Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 85 , Issue 12
Showing 1-13 articles out of 13 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for 2011
  • Matthew Asay, Akira Sekiguchi
    2012 Volume 85 Issue 12 Pages 1245-1261
    Published: December 15, 2012
    Released: December 15, 2012
    [Advance publication] Released: November 23, 2012
    JOURNALS FREE ACCESS
    Unsaturated main group 14 species have unique properties and reactivity compared with their organic analogues. The isolation of stable disilynes, one of the most recent and intriguing additions to the catalog of unsaturated main group species, has opened the way for further studies into the differences between organic molecules and their heavy analogues. Since the isolation of the first disilyne, the reactivity and properties of these species has been the subject of numerous studies. Herein, the recent developments and results pertaining to the reactivity of disilynes are discussed.
    The isolation of stable disilynes, species with Si–Si triple bonds, has opened the way for in-depth studies of the reactivity of these once ephemeral species. Herein, the recent developments and results pertaining to the reactivity of disilynes are discussed. Fullsize Image
     
BCSJ Award Article
  • Yasuhiko Hirana, Yasuro Niidome, Naotoshi Nakashima
    2012 Volume 85 Issue 12 Pages 1262-1267
    Published: December 15, 2012
    Released: December 15, 2012
    [Advance publication] Released: November 14, 2012
    JOURNALS FREE ACCESS
    The determination of electronic states of single-walled carbon nanotubes (SWNTs) has been a central issue in science and nanotechnology of carbon nanotubes. Previously, we reported the electronic states of (n,m)SWNTs that were embedded in an anionic polymer, carboxymethylcellulose sodium salt (CMC). It is important to reveal how the electronic properties of individual (n,m)SWNTs are affected by the surrounding microenvironment. In this study, we focused on the effect of charge of the SWNT solubilizers. We used a cationic polymer, hydroxyethylcellulose ethoxylate (quaternized) (HEQ) as the SWNT solubilizer in place of CMC, and the isolated (n,m)SWNTs were embedded in a film of HEQ (matrix polymer) on an electrode. We found that the charge of HEQ virtually does not affect the electronic parameters, i.e., oxidation/reduction potentials, Fermi levels, and band gaps of the (n,m)SWNTs, indicating that the presented electronic parameters are the parameters of the intrinsic (n,m)SWNTs.
 
  • Masato M. Maitani, Conghong Zhan, Ching-Chun Huang, Chi-Chang Hu, Dai ...
    2012 Volume 85 Issue 12 Pages 1268-1276
    Published: December 15, 2012
    Released: December 15, 2012
    [Advance publication] Released: December 01, 2012
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    Water splitting under visible irradiation is of significant importance for the ultimate purpose of producing fuel from abundant water and sunlight for a sustainable future society. The efficient photon collection in the visible region and proper construction of the reaction site on the semiconductor surface have been desired and studied to provide an efficient system to create a photoexcited hole–electron pair to proceed toward surface chemical reactions. In this paper, a dye-sensitized nanocrystalline TiO2 colloidal suspension in an aqueous system is applied for H2 evolution under visible light (>390 nm). The efficiency of H2 evolution is strongly influenced by the dye-sensitizers, Ru complex (N719) and porphyrin derivatives, and the combination with coexisting electron donor species, methanol (MeOH) and triethanolamine (TEOA), in the suspension system. The analysis of fluorescence quenching of the porphyrin dye-sensitized nanocrystalline TiO2 in the colloidal suspensions and photoelectrochemical studies of dye-sensitized nanocrystalline TiO2 porous films reveal that the charge-transfer kinetics of the electron injection from the excited dye-sensitizers into TiO2 is strongly influenced by the surroundings, especially the concentration of coexisting electron donor species rather than the pH values of the surrounding solution, resulting in significant differences in the efficiencies of the proton reduction into H2.
  • Koji Miki, Katsuya Nakano, Hideki Matsuoka, Chan Joo Yeom, Hiroshi Har ...
    2012 Volume 85 Issue 12 Pages 1277-1286
    Published: December 15, 2012
    Released: December 15, 2012
    [Advance publication] Released: December 01, 2012
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    Amphiphilic brush-like copolymers having simple amino acids or oligopeptides and poly(ethylene glycol) as side chains were synthesized via ring-opening metathesis polymerization and further transformations. All of the synthesized copolymers formed spherical self-assemblies in water and their hydrodynamic diameters were 100–250 nm, as measured by dynamic light scattering. Amphiphilic polymers bearing leucine and valine can form stable spherical self-assemblies in water because of the synergistic effects of intermolecular hydrogen bonding and hydrophobic interaction. The oligomerization of leucine moieties and capping with the proper length of fatty acyl groups at an N-terminus could significantly affect both the stability and fluorescence intensity of near-infrared fluorescent (NIRF) dye-containing polymeric self-assemblies. All of the self-assemblies consisting of leucine- and oligoleucine-grafted copolymers with a NIRF indocyanine green dye and hydrophilic targeting agents showed low cytotoxicity in cell viability tests. Furthermore, self-assemblies consisting of N-acetylleucine-grafted copolymers with strong fluorescence could visualize a tumor site with high-contrast in vivo, while low contrast images were obtained by utilizing oligoleucine-grafted self-assemblies because of their weak fluorescence. These results indicate that the precise control of both the number of leucine moieties and the length of the fatty acyl groups is important to produce highly functionalized tumor-targeting vehicles delivering a NIRF dye.
  • Sawako Miyamoto, Tetsuya Hasegawa, Hiroyuki Takahashi, Tetsu Yonezawa, ...
    2012 Volume 85 Issue 12 Pages 1287-1292
    Published: December 15, 2012
    Released: December 15, 2012
    [Advance publication] Released: December 06, 2012
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    We report a method to produce vapor species from ZnO powder for the fabrication of ZnO nanorods. Mixing ethanol vapor with the inert carrier gas substantially lowered the gasification temperature of ZnO. c Axis-aligned ZnO nanorods were obtained by dispersing gold nanoparticles on Si substrates. The growth was identified as a vapor–solid (VS) mechanism. Choice of the substrate materials and their surface morphology were both critically important to control the shapes and orientation of grown ZnO.
  • Waro Nakanishi, Satoko Hayashi, Kohei Matsuiwa, Masayuki Kitamoto
    2012 Volume 85 Issue 12 Pages 1293-1305
    Published: December 15, 2012
    Released: December 15, 2012
    [Advance publication] Released: December 06, 2012
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    Normal coordinates of internal vibrations (NIV) are employed to generate the perturbed structures necessary in the atoms-in-molecules (AIM) dual functional analysis for a wide range of weak to strong interactions. Hb(rc) are plotted versus Hb(rc) − Vb(rc)/2 [= (ħ2/8m)∇2ρb(rc)] at bond critical points in the treatment, which incorporates the classification of interactions by signs of ∇2ρb(rc) and Hb(rc). The plots are analyzed using the polar (R, θ) representation. Each plot for an interaction shows a specific curve, which is expressed by (θp, κp): θp corresponds to the tangent line for the plot measured from the y-direction and κp is the curvature. While (R, θ) correspond to the static behavior of interactions at the fully optimized structures, (θp, κp) exhibit the dynamic nature. The (θp, κp) values evaluated employing the perturbed structures with NIV are shown to be very close to those obtained using perturbed structures partially optimized with the distances in question being fixed suitably (POM). The magnitudes of differences in θp and κp between those evaluated with NIV and POM are ≤2° and ≤2 au−1, respectively, for usual interactions. It is demonstrated that NIV is applicable to wide range of usual interactions, as well as POM.
  • Israfil I. Guseinov
    2012 Volume 85 Issue 12 Pages 1306-1309
    Published: December 15, 2012
    Released: December 15, 2012
    [Advance publication] Released: December 06, 2012
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    In standard convention, the new complete orthonormal sets of ψ(α*)-exponential type orbitals (ψ(α*)-ETOs) are introduced as functions of the complex or real spherical harmonics and )-modified and L(p)-generalized Laguerre polynomials ()-MLPs and L(p)-GLPs),

    where, 0 < ζ < ∞, x = 2ζr, p* = 2l + 2 − α*, q* = n + l + 1 − α* and α* is the noninteger or integer (−∞ < α ≤ 2 for α* = α) frictional quantum number (−∞ < α*< 3 for α* ≠ α). It is shown that the origin of the ψ(α*)-ETOs, )-MLPs and L(p)-GLPs is the self-frictional quantum forces which are analog of radiation damping or self-frictional forces introduced by Lorentz in classical electrodynamics. The relations for the quantum self-frictional potentials in terms of ψ(α*)-ETOs, )-MLPs, and L(p)-GLPs, respectively, are established. We note that, in the case of disappearing frictional forces (for α* = 1 and ζ = Z/n), the ψ(α*)-ETOs and eigenvalue are reduced to the Schrödinger’s results in nonstandard convention for the hydrogen-like atom and, therefore, the ψ(α*)-ETOs become the noncomplete, i.e., ψnlm(1) ≡ ψnlm. Here, the ψnlm is Schrödinger’s wave function in nonstandard convention. As examples of an application of ψ(α*)-ETOs as basis sets, the calculations have been performed for the total energies of some atomic and ionic systems.
  • Neeraj Sharma, Shamsher Singh Kanwar, Reena Gupta, Lata Kumari, Reena ...
    2012 Volume 85 Issue 12 Pages 1310-1317
    Published: December 15, 2012
    Released: December 15, 2012
    [Advance publication] Released: December 01, 2012
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    Complexes of composition [VO(Q)2−n(HL1,2)n] (I–IV) (where Q: C9H6NO (quinolin-8-olato ion); HL1: [C6H4(OH)CONHO] (salicyloylhydroxamate ion); HL2: [C6H3(OH)(5-Cl)CONHO] (5-chlorosalicyloylhydroxamate); n = 1 and 2) have been synthesized by the reactions of [VO(Q)2] with predetermined molar ratios of potassium salicyloylhydroxamate and 5-chlorosalicyloylhydroxamate in THF + MeOH solvent medium. The characterization of complexes has been accomplished by elemental analyses, molar conductivity, molecular weight determinations, magnetic measurements, electrochemical and IR, electronic, mass, and ESR spectral studies. The spectroscopic studies suggested bidentate nature of hydroxamate ligands involving O,O coordination. A square-pyramidal environment around vanadium has been proposed. The antimicrobial activity of newly synthesized complexes, ligands and precursor [VO(Q)2] have been assayed against some pathogenic bacteria E. coli, S. aureus, S. typhi, S. paratyphi, S. epidermidis, and K. pneumoniae and fungi A. niger, B. fulva, and M. circinelloides by MIC method. The complexes exhibited improved antimicrobial activity over the free ligands. Cytotoxicity of complexes was studied on mammalian transformed cell line Hep2C, a derivative of human cervix carcinoma HeLa cells by MTT assay.
  • Koji Ogata, Jun-Wei Shen, Satoshi Sugawa, Shinichiro Nakamura
    2012 Volume 85 Issue 12 Pages 1318-1328
    Published: December 15, 2012
    Released: December 15, 2012
    [Advance publication] Released: December 06, 2012
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    Molecular dynamics (MD) simulations were used to investigate the dissociation of the Ras/Raf complex. Three models of Ras/Raf complexes were used in this study: two active GTP-bound forms with either GTP or GDP and one inactive GDP-bound form. The dissociation process in these short time scale (10 ns) MD simulations was accelerated by adding random velocities to phosphate groups in the GTP or GDP molecule. Only the complex with the inactive GDP-bound form heated with the random velocities showed dissociation. The Raf in it was unable to recover its initial position during the MD simulations. In simulations with and without added random velocities the Raf in the other complexes moved back to its initial position. The Raf in complexes with the active GTP-bound form recovered its initial position even when the ligands in the complexes were heated. The details of these mechanisms are discussed here.
  • Shoji Matsumoto, Tatsuro Aoki, Tasutaka Suzuki, Motohiro Akazome, Atsu ...
    2012 Volume 85 Issue 12 Pages 1329-1331
    Published: December 15, 2012
    Released: December 15, 2012
    [Advance publication] Released: December 01, 2012
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    The performance of dyes containing carboxylated 1,3-indandiones as electron acceptors was examined. The compounds that included a monocarboxylic group on the 1,3-indandione moiety showed good overall power conversion efficiencies (ca. 2.38%), the values of which were comparable to those of cyanoacrylate derivatives with the same donor–π-linker structure.
  • Javad Safari, Zohre Zarnegar, Marzieh Heydarian
    2012 Volume 85 Issue 12 Pages 1332-1338
    Published: December 15, 2012
    Released: December 15, 2012
    [Advance publication] Released: December 06, 2012
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    A simple and efficient protocol for one-pot three-component coupling of aldehyde, malononitrile, and resorcinol in water using magnetically recoverable Fe3O4 nanoparticles at room temperature is reported. The high yields of products and short reaction time were attributed to the nanosize of about 18 nm in which the catalyst could act as a nanoreactor. This methodology is found to be fairly general and catalyst is easily separated by magnetic devices and can be reused without any apparent loss of activity for the reaction.
  • Yanqing Wang, Ling Sun, Bunshi Fugetsu
    2012 Volume 85 Issue 12 Pages 1339-1344
    Published: December 15, 2012
    Released: December 15, 2012
    [Advance publication] Released: December 08, 2012
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    Mass production of solution-based graphene derived from the precursor graphene oxide is a challenging step toward achieving industrialization of graphene. Inspired by a classical reducing method performed in the textile and paper making industries, we report here a rapid, cost-effective, and safer approach to the facile production of graphene that employs thiourea dioxide (TDO) as the green reductant. Graphene oxide was converted into high quality graphene within 30 min with TDO as the reductant under moderate reaction conditions. The C/O ratio of the TDO reduced graphene was ca. 5.9 with the yield of graphene from graphene oxide >99%. This is better than the reduction efficiency under the identical experimental conditions by using L-ascorbic acid as the reductant which required a reaction time of about 48 h. This simple and effective procedure should offer an alternative route to the mass production of solution-based graphene for practical applications.
  • Kana Sato, Shota Yamamoto, Shin’ichi Ishimaru
    2012 Volume 85 Issue 12 Pages 1345-1350
    Published: December 15, 2012
    Released: December 15, 2012
    [Advance publication] Released: December 06, 2012
    JOURNALS RESTRICTED ACCESS
    Nanocomposites consisting of clay and poly(N-isopropylacrylamide) (PNIPAAm) were synthesized by photopolymerization using several clay minerals. Uniform hydrogels were obtained by adding saponite-, hectorite-, and fluorohectorite-type synthetic clays to whole clay/NIPAAm with weight-ratios ranging from 0.2 to 1.0. No gels or very brittle gels were produced when synthetic mica and natural montmorillonite were used. The appearance of the obtained hydrogel for the composite of saponite was translucent and relatively stiff, whereas that for fluorohectorite was highly transparent and soft. DSC measurements showed an endothermic anomaly at the volume phase transition in each hydrogel upon increasing temperature. The transition heat decreased with increasing clay content. Swelling behaviors were significantly different between the composites of saponite and fluorohectorite. The amount of absorbed water in the fluorohectorite-composite containing 60 wt % of clay versus NIPAAm was 3 times greater than that in the saponite-composite with the same clay content. The equilibrium water content in the hydrogel decreased with increasing amount of saponite; however, an inverse tendency in the composite of fluorohectorite was observed.
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