Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 85 , Issue 4
Showing 1-16 articles out of 16 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for Young Chemists for 2010
  • Michiya Matsusaki
    2012 Volume 85 Issue 4 Pages 401-414
    Published: April 15, 2012
    Released: April 15, 2012
    [Advance publication] Released: March 17, 2012
    JOURNALS FREE ACCESS
    The creation of artificial three-dimensional (3D) tissues possessing structure and function similar to natural tissue is a key challenge for implantable tissues in tissue engineering, and for model tissues in pharmaceutical assays. This account is a summary of our current research toward this challenge. We have developed a simple and unique bottom-up approach, hierarchical cell manipulation technique, using nanometer-sized layer-by-layer films consisting of fibronectin and gelatin (FN–G) as a nano-extracellular matrix (nano-ECM). The FN–G nanofilms were prepared directly on the cell surface, and we discovered that at least 6 nm thick FN–G films acted as a stable adhesive surface for adhesion of the second cell layer. Various 3D-layered constructs consisting of single or multiple types of cells were successfully fabricated, and the higher cellular activities induced from the 3D-structures as compared to monolayer structure were observed. Furthermore, the multilayered constructs like a blood vessel wall structure indicated almost the same drug response as in vivo natural blood vessels, suggesting the possibility to use as an in vitro blood vessel model to analyze drug response. Recently, we also developed a rapid bottom-up approach by a single cell coating using FN–G nanofilms, because the fabrication of two-layers (2L) is limited through the above technique due to the time required for stable cell adhesion. This rapid approach easily provided approximately eight-layered (8L) 3D-tissues after only one day of incubation. The layer number, cell type, and location were all successfully controlled by altering the seeding cell number and order. Moreover, fully and homogeneously vascularized tissues of 1 cm width and 50 µm height were obtained by a sandwich culture of the endothelial cells. These hierarchical cell manipulations will be promising to achieve one of the dreams of biomedical field, in vitro creation of artificial 3D-tissue models.
    Three-dimensional multilayered architectures were developed by layer-by-layer assembly of proteins and cells. These multilayered constructs are valuable as an artificial tissue model for drug response or toxicity experiment in pharmaceutical and tissue engineering fields. Fullsize Image
The Chemical Society of Japan Award for Young Chemists for 2005
  • Koji Fujita
    2012 Volume 85 Issue 4 Pages 415-432
    Published: April 15, 2012
    Released: April 15, 2012
    [Advance publication] Released: April 10, 2012
    JOURNALS FREE ACCESS
    This account presents the preparation, characterization, and applications of porous sol–gel materials with particular emphasis on non-siliceous oxide compositions and morphology control. The potential and versatility of innovative synthesis strategies that have been developed to broaden the range of achievable compositions and functionalities are briefly discussed. The synthesis approach involves polymerization-induced phase separation and concurrent sol–gel transition under well-controlled reactions conditions, producing monolithic gels with well-defined macroporous bicontinuous structures. By optimizing the template-free synthesis routes including the postgelation treatments, one can obtain non-siliceous monolithic materials with controllable macropores and mesopores. Promising results for chromatographic and optical applications are also demonstrated taking porous titania monoliths as a example.
    Non-siliceous monolithic gels with bicontinuous macropores are obtained through sol–gel reactions involving the stabilization of precursor sols and subsequent well-controlled condensation. The porous monolithic oxides hold great promise for a new generation of functional materials with improved and tailorable properties. Fullsize Image
BCSJ Award Article
  • Satoshi Matsunaga, Ken-ichi Hasada, Kenji Sugiura, Naoki Kitamura, Yur ...
    2012 Volume 85 Issue 4 Pages 433-438
    Published: April 15, 2012
    Released: April 15, 2012
    [Advance publication] Released: March 24, 2012
    JOURNALS FREE ACCESS
    We have successfully synthesized rhodium-containing MOFs with 1:1 abundance ratios of paddle-wheel units of Rh2 and Cu2/Zn2, i.e., [Rh2M2(1,4-bdc)4nSolvent (M = Cu: RhCu-DMF, RhCu-EtOH; M = Zn: RhZn-DMF; 1,4-bdc: 1,4-benzenedicarboxylate) by a novel synthetic method involving assembly of discrete paddle-wheel dirhodium(II) tetra(1,4-benzenedicarboxylate) with Cu2+ or Zn2+ ions. The diffraction patterns of these complexes were very similar to the predicted and experimental XRPD patterns reported for [Cu2(1,4-bdc)2]. This result indicates that this method enables the incorporation of coordinatively unsaturated noble-metal sites for the many reported MOFs with multi-carboxy ligands and paddle-wheel nodes.
    We have proposed a novel synthetic method for hetero bi-paddle-wheel MOFs that enables the successful synthesis of high crystallinity and high purity Rh-containing MOFs by assembly of discrete paddle-wheel rhodium terephthalate and Cu2+ or Zn2+ ions. Fullsize Image
 
  • Shinsaku Fujita
    2012 Volume 85 Issue 4 Pages 439-449
    Published: April 15, 2012
    Released: April 15, 2012
    [Advance publication] Released: April 10, 2012
    JOURNALS RESTRICTED ACCESS
    The restricted-subduced-cycle-index (RSCI) method for generating Z-counting polynomials and the Hosoya indices (Z-indices) as well as matching polynomials has been developed by starting from subduced cycle indices (SCI) defined in the unit-subduced-cycle-index (USCI) approach (S. Fujita, Symmetry and Combinatorial Enumeration in Chemistry, Springer-Verlag, 1991). In the RSCI method, k-matchings of a given skeleton (or graph) for deriving these matters are regarded as restricted structures in which vertex substitution and edge substitution occur concurrently under a restricted condition that occupation of a common vertex does not occur. For the purpose of counting such restricted structures, the concepts of territory indicators and territory discriminants are introduced. Thereby, an RSCI for the skeleton (or graph) is derived from an SCI by the subduction to C1 (nonsymmetry). The RSCI gives the generating function for counting the numbers of restricted structures, which is further converted into a Z-counting polynomial, the Hosoya indices, as well as a matching polynomial. The versatility of the RSCI method is illustrated by applying to benzene, naphthalene, dodecahedron, and fullerene C60.
  • Shuhei Higashibayashi, Ryoji Tsuruoka, Yarasi Soujanya, Uppula Purusho ...
    2012 Volume 85 Issue 4 Pages 450-467
    Published: April 15, 2012
    Released: April 15, 2012
    [Advance publication] Released: March 28, 2012
    JOURNALS OPEN ACCESS
    C3 symmetric chiral trimethylsumanene was enantioselectively synthesized through Pd-catalyzed syn-selective cyclotrimerization of an enantiomerically pure iodonorbornenone, ring-opening/closing olefin metathesis, and oxidative aromatization where the sp3 stereogenic center was transmitted to the bowl chirality. Chiral HPLC analysis/resolution of the derivatives were also achieved. Based on theoretical calculations, the columnar crystal packing structure of sumanene and trimethylsumanene was interpreted as due to attractive electrostatic or CH–π interaction. According to the experimental and theoretical studies, the bowl depth and inversion energy were found to increase on methylation for sumanene in contrast to corannulene. Dissimilarities of the effect of methylation on the bowl structure and inversion energy of sumanene and corannulene were ascribed to differences in steric repulsion. A double-well potential model was fitted to the bowl structure–inversion energy correlation of substituted sumanenes, with a small deviation. The effects of various substituents on the sumanene structure and bowl-inversion energy were analyzed by density functional theory calculations, and it was shown that the bowl rigidity is controlled by a combination of electronic and steric effects of the substituents. The electron conductivity of trimethylsumanene was investigated by time-resolved microwave conductivity method, compared with that of sumanene.
  • Keita Ikeue, Satoshi Hinokuma, Kazuma Watanabe, Takayuki Minekishi, Ta ...
    2012 Volume 85 Issue 4 Pages 468-474
    Published: April 15, 2012
    Released: April 15, 2012
    [Advance publication] Released: March 24, 2012
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    The synthesis route of 10Al2O3·2B2O3 (10A2B) and effect of additives were studied to use this compound as a thermally stable support material for Pd catalysts. The preparation by reverse coprecipitation was found to have a beneficial effect on the BET surface area of 10A2B and thus Pd metal dispersion, compared to other preparation routes via solid-state reaction and hydrolysis of metal alkoxides. The addition of 3 wt % BaO suppressed the sintering of 10A2B and Pd during thermal aging at 900 °C in a stream of air containing 10% H2O. Although direct interactions between Pd and the support material were not detected by EXAFS, the catalytic performance for NO–CO–C3H6–O2–H2O reactions under modulated air-to-fuel ratio (A/F) conditions was strongly influenced by the Ba additive. The activity for NO and C3H6 in a rich region (A/F < 14.6) was especially enhanced in the presence of Ba because of accelerated elemental reactions including NO–CO and NO–C3H6. In situ FT-IR of CO suggested that the Pd electronic state changed by electrostatic effect of Ba additives would activate NO and weaken the self-poisoning effect of C3H6.
  • Yuto Nakagami, Nobu-Yuki Suzuki, Rika Sekine, Taisuke Matsuura, Jun-ic ...
    2012 Volume 85 Issue 4 Pages 475-480
    Published: April 15, 2012
    Released: April 15, 2012
    [Advance publication] Released: March 28, 2012
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    The energy of the lowest π molecular orbital in a planar boron cluster can be estimated from the connectivity of constituent boron atoms, or the mean valency of the boron atoms. Low-energy π molecular orbitals were then predicted to occur in all realistic planar polycyclic boron clusters. In fact, all such boron clusters studied have one or more π molecular orbitals with two or more π electrons. They are aromatic with positive topological resonance energies. π Conjugation and aromaticity must be totally or partially responsible for the planarity of low-energy boron clusters.
  • Rong Li, Chunyue Pan, Shaohui Xiong, Guipeng Yu, Pingshan Wang, Yingpi ...
    2012 Volume 85 Issue 4 Pages 481-486
    Published: April 15, 2012
    Released: April 15, 2012
    [Advance publication] Released: April 10, 2012
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    Tetrakis(1-adamantanecarboxymethyl)methane was prepared by indirect esterification. DSC traces of tetrakis(1-adamantanecarboxymethyl)methane showed two endothermic peaks. Entropy ratio of these two peaks is: ΔStrsSfus = 1.58 > 1. XRD confirmed the solid–solid transition and analysis of XRD by DICVOL demonstrated tetrakis(1-adamantanecarboxymethyl)methane is a new compound with a highly disordered crystalline phase. Analysis of entropy changes at transitions showed why fusion entropy (ΔSfus = 70.07 J mol−1 K−1) of tetrakis(1-adamantanecarboxymethyl)methane is much larger than Timmermans’ criterion.
  • Szabolcs Vass, István Lakatos, György Jákli, Istv&a ...
    2012 Volume 85 Issue 4 Pages 487-489
    Published: April 15, 2012
    Released: April 15, 2012
    [Advance publication] Released: April 10, 2012
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    Density ρ and apparent molar volume Vφ are determined in aqueous micellar solutions of ethoxylated nonylphenol (ENP) mixtures. The ratio Δρ/c of the excess solution density Δρ and the molar concentration c lays the foundation of a model, which satisfactorily reproduces Δρ and Vφ of the mixtures; predicts these quantities for known composition mixtures; and allows estimation of the partial molar volumes Vi of the components and the volume Vmix of mixing.
  • Masafumi Yano, Hidehiro Takemoto, Masakazu Tatsumi, Hiroyuki Miyake, H ...
    2012 Volume 85 Issue 4 Pages 490-496
    Published: April 15, 2012
    Released: April 15, 2012
    [Advance publication] Released: April 10, 2012
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    A combination of two bridged bis(2-pyridylmethyl)amine-type ligands offered efficient separation of lanthanoid tris(β-diketonates) complexes. The employed ligands bridged two lanthanoid tris(β-diketonates) to form crystalline ternary complexes. Since the complexes containing larger lanthanoid centers were preferentially precipitated, the bridging ligands selectively recognized the lanthanoid tris(β-diketonates) in the crystallization process, and offered an efficient separation method.
  • Takeo Yamaguchi, Yohei Iwata, Shingo Miura, Yukari Maehara, Kazuyuki N ...
    2012 Volume 85 Issue 4 Pages 497-503
    Published: April 15, 2012
    Released: April 15, 2012
    [Advance publication] Released: April 10, 2012
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    Pressure-induced hemolysis reflects sensitively membrane perturbations in erythrocytes. The functions of transporters and channels are inhibited by sodium p-chloromercuribenzoate (pCMB). So, we tested the effects of pCMB on hemolysis of human erythrocytes at 200 MPa. Pressure-induced hemolysis was enhanced by pCMB, but restored by dithiothreitol. Such effects of pCMB were also observed in N-ethylmaleimide-pretreated erythrocytes. Similar hemolytic properties were observed by aquaporin-1 (AQP1) inhibitors such Hg2+ and Au3+, but not by inhibitors of Na+–K+ pump, Gardos channels, and glucose transporter. In fact, the results of atomic absorption spectrometry showed the binding of mercury to AQP1. From the 1H spin–spin relaxation time of water, we found that pressure-induced hemolysis was enhanced upon inhibition of water transport. Flow cytometric analysis demonstrated the enhancement of hemolysis by suppression of fragmentation under pressure. Detachment of cytoskeletal proteins from the membrane by low ionic strength buffer was unaffected by pCMB. Moreover, diameters of vesicles released from intact and pCMB-treated erythrocytes at 200 MPa were 438 and 584 nm, respectively. In both vesicles, spectrin contents were almost the same. Taken together, these data suggest that pCMB bound to AQP1 inhibits water transport and enhances the hemolysis due to the suppression of fragmentation under pressure, but not affect membrane–cytoskeleton interactions.
  • Takashi Sugimura, Eigo Mitani, Takahiro Tei, Tadashi Okuyama, Katsumas ...
    2012 Volume 85 Issue 4 Pages 504-510
    Published: April 15, 2012
    Released: April 15, 2012
    [Advance publication] Released: March 28, 2012
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    The intramolecular [2 + 2] cycloaddition between alkene and ketene linked with 2,4-pentanediol tether was performed in a wide range of temperature, −60 to +400 °C. When the ketene was generated by photolysis at the diazoester in a pentane solution, the cycloadduct obtained was of 90–98% de depending on the structure of the olefinic part as well as the structure of the tether. Notably, each substrate showed practically constant selectivity in a temperature range of −60 to +130 °C. The thermolysis in vapor phase above 250 °C also gave the same cycloadducts; the de values of the kinetic products are similar to those obtained by photolysis. The observed temperature-independent stereoselectivity should be controlled by the entropy term, which is also investigated by ab initio calculations in the framework of density functional theory.
  • Kunimasa Sagata, Hidenori Yahiro
    2012 Volume 85 Issue 4 Pages 511-516
    Published: April 15, 2012
    Released: April 15, 2012
    [Advance publication] Released: April 10, 2012
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    FeOx-promoted Cu/Al2O3 catalysts active for low-temperature water–gas-shift (LT-WGS) reaction, reported previously (H. Yahiro, K. Sagata, T. Yamamoto, K. Saiki, M. Asamoto, H. Yamaura, Catal. Lett. 2008, 124, 233.), were characterized by TPR, TPO, XRD, and XPS measurements. These techniques proved that Fe2O3 was partially reduced by H2 to Fe3O4 at 573 K in the presence of Cu0 and that the obtained Fe3O4 was reoxidized by O2 at the same temperature. The pronounced effect of Fe addition to Cu/Al2O3 on the catalytic activity for WGS reaction was observed at 523–623 K. It is concluded that partially reduced Fe2O3, probably Fe3O4, acts as an active site for LT-WGS reaction in the addition to Cu0, resulting in the improvement of the catalytic activity at 523–623 K.
  • Yuji Ando, Koichi Matsuoka, Hideyuki Takagi, Koji Kuramoto
    2012 Volume 85 Issue 4 Pages 517-521
    Published: April 15, 2012
    Released: April 15, 2012
    [Advance publication] Released: March 28, 2012
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    We investigated ethanol steam reforming over Rh/SiO2, Pt/SiO2, Pd/SiO2, and Ru/SiO2 at 573–723 K using a fluidized-bed quartz reactor to determine which reaction conditions suppressed CH4 production and increased H2 and CO2 production. At temperatures under 623 K over Rh/SiO2 and Ru/SiO2, CH4 was produced not only by ethanol decomposition but also by the reduction of CO2 and CO to CH4. At 723 K, the product yields over all four catalysts were strongly influenced by the partial pressure of ethanol: CH4 production was suppressed, and H2 and CO2 production was increased, at low partial pressure of ethanol. These experimental results can be explained in terms of the partial pressures of CO2 and H2.
  • Keisuke Yasuda, Atsuki Yoshimura, Atsushi Katsuma, Toshiyuki Masui, No ...
    2012 Volume 85 Issue 4 Pages 522-526
    Published: April 15, 2012
    Released: April 15, 2012
    [Advance publication] Released: March 24, 2012
    JOURNALS RESTRICTED ACCESS
    Catalytic combustion of volatile organic compounds (VOCs) such as ethylene, toluene, and acetaldehyde over novel Pt/CeO2–ZrO2–SnO2/γ-Al2O3 catalysts prepared by a coprecipitation method was investigated. The introduction of a small amount of SnO2 within the CeO2–ZrO2 lattice as a promoter was considerably effective to enhance the oxygen release and storage abilities of the catalysts, so that complete oxidation of VOCs was markedly activated. This improvement of the reducibility of the catalyst can be ascribed to the simultaneous reduction of Ce4+ and Sn4+ in the CeO2–ZrO2–SnO2 solid solutions. By the optimization of the composition and the Pt amount, complete oxidation of ethylene, toluene, and acetaldehyde was realized at temperatures as low as 55, 110, and 140 °C over a Pt(10 wt %)/Ce0.68Zr0.17Sn0.15O2.0(16 wt %)/γ-Al2O3 catalyst, respectively.
  • Riichiro Kimura, Dinh Thanh Nghia, Junji Wakabayashi, Shanmugam Palani ...
    2012 Volume 85 Issue 4 Pages 527-532
    Published: April 15, 2012
    Released: April 15, 2012
    JOURNALS RESTRICTED ACCESS
    In this study, phase changes, catalytic active species that appeared at the phase change, and the corresponding water tolerance of samples obtained upon thermal treatment from K2CO3-supported microsized and nanosized sodalite as diesel-soot combustion catalyst are examined. We have shown the successful preparation of nepheline with water tolerance from sodalite as starting material. It is confirmed that the interaction between alkali metal carbonate and crystalline aluminosilicate is prerequisite for enhancing water tolerance of the catalytically active component, Na/K carbonate, located on the nepheline.
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