Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 79 , Issue 5
Showing 1-21 articles out of 21 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for Young Chemists for 2004
Accounts
  • Kazuki Nakanishi
    2006 Volume 79 Issue 5 Pages 673-691
    Published: 2006
    Released: May 12, 2006
    JOURNALS FREE ACCESS
    A versatile sol–gel method for fabricating porous oxide materials with well-defined co-continuous macropores has been reviewed. The chemical instability, in many cases induced by polymerization of the network-forming components, triggers the formation of biphasic morphologies, followed by an irreversible freezing of the transient morphology by the sol–gel transition of the gelling phase. Upon removal of the non-gelling phase, an oxide framework comprising of controlled macropores can be obtained. The mesopore system of such macroporous materials can be further modified either by a physico-chemical treatment or a supramolecular templating technique. Pure silica and siloxane-based organic–inorganic hybrids with a hierarchical pore system in monolithic form have been successfully applied to the novel type of separation medium for high performance liquid chromatography, HPLC. Additional topics are also described including recent advances in the 3D-analysis of the interfacial properties of macroporous systems, extended compositional variations in the network-forming phase, and emerging applications in areas of biochemistry.
BCSJ Award Article
  • Takaaki Hosoya, Hidehiro Uekusa, Yuji Ohashi, Takashi Ohhara, Ryota Ku ...
    2006 Volume 79 Issue 5 Pages 692-701
    Published: 2006
    Released: May 12, 2006
    JOURNALS FREE ACCESS
    The 4-cyanobutyl group of (4-cyanobutyl)[3,4-lutidine](dimethylglyoximato)[O-(diphenylboryl)dimethylglyoximato]cobalt(III) was isomerized to the 1-cyanobutyl group with retention of the single-crystal form, although the corresponding cobaloxime complex without diphenylboryl in the equatorial ligands did not show such a photoisomerization. The transciscis conformation of the 4-cyanobutyl group caused by the steric repulsion from the diphenylboryl group is favorable to the crystalline-state reaction. In order to elucidate the detailed isomerization mechanism, two hydrogen atoms of the 4-cyanobutyl group were replaced with the deuterium atoms such as –CH2CH2CH2CD2CN. After the photoisomerization, the crystal structure with deuterated 4-cyanobutyl group was analyzed by neutron diffraction. Only one of the two deuterium atoms of the 4-cyanobutyl group was transferred to the C1 atom such as –CD(CN)CH2CH2CDH2. This result made clear that the photo-produced cyanobutyl radical turned upside down after homolytic cleavage of the Co–C bond, and then the Co(II) atom and the radical made a bond to form the 1-cyanobutyl group.
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