Raman Scattering Intensities of the NO2 Symmetric Stretching Vibration Band of Some Aromatic Nitrocompounds (II)

The Raman scattering intensities of the NO₂ symmetric stretching vibration band were investigated experimentally for some para and meta substituted nitrobenzenes. The excitation profiles obtained with the six excitation wavelengths from 457.9 to 514.5 nm were presented. The results were examined in terms of the Albrecht-Hutley's theory, and the electronic states involved in the preresonance Raman intensity enhancement were suggested.     

Determination of radioactive and stable cobalt in marine biological materials (author's transl)]

Studies were made to develop the method for rapid determination of radioactive and stable cobalt in a single specimen of marine biological materials. The sample was dried, ashed, and dissolved in acid. The cobalt was extracted with 1-nitroso-2-naphthol benzene and determined by absorptiometry on the benzene phase. Then, the organic solution was evaporated to dryness, and the residue was treated with nitric-perchloric acid mixture to decompose any organic matter, and taken up with hydrochloric acid. The cobolt was extracted from the solution with TIO A-toluene, and the radioactive cobalt was determined by liquid scintillation counting on the toluene phase. Examinations were made on the chemical yield and on the decontamination factor of the fission product nuclides. Analysis were made on the marine biological samples of Urazoko Bay, Fukui prefecture. Agreement of the radioactive cobalt data between that by the present method and that by Ge(Li) gamma ray spectometry was good. Also, the stable cobalt value by the present method agreed well with that by neutron activation analysis method.     

A novel redox system consisting of π-conjugated polymers and transition metals

Coordination of π-conjugated polymers to transition metals constructs a novel redox system due to interchangeable various oxidation states of the polymers, which permits transition metals to interact with each other through a π-conjugate chain. The redox characteristics were found to depend on the electronic interaction with metals and the doping. A combination of copper(II) or iron(III) chloride and polyanilines afforded the complex catalysts with the higher oxidation capability for dehydrogenative oxidation. A catalytic system was also realized in the transition-metal-induced oxidation reaction, in which π-conjugated polymers serve as redox-active ligands participating in the reversible redox cycle. The Wacker oxidation of terminal olefins proceeded catalytically in the presence of a catalytic amount of polyaniline or polypyrrole derivative under oxygen.     

Preparation of 2,2-disubstituted 1,2-dihydro-3H-indol-3-ones via oxidation of 2-substituted indoles and Mannich-type reaction

A novel preparative method for 2,2-disubstituted 1,2-dihydro-3H-indol-3-ones through the oxidation of 2-arylindoles followed by a Mannich-type reaction with carbon nucleophiles is described.     

Gas permeation of fullerene‐dispersed poly(1‐trimethylsilyl‐1‐propyne) membranes

Homogeneously fullerene‐dispersed membranes were prepared under the conditions in which a 10 wt % poly(1‐trimethylsilyl‐1‐propyne) solution containing 0.5 wt % fullerene was dried under a reduced pressure of 50 cmHg at 100 °C. UV‐vis spectra and microscopic observations of the fullerene membranes indicated that the fullerene was homogeneously dispersed in the membranes. The permeability coefficients of 1‐butene were found to be higher than those of n‐butane in the fullerene membranes, although the permeability coefficients of olefin gases were nearly equal to those of paraffin gases having the same number of carbon in poly(1‐trimethylsilyl‐1‐propyne) membranes containing no fullerene. Pressure dependence of permeability coefficients was clearly observed for the permeation of carbon dioxide, ethylene, ethane, 1‐butene, and n‐butane through the fullerene membranes, while no significant dependence was found for poly(1‐trimethylsilyl‐1‐propyne) membranes except for the permeation of 1‐butene and n‐butane. The pressure dependence of the permeability was explained by the dual‐mode sorption model. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1749–1755, 2000     

Photoinduced face-inversion of conjugated tetraene ligands on a Pd-Pd-Pd moiety

The linear sandwich tripalladium complexes [Pd3{Ar(CH=CH)4Ar}2[BArf]2 (Ar = Ph, p-t-Bu-C6H4, p-styryl-C6H4) undergo photoinduced isomerization involving face-inversion of the tetraene ligands. Irradiation of these complexes with visible light (>510 nm) resulted in rac (staggered sandwich) to meso (eclipsed sandwich) isomerization. The structures of rac and meso isomers are determined by X-ray crystallographic analyses.     

Poly‐ε‐Lysine Modified Nanocarbon Film Electrodes for LPS Detection

We developed an electrochemical system for detecting lipopolysaccharide (LPS) that uses an ultraflat nanocarbon film electrode modified with poly‐ε‐lysine with a high affinity to LPS. LPS was captured on the modified electrode, and then ferrocene labeled polymyxin B (FcPMB) was captured on the LPS adsorbed electrode via the LPS‐PMB affinity interaction. The adsorbed FcPMB provided an amplified response with Fe²⁺ ions, and the current response was dependent on the amount of captured LPS (LOD=2.0 ng/mL). This was due to the efficient accumulation of the obtained current for LPS and the very low noise made possible by the ultraflat surface.