Electron localization and a confined electron gas in nanoporous inorganic electrides

The nanoporous main group oxide 12CaO.7Al(2)O3 (C12A7) can be transformed from a wide-gap insulator to an electride where electrons substitute anions in cages constituting a positive frame. Our ab initio calculations of the electronic structure of this novel material give a consistent explanation of its high conductivity and optical properties. They show that the electrons confined in the inert positive frame are localized in cages and undergo hopping between neighboring cages. The results are useful for the understanding of behavior of confined electron gas of different topology and electron-phonon coupling, and for designing new transparent conductors, electron emitters, and electrides.     

Trifluoroacetaldehyde: A useful industrial bulk material for the synthesis of trifluoromethylated amino compounds

The synthesis of various trifluoromethylated amino compounds was studied using trifluoroacetaldehyde, an industrial bulk material, as a starting compound. One general application of trifluoroacetaldehyde is the preparation of trifluoroethylamino derivatives via reductive amination reaction. This synthesis includes the formation of the corresponding N,O-acetal intermediates followed by their reduction using NaBH₄ or 2-picoline borane complex, affording the target trifluoroethylamino compounds in moderate to good yields (47-87%).Another general application of trifluoroacetaldehyde is the synthesis of chiral α-substituted trifluoroethylamino compounds. In this synthesis, trifluoroacetaldehyde was first converted into the chiral trifluoromethyl tert-butyl sulfinimine, which was subjected to 1,2-nucleophilic addition reactions across its CN double bond. The addition of phenyllithium afforded α-(phenyl)trifluoroethylamino derivative in 83% yield and with 96% de. Allylation and Reformatsky reactions produced the corresponding α-substituted trifluoroethylamino derivatives in 82 and 58% yields and with 90 and 91% de, respectively.     

Control of mixed protonic and electronic conductivity by mixing rare-earth ortho-borates

In order to develop mixed protonic and electronic conductors, we proposed a novel concept for material design that enables to control partial conductivities by fabricating solid solutions of protonic and electronic conductors. In this work, Sr-doped LaBO₃ and Sr-doped CeBO₃ were chosen as model compounds conducting protons and electron holes, respectively. Solid solutions of the above borates, Sr-doped La_1 − xCe_xBO₃, were prepared, and their electrical conductivities were investigated in 8.5 × 10²-4.2 × 10³ Pa of p(H₂O) and 1.0 × 10-1.0 × 10⁵ Pa of p(H₂) at 1073 K. From the experimental results of the gas partial pressure dependences of the conductivities, major charge carrier species were identified as a function of x. It was found that proton was the major charge carrier when x < 0.2 while the contribution of the electron hole conduction became remarkable as x increased above 0.2. The contribution of the electron hole conduction can be interpreted by the percolation model.     

Interaction and arrangement of nitrogen and carbon atoms in fcc γ-iron

A Mössbauer effect measurement has been done for Fe?N, Fe?Al?C and Fe?Ni?C austenite in order to study the interaction between the interstitial atoms and their distribution among the octahedral sites of the fcc lattice, together with the influence of Al and Ni atoms. The spectra for Fe?N and Fe?Al?C austenite are decomposed into three components; one singlet γ₀, and two sets of doublet γ₁ and γ₂, with different quadrupole splittings, while no γ₂ component is found in the spectrum for Fe?Ni?C. By analyzing the component ratio in each spectrum, it is concluded that, in Fe?N and Fe?Al?C, the interaction between 2nd nearest neighboring nitrogen or carbon atoms is attractive, and is repulsive between 1st nearest for Fe?N, and that the interaction between 2nd nearest atoms is repulsive for Fe?Ni?C. By measuring the spectra of Fe?Ni?C in magnetic field, the sign of EFG for most of the γ₁ component is determined to be negative.     

Fluorine and chlorine behavior in chlorine-rich volcanic rocks from White Island, New Zealand

Extraordinarily high chlorine-bearing volcanic bombs were erupted from White Island volcano on January 25, 1987. The concentrations of fluorine and chlorine were measured in these paralava bombs and their likely parent rocks. The paralavas contain glass with over 1.0 wt.% and up to 1.7% of chlorine. The F/Cl ratios and their relationship with other constituents show that the fluorine and chlorine in the bombs were derived from hydrothermal fluid, most likely concentrated brine in an active Crater Pool.     

Electromagnetic Properties of Lanthanum Manganese Oxides Doped with Iron

The mechanism of GMR effects in La(Mn_1–x Fe _x )O₃ (x=0, 0.01, 0.03) oxides has been investigated by means of magnetic measurements, resistivity measurements in magnetic field and Mössbauer spectroscopy. For the x=0.01 sample, the GMR behavior is similar to that of the conventional (La, A)MnO₃ (A: divalent cations) oxides. For the x=0.03 sample, even though the temperature dependence of the Mössbauer spectra was similar to that of the x=0.01 sample, the mechanism for the occurrence of the GMR effect seems to be different. The x=0 sample shows a similar behavior to the x=0.03 sample. A thermal stabilization of spin fluctuation is proposed for the x=0 and x=0.03 sample.     

A new synthetic method for α-ketosilanes employing methoxy(phenylthio)trialkylsilylmethane as an α-silylacyl anion equivalent

Development of a new synthetic method for α-ketosilanes can be achieved by a sequence of alkylation of methoxy(phenylthio)trialkylsilylmethane and oxidation with NaIO₄.     

Raman studies of (Fe,V)3S4 solid solution

Raman scattering of Fe_xV_3-xS₄ with 0?x?2 has been studied. The observed spectra of V₃S₄, one of the end members of this solid solution, have been assigned to the Raman active lattice modes based on the C_2h³ space group symmetry. On the basis of the results obtained for V₃S₄, the nature of the metal-metal interactions and the site distributions of Fe atoms in (Fe, V)₃S₄ have been discussed.     

Palladium-catalyzed rearrangement of α-cyanoallylic acetates application to a new synthetic method for furans

Various types of α-cyanoallylic acetates were undergone the palladium-catalyzed rearrangement to give the γ-acetoxy-α,β-unsaturated nitriles in high yields. These rearranged acetates were conveniently transformed into the furan derivatives often encountered in natural products by the reduction using diisobutylaluminum hydride.