Department of Chemical Engineering,Tokyo Institute of Technology,Meguro, Tokyo 152, JapanReaction of organoaluminates with lead(IV) acetate. A convenien route from 1-alkenes to primary alkyl acetates via hydroaluminatio reactions

Hydroalumination of 1-alkenes with lithium aluminum hydride by catalysis of titanium tetrachloride followed by treatment with lead(IV) acetate was found to be a convenient method for the preparation of primary alkyl acetates.     

Synthesis of lipid A analogues containing glucose instead of glucosamine and their LPS-antagonistic activities

Lipid A analogues containing glucose in substitution for glucosamine on the reducing end were synthesized, and the inhibitory activities on LPS-induced TNFα production (LPS-antagonistic activity) in vitro using human whole blood cells were measured. The IC₅₀ values (nM) of these ten compounds, 8, 14, 21, 31, 40, 51, 57, 62, 67 and 72, were 11.2, 15.4, 2.7, 0.1, 0.4, 1.3, 3.2, 3.2, 1.4 and 14.4, respectively. And also inhibitory activities (ID₅₀) on TNFα production toward galactosamine loaded C3H/HeN mice in vivo of compounds 21, 31, 57, 62 and 67 were measured. The values of these compounds were 0.29, 0.50, 0.61, not dose-dependent and 0.33 mg/kg, respectively.     

Successive Linearization Methods for Nonlinear Semidefinite Programs

We present a successive linearization method with a trust region-type globalization for the solution of nonlinear semidefinite programs. At each iteration, the method solves a quadratic semidefinite program, which can be converted to a linear semidefinite program with a second order cone constraint. A subproblem of this kind can be solved quite efficiently by using some recent software for semidefinite and second-order cone programs. The method is shown to be globally convergent under certain assumptions. Numerical results on some nonlinear semidefinite programs including optimization problems with bilinear matrix inequalities are reported to illustrate the behaviour of the proposed method.The research of the fourth author was supported in part by a Grant-in-Aid for Scientific Research from Japan Society for the Promotion of Science. The research of the second author was supported by the DFG (Deutsche Forschungsgemeinschaft).     

Domain and surface structures of sodium tungsten bronzes,NaxWo3 (0.4 < x < 1)

Polarized-light microscopic observations have shown that the birefringent, twin-domain structure of metallic sodium tungsten bronze is exhibited by Na-deficient surface films and hence is not, as had been reported elsewhere, a bulk property. The film can be synthesized by anodic electrolysis in alkaline solution. It is chemically inert, translucent, and often laminates to a multiple layer. The domain structure of the film is hypersensitive to lateral stress and to thermal variation, exhibiting a marked change at the phase transition of the substrate through apparent epitaxial coherence. The domain-wall movement is often slow enough to be visible, and the thermally induced domain modulation is occasionally accompanied by audible high-pitched sound. The bulk structure of the substrate exhibits pseudoperiodic subboundaries that are probably caused by growth defects and the segregation of the sodium atoms. The near-surface of the substrate also shows the sodium segregation that tends to precipitate in periodic patterns. Optical and morphological properties of the substrate structures exhibited no detectable change due to thermal variation or external stress.     

4.6-dimethyl-7-hydroxy-nonan-3-one,a sex pheromone of the cigarette beetle (Lasioderma serricorne F.)

A structure of the sex pheromone produced by the female cigarette beetle (Lasioderma serricorne F.) is established as 4,6-dimethyl-7-hydroxy-nonan-3-one (Ia) by chemical and spectroscopic evidences.     

Migration of excimers in pyrene crystals

Emission decay times of the new excimer were measured for undoped and perylene doped pyrene crystals. From the decay times obtained, the temperature dependence of the diffusion coefficient of the excimers was deduced by assuming a model in which two electronic states of the new excimer are involved in the energy transfer process. Within this model, it was found that in the upper excimer state the excimers migrated by a hopping process, while in the lower excimer state they migrated as free excimer excitons while undergoing phonon scattering.     

Chemical reactions in cracks of aluminum crystals: Generation of hydrogen from water

Pure hydrogen is generated from water molecules which are dissociated by specific aluminum particles called activated Al powder. Reaction mechanism of Al atoms with H₂O molecules is investigated in micro-cracks of Al crystals. It becomes obvious that hydrogen atoms exist in Al crystal mainly in states of AlH₃ hydrides. It is concluded that virgin walls of micro-cracks right after the creation provide virtually Al radical atoms of (Al−) or (Al=) with one or two free bonds, which react with H₂O molecules via surface diffusion resulting in producing AlH₃ and eventually in producing H₂. The production of H₂ seems to be a result of micro-tribochemical reactions in cracks, which are produced by mechanical crushing of Al crystals in water; tips of cracks as stress-focused points play a major role to create AlH_3. Peculiar environments of nano-spaces in micro-cracks surrounded by reactive atoms enable us to realize unusual chemical reactions at low temperatures as exemplified in the present paper.     

Calcium isotope fractionation in liquid chromatography with crown ether resin in methanol medium

Breakthrough mode liquid chromatography was employed to investigate calcium (Ca) isotope fractionation in methanol medium. Highly porous silica beads, the inner pores of which were embedded with a benzo-18-crown-6 ether resin, were used as column packing material. Enrichment of heavier isotopes of Ca was observed in the frontal part of the respective Ca chromatograms. The values of the isotope fractionation coefficient (?) were in the order of 10^?3 at 25 °C. Use of methanol as solvent has little advantage over the aqueous system as far as the values of ? are concerned. However, a substantial improvement was observed concerning the adsorption capacity of the crown ether resin for Ca ions. Molecular orbital calculations supported the present isotopic results in a qualitative fashion.     

Computer Simulation of High-speed Bending Deformation in Copper

According to one suggested model, bending of a single crystal introduces edge dislocations of the same sign. In the present study, this model is examined by computer simulation using molecular dynamics. When a notch is present on the tension surface, Heidenreich-Shockley partial dislocations are created near the tip of the notch. In the compression surface, partial dislocations are created due to wrinkling of the crystal plane. The results of simulation shows that dislocations are more easily created in a compressive bending region than in a tension bending region or simple tension region.     

Study of Strangeness Photoproduction on the Neutron in the Threshold Region

Photoproduction of the neutral kaon on the deuteron has been investigated at the Research Center for Electron Photon Science, Tohoku University. We constructed the Neutral Kaon Spectrometer-2 for the detection of charged particles from the decay of the neutral kaon and the hyperon. We obtained a momentum distribution of K ⁰ with the inclusive measurement. It was consistent with the previous measurement. The total cross section of γ + d → K ⁰ + Λ + p was estimated from the measured integral cross section of γ + d → Λ + X. The total cross section with respect to the photon energy was compared with the theoretical calculations. It favored the Saclay-Lyon A model calculation with the ratio of the neutral to charged coupling constants of the axial-vector meson, K ₁, as ~ ?1.5. The energy dependence and the magnitude of the total cross section were similar to the total cross section of γ + p → K ⁺ Λ.