Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 86 , Issue 12
Showing 1-11 articles out of 11 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for Creative Work for 2007
  • Masashi Kawasaki
    2013 Volume 86 Issue 12 Pages 1341-1358
    Published: December 15, 2013
    Released: December 15, 2013
    JOURNALS FREE ACCESS
    A review is given for our originally-developed thin film technology, “combinatorial lattice engineering.” This is extended from a conventional pulsed laser deposition, where the surface of a sintered oxide tablet (target) is irradiated with focused laser pulses and the evaporated precursors are condensed on a heated substrate to grow single crystalline thin films. By this method, it has become possible to concurrently synthesize many oxide thin films on a substrate at different locations (segments) with such diversities as composition, growth conditions, and the sequence of heterostructures. By inserting a masking system between the target and substrate and computer controlling the mask motion as well as target switching, one can integrate many oxide thin film segments on the substrate. Starting from the background of and demand for this technology as well as the advancement of the key ingredient technology, i.e., atomically regulated epitaxial growth of oxide thin films, the concept and examples of this combinatorial lattice engineering are introduced highlighting the representative demonstration on magnetic, photonic, and electronic functionalities, especially emphasizing the benefit of this combinatorial technology. In addition, further progress of device physics triggered by the combinatorial discoveries are introduced, for example, electric field control of magnetism, bright ultraviolet light emitting devices, and quantum effects in oxide semiconductors.
    High throughput experiments for materials discovery are developed using combinatorial chemistry and cutting-edge oxide thin film growth technology. Novel materials and devices realized in oxide semiconductors are highlighted. Fullsize Image
     
The Chemical Society of Japan Award for Young Chemists for 2008
  • Hiromitsu Maeda
    2013 Volume 86 Issue 12 Pages 1359-1399
    Published: December 15, 2013
    Released: December 15, 2013
    [Advance publication] Released: September 21, 2013
    JOURNALS FREE ACCESS
    This article summarizes the supramolecular chemistry of pyrrole-based π-conjugated molecules, with specific focus on the work carried out by the author’s group over the last nine years. The author provides a number of examples of supramolecular assemblies and functional materials comprising pyrrole-based molecules stabilized by noncovalent interactions such as metal coordination, hydrogen bonding, π–π stacking, and van der Waals forces. In particular, pyrrole-based π-conjugated molecules showed anion-binding behavior, and formed ion-based materials, wherein positively and negatively charged species were arranged in an ordered form by combination with appropriate cations.
    This article summarizes the supramolecular chemistry of pyrrole-based π-conjugated molecules using noncovalent interactions such as metal coordination, hydrogen bonding, π–π stacking, and van der Waals forces, with specific focus on the work carried out by the author’s group over the last nine years. Fullsize Image
     
The Chemical Society of Japan Award for Young Chemists for 2012
BCSJ Award Article
  • Ayako Taketoshi, Patricia Concepción, Hermenegildo Garcí ...
    2013 Volume 86 Issue 12 Pages 1412-1418
    Published: December 15, 2013
    Released: December 15, 2013
    JOURNALS FREE ACCESS
    Although selective oxidation of sulfides to sulfoxides with molecular oxygen is a difficult reaction due to the overoxidation to sulfone, manganese oxides were found to catalyze the aerobic oxidation of sulfides to sulfoxides in 1,2-dichlorobenzene at 100 °C with a high selectivity above 99%. The catalytic activity depends on the preparation methods and conditions of manganese oxides but not on the valences of manganese. The deposition of Pd and Pt on manganese oxides was detrimental, whereas the deposition of Au enhanced the catalytic activity and selectivity.
    Manganese oxides are catalytically active and selective in the aerobic oxidation of sulfide to sulfoxide. Although Pd and Pt were inhibitors, gold NPs deposited on manganese oxides acted as a promoter. Fullsize Image
     
 
  • Ramesh Chitrakar, Yoji Makita, Akinari Sonoda
    2013 Volume 86 Issue 12 Pages 1419-1425
    Published: December 15, 2013
    Released: December 15, 2013
    [Advance publication] Released: October 05, 2013
    JOURNALS RESTRICTED ACCESS
    The ion-exchange properties of the layered perovskite HCa2Nb3O10·1.5H2O toward cesium ion were examined. The Cs+ uptake by the protonated material follows the Langmuir model with uptake capacity of 0.82 mmol g−1 at equilibrium pH 3.3. The Cs+ uptake capacity decreased with increase in equilibrium pH showing 1.0 mmol g−1 at pH 1.6 and 0.70 mmol g−1 at pH 10.2. The selectivity order determined by comparison of the distribution coefficient (Kd) values was Cs+ > Na+ > K+ >> Ca2+ > Mg2+ at equilibrium pH 3.4 or 2.5 from initial concentration of 0.10 or 1.0 mmol dm−3 solution containing cations, respectively. The protonated material was efficient for Cs+ decontamination (ca. 100%) from drinking water spiked with 0.01 or 0.10 mmol dm−3 CsCl at volume to mass ratio (V/m) of 0.1–1.0 dm3 g−1. The protonated material can be regenerated after treatment of Cs+-exchanged material with 5 mol dm−3 HNO3 solution.
  • Toshiaki Matsubara, Chisato Sasamoto
    2013 Volume 86 Issue 12 Pages 1426-1434
    Published: December 15, 2013
    Released: December 15, 2013
    JOURNALS RESTRICTED ACCESS
    The reaction mechanism of the covalent binding of complement component 3 (C3) with antigen, which significantly contributes to the immune system by enhancing the phagocytosis of phagocytes, is examined by density functional theory (B3LYP). The covalent binding reaction takes place by the cleavage of the hydroxy O–H bond of the antigen on the thioester bond of the C3b formed by the activation of C3. We performed the calculations assuming a mechanism II that mimics that of serine protease in addition to the conventional mechanism I. Our calculations suggest that the conventional mechanism I proceeds with little participation of a His residue contrary to the previous consensus. Mechanism I, which has a large energy barrier of more than 30 kcal mol−1, is not realistic. On the other hand, in mechanism II, the energy barrier is about 10 kcal mol−1, due to an efficient mediation of a His residue by the collaboration with a neighboring Glu residue. Therefore, the covalent binding reaction of the activated C3b with the antigen was thought to proceed by mechanism II we proposed rather than by the conventional mechanism I.
  • Harsh Kumar, Varun Kundi, Meenu Singla, Sanjay Sharma
    2013 Volume 86 Issue 12 Pages 1435-1446
    Published: December 15, 2013
    Released: December 15, 2013
    [Advance publication] Released: October 05, 2013
    JOURNALS RESTRICTED ACCESS
    Densities, ρ, and speed of sound, u for binary mixtures dipropylene glycol monomethyl ether and tripropylene glycol monomethyl ether with 2-methyl-1-propanol, 3-methyl-1-butnaol, and 2-methyl-2-butanol at T = 288.15, 298.15, and 308.15 K and atmospheric pressure over the entire range of composition have been measured using an Anton–Paar DSA 5000M densimeter. Excess molar volumes VmE, and deviations in isentropic compressibilities ΔκS have been calculated from experimental densities and speeds of sound. Comparison of the results has been made with earlier results. Deviations in intermolecular free length and deviations in acoustic impedance have also been calculated. The results have been discussed in terms of intermolecular interactions between component molecules of the mixtures.
  • Yoshifumi Tanimoto, Chikako Udagawa, Akio Katsuki, Syou Maki, Shotaro ...
    2013 Volume 86 Issue 12 Pages 1447-1449
    Published: December 15, 2013
    Released: December 15, 2013
    [Advance publication] Released: September 13, 2013
    JOURNALS RESTRICTED ACCESS
    Effects of a weak magnetic field (<0.1 T) on silver dendrite formation were studied using a ferrite magnet. By application of a 87 mT field, the silver dendrite pattern changed considerably, although chemical yields of formed silver dendrite, formed copper ion, and consumed copper metal decreased very slightly.
  • Ukyo Yamashita, Pei-Shan Lee, Naoto Kuwamura, Nobuto Yoshinari, Takumi ...
    2013 Volume 86 Issue 12 Pages 1450-1452
    Published: December 15, 2013
    Released: December 15, 2013
    JOURNALS RESTRICTED ACCESS
    Treatment of a sulfur-bridged RhIII4ZnII4 octanuclear complex, (Δ)4-K6[(Zn4O){Rh(L-cys-κ2N,S)3}4] (K6[1]; H2cys: cysteine) with AgI in an acidic aqueous medium gave a new RhIII2AgI3 pentanuclear complex, (Δ)2-H4[Ag3{Rh(L-cys-κ2N,S)3}2]NO3 ([H42]NO3). The structure in [H42]+ that possesses unique, multiple intermolecular interactions was determined by X-ray crystallography.
  • Kazuaki Shibata, Masahito Yoshida, Takashi Takahashi, Motoki Takagi, K ...
    2013 Volume 86 Issue 12 Pages 1453-1465
    Published: December 15, 2013
    Released: December 15, 2013
    [Advance publication] Released: September 13, 2013
    JOURNALS OPEN ACCESS
    We have demonstrated various synthetic routes to heptaoxazole macrocyclic analogues of telomestatin and evaluated their inhibitory activities against telomerase. We synthesized three heptaoxazole macrocycles consisting of different numbers of methyloxazole moieties and another heptaoxazole analogue with a bromooxazole moiety instead of one of the two methyloxazole moieties found in the structure of telomestatin. The bromooxazole analogue underwent Suzuki–Miyaura coupling leading to six analogues having aromatic substituents on the oxazole moiety. The substituents on the oxazole moiety in the heptaoxazole macrocycles, which include a methyl group, a bromine atom, and aromatic substituents, did not affect the inhibitory activity of the overall molecule. In addition, three amine-linked analogues were synthesized by modification of the S-tert-butyl group in the bromooxazole analogue with amine-linked α-bromoacetamides. Notably, one of the amine-linked heptaoxazole analogues exhibited almost the same inhibitory activity as telomestatin.
  • Vladimir Ya. Lee, Risa Kato, Akira Sekiguchi
    2013 Volume 86 Issue 12 Pages 1466-1471
    Published: December 15, 2013
    Released: December 15, 2013
    [Advance publication] Released: October 05, 2013
    JOURNALS RESTRICTED ACCESS
    Metallocene (ferrocene and ruthenocene) derivatives, featuring three heavy group 14 elements in one of the cyclopentadienyl ligands, were synthesized by the reaction of the lithium disilagermacyclopentadienide [(tBu2MeSi)3GeSi2(CH)(CPh)]·[Li+(thf)] with either in situ-generated [Cp*Fe(acac)] or tetrameric [(Cp*RuCl)4] complexes. X-ray structural and NMR spectroscopic studies showed that both heavy ferrocene and heavy ruthenocene exhibited remarkable cyclic π-delocalization within the heavy cyclopentadienyl ligand and its powerful π-donating ability toward the transition metal.
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