A new electrochemical system for stereoselective allylic hydroxylation of cholesteryl acetate with dioxygen induced by iron picolinate complexes

The oxygenation reaction of cholesteryl acetate 1 was examined with the Fe(III)(PA)(3)/O(2)/MeCN system using an electrochemical method. The constant potential technique gave mainly the 7-hydroxylated product stereoselectively, along with the 7-oxo product. This oxygenation system is mechanistically unique, requiring iron catalyst, dioxygen, and both cathode and anode.     

Anisotropy in conductance of a quasi-one-dimensional metallic surface state measured by a square micro-four-point probe method

We have devised a "square micro-four-point probe method" using an independently driven ultrahigh-vacuum four-tip scanning tunneling microscope, and succeeded for the first time to directly measure anisotropic electrical conductance of a single-atomic layer on a solid surface. A quasi-one-dimensional metal of a single-domain Si(111)4 x 1-In had a surface-state conductance along the metallic atom chains (sigma(axially)) to be 7.2(+/-0.6) x 10(-4) S/square at room temperature, which was larger than that in the perpendicular direction (sigma(radially)) by approximately 60 times. The sigma(axially) was consistently interpreted by a Boltzmann equation with the anisotropic surface-state band dispersion, while the sigma(radially) was dominated by a surface-space-charge-layer conductance.     

Depth control of a silicon structure fabricated by 100q keV Ar ion beam lithography

Ion beam lithography of a silicon surface using an Ar ion beam with an ion energy in the order of hundreds of keV is demonstrated in this study. A specially designed ion irradiation facility was employed that enabled generation and irradiation with a highly accelerated and highly charged Ar ion beam. An ion-beam-induced amorphous layer on a silicon substrate can be selectively etched in hydrofluoric acid, whereas, a non-irradiated area is scarcely etched and, consequently, a concave structure can be fabricated on the irradiated area. To control the depth of the structure, parameters for dependence of the depth on ion irradiation were investigated. As a result, the depth of irradiated area can be controlled by the ion energy that is adjusted by the acceleration voltage and the ion charge. In addition, the etch resistance of the irradiated area increases with an increase in ion energy due to the crystalline layer formed on the surface. Simulation results reveal that the depth is strongly related to the defect distribution induced by ion irradiation. These results indicate the potential use of this method for novel three-dimensional lithography.     

Constitution of two coloring matters in the flower petals of CarthamusTinctorius L.

Structures of the safflower red pigment carthamin and the yellow pigment safflor yellow A are shown to be expressed by 3 and 4 respectively, mainly on the basis of spectroscopic evidence.     

Electron-phonon interaction and localization of surface-state carriers in a metallic monolayer

Temperature-dependent electron transport in a metallic surface superstructure, Si(111)sqrt[3] x sqrt[3]-Ag, was studied by a micro-four-point probe method and photoemission spectroscopy. The surface-state conductivity exhibits a sharp transition from metallic conduction to strong localization at approximately 150 K. The metallic regime is due to electron-phonon interaction while the localization seemingly originates from coherency of electron waves. Random potential variations, caused by Friedel oscillations of surface electrons around defects, likely induce strong carrier localization.     

Organogels of 8-quinolinol/metal(II)-chelate derivatives that show electron- and light-emitting properties

8-quinolinol/copper(II)-, palladium(II)-, and platinum(II)-chelate-based organogelators (1 M) and their nongelling reference compounds (2 M) were synthesized. Complexes 1 M could gelate various organic solvents at very low concentrations. Electron microscope measurements gave visual images of well-developed fibrous structures characteristic of low-molecular-weight organogels. UV/Vis and FTIR spectroscopy revealed that the good gelation ability of 1 M arises from the pi-pi interactions of the chelate moieties and the hydrogen-bond interactions among the amide groups. Very interestingly, field emission performances of the nanofibers prepared from the 1 M gels are evidently different depending on the electronic states of the three kinds of central metals. In addition, the 1 Pt gel shows unique thermo- and solvatochromism of visible and phosphorescent color in response to a sol-gel phase transition. Furthermore, the 1 Pt gel possesses an attractive ability to inhibit dioxygen quenching of excited triplet states, which increases the phosphorescence quantum yield of this gel. This effect is attributed to the isolation effect of the phosphorescent chelate moiety from the dioxygen-containing solution phase.     

Plate, wire, mesh, microsphere, and microtube composed of sodium titanate nanotubes on a titanium metal template

Sodium titanate nanotube/titanium metal composites were synthesized by hydrothermal treatment of titanium metals with various morphologies such as plate, wire, mesh, microsphere, and microtube at 160 degrees C in aqueous NaOH solution and by the subsequent fixation treatment by calcination at 300 degrees C. The surface of the composite was covered with sodium titanate nanotubes with a diameter of approximately 7 nm, and the core part of the composite was titanium metal phase. The raw titanium metal acts as a template or a morphology-directing agent of micrometer size or more to arrange the nanotubes as well as a titanium source for the formation of nanotubes. The concentration of titanium species increases in the reaction solution as the dissolution of titanium metal is accelerated by the reaction between titanium and OH-. Furthermore, with an increase in concentration of titanium species in the reaction solution, the titanium species are re-precipitated as sodium titanate nanotubes onto the titanium metal. Titanium metal with a large surface area and volume can form sodium titanate nanotubes on the surface of the titanium metal, though titanium metal with a small volume and surface area tends to dissolve with the hydrothermal treatment. Even in the synthesis using titanium metal with a small volume and surface area, sodium titanate nanotubes are formed and cover the surface of the titanium metal by adding another titanium metal as a source of titanium species in the reaction solution.     

Evaluation of reactivity for nitroxide radical trapping by correlation analysis using steric substituent parameter (ΩS)

The reactivity of nitroxide radical trapping (NRT), where stable nitroxide radicals react with transient carbon-centered radicals to form diamagnetic molecules, was evaluated. This was done with the use of the steric substituent parameter of both radicals by correlation analysis on the basis of the reactivity data determined by Ingold's group. In the case where the transient carbon-centered radicals were not resonance stabilized, the rate constant could be well correlated by using only Ω_S parameters of R₂NO⋅ and U⋅. If the transient radicals were stabilized by resonance, the parameter to estimate the amount of the resonance stabilization of U⋅ was necessary in the regression equation to evaluate the reactivity correctly. When the spin density, calculated by PM3 UHF molecular orbital calculations, was used as the resonance stabilization parameter, the rate constant could be well evaluated by a dual-parameter regression equation. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 215–221, 1998.