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.     

Does in-source decay occur independent of the ionization process in matrix-assisted laser desorption?

The influence of the acidic and basic characters of constituent amino acid residues on the peptide fragment ions produced by in-source decay under matrix assisted laser desorption/ionization (MALDI) conditions has been studied using positive- and negative-ion experiments. Whereas the in-source decay spectra of peptides containing basic Arg and/or Lys residues near the N-terminus showed so-called c_n- and a_n-series ions in positive-ion mode, a peptide that has an acidic amino acid cluster near the N-terminus and a basic residue near the C-terminus characteristically formed y_n- and z_n-series ions in the positive-ion in-source decay spectrum. These results indicated that fragment ion series produced by in-source decay depend strongly upon the acidic and basic characters of the constituent amino acid residues and the near N- and C-termini. It was suggested that in-source decay processes occur intrinsically at NH–C^α and CO–NH bonds independent of the formation of molecular-related ions, and that the cleavages at the NH–C^α and CO–NH bonds occurred independently and were dependent on the matrix used.     

Preparation and evaluation of oral dosage form using acylglycerols. II. Effect of food ingestion on dissolution and absorption of aspirin from the granules prepared by acylglycerols in human subjects.

The dissolution behavior of the aspirin enteric granule prepared using acylglycerols, glyceryl monostearate (GMS) and glyceryl trilaurate (GTL), was investigated in vitro and in human subjects in a fasting or non-fasting state. Aspirin was slowly released from the granule in vitro at pH 1.2. No acceleration of the aspirin dissolution rate in the medium without lipase and cholic acid was observed when the pH level of the medium increased to a neutral region (pH 6.4). However, the dissolution of aspirin was significantly increased by increasing the concentrations of lipase and cholic acid in the medium. Lipase appears to play an essential role in the dissolution process of aspirin granules. In human subjects, the average levels of the cumulative amount of total salicylate excreted in a urine-time curve, and the mean residence time (MRT) obtained after oral administration of a granule in the fasting state were markedly delayed in comparison with the results observed using an aqueous solution and a crystalline form of aspirin. In comparing the fasting condition with the non-fasting condition (after food ingestion), no significant difference was recognized in the total amount of salicylate excreted in urine to an infinite time (Ae(infinity)), whether the MRT was obtained by granule, crystalline form or aqueous solution. It can be concluded that aspirin granule prepared by GMS and GTL has a property of pancreatic lipase-sensitive dissolution, and its bioavailability is unaffected by food intake.     

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.     

Effect of d-limonene on the amounts of ethanol and indomethacin penetrated from aqueous gel ointments to rat skin.

The amounts of d-limonene, ethanol and indomethacin (IMC) which were transferred from aqueous gel ointments to the skin were determined in rats. The concentration of IMC in the skin correlated well with the plasma concentration of IMC percutaneously absorbed from the gel ointment. The increase of d-limonene concentration in the gel ointments was directly proportional to the accumulation of ethanol in the skin. The amount of ethanol in the skin was closely associated with the percutaneous absorption of IMC. As a possible mechanism for enhancement action of d-limonene and ethanol, it was considered that, at first, d-limonene penetrates into the skin under coexistence with ethanol and may change the barrier structure of the stratum corneum. The transfer of ethanol to the skin is thereby enhanced under the coexistence of d-limonene in the skin. Thus, the permeation of IMC can be promoted due to its affinity with ethanol.     

The high‐pressure form of cadmium vanadate,CdV2O6

The crystal structure of a new high‐pressure modification of cadmium divanadium hexaoxide, CdV₂O₆, was refined from X‐ray single‐crystal data. It contains zigzag chains of edge‐sharing VO₆ octahedra. Octahedra in adjacent chains share corners and form corrugated layers. Octahedrally coordinated Cd atoms, which lie on twofold axes, are situated between the layers. The columbite‐like structure results in a strong distortion of the CdO₆ octahedra which may be stabilized only at high pressure.     

Simultaneous catalytic removal of NOϰ and diesel soot particulates

The simultaneous removal of NO_? and soot particulates in an oxidizing atmosphere is desirable for the aftertreatment of diesel exhausts. After briefly reviewing the development of catalysts for reactions involving carbons, our recent studies on the simultaneous NO_?–soot removal using perovskite-related and spinel-type oxides are described.