Electronic properties of CrF and CrCl in the X 6Sigma+ state: observation of the halogen hyperfine structure by Fourier transform microwave spectroscopy

The rotational spectra of the CrF and CrCl radicals in the X 6Sigma+ state were observed by employing a Fourier transform microwave spectrometer. The CrF and CrCl radicals were generated by the reaction of laser-ablated Cr with F2 and Cl2, respectively, diluted in Ar. A chromium rod made of chromium powder pasted with epoxy resin was ablated by a Nd:YAG laser. Rotational transitions were measured in the region between 8 and 26 GHz. Several hyperfine constants due to the halogen nuclei were determined by a least-squares analysis. The electronic properties of CrF and CrCl were derived from their hyperfine constants and were compared with those of other 3d transition metal monohalides: TiF, MnF, FeF, CoF, NiF, and FeCl.     

Fourier transform microwave spectroscopy of the Rg-SH(2Pi(i)) complexes (Rg:Ne, Kr): determination of the intermolecular potential energy surfaces

Pure rotational spectra of Ne-SH and Kr-SH have been studied by Fourier transform microwave spectroscopy. R-branch transitions in the lower-spin component (Omega=3/2) corresponding to a linear (2)Pi(i) radical were observed for J(")=1.5-4.5 in the region 11-25 GHz for Ne-SH and for J(")=1.5-6.5 in the region 5-20 GHz for Kr-SH, respectively, with parity doublings and hyperfine splittings associated with the H nucleus. Although the spectral pattern of Kr-SH is relatively regular, that of Ne-SH is irregular with the J dependence of the parity doublings quite different from other Rg-SH or Ar-OH complexes. Two-dimensional intermolecular potential energy surfaces (IPSs) for both of the species have been determined from the least-squares fittings of the observed rotational transitions utilizing results of high-level ab initio calculations. These IPSs reproduce the observed transition frequencies within the experimental error and provide accurate knowledge on the intermolecular interaction and internal dynamics. Systematic comparisons of Rg-SH complexes have clarified various features of this series of complexes.     

Tissue velocity imaging of coronary artery by rotating-type intravascular ultrasound

Intravascular ultrasound (IVUS) provides not only the dimensions of coronary artery but the information of tissue components. In catheterization laboratory, soft and hard plaques are classified by visual inspection of echo intensity. So-called soft plaque contains lipid core or thrombus and it is believed to be more vulnerable than a hard plaque. However, it is not simple to analyze the echo signals quantitatively. When we look at a reflection signal, the intensity is affected by the distance of the object, the medium between transducer and objects and the fluctuation caused by rotation of IVUS probe. The time of flight is also affected by the sound speed of the medium and Doppler shift caused by tissue motion but usually those can be neglected. Thus, the analysis of RF signal in time domain can be more quantitative than intensity of RF signal. In the present study, a novel imaging technique called "intravascular tissue velocity imaging" was developed for searching a vulnerable plaque. Radio-frequency (RF) signal from a clinically used IVUS apparatus was digitized at 500 MSa/s and stored in a workstation. First, non-uniform rotation was corrected by maximizing the correlation coefficient of circumferential RF signal distribution in two consecutive frames. Then, the correlation and displacement were calculated by analyzing the radial difference of RF signal. Tissue velocity was determined by the displacement and the frame rate. The correlation image of normal and atherosclerotic coronary arteries clearly showed the internal and external borders of arterial wall. Soft plaque with low echo area in the intima showed high velocity while the calcified lesion showed the very low tissue velocity. This technique provides important information on tissue character of coronary artery.     

An HPLC assay of hydroxyl radicals by the hydroxylation reaction of terephthalic acid

An HPLC assay for hydroxyl radicals is described. The hydroxyl radical was trapped by terephthalic acid (non-fluorescent), and 2-hydroxyl terephthalic acid (fluorescent) was quantitated by HPLC-fluorescence detection. At a terephthalic acid concentration of 4.25 mmol/L, the hydroxyl radical formed in the Fenton reaction was successfully assayed in the concentration range of hydrogen peroxide of 2.5-50 micro mol/L, where the concentration of Fe(II) was 50 micro mol/L. The fluorescence of 2-hydroxy terephthalate was stable at 24 h, and its detection limit by this method was 5 nmol/L (100 fmol).     

Lipase TL-mediated kinetic tesolution of 5-benzyloxy-1-tert-butyldimethylsilyloxy-2-pentanol at low temperature: concise asymmetric synthesis of both enantiomers of a piperazic acid derivative

Lipase TL-mediated kinetic resolution of (+/-)-5-benzyloxy-1-tert-butyldimethylsilyloxy-2-pentanol (5) at low temperature proceeded to give the corresponding (S)-alcohol 5 and (R)-acetate 6 in quantitative yields with high enantiomeric purity. The addition of bases such as pyridine, DMAP, 2,4- and 2,6-lutidines, or triethylamine considerably enhanced the rate of kinetic resolution. The alcohol (S)-5 and the acetate (R)-6 were converted to piperazic acid derivatives (R)- and (S)-3, respectively, via the intramolecular Mitsunobu reaction as a key step.     

Synthesis and properties of novel thiaarenecyclynes

Novel thiaarenecyclynes 3 and 4 in which two thioether units and two benzene rings are alternately inserted into the single bonds of cyclooctatetrayne are synthesized. Their unique properties are described.     

In situ FTIR studies of primary intermediates of photocatalytic reactions on nanocrystalline TiO2 films in contact with aqueous solutions

Multiple internal reflection infrared spectroscopy was applied to in situ investigations of surface intermediates of photocatalytic reactions on nanocrystalline TiO(2) films in contact with aqueous solutions. UV irradiation in the presence of dissolved O(2) caused the appearance of new bands peaked at 943, 838, and 1250-1120 cm(-)(1) together with intensity changes in other bands. Investigations of influences of the solution pH, the presence or absence of hole and electron scavengers, and isotopic H(2)O --> D(2)O exchange on the spectral changes have revealed that the primary step of photocatalytic O(2) reduction is the formation of the surface peroxo species, Ti(O(2)), giving the 943 cm(-)(1) band, probably with the surface superoxo species, TiOO., as a precursor, in neutral and acidic solutions. The surface peroxo species is then transformed to the surface hydroperoxo, TiOOH, giving the 838 and 1250-1120 cm(-)(1) bands, by protonation in the dark. This is, to our knowledge, the first direct in situ spectroscopic detection of primary intermediates for the photocatalytic O(2) reduction in aqueous solutions. On the basis of the assignment, a possible reaction scheme for various processes of the photocatalytic O(2) reduction is proposed, which is in harmony with other spectral changes induced by the UV irradiation.     

One-pot alpha-glycosylation method using Appel agents in N,N-dimethylformamide

[reaction: see text] A concept for the development of practical glycosylation is presented and demonstrated by one-pot alpha-glycosylation applying Appel agents for 2-O-benzyl-1-OH hexoses in DMF. The reaction, in situ giving the equilibrium of glycosyl bromides and more reactive O-glycoside intermediates, accomplishes a near-quantitative alpha-glycosylation removing the water molecules.     

Systematic study on synthesis and structural, electrical transport and magnetic properties of Pb-substituted Bi-Ca-Co-O misfit-layer cobaltites

Single-phases of Pb-substituted Bi-Ca-Co-O misfit-layer cobaltites with various Pb concentrations have been synthesized and the Pb-substitution effects on the structural, electrical and magnetic properties have been systematically investigated. Powder X-ray diffraction analysis showed that the single-phases of Bi_1.8−x/2Pb_xCa₂Co₂O_z were obtained up to x=0.6-0.7 under the optimized synthesis conditions. The lattice parameters of Bi_1.8−x/2Pb_xCa₂Co₂O_z continuously changed with increasing Pb concentration. The electron diffraction analysis suggested that the structure consisted of two different sublattices with a rock salt structure (RS) and a hexagonal CdI₂ structure (H), respectively, without modulation. In combined with the chemical composition analysis, the chemical formulas of the x=0 and x=0.6 samples were determined approximately as [Bi_1.74Co_0.31Ca_2.01O₄]^RS[CoO₂]_1.69 and [Bi_1.47Pb_0.38Co_0.29Ca_1.98O₄]^RS[CoO₂]_1.71, respectively. The electrical resistivity became more metallic with increasing the Pb concentration up to x=0.6. Moreover, the Pb-substitution simultaneously increased the antiferromagnetic Weiss temperatures and decreased the effective magnetic moments of the Co ions.     

High-Quality Protein Crystal Growth of Mouse Lipocalin-Type Prostaglandin D Synthase in Microgravity

Lipocalin-type prostaglandin (PG) D synthase (L-PGDS) catalyzes the isomerization of PGH(2) to PGD(2) and is involved in the regulation of pain and of nonrapid eye movement sleep and the differentiation of male genital organs and adipocytes, etc. L-PGDS is secreted into various body fluids and binds various lipophilic compounds with high affinities, acting also as an extracellular transporter. Mouse L-PGDS with a C65A mutation was previously crystallized with citrate or malonate as a precipitant, and the X-ray crystallographic structure was determined at 2.0 ? resolution. To obtain high-quality crystals, we tried, unsuccessfully, to crystallize the C65A mutant in microgravity under the same conditions used in the previous study. After further purifying the protein and changing the precipitant to polyethylene glycol (PEG) 8000, high-quality crystals were grown in microgravity. The precipitant solution was 40% (w/v) PEG 8000, 100 mM sodium chloride, and 100 mM HEPES-NaOH (pH 7.0). Crystals grew on board the International Space Station for 11 weeks in 2007, yielding single crystals of the wild-type L-PGDS and the C65A mutant, both of which diffracted at around 1.0 ? resolution. The crystal quality was markedly improved through the use of a high-viscosity precipitant solution in microgravity, in combination with the use of a highly purified protein.