using two different temperature programs. The heating rate was found to affect the quality of the degradation oil and yield of products (liquid, gas and residue). Data on the effect of the temperature program on the accumulation of liquid products was presented. It was found that the majority of the bromine was concentrated in the carbon residue and while majority of the nitrogen accumulates in the liquid products irrespective of degradation mode. The use of a one step constant heating rate process (I) produced a higher liquid yield (39%), than a two step process (29%). Differences were also noted in the Br and N contained in the liquids produced by the two processes.     

Multi-Terabit Long-Haul Transmission System Utilizing Distributed Raman Amplification Technologies

Here we summarize multi-terabit long-haul transmission experiment and distributed Raman amplification (DRA) technologies. As well, we investigate the configuration of dispersion-managed fibers for the DRA-based system from the viewpoint of the fiber non-linear effect and required pumping power.     

Photoluminescence characteristics of nitrogen atomic-layer-doped GaAs grown by MOVPE

Nitrogen atomic-layer-doped and uniformly doped GaAs were grown by MOVPE using dimethylhydrazine on a (001) plane. They showed several sharp photoluminescence lines with a full width at half maximum less than 1 meV at 8 K. Compared with uniformly doped GaAs, the photoluminescence intensity of the nitrogen-related line at the longest wavelength is enhanced in nitrogen atomic-layer-doped GaAs, suggesting that it is easier to form nitrogen pairs during atomic layer doping. To investigate the sharp nitrogen-related lines, we also grew GaAs with double atomic-layer-doped planes and varied the distance between the two planes. When the two planes are brought close to 1 nm, two new lines, NN_C and NN_D, appear between the two nitrogen-related lines, NN_A and NN_B, observed in a single nitrogen atomic-layer-doped GaAs. The NN_C and NN_D lines are also observed in uniformly doped GaAs. Therefore, NN_A and NN_B originate from excitons bound to pairs of nitrogen atoms, both of which are in the (001) plane, while NN_C and NN_D originate from those bound to pairs of nitrogen atoms, of which pairing directions are not included in the (001) plane. From the photoluminescence characteristics, distances between nitrogen atoms of a pair are estimated for each line.