Manganese‐Corrole Complexes as Versatile Catalysts for the Ring‐Opening Homo‐ and Co‐Polymerization of Epoxide

Manganese‐corrole complexes in combination with a co‐catalyst [PPN]X ([PPN]⁺=bis(triphenylphosphoranylidene)iminium) were found to be new versatile catalysts for the polymerization of epoxides, copolymerization of epoxides with CO₂, and copolymerization of epoxides with cyclic anhydrides affording a wide range of polymeric materials. This work should allow the synthesis of new types of improved innovative (co)polymers with original properties and would clearly increase the number of applications for polyesters, polycarbonates, and polyethers.     

Preparation and properties of a fullerene/polysiloxane hybrid from chemically modified fullerene and polymethoxysiloxane

An organic–inorganic hybrid was prepared by simply mixing a fullerene derivative with polymethoxysiloxane. First, C₆₀ was subjected to a radical addition reaction with 4,4′-azobis(4-cyanovaleric acid) to provide a C₆₀ derivative. Polymethoxysiloxane was prepared by a controlled hydrolytic condensation of tetramethoxysilane. These two compounds were mixed and heated to provide hybrid bulk body. The hybrid bulk body showed high mechanical strength and elastic modulus compared with polymethoxysiloxane or the C₆₀/polymethoxysiloxane hybrid. The formation of a dense siloxane network was established by a homogeneous mixing of the C₆₀ derivative with polymethoxysiloxane.     

Syntheses of β-amidovinyltellurides and oxazoles by addition reactions of alkynes with benzenetellurinyl trifluoromethanesulfonate in acetonitrile

Benzenetellurinyl trifluoromethanesulfonate in conjunction with acetonitrile readily effected amidotellurinylation reactions with alkynes. Most of the addition reactions proceeded in a trans fashion to form the (E)-β-acetamidovinyl phenyl telluroxides. Subsequently, it was found that the prevailing Markovnikov adducts from terminal alkynes immediately isomerized to (Z)-isomers which were isolated as the corresponding vinyltellurides. On the other hand, the adducts derived from internal alkynes thermally underwent a spontaneous intramolecular cyclization to be transformed eventually into oxazoles.     

Studies on the syntheses of polymetalloxanes and their properties as a precursor for amorphous oxide. IV. Properties of SiO2–TiO2 oxide fibers from polytitanosiloxane

From polytitanosiloxanes (PTS), SiO₂–TiO₂ oxide fibers with fairly good tensile strength were prepared, and their mechanical and thermal properties were investigated. The precursor fibers PTS-0.5 and PTS-1.0 were obtained by dry spinning of a highly viscous PTS solution which were formed as the reaction mixture of silicic acid (SA) with bis(2,4-pentanedionato)titanium diisopropoxide (PTP) in the molar ratios (SA/PTP) of 0.5 and 1.0. The precursor fibers PTS-0.5 were too brittle to measure their tensile strength, whereas PTS-1.0 and the heat-treated fibers were found to have tensile strength of 130 (precursor), 540 (500°C), and 450 (900°C) MPa, respectively. Heat-treatment of the fibers PTS-1.0 at above 1000°C forms anatase and rutile of titanium dioxide. The crystallization is resulted from the unreacted PTP which is not incorporated into the polymer network.     

High-Affinity Ratiometric Fluorescence Probe Based on 6-Amino-2,2′-Bipyridine Scaffold for Endogenous Zn2+ and Its Application to Living Cells

Zinc is an essential trace element involved in many biological activities; however, its functions are not fully understood. To elucidate the role of endogenous labile Zn²⁺, we developed a novel ratiometric fluorescence probe, 5-(4-methoxyphenyl)-4-(methylsulfanyl)-[2,2′-bipyridin]-6-amine (6 (rBpyZ)) based on the 6-amino-2,2′-bipyridine scaffold, which acts as both the chelating agent for Zn²⁺ and the fluorescent moiety. The methoxy group acted as an electron donor, enabling the intramolecular charge transfer state of 6 (rBpyZ), and a ratiometric fluorescence response consisting of a decrease at the emission wavelength of 438 nm and a corresponding increase at the emission wavelength of 465 nm was observed. The ratiometric probe 6 (rBpyZ) exhibited a nanomolar-level dissociation constant (K_d = 0.77 nM), a large Stokes shift (139 nm), and an excellent detection limit (0.10 nM) under physiological conditions. Moreover, fluorescence imaging using A549 human lung adenocarcinoma cells revealed that 6 (rBpyZ) had good cell membrane permeability and could clearly visualize endogenous labile Zn²⁺. These results suggest that the ratiometric fluorescence probe 6 (rBpyZ) has considerable potential as a valuable tool for understanding the role of Zn²⁺ in living systems.     

A compact permanent‐magnet system for measuring magnetic circular dichroism in resonant inelastic soft X‐ray scattering

A compact and portable magnet system for measuring magnetic dichroism in resonant inelastic soft X‐ray scattering (SX‐RIXS) has been developed at the beamline BL07LSU in SPring‐8. A magnetic circuit composed of Nd–Fe–B permanent magnets, which realised ～0.25 T at the center of an 11 mm gap, was rotatable around the axis perpendicular to the X‐ray scattering plane. Using the system, a SX‐RIXS spectrum was obtained under the application of the magnetic field at an angle parallel, nearly 45° or perpendicular to the incident X‐rays. A dedicated sample stage was also designed to be as compact as possible, making it possible to perform SX‐RIXS measurements at arbitrary incident angles by rotating the sample stage in the gap between the magnetic poles. This system enables facile studies of magnetic dichroism in SX‐RIXS for various experimental geometries of the sample and the magnetic field. A brief demonstration of the application is presented.     

Direct Fabrication Methods of Surface Relief Electro-Optic Gratings in Azo-Polymer Films

Two fabrication methods of surface relief electro-optic (EO) gratings in azo-polymer films are described: surface deformation by a continuous wave laser and laser ablation by a pulse laser. In the fabrication process, the periodic intensity modulation of laser beams is formed by an interference fringe or a phase mask. The surface relief EO grating is fabricated by poling the surface relief grating (SRG) after the SRG fabrication process. The linear dependence of an applied voltage in the modulation efficiency of the first-order diffraction beam is observed. The proposed methods are effective for highly-efficient surface relief EO grating fabrication.     

The pion velocity at chiral restoration and the vector manifestation

We study the effects of Lorentz non-invariance on the physical pion velocity at the critical temperature T_c in an effective theory of hidden local symmetry (HLS) with the “vector manifestation” fixed point. We match at a “matching scale” Λ_M the axial-vector current correlator in the HLS with the one in the operator product expansion for QCD, and present the matching condition to determine the bare pion velocity. We find that the physical pion velocity, which is found to be one at T=T_c when starting from the Lorentz invariant bare HLS, remains close to one with the Lorentz non-invariance, v_π(T_c)=0.83–0.99. This result is quite similar to the pion velocity in dense matter.