Photocatalytic Property and Electronic Structure of Lanthanide-based Oxysulfides

Lanthanide-based oxysulfides and sulfide, LnTaO_3.5S_0.5, Ln₁₀OS₁₄ (Ln = La, Pr, Nd, Sm) and La₄In₅S₁₃, were successively synthesized by sulfurization in a flowing H₂S. The sulfurization decreased the band-gap energies from >4 eV to <3eV, because of the formation of occupied S3p orbitals on the top of valence band. In accordance with the small band gap, the H₂ evolution from a 0.01 M Na₂S and 0.01 M Na₂SO₃ solution system was observed under irradiation of light up to >500 nm. The rate of H₂ evolution under light irradiation of >500 nm increased in the order of Ni/LaTaO_3.5S_0.5 < Ru/La₁₀OS₁₄ < Pt/La₄In₅S₁₃.     

Crack opening displacement of a through-wall crack in a plate subjected to bending load

This study was performed in order to clarify crack opening displacement (COD) of through-wall cracks in a plate subjected to bending load. The former COD evaluation methods were mainly developed corresponding to tensile load, but there has been nothing that has been developed corresponding to bending load. Therefore, the authors evaluated CODs of the through-wall cracks in plates which were subjected to a bending load using finite element method (FEM) analyses, and proposed a simplified COD evaluation method accounting for both tensile and bending loads. The proposed method is useful for leakage evaluation at a crack opening of an elbow crown or in the vicinity of the coolant surface of a vessel in which the bending stress is relatively large.     

Magnetic breakdown phenomena in quasi-two dimensional organic conductors

Magneto-oscillation phenomena of the magnetization in low dimensional organic conductors (BEDT-TTF)₂X, are investigated theoretically, focusing on the magnetic breakdown (MB) occured in high fields. Our full quantum mechanical theory reproduces various oscillations, including the interference difference oscillation, which is prohibited in the so-called network model of semi-classical theory, and demonstrates a smooth crossover to the MB orbit oscillation, or MB phenomenon. This is interpreted in terms of the recursive band structures.     

Living cationic polymerization of p-methoxystyrene by hydrogen iodide/zinc iodide at room temperature

Summary Cationic polymerization of p-methoxystyrene initiated by HI/ZnI₂ in toluene afforded living polymers not only at low temperature (–15°C) but at room temperature (+25°C) as well. The number-average molecular weight of the polymers was directly proportional to monomer conversion and in excellent agreement with the calculated value assuming that one polymer chain forms per unit hydrogen iodide. On addition of a fresh feed of monomer at the end of the first-stage polymerization, the added feed was smoothly polymerized at nearly the same rate as in the first stage; the polymer molecular weight further increased in direct proportion to monomer conversion and was close to the calculated value for living polymer. Throughout these reactions, the molecular weight distribution of the polymers stayed very narrow (¯M_w/¯M_n<1.1). This is the first example of living cationic polymerizations of styrene derivatives that proceed even at room temperature.     

Promotion of hydrogen permeation on metal-dispersed alumina membranes and its application to a membrane reactor for methane steam reforming

A mesoporous membrane for selective separation of hydrogen was prepared usingthe sol-gel method. Some metal salts such as RuCl₃, Pd(NH₃)₄Cl₂, RhCl₃,, and H ₂PtCl₆, were added to the boehmite sol and coated on a porous alumina substrate before firing at 500°C. It was foundthat the permeability of hydrogen and the separation factor for a hydrogen-nitrogen gaseous mixture of these metaldispersed membranes exceeded the limitations of the Knudsen diffusion mechanism. Although the gas permeation through a neat alumina membrane is governed by the Knudsen diffusion, the metals dispersed in alumina membranes were effective in promoting hydrogen permeation. These metaldispersed alumina membranes were also used in a membrane reactor for methane steam reforming at low temperature. In the temperature range of 300 to 500°C, the membrane reactor attained a methane conversion twice as high as the equilibrium value of the packed bed catalytic reactor system as a result of the selective removal of hydrogen from the reaction system.     

Wide-gap layered oxychalcogenide semiconductors: Materials, electronic structures and optoelectronic properties

Applying the concept of materials design for transparent conductive oxides to layered oxychalcogenides, several p-type and n-type layered oxychalcogenides were proposed as wide-gap semiconductors and their basic optical and electrical properties were examined. The layered oxychalcogenides are composed of ionic oxide layers and covalent chalcogenide layers, which bring wide-gap and conductive properties to these materials, respectively. The electronic structures of the materials were examined by normal/inverse photoemission spectroscopy and energy band calculations. The results of the examinations suggested that these materials possess unique features more than simple wide-gap semiconductors. Namely, the layered oxychalcogenides are considered to be extremely thin quantum wells composed of the oxide and chalcogenide layers or 2D chalcogenide crystals/molecules embedded in an oxide matrix. Observation of step-like absorption edges, large band gap energy and large exciton binding energy demonstrated these features originating from 2D density of states and quantum size effects in these layered materials.     

Controlling Pyrene Association in DNA Duplexes by B- to Z-DNA Transitions

B- to Z-DNA transitions play a crucial role in biological systems and have attracted the interest of researchers for their applications in DNA nanotechnology. DNA and DNA analogues have also been used as templates to construct helical chromophore associations with π interactions. In this work, the B- to Z-DNA transition-induced switching of pyrene in an association manner was evaluated using DNA duplexes with non-nucleosidic pyrene residues in the middle of d(CG) repeat sequences. One of the pyrene-labeled DNAs was shown to exhibit inverted exciton coupled circular dichroism signals upon pyrene association through a B- to Z-DNA transition. This observation indicates that pyrene association switches the DNA conformation from right- to left-handed. Interestingly, the fluorescence of the pyrene-labeled DNA duplex also dynamically changed upon switching of the pyrene in an association-based manner. Taken together, these studies demonstrate that pyrene-labeled DNA shows promise as a chiroptical molecular switch.     

Determination of atomistic deformation of tricalcium silicate paste with high-volume fly ash

We examined the effect of incorporating high-volume fly ash on the atomic arrangement and interatomic deformation behavior of calcium silicate hydrates in tricalcium silicate paste upon exposure to external forces. The interatomic structural changes and strains under compressive load were assessed using synchrotron in situ high-energy X-ray scattering-based atomic pair distribution function analysis. Three different types of strains, which were (a) macroscopic strains from gauges on the surfaces of specimen, (b) strains in a reciprocal space (Bragg peak shift), and (c) strains in real space (PDF peak shift), were compared to each other. All monitored and calculated strains for tricalcium silicate-fly ash (50 wt% fly ash) paste were compared with the counterparts of the pure tricalcium silicate paste. Pair distribution function analysis in the range of r < 10 Å indicated that the atomic arrangement of tricalcium silicate-fly ash was similar to that of synthetic calcium silicate hydrates followed by that of pure tricalcium silicate paste. Moreover, the pair distribution function refinement results revealed that the calcium silicate hydrate structure in tricalcium silicate-fly ash paste was similar to tobermorite 11 Å, unlike that in pure tricalcium silicate paste. The interatomic strain of tricalcium silicate-fly ash in the real space (r < 20 Å) was smaller than that of tricalcium silicate under compression, which suggested that the incompressibility of calcium silicate hydrates at atomistic scale was enhanced by the incorporation of fly ash into it. This was likely to be caused by the increased silicate polymerization of calcium silicate hydrates, which was attributed to the increase in the amount of silicate in their structure via the addition of fly ash.