Asymmetric problem of a semi-infinite body having a hemispherical pit under uniaxial tension

This paper presents an asymmetric solution for the stress distributions around a hemispherical pit at a plane surface of a semi-infinite body under uniaxial tension. In this analysis, eight stress functions were chosen so as to fulfill the boundary conditions automatically, both at the plane surface and at infinity. On the other hand, the remaining boundary conditions at the surface of the pit were satisfied with the aid of the half-range expansion technique. Numerical results are given for the variations around the pit and along the z-axis and compared with the corresponding results under biaxial tension.     

Electrochemical and ferromagnetic couplings in 4,4',4' '-(1,3,5-benzenetriyl)tris(phenoxyl) radical formation

4,4',4' '-(1,3,5-Benzenetriyl)tris(2,6-di-tert-butylphenol) was prepared by the cross-coupling of 1,3,5-tribromobenzene and [4-(trimethylsiloxy)phenyl]magnesium bromide. X-ray analysis of the single crystal showed a propeller-like structure with a mean dihedral angle of 39 degrees between the hydroxyphenyl and the core benzene. The phenoxyl mono-, di-, and triradicals were generated by the electrochemical oxidation of the trianion. A stepwise radical formation was revealed by a differential pulse voltammogram, electrolytic ESR spectroscopy, and a comproportionation reaction between the radicals, which was discussed as an effect of the pi-conjugated but non-Kekulé-type coupler. The quartet and triplet ground state for the tri- and diradical, respectively, were confirmed by a SQUID measurement.     

Theoretical Limit of the Color-Change Sensitivity of a Composite Resin Dosimeter Film Based on Spiropyran/BaFCl : Eu2+/Polystyrene

The theoretical limit of the color-change sensitivity of a composite resin dosimeter film based on 6-nitro BIPS/BaFCl : Eu²⁺/polystyrene under X-ray exposure has been estimated. Each photophysical and photochemical process occurring inside the composite resin dosimeter was quantitatively determined, and the obtained values were used to estimate the theoretical limit of the color-change sensitivity for the composite resin dosimeter. The values obtained were 70.6 % for the X-ray absorption efficiency, 13 % for the fluorescence quantum yield, 73.5 % for the UV absorption efficiency and 37.6 % for the photochemical quantum yield. Assuming that the figure-of-merit is their product, its value is estimated to be 2.5 %, which contributes to the chromaticity difference and leads to a color-change sensitivity of 100 mGy. The figure-of-merit of a structurally optimized composite dosimeter was estimated to be 1.9 times that of the dosimeter without structural optimization, which showed a sensitivity of 100 mGy. We predicted that the structurally optimized composite resin dosimeter film, which eliminates optical losses due to the structure, will be able to detect X-ray exposure doses on the order of approximately 28 mGy.     

First-principles molecular dynamics study on aqueous sulfuric acid solutions

The properties of aqueous sulfuric acid have been studied employing density functional theory-based molecular dynamics simulations in conjunction with norm-conserving pseudopotentials. The simulations were carried out for two different concentrations whose molar concentrations were fixed at 0.84 and 10.2 mol/l. The structural features of aqueous sulfuric acid solutions show a strong dependency on the concentration. The Gr?tthuss-type proton transfer mechanism is not effectively operative at the higher concentration because of the broken hydrogen bond network of water induced by ions generated by the dissociation of sulfuric acid. In addition, to evaluate electrical properties, we carried out a simulation that takes an electric field into account. Results are compared with those of the simulation undertaken with no external electric field.     

Crystal structure of thermosensitive gel spheres of poly(N-isopropylacrylamide) in the deionized aqueous suspension as studied by the static light-scattering measurements

Static light-scattering measurements of deionized suspensions of the thermosensitive gels of poly(N-isopropylacrylamide) with various degrees of cross-linking and sizes were made at 20 and 40 °C. Sharp scattering peaks are observed in the scattering curve, and they were attributed to the face-centered cubic (fcc) and/or body-centered cubic lattices (bcc) in the distribution of gel spheres. The fcc and bcc crystal structures formed in the stable and unstable conditions, respectively, i.e., the former formed more favorably at high sphere concentrations and/or low temperatures. The closest intersphere distances were much longer than the hydrodynamic diameters of the gel spheres especially at low sphere concentrations. These experimental results emphasize the important role of the extended electrical double layers in the crystallization of gel spheres, though the contribution of the double layers in gel systems is weak compared with that in the typical colloidal spheres.     

Synthesis of Oligo (Phenyleneoxide) by Electro-Oxidative Polymerization

Anodic oxidation of 2,6-disubstituted phenols gave poly(2,6-disubstituted-1,4-phenyleneoxide)s quantitatively by using dichloromethane and tetraethyl ammonium bromide as the solvent and the supporting electrolyte respectively. Phenol was also electro-oxidatively polymerized to yield oligo(1,4-phenyleneoxide) with molecular weight of 1200～2500. The 2-step polymerization and the polymerization in the presence of bisphenol were carried out to increase the molecular weight of the oligo(phenyleneoxide). The mechanism of the electro-oxidative polymerization was discussed by electrochemical and ESR measurements.     

Polythiophenylene synthesis through multi-electron transfer process

Superacidification of aromatic sulfoxides effects the electrophilic substitution reaction of the resulting hydroxysulfonium ions onto aromatic rings with the elimination of H₂O at room temperature. The product, the alkyldiarylsulfonium ion, allows the synthesis of alkylsulfonio-bridged (λ⁴-alkylsulfanyliumdiyl) aromatic polymers. High molecular-weight poly(alkylsulfonioarylene) salts have been made accessible by the regioselective condensation of aryl sulfoxides. Polymers having a wide variety of structural dimensionalities such as linear, hyper-branched and ladder-type structures can be prepared by this method, which possess interesting properties such as good solubility in polar organic solvents and sometimes even in H₂O, susceptibility to nucleophiles to provide thioarylene derivatives, photo-degradability, and electric semiconductivity based on a 3d-2p interaction in aryl sulfonium ion.