Theory of resonant forbidden Raman scattering in semiconductors

The Raman tensors for the electric field-induced and wavevector dependent scattering from LO phonons in semiconductors have been calculated near critical points using a perturbation treatment. The resulting expressions have analytic closed forms such that the dependence of the forbidden scattering intensity on the incident photon energy and the applied d.c. electric field can be evaluated from available energy band parameters. The forbidden LO scattering intensity of GaAs in the back scattering configuration has been numerically calculated near the e₁ and E₁ gaps as functions of the incident photon energy and the dc electric field. The result shows strong interference between the two scattering processes. The allowed TO and LO Raman scattering intensities of GaAs were also calculated at a wavelength of 1.06 μm from the SHG and Faust-Henry coefficients, and compared with the forbidden LO intensity.     

15N NMR study on site-selective binding of metal ions to guanine runs in DNA: a good correlation with HOMO distribution

15N NMR of DNA containing 15N-N7-enriched guanine (G) in the presence of paramagnetic ions (Mn(II) and Co(II)) was investigated. As the concentration of metal ion was increased, 15N NMR signals of the 5'G of GG and the middle G of GGG broadened site-selectively, indicating that electron-donating sites in G runs preferentially localize on the 5'G of GG and the middle G of GGG. The selectivity for G-metal ion interaction observed in this study was in good agreement with calculated HOMO distribution of G runs.     

The effect of the particle size on the kinetics of CO electrooxidation on high surface area Pt catalysts

Using high-resolution transmission electron microscopy (TEM), infrared reflection-absorption spectroscopy (IRAS), and electrochemical (EC) measurements, platinum nanoparticles ranging in size from 1 to 30 nm are characterized and their catalytic activity for CO electrooxidation is evaluated. TEM analysis reveals that Pt crystallites are not perfect cubooctahedrons, and that large particles have "rougher" surfaces than small particles, which have some fairly smooth (111) facets. The importance of "defect" sites for the catalytic properties of nanoparticles is probed in IRAS experiments by monitoring how the vibrational frequencies of atop CO (nu(CO)) as well as the concomitant development of dissolved CO(2) are affected by the number of defects on the Pt nanoparticles. It is found that defects play a significant role in CO "clustering"on nanoparticles, causing CO to decrease/increase in local coverage, which yields to anomalous redshift/blueshift nu(CO) frequency deviations from the normal Stark-tuning behavior. The observed deviations are accompanied by CO(2) production, which increases by increasing the number of defects on the nanoparticles, that is, 1 < or = 2 < 5 < 30 nm. We suggest that the catalytic activity for CO adlayer oxidation is predominantly influenced by the ability of the surface to dissociate water and to form OH(ad) on defect sites rather than by CO energetics. These results are complemented by chronoamperometric and rotating disk electrode (RDE) data. In contrast to CO stripping experiments, we found that in the backsweep of CO bulk oxidation, the activity increases with decreasing particle size, that is, with increasing oxophilicity of the particles.     

Drastic enhancement of TiO2-photocatalyzed reduction of nitrobenzene by loading Ag clusters

Ag clusters (mean diameter = 1.5 nm, standard deviation = 0.37 nm) were photodeposited on TiO(2) particles in a highly dispersed state. The loading of a small amount of the Ag clusters (0.24 wt %) dramatically enhanced both the activity for the TiO(2) photocatalytic reduction of nitrobenzene and the product selectivity of aniline. The essential action mechanism of the Ag clusters is discussed.     

Evaluation of gardenia yellow using crocetin from alkaline hydrolysis based on ultra high performance liquid chromatography and high‐speed countercurrent chromatography

Gardenia yellow is globally the most valuable spice and food color. It is generally a mixture of water‐soluble carotenoid glycosyl esters which consist of crocetin bis(gentiobiosyl) ester as the main component. Crocetin is a natural carotenoid dicarboxylic acid that may be a candidate drug for pharmaceutical development, however, it is either present in trace amounts or is absent in natural gardenia yellow products. We here propose that crocetin produced by alkaline hydrolysis can be used to qualitatively evaluate gardenia yellow products using an ultra high performance liquid chromatographic assay. A useful and efficient isolation technique for isolating high‐purity crocetin from gardenia yellow using high‐speed countercurrent chromatography is described. High‐speed countercurrent chromatographic fractionation followed by an ultra high performance liquid chromatographic assay showed that trans‐crocetin is easily converted to about 15% cis‐crocetin (85% trans‐crocetin). Crocetin in gardenia yellow was quantitatively evaluated. Our approach is based on the hydrolysis process for converting crocetin glycosyl esters to crocetin before evaluation and isolation using the ultra high performance liquid chromatographic and high‐speed countercurrent chromatographic methods. The combination of hydrolysis and chromatographic methods allows evaluation of the purity and quantity of crocetin in gardenia yellow.     

One-pot reactions of bicyclic zinc enolate generated from Ni-catalyzed reductive cyclization to furnish octahydro-4,7-ethanobenzofuran-9-one derivatives

The one-pot reactions of catalytically generated bicyclic zinc enolate with various electrophiles are reported. The zinc enolate as a key intermediate is efficiently delivered from Ni-catalyzed reductive cyclization of alkynyl cyclohexadienone. Employing aldehydes, imine, nitroalkene, and α,β-unsaturated carbonyl compounds as electrophiles, this new class of one-pot reactions gave multi-functionalized cis-hydrobenzofurans and octahydro-4,7-ethanobenzofuran-9-one derivatives in moderate to good yields.