Oxidative synthesis of azacyclic derivatives through the nitrenium ion: application of a hypervalent iodine species electrochemically generated from iodobenzene

Oxidation of the methoxyamide derivatives 1, 4, and 7 has been examined to elaborate efficient synthetic methodology of the azacyclic derivatives 2, 3, 5, 6, and 8, which would be applicable as synthetic intermediates of complicated bioactive substances. In addition to direct anodic and PIFA [phenyliodine(III) bis(trifluoroacetate)] oxidations, an active species derived from iodobenzene generated under electrolytic conditions was examined as an oxidant, and its synthetic efficacy was demonstrated in comparison of the reaction outcomes with other oxidation methods. In the oxidation, the methoxy substitution of substrates modulated the cyclization mode to provide the azaspiro- (2, 8) or quinolinone-type (3, 5, 6) products.     

Photocatalytic oxidation of propylene with molecular oxygen over highly dispersed titanium, vanadium, and chromium oxides on silica

Photocatalytic oxidation of propylene with molecular oxygen at room temperature was investigated over various silica-supported metal oxides with low loading. The photocatalytic active site is assumed to be the isolated tetrahedrally coordinated metal oxides in the ligand-to-metal charge-transferred state, such as (Mdelta- -OLdelta+). Photocatalytic epoxidation of propylene into propylene oxide was promoted over silica-supported V and Ti oxides at steady state. Over silica-supported Cr oxide, the propylene oxide formation rate was remarkably decreased with the time course in the reaction. The oxidation state and the coordination environment of the supported Ti, V, and Cr oxide species were determined by diffuse reflectance UV-vis spectroscopy (DRS) and electron spin resonance (ESR). During the photocatalytic oxidation, the oxidation state of the Ti4+ species was not varied. On the other hand, the V5+ species was partially reduced to V4+ and the Cr6+ species was successively reduced to Cr5+ and Cr3+. An isotopic tracer study of the C3H6-18O2 reaction suggests the difference of the active oxygen species between TiO2/SiO2 and V2O5/SiO2. The active oxygen species on TiO2/SiO2 is derived from molecular oxygen. On the other hand, the photogenerated products on V2O5/SiO2 incorporate the lattice oxygen of the surface metal oxide species. It is suggested that the kinds of terminal ligand (hydroxyl or oxo) of the tetrahedrally coordinated metal oxides on silica decide the active oxygen species in the photocatalytic oxidation. A photoinduced hole center on the monohydroxyl (SiO)3Ti-OH species activates molecular oxygen that reacts with propylene. In the case of the monooxo (SiO)3V=O and dioxo (SiO)2Cr=O2 species, the photoactivated lattice oxygen (OL-) directly reacts with propylene.     

Reversible photoregulation of helical structures in short peptides under indoor lighting/dark conditions

[reaction: see text] A photochromic cross-linking agent with a spiropyran skeleton was developed for the reversible photoregulation of helical structures in short peptides. The helical contents of the cross-linked peptides could be regulated by ambient light and dark conditions at room temperature. This switching of the helical contents could be repeated several times without substantial loss of any activity.     

Switching of structural order in a cross-linked polymer triggered by the desorption/adsorption of guest molecules

A cross-linked polymer, prepared by the in situ polymerization of a thermotropic columnar liquid crystal, was found to work as a host with a flexible framework, which was reminiscent of intercalation hosts, such as clays, graphites, and coordination polymers. The structural order of the cross-linked polymer was reversibly switched by changing the amount or shape of a guest incorporated in the polymer.     

Compensation effect of Mg-doped a- and c-plane GaN films grown by metalorganic vapor phase epitaxy

The electrical and optical properties of Mg-doped a- and c-plane GaN films grown by metalorganic vapor phase epitaxy were systematically investigated. The photoluminescence spectra of Mg-doped a- and c-plane GaN films exhibit strong emissions related to deep donors when Mg doping concentrations are above 1×10²⁰ cm⁻³ and 5×10¹⁹ cm⁻³, respectively. The electrical properties also indicate the existence of compensating donors because the hole concentration decreases at such high Mg doping concentrations. In addition, we estimated the N_D/N_A compensation ratio of a- and c-plane GaN by variable-temperature Hall effect measurement. The obtained results indicate that the compensation effect of the Mg-doped a-plane GaN films is lower than that of the Mg-doped c-plane GaN films.     

Simultaneous biobehavior of trace elements, Sc, Mn, Fe, Co, Zn, Se, Rb and Zr in the brain and other organs of C57BL/6N mice

The radioactive multitracer technique was applied to a study on the uptake of trace elements in normal C57BL/6N mice. Comparative uptake behavior of⁴⁶Sc,⁵⁴Mn,⁵⁹Fe,⁵⁸Co,⁶⁵Se,⁸³Rb and⁸⁸Zr tracers was examined among 11 organs (brain, cardiac muscle, lung, liver, spleen, pancreas, kidneys, bone, muscle, eyeballs and testes) and blood, and evaluated in terms of the “tissue uptake rate (the radioactivity percentage of injected dose per gram of tissue, %dose/g)”. The multitracer technique revealed reliable data demonstrating characteristic uptake of the 8 trace elements, Sc, Mn, Fe, Co, Zn, Se, Rb and Zr by the brain and other organs, as well as the distinctive features of the accumulation and retention of each element in the brain.     

Applications of a higher‐order bounded numerical scheme to turbulent flows

This paper applies the higher‐order bounded numerical scheme Weighted Average Coefficients Ensuring Boundedness (WACEB) to simulate two‐ and three‐dimensional turbulent flows. In the scheme, a weighted average formulation is used for interpolating the variables at cell faces and the weighted average coefficients are determined from a normalized variable formulation and total variation diminishing (TVD) constraints to ensure the boundedness of the solution. The scheme is applied to two turbulent flow problems: (1) two‐dimensional turbulent flow around a blunt plate; and (2) three‐dimensional turbulent flow inside a mildly curved U‐bend. In the present study, turbulence is evaluated by using a low‐Reynolds number version of the k–ω model. For the flow simulation, the QUICK scheme is applied to the momentum equations while either the WACEB scheme (Method 1) or the UPWIND scheme (Method 2) is used for the turbulence equations. The present study shows that the WACEB scheme has at least second‐order accuracy while ensuring boundedness of the solutions. The present numerical study for a pure convection problem shows that the ‘TVD’ slope ranges from 2 to 4. For the turbulent recirculating flow, two different mixed procedures (Method 1 and Method 2) produce a substantial difference for the mean velocities as well as for the turbulence kinetic energy. Method 1 predicts better results than Method 2 does, comparing the analytical solution and the experimental data. For the turbulent flow inside the mildly curved U‐bend, although the predictions of velocity distributions with two procedures are very close, a noticeable difference of turbulence kinetic energy is exhibited. It is noticed that the discrepancy exists between numerical results and the experimental data. The reason is the limit of the two‐equation turbulence model to such complex turbulent flows with extra strain‐rates. Copyright © 2001 John Wiley & Sons, Ltd.