Elementary Reactions of Metal Alkyl in Anionic Polymerization. III. Reaction Mode of n-Butylmagnesium Bromide with α,β-Unsaturated Carbonyl Compounds∗

Reaction modes of n-butylmagnesium bromide with α,β-unsaturated esters, ketones, and nitriles were investigated in ether under anionic polymerization conditions. n-Butane and conjugate addition products observed were with all the monomers examined, but carbonyl addition products were not detected except with the unsaturated esters. Product distribution depends mainly upon reaction temperature and the concentration of the Grignard reagent, not upon the concentration of the unsaturated compounds. n-Butyl-magnesium bromide etherate in toluene gave similar results.     

Two‐Step direct arylation for synthesis of naphthalenediimide‐based conjugated polymer

A naphthalenediimide (NDI)‐based conjugated polymer was synthesized by a two‐step direct C‐H arylation sequence. In the first step, two ethylenedioxythiophene units were coupled to NDI by direct arylation. In the second step, the direct arylation polycondensation of the monomer, formed in the first step, with 2,7‐dibromo‐9,9‐dioctylfluorene afforded the corresponding NDI‐based conjugated polymer ( PEDOTNDIF ) with molecular weight of 21,500 in 91% yield. The optical and electrochemical properties of the polymer were evaluated. The polymer showed ambipolar behavior in organic field‐effect transistors (OFETs). The electron mobility of PEDOTNDIF was estimated to be 2.3 × 10^?6 cm² V^?1 s^?1 using an OFET device with source‐drain (S‐D) Au electrodes. A modified OFET device with S‐D MgAg electrodes increased the electron mobility for PEDOTNDIF to 1.0 × 10^?5 cm² V^?1 s^?1 due to the more suitable work function of these electrodes, which reduced the injection barrier to the semiconducting polymer. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1401–1407     

Synthesis of (Z)-β-(Carbonylamino)alkenylindium through Regioselective anti-Carboindation of Ynamides and Its Transformation to Multisubstituted Enamides

The regioselective anti-carboindation of ynamides by using InBr₃ and silylated nucleophiles was developed to synthesize (Z)-β-(carbonylamino)alkenylindiums. The X-ray crystallographic analysis of an alkenylindium suggested that the reaction proceeded in an anti-addition fashion. In contrast to reported syn-carbometalations of ynamides by using organometallics, a cooperation of InBr₃ and silylated nucleophiles to ynamides achieved an anti-addition, which was supported by DFT calculations. The scope of substrates included various ynamides and silylated nucleophiles, such as silyl ketene acetals and silyl ketene imines. The transformation of synthesized alkenylindiums by iodination, radical coupling, and Pd-catalyzed cross-coupling successfully afforded trisubstituted enamines with high regio- and stereoselectivities.     

Microstructure of metallic copper nanoparticles/metallic disc interface in metal–metal bonding using them

This paper describes a metal–metal bonding technique using metallic Cu nanoparticles prepared in aqueous solution. A colloid solution of metallic Cu particles with a size of 54 ± 15 nm was prepared by reducing Cu²⁺ (0.01 M (CH₃COO)₂Cu) with hydrazine (0.6 M) in the presence of stabilizers (5 × 10^?4 M citric acid and 5 × 10^?3 M cetyltrimethylammonium bromide) in water at room temperature in air. Discs made of metallic materials (Cu, Ni/Cu, or Ag/Ni/Cu) were successfully bonded under annealing at 400 °C and pressurizing at 1.2 MPa for 5 min in H₂ gas with help of the metallic Cu particle powder. Shear strength required for separating the bonded discs was 27.9 ± 3.9 for Cu discs, 28.1 ± 4.1 for Ni/Cu discs, and 13.8 ± 2.6 MPa for Ag/Ni/Cu discs. Epitaxial crystal growth promotes on the discs with a good matching for the lattice constants between metallic nanoparticles and metallic disc surfaces, which leads to strong bonding. Copyright © 2013 John Wiley & Sons, Ltd.     

Photoaddressable polymers for liquid crystal alignment

We demonstrate reversible photoinduced in situ reorientation of low molecular mass liquid crystals (LCs) by means of photoaddressable polymers (PAPs). These polymers contain mesogenic azobenzene side chains optimized to reorient cooperatively and effectively upon illumination with polarized light. Various low molecular mass LCs were introduced between two PAP layers and these sandwich devices were tested with respect to stability and reversibility of photoinduced orientation. Dissolution of the PAP layer by the low molecular mass LC was observed for several material combinations and systematically investigated. Different anisotropic dyes were added as fluorescence markers in order to monitor the photoinduced LC orientation. With an optimized material combination, more than 10 reversible reorientation processes could be realized with polarized light of either 514 or 405 nm wavelength, without any reduction in alignment quality. Further, microscopic polarized fluorescence patterns could be produced and erased within short exposure times.     

Challenge to ultra-trace analytical techniques of nuclear materials in environmental samples for safeguards at JAERI: methodologies for physical and chemical form estimation

From a viewpoint of physical and chemical form estimation, ultra-trace analytical techniques of nuclear materials in environmental samples for safeguards have been investigated at Japan Atomic Energy Research Institute. This article deals with (1) an outline of the developed techniques for bulk and particle analyses of uranium and plutonium in the safeguards environmental samples; (2) current R&D on techniques relating to estimation of the physical and chemical form, such as SEM images and EDX spectra for fine particles of nuclear materials and fission track observation applicable to fissile materials; and (3) possible analytical methodologies, as future works, applicable to ultra-trace amounts of nuclear materials in environmental samples.