Isotopic Exchange in Porous and Dense Magnesium Borohydride

Magnesium borohydride (Mg(BH₄)₂) is one of the most promising complex hydrides presently studied for energy‐related applications. Many of its properties depend on the stability of the BH₄^? anion. The BH₄^? stability was investigated with respect to H→D exchange. In situ Raman measurements on high‐surface‐area porous Mg(BH₄)₂ in 0.3 MPa D₂ have shown that the isotopic exchange at appreciable rates occurs already at 373 K. This is the lowest exchange temperature observed in stable borohydrides. Gas–solid isotopic exchange follows the BH₄^?+D^.→BH₃D^?+H^. mechanism at least at the initial reaction steps. Ex situ deuteration of porous Mg(BH₄)₂ and its dense‐phase polymorph indicates that the intrinsic porosity of the hydride is the key behind the high isotopic exchange rates. It implies that the solid‐state H(D) diffusion is considerably slower than the gas–solid H→D exchange reaction at the surface and it is a rate‐limiting steps for hydrogen desorption and absorption in Mg(BH₄)_2.     

Electric Field Effects on Sensitized Fluorescence Emission From Nematic Liquid Crystal Cells

Remarkable electric field effects were observed with sensitized fluorescence intensities of a perylene derivative (BPDC), when rectangular AC waves (up to 10 V_0-p ) were applied to nematic liquid crystal cells containing a sensitizer (C307 or AHDA) and an acceptor (BPDC) as the guest molecules. Measurements of the fluorescence lifetime of AHDA indicated that the rates of energy transfer from AHDA to BPDC were independent of the electric fields. The electric field effects completely changed the sign when the intensity variation detected at vertical direction was compared with that at the horizontal direction with respect to the liquid crystal cell. The observed electric field effects on the sensitized fluorescence were consequently suggested to come from the orientation control of transition dipole moment of BPDC through the molecular alignment of the liquid crystal. The suggestion was confirmed by the measurement of dichroic absorption of the donor-acceptor systems.     

Evidence for a weakening ‘dead zone’ in Tokyo Bay over the past 30?years

Weakened hypoxia in the past 30?years at a dredged area in Tokyo Bay was proven by the existence of amorphous hematite (α-Fe2O3) in sediments. The chemical states of iron in sediments can become a proxy for the scale of anoxia at the time of sedimentation. In 2009, we collected core sediments from a dredged area off Makuhari in Tokyo Bay that is very strongly anoxic in the summer. Every layer of the sediments was analysed by ⁵⁷Fe M?ssbauer spectroscopy and excess 210Pb dating, and amorphous hematite was identified in the sediments from the 1976–1979, 1986–1989 and 2006–2009 layers. Using an estimate based on the Eh-pH diagram optimized for the sedimental environment, the existence of hematite in the dredged area proves that the scale of hypoxia/anoxia is decreasing, and these results agree well with the observed dissolved oxygen level of the seawater mass.     

Electrical and self‐heating properties of UHMWPE‐EMMA‐NiCF composite films

Conductive polymer composites (CPC) containing nickel‐coated carbon fiber (NiCF) as filler were prepared using ultra‐high molecular weight polyethylene (UHMWPE) or its mixture with ethylene‐methyl methacrylate (EMMA) as matrix by gelation/crystallization from dilute solution. The electrical conductivity, its temperature dependence, and self‐heating properties of the CPC films were investigated as a function of NiCF content and composition of matrix in details. This article reported the first successful result for getting a good positive temperature coefficient (PTC) effect with 9–10 orders of magnitude of PTC intensity for UHMWPE filled with NiCF fillers where the pure UHMWPE was used as matrix. At the same time, it was found that the drastic increase of resistivity occurred in temperature range of 120–200 °C, especially in the range of 180–200 °C, for the specimens with matrix ratio of UHMWPE and EMMA (UHMWPE/EMMA) of 1/0 and 1/1 (NiCF = 10 vol %). The SEM observation revealed to the difference between the surfaces of NiCF heated at 180 and 200 °C. Researches on the self‐heating properties of the composites indicated a very high heat transfer for this kind of CPCs. For the 1/1 composite film with 10 vol % NiCF, surface temperature (T_s) reached 125 °C within 40 s under direct electric field where the supplied voltage was only 2 V corresponding to the supplied power as 0.9 W. When the supplied voltage was enough high to make T_s beyond the melting point of UHMWPE component, the T_s and its stability of CPC films were greatly influenced by the PTC effect. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1253–1266, 2009     

New methodology for synthesizing polyolefinic graft block copolymers and their morphological features

This paper describes a new synthetic route for polyolefinic graft block copolymers by adopting coupling reaction between terminally hydroxylated polyolefins and maleic anhydride grafted polyolefins. Terminally hydroxylated polypropylene (PP-OH) was coupled with maleic anhydride modified polyethylene (PE-g-MAH) and such ethylene-propylene random copolymer (EPR-g-MAH) to give polyolefinic graft block copolymers (PE-g-PP and EPR-g-PP, respectively). The formation of PE-g-PP was confirmed by enhancement on molecular weight and it brought about distinctive decrease in size of dispersed domain in its phase separation morphology. Occurrence of coupling reaction to give EPR-g-PP was indicated by extreme decrease in its solubility to n-decane and it led to unique morphology demonstrating lamella microstructure that had never been reported for a comparable polyolefin composite.     

Photoinduced Atom Transfer Radical Addition/Cyclization Reaction between Alkynes or Alkenes with Unsaturated α-Halogenated Carbonyls

We have developed a photochemical ATRA/ATRC reaction that is mediated by halogen bonding interactions. This reaction is caused by the reaction of malonic acid ester derivatives containing bromine or iodine with unsaturated compounds such as alkenes and alkynes in the presence of diisopropylethylamine under visible light irradiation. As a result of various control experiments, it was found that the formation of complexes between amines and halogens by halogen-bonding interaction occurs in the reaction system, followed by the cleavage of the carbon–halogen bonds by visible light, resulting in the formation of carbon radicals. In this reaction, a variety of substrates can be used, and the products, cyclopentenes and cyclopentanes, were obtained by intermolecular addition and intramolecular cyclization.