The Reduction of Sulfoxide by Iodide/Organic Acid System in the Solid State

A novel solid state reduction of sulfoxides including methionine sulfoxide to the corresponding sulfides by iodide/organic acid system is described.     

Versatile method for the detection of covalently bound substrates on solid supports by DART mass spectrometry

Analysis of substrates directly on solid phase resins without the need for separate cleavage conditions remains an outstanding challenge in the field of solid phase synthesis. We now present the first example of simultaneous cleavage and mass spectrometric analysis of peptides from solid supports using direct analysis in real time (DART) mass spectrometry. We have shown that this method is compatible with a diverse array of solid phase resins and is suitable for analysis of both peptides and organic substrates.     

Fermi surface and superconductivity in low-density high-mobility δ-doped SrTiO3

The electronic structure of low-density n-type SrTiO3 δ-doped heterostructures is investigated by angular dependent Shubnikov-de Haas oscillations. In addition to a controllable crossover from a three- to two-dimensional Fermi surface, clear beating patterns for decreasing dopant layer thicknesses are found. These indicate the lifting of the degeneracy of the conduction band due to subband quantization in the two-dimensional limit. Analysis of the temperature-dependent oscillations shows that similar effective masses are found for all components, associated with the splitting of the light electron pocket. The dimensionality crossover in the superconducting state is found to be distinct from the normal state, resulting in a rich phase diagram as a function of dopant layer thickness.     

Complete Fermi surface in BaFe2As2 observed via Shubnikov-de Haas oscillation measurements on detwinned single crystals

We show that the Fermi surface (FS) in the antiferromagnetic phase of BaFe(2)As(2) is composed of one hole and two electron pockets, all of which are three dimensional and closed, in sharp contrast to the FS observed by angle-resolved photoemission spectroscopy. Considerations on the carrier compensation and Sommerfeld coefficient rule out existence of unobserved FS pockets of significant sizes. A standard band structure calculation reasonably accounts for the observed FS, despite the overestimated ordered moment. The mass enhancement, the ratio of the effective mass to the band mass, is 2-3.     

Flow of a single magnetic vortex in a submicron-size superconducting Al disk controlled by radio-frequency currents

We report the first observation of a single-vortex flow in a mesoscopic superconductor. A flow of a single vortex is successfully controlled by an rf current superimposed on a dc current, evidence of which is provided by voltage steps in current-voltage (I-V) characteristics. Irrespective of the number of vortices confined to the disk, we unambiguously observe that when a single vortex inside the disk is driven out of the disk, another vortex enters the disk similarly to two balls colliding in billiards: only one vortex passes through the Al disk at the same time in mesoscopic systems.     

Hydrogen sensor based on oxide proton conductors and its application to metallurgical engineering

Galvanic cell-type hydrogen sensor for high temperature use is now available thanks to the discovery of oxide-type proton conducting solid electrolyte such as acceptor-doped perovskite-type oxides. In order to develop the practically functional hydrogen sensor based on these electrolytes, the electrochemical properties of these oxides should be understood as a function of hydrogen and oxygen potentials at the temperature range where the sensor is to be used. In this review, the properties of indium-doped calcium zirconate (represented by the composition CaZr_0.9In_0.1O_3–δ) known as, among these oxides, the most chemically stable and mechanically strong were explained briefly on the basis of the thermodynamics of the crystal imperfections. Then the structure of hydrogen sensor for molten aluminum and that for molten copper, which were designed to make the best use of the properties of the electrolyte for the respective process conditions, were shown. Lastly, the performance of these sensors examined in the laboratory scale and the practical industrial conditions was overviewed. Paper presented at the 9th EuroConference on Science and Technology of Ionics, Rhodes, Greece, Sept. 15 – 21, 2003.     

Berberine alkaloid: Quantum chemical study of different forms by the DFT and MP2 methods

The stable structures and electronic properties for the berberine cation as well as possible ammonium, carbinol and amino-aldehyde forms of protoberberine salts in the presence of hydroxyl ions were investigated by the B3LYP/6-31G(d,p) and MP2/6-31++G(d,p) methods. The geometry optimizations by both methods lead to the nonplanar propeller-twisted and buckled structure for the all forms. The obtained bond lengths and bond angles agree with the experimental values. The comparison of total energies elucidates that the amino-aldehyde form is the most preferable tautomer in gas phase, while the carbinol form is less stable. The least stable tautomer is the ammonium form.     

Photocatalytic oxidation of natural organic adsorbates on anatase TiO2 films observed by infrared adsorption spectroscopy with a multiple internal reflection geometry

Photocatalytic oxidation of organic adsorbates on anatase TiO₂ films has been examined in different atmospheres of humid air, dry air and vacuum. The photocatalytic oxidation was observed by IR absorption spectroscopy (IRAS) with a multiple-internal-reflection (MIR) geometry. The photocatalytic oxidation is the fastest in the air at a humidity of 70% where oxygen and water vapor are consuming to produce OH radicals and O₂⁻ anions on the TiO₂ surface with the UV exposure. In the dry air, a rate of the photocatalytic oxidation is almost 30% of that in the humid air, where only O₂⁻ anions oxidize the organic adsorbates. In vacuum, on the other hand, it is negligible, which suggests that adsorbed H₂O molecules do not play an important role in the photocatalytic reaction. It is suggested that an addition of the water vapor is necessary to achieve the higher catalytic activity.     

Thermal phase transition behaviour of liquid crystals in submicron pores formed with stretched polymer fibrils

This paper discusses thermal phase transitions in a nematic liquid crystal material, filling a highly strained porous polyolefin film. Ruptured and aligned polymer fibrils, whose minimum diameter reaches several tens of nm, formed polymer networks in the porous film. From observations of temperature-controlled composite films using a polarizing microscope, it was noted that the isotropic-to-nematic phase transition temperatures of submicron liquid crystal domains, located in or near molecularly aligned streak-like polymer areas, were significantly higher than those located at some distance from these areas. It was assumed that the highly aligned polymer chains in the fine fibrils promote the nematic phase of the liquid crystal. The stretched porous polymer, exhibiting spatial ordering on a submicron scale, is thus suitable for the control of thermal phase transitions in a liquid crystal.