Development of a two‐dimensional imaging system of X‐ray absorption fine structure

A two‐dimensional imaging system of X‐ray absorption fine structure (XAFS) has been developed at beamline BL‐4 of the Synchrotron Radiation Center of Ritsumeikan University. The system mainly consists of an ionization chamber for I₀ measurement, a sample stage, and a two‐dimensional complementary metal oxide semiconductor (CMOS) image sensor for measuring the transmitted X‐ray intensity. The X‐ray energy shift in the vertical direction, which originates from the vertical divergence of the X‐ray beam on the monochromator surface, is corrected by considering the geometrical configuration of the monochromator. This energy correction improves the energy resolution of the XAFS spectrum because each pixel in the CMOS detector has a very small vertical acceptance of ～0.5 µrad. A data analysis system has also been developed to automatically determine the energy of the absorption edge. This allows the chemical species to be mapped based on the XANES feature over a wide area of 4.8 mm (H) × 3.6 mm (V) with a resolution of 10 µm × 10 µm. The system has been applied to the chemical state mapping of the Mn species in a LiMn₂O₄ cathode. The heterogeneous distribution of the Mn oxidation state is demonstrated and is considered to relate to the slow delocalization of Li⁺‐defect sites in the spinel crystal structure. The two‐dimensional‐imaging XAFS system is expected to be a powerful tool for analyzing the spatial distributions of chemical species in many heterogeneous materials such as battery electrodes.     

Collisional properties of p-wave Feshbach molecules

We have observed p-wave Feshbach molecules for all three combinations of the two lowest hyperfine spin states of 6Li. By creating a pure molecular sample in an optical trap, we measured the inelastic collision rates of p-wave molecules. We have also measured the elastic collision rate from the thermalization rate of a breathing mode which was excited spontaneously upon molecular formation.     

Critical temperature and condensate fraction of a fermion pair condensate

We report on measurements of the critical temperature and the temperature dependence of the condensate fraction for a fermion pair condensate of 6Li atoms. Bragg spectroscopy is employed to determine the critical temperature and the condensate fraction after a fast magnetic field ramp to the molecular side of the Feshbach resonance. Our measurements reveal evidence of level off of the critical temperature and limiting behavior of condensate fraction near the unitarity limit.     

Ruthenium-catalyzed propargylation of aromatic compounds with propargylic alcohols

A novel ruthenium-catalyzed propargylation of aromatic compounds with propargylic alcohols has been found to afford the corresponding propargylated aromatic products in good yields with complete regioselectivity. The catalytic reaction provides a potential usefulness for practical application in organic synthesis, because the selective propargylation of aromatic compounds with an aromatic C-H bond cleavage is generally difficult.     

Ruthenium- and platinum-catalyzed sequential reactions: selective synthesis of fused polycyclic compounds from propargylic alcohols and alkenes

A simple method for the preparation of fused polycyclic compounds by an intramolecular cyclization of propargylic alcohols bearing an alkene moiety at a suitable position has been developed, where the presence of both Ru and Pt catalysts promotes a sequence of catalytic cycles in the same medium. This sequential system can be applied to an intermolecular reaction between a propargylic alcohol and an alkene to obtain the corresponding bicyclo[3,1,0]hex-2-ene derivative. These sequential reactions provide a conceptually new type of cycloaddition system between propargylic alcohols and alkenes.     

Chlorophyllin coupled with polyethylene glycol: A potent photosensitizer

Chlorophyllin a prepared by the saponification of chlorophyll a was conjugated with α-(3-aminopropyl)-ω-methoxypoly(oxyethylene), PEG-NH₂, to form PEG-chlorophyllin through acid-amide bonds. PEG-chlorophyllin was readily soluble not only in aqueous solution but also in organic solvents. The absorption maxima of the conjugate were located at 657 nm and 418 nm in aqueous solution, and at 656 nm and 422 nm in benzene. The conjugate seems to be more stable toward light-illumination than uncoupled chlorophyllin. Furthermore, PEG-chlorophyllin possessed a potent photosensitizing activity to produce superoxide anion during the illumination, although chlorophyllin immediately lost its activity by light-illumination.     

Studies on thermophile products. IV. Structural elucidation of cytotoxic substance, BS-1, derived from Bacillus stearothermophilus.

A new cytotoxic substance designated as BS-1 was isolated from the autolysate and culture filtrate of Bacillus stearothermophilus UK563. On the basis of spectral data, the structure of BS-1 was determined as bis(2-hydroxyethyl) trisulfide and confirmed by direct comparison with the synthetic compound. BS-1 exhibited potent cytotoxicity against leukemia P388-D1, leukemia P388, mastocytoma P815, lymphoma EL4 and lymphoma MOLT4.