Preparation, structure and properties of novel 1,3-dithiol-2-ylidene derivatives containing bis(ethynylpyridine) units

1,3-Dithiol-2-ylidene derivatives containing bis(ethynylpyridine) units were synthesized using a Pd-catalyzed reaction of the corresponding dibromide. X-Ray crystal analysis revealed unique crystal structures depending on the aromatic groups. The absorption spectra and redox properties indicated intramolecular charge-transfer interactions between the 1,3-dithiole unit and the pyridyl parts.     

Rhodium-catalyzed addition of arylstannanes to carbon-heteroatom double bond

The addition of arylstannanes to the carbon-heteroatom double bond in the presence of a catalytic amount of a cationic rhodium complex ([Rh(cod)(MeCN)₂]BF₄) was examined. The reactions of aldehydes, α-dicarbonyl compounds, and N-substituted aldimines with the arylstannanes gave corresponding alcohols, α-hydroxy carbonyl compounds, and amines, respectively. An arylrhodium complex generated by the transmetalation with the arylstannane was probably the active catalytic species.     

Visible-light-sensitive photocatalytic reaction on chromium-containing mesoporous silica: selective partial oxidation of propane with molecular oxygen

The photocatalytic reactivities of chromium-containing mesoporous silica molecular sieves (Cr-HMS) under visible light irradiation have been investigated. Cr-HMS involves tetrahedral chromium oxide (Cr-oxide) moieties which are highly dispersed and incorporated in the framework of molecular sieve with two terminal Cr=O groups. In the presence of propane with molecular oxygen, a partial oxidation proceeded under visible light irradiation to produce acetone and acrolein, with high selectivity, while a complete oxidation proceeded under UV light irradiation mainly to produce CO₂. The charge-transfer excited state of the tetrahedral Cr-oxide moieties plays a significant role in the photocatalytic reactions.     

Formation of Defect-Spinel Phase in CdSnO3

A spinel-type structure was found in cadmium stannate CdSnO₃ prepared by thermal decomposition of the hydroxostannate CdSn(OH)₆ at 550–800°C. Its occurrence depends strongly on the precipitation conditions of CdSn(OH)₆ from CdCl₂ and Na₂Sn(OH)₆ aqueous solutions. In the (Cd_1–xCa_x)SnO₃ system, the spinel phase appears in the composition range of 0.0 ≤ x ≤ 0.35. The experimental results suggest the presence of cation vacancies in the spinel octahedral sites.     

Spin-relaxation and magnetoresistance in FM/SC/FM tunnel junctions

The effect of spin relaxation on tunnel magnetoresistance (TMR) in a ferromagnet/superconductor/ferromagnet (FM/SC/FM) double tunnel junction is theoretically studied. The spin accumulation in SC is determined by balancing of the spin-injection rate and the spin-relaxation rate. In the superconducting state, the spin-relaxation time τ_s becomes longer with decreasing temperature, resulting in a rapid increase of TMR. The TMR of FM/SC/FM junctions provides a useful probe to extract information about spin-relaxation in superconductors.     

A novel greener glycosidation using an acid-ionic liquid containing a protic acid

The glycosidations of glucopyranosyl diethyl phosphite and alcohols using an ionic liquid, 1-n-hexyl-3-methylimidazolium trifluoromethanesulfonimidide (C₆mim[NTf₂]) containing a protic acid, trifluoromethanesulfonimide (HNTf₂), as a novel solvent-catalyst system, effectively proceeded under mild conditions to give the corresponding glycosides in good to high yields. Furthermore, this acid-ionic liquid combination could be reused many times for the glycosidations without any loss in efficiency.     

Quantitative assessment of solid oxide electrochemical doping

Quantitative analysis of metal cation doping by solid oxide electrochemical doping (SOED) has been performed under galvanostatic doping conditions. A M–β″-Al₂O₃ (M=Ag, Na) microelectrode (contact radius: about 10 μm) was used as cation source to attain a homogeneous solid–solid contact between the β″-Al₂O₃ and doping target. In Ag doping into alkali borate glass, the measured dopant amount closely matched the theoretical value. High Faraday efficiencies of above 90% were obtained. This suggests that the dopant amount can be precisely controlled on a micromole scale by the electric charge during electrolysis. On the other hand, current efficiencies of Na doping into Bi₂Sr₂CaCu₂O_y (BSCCO) ceramics depended on the applied constant current. Efficiencies of above 80% were achieved at a constant current of 10 μA (1.6 A cm⁻²). The relatively low efficiencies were explained by the saturation of BSCCO grain boundaries with Na. By contrast, excess Na was detected on the anodic surface of ceramics at a constant current of 100 μA (16 A cm⁻²). In the present study, we demonstrate that SOED enables micromole-scale control over dopant amount.     

Polarization Sensitive Spectral Interferometric Optical Coherence Tomography for Biological Samples

A spectral interferometric optical coherence tomography (OCT) system which has polarization sensitivity is developed. This system reduces the mechanical scanning dimension by employing the principle of spectral interferometry, and measures a two dimensional cross-sectional image of biological tissue with one dimensional mechanical scanning. Sixteen OCT images with different polarization conditions are measured, and two dimensional distributions of each element of the Müller matrix of a sample to be measured are calculated.