Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 81 , Issue 12
Showing 1-19 articles out of 19 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for 2007
  • Norio Miyaura
    2008 Volume 81 Issue 12 Pages 1535-1553
    Published: December 15, 2008
    Released: December 12, 2008
    JOURNALS FREE ACCESS
    Metal-catalyzed B–C and C–C bond-forming reactions of organoboronic acids that have been pursued in the past three decades by our group are summarized in this article. B–C bond-forming reactions for the synthesis of organoboronic acid derivatives include metal-catalyzed addition reactions of pinacolborane or catecholborane (hydroboration), bis(pinacolato)diboron (diboration), and alkylthioboranes (thioboration) to alkenes, alkynes, 1,3-alkadienes, or 1,2-alkadienes (allenes). Other B–C bond-forming reactions include coupling reactions of pinacolborane or bis(pinacolato)diboron for borylation of C–halogen bonds with palladium catalysts and C–H bonds of arenes and alkenes with iridium catalysts. These reactions have provided a convenient new access to aryl-, 1-alkenyl-, allyl-, or benzylboronates. Metal-catalyzed C–C and C–N bond-forming reactions using boronic acid derivatives include synthesis of novel cyclic triolborate salts for palladium- or copper-catalyzed cross-coupling reactions with organic halides or amines, rhodium- or palladium-catalyzed 1,4-addition reactions of arylboronic acids to α,β-unsaturated carbonyl compounds and rhodium-catalyzed addition of aryl- and 1-alkenylboronic acids to aldehydes and imines.
    Syntheses of organoboronic acid derivatives via metal-catalyzed hydroboration and diboration of alkenes and alkynes, or borylation of C–halogen bonds and C–H bonds, and synthetic applications of 1-alkenyl-, aryl-, allyl-, and benzylboronic acids or esters thus synthesized. Fullsize Image
The Chemical Society of Japan Award for Creative Work for 2006
  • Toshimi Shimizu
    2008 Volume 81 Issue 12 Pages 1554-1566
    Published: December 15, 2008
    Released: December 12, 2008
    JOURNALS FREE ACCESS
    This review article focuses on the self-assembly of amphiphilic molecules into discrete, hollow cylindrical tubular architectures (organic nanotubes). Research on nanotube formation from dumbbell-shaped peptide lipids, 1-O-glucopyranoside and 1-N-glucopyranosylamide lipids, and wedge-shaped bolaamphiphilic glycolipids with carboxylic, amino, or oligoglycine groups at one end has been outlined with their characteristic self-assembly. Finally, recent progress in mass production, dimension control, and novel functions of organic nanotubes are described.
    This review article focuses on the self-assembly of amphiphilic molecules into discrete, hollow cylindrical tubular architectures. Recent progress on dimension and size control of the self-assembled nanotubes, massive production, and their novel functions are also described. Fullsize Image
BCSJ Award Article
  • Kazuhiko Kandori, Kiri Tada, Masao Fukusumi, Yoshiaki Morisada
    2008 Volume 81 Issue 12 Pages 1567-1574
    Published: December 15, 2008
    Released: December 12, 2008
    JOURNALS FREE ACCESS
    Calcium phosphate particles were prepared by aging a solution of CaCl2 and sodium triphosphate (sodium tripolyphosphate, Natpp: Na5P3O10) at 100–150 °C for 16 h in a Teflon-lined screw-capped Pyrex test tube. The rod-like and spherical particles were precipitated at an extremely fast rate of reaction under 100 °C. The spherical particles were only produced in a very narrow region at 100 °C by aggregation of primary small particles. The rod-like particles were CaNa2P2O7·4H2O but the uniform spherical ones were amorphous and the latter ones were crystallized to β-Ca2P2O7 after being calcined above 600 °C. The aging temperature drastically varied the particle shape under conditions for producing uniform spherical particles; solid spherical particles were produced up to the aging temperature of 115 °C but balloon-like hollow spheres were precipitated at 120 °C. However, large and irregular agglomerates made up of extremely small rod-like particles were precipitated after aging the solution above 125 °C. TEM observation and ICP-AES measurements revealed that the balloon-like hollow spheres were produced by dissolving the interior of solid spherical particles after reinforced their shell by the adsorption of unhydrolyzed tpp. The spherical and balloon-like calcium phosphate particles with amorphous crystal form showed high selective adsorption of H2O by rehydration of Ca2+ ions by penetrated H2O molecules into the particles. In particular, the balloon-like hollow spheres of calcium phosphate may hold potential as drug delivery vehicles and have biocompatibility advantages.
    Calcium phosphate particles were prepared by aging a solution of CaCl2 and Na5P3O10 at 100–150 °C. The solid spherical particles were produced up to the aging temperature of 115 °C but transparent balloon-like hollow spheres were precipitated at 120 °C. Fullsize Image
  • Yun-Lei Teng, Qiang Xu
    2008 Volume 81 Issue 12 Pages 1575-1579
    Published: December 15, 2008
    Released: December 12, 2008
    JOURNALS RESTRICTED ACCESS
    Laser-ablated dysprosium hydride has been co-deposited at 4 K with carbon monoxide in excess argon. Product HDyCO has been formed in the present experiments and characterized using infrared spectroscopy on the basis of the results of the isotopic shifts, mixed isotopic splitting patterns, stepwise annealing, and the comparison with theoretical predictions. Density functional theory calculations have been performed. The agreement between the experimental and calculated vibrational frequencies, and isotopic shifts supports the identification of the molecule from the matrix infrared spectra. A plausible reaction mechanism has been proposed to account for the formation of this molecule.
  • Kazumasa Okada, Masamichi Sakai, Keiichi Ohno
    2008 Volume 81 Issue 12 Pages 1580-1583
    Published: December 15, 2008
    Released: December 12, 2008
    JOURNALS RESTRICTED ACCESS
    Fragmentation of 2-amino-3-methylpyridine has been investigated by electron impact in the carbon and nitrogen K-shell excitation regions with a comparison to that of 3-methylpyridine. Fragment ions were analyzed with a quadrupole mass spectrometer. Yields of the NCNH2+ and C5H3+/C4HN+ fragment ions characteristically increase at the N 1s edge when compared to the C 1s excitation/ionization and valence ionization. This observation indicates that a valence electron forming the C–N bond in the pyridine ring is preferentially released through an Auger electron emission at the N 1s edge. The fragment ions produced via a hydrogen atom shift were observed as well.
  • Yoko Iizumi, Toshiya Okazaki, Minfang Zhang, Masako Yudasaka, Sumio Ii ...
    2008 Volume 81 Issue 12 Pages 1584-1588
    Published: December 15, 2008
    Released: December 12, 2008
    JOURNALS RESTRICTED ACCESS
    Although fullerenes have been known as strong photosensitizers (PS), the quantitative evaluations of their activities have been insufficient, especially in water. We measured the near-infrared (NIR) emission from the singlet oxygen (1O2) produced by C60 and C70 dissolved in water using dispersants of γ-cyclodextrin (γ-CD) or poly(vinylpyrrolidone) (PVP), and estimated the 1O2 generation efficiencies. The obtained results show that C60 and C70 can generate 1O2 with 2–3 times higher efficiencies than the well-known PS, rose bengal (RB), and the 1O2 generation efficiencies depends on the dispersants. Phototoxicity of C60 and C70 were also examined by using rat fibroblast cell line (5RP7). The cell viabilities after irradiations were consistent with the corresponding 1O2 generation efficiencies. Our results that fullerenes have high 1O2 generation efficiencies assure the potential applications of fullerenes as PS for photodynamic therapy (PDT).
  • Fuyuki Sato, Miki Tsukano, Koki Sakamoto, Wakako Umemoto, Takeshi Hash ...
    2008 Volume 81 Issue 12 Pages 1589-1594
    Published: December 15, 2008
    Released: December 12, 2008
    JOURNALS RESTRICTED ACCESS
    Amphiphilic azoprobes having a crown ether moiety (15C5–Azo–Cn; n=4, 6, 8, and 12 and 18C6–Azo–Cn; n=4, 6, and 8) were synthesized. We examined the effect of alkyl spacer length of the amphiphilic azoprobes on the spectral response to alkali metal ions in water by UV–vis spectral and 1H NMR measurements. 15C5–Azo–Cn exhibited self-assembly in response to K+ selectively and the most selective response to K+ was observed for an azoprobe possessing a hexyl spacer unit (15C5–Azo–C6). 15C5–Azo–C12 formed nano-size aggregates. 18C6–Azo–Cn (n=6 and 8) showed Cs+ selectivity and its molecular aggregation behavior was similar to that of 15C5–Azo–Cn.
  • Michael Schmittel, Hengwei Lin
    2008 Volume 81 Issue 12 Pages 1595-1598
    Published: December 15, 2008
    Released: December 12, 2008
    JOURNALS RESTRICTED ACCESS
    As a proof of principle for the overload displacement strategy a luminescent ruthenium(II) azacrown ether phenanthroline with restrained sensoric properties has been converted into a light-up chemosensor for lead(II) ions by overloading the system with copper(II) ions.
  • Mitsuru Sakai, Minoru Furuya, Hiroko Endo, Kazuyoshi Yamaoka, Shiro Ko ...
    2008 Volume 81 Issue 12 Pages 1599-1604
    Published: December 15, 2008
    Released: December 12, 2008
    JOURNALS RESTRICTED ACCESS
    Affinity chromatography is widely utilized as a tool in biomedical research and biotechnology. This purification method provides increased sensitivity for various kinds of analyses, such as mass spectrometry. This report describes a protocol to identify a specific binding protein for a bioactive compound (BAC) using BAC-affinity beads and nanoflow liquid chromatography tandem mass spectrometry (nano-LC/MS/MS). After the target protein was digested directly on the affinity beads, the obtained peptide fragments were determined by MS analysis. The binding-specificity was shown by a competition experiment using beads lacking bound BAC. In this study, we describe two examples for benzenesulfonamide- and methotrexate-binding proteins.
  • Satoko Hayashi, Waro Nakanishi
    2008 Volume 81 Issue 12 Pages 1605-1615
    Published: December 15, 2008
    Released: December 12, 2008
    JOURNALS RESTRICTED ACCESS
    Homonuclear Z···Z (Z=O, S, Se, and Te) interactions are investigated employing naphthalene 1,8-positions in 1,8-(MeZ)2C10H6 (1a1d: Z=O (a), S (b), Se (c), and Te (d)), 1-MeZ-8-PhZC10H6 (2a2c), and 1,8-(PhZ)2C10H6 (3a3d). Three types of structures are detected for 1a3d: BB for 1a, CC for 1b, 1c, 2c, and 3d, and AB for 2a, 2b, and 3a3c, in our definition, by X-ray crystallographic analysis, although some have already been reported. Quantum chemical calculations are performed on 1a1d and 3c, together with model c, Me(H)Se···Se(H)Me, to elucidate how the fine structures are controlled by the interactions. AB are stabilized by the np(Z)···σ*(Z–C) 3c–4e interactions for Z=S, Se, and Te. While CC are substantially stabilized by the n(Z)···σ*(Z–C) interactions, they are well summarized as the disappearance of the nodal plane in π*(Z···Z). Factors to control the fine structures are clarified and visualized using the HOMO or HOMO−1 of model c. The energy profile of model c helps us to imagine the whole picture of the noncovalent Se···Se interactions.
  • Jui-Hsin Su, Ching-Li Lo, Yi Lu, Zhi-Hong Wen, Chiung-Yao Huang, Chang ...
    2008 Volume 81 Issue 12 Pages 1616-1620
    Published: December 15, 2008
    Released: December 12, 2008
    JOURNALS RESTRICTED ACCESS
    Four new polyhydroxylated steroids (14) were isolated from a Formosan soft coral Sinularia sp. The structures of these metabolites were determined on the basis of spectroscopic (IR, MS, and 1D and 2D NMR) analyses. Among these metabolites, 3 and 4 are rarely found marine steroids with a C-9/C-10 double bond. Compounds 1 and 2 have shown significant inhibition of the accumulation of the pro-inflammatory COX-2 protein of LPS-stimulated RAW264.7 macrophage cells at 10 μM.
  • Yoshihiro Matano, Takeshi Suzuki, Takaharu Iwata, Tomonori Shinokura, ...
    2008 Volume 81 Issue 12 Pages 1621-1628
    Published: December 15, 2008
    Released: December 12, 2008
    JOURNALS RESTRICTED ACCESS
    Substituent effects on the oxidizing ability of tetraarylbismuthonium tetrafluoroborates in alcohol oxidation are reported. Intermolecular and intramolecular competition experiments on geraniol oxidation by the combined use of tetraarylbismuthonium tetrafluoroborates and N,N,N′,N′-tetramethylguanidine (TMG) have revealed that the oxidizing ability of the bismuthonium salt increases by the introduction of methyl groups at the ortho position and an electron-withdrawing group at the para position of the aryl ligands. The intermolecular and intramolecular H/D kinetic isotope effects observed for the competitive oxidation of p-bromobenzyl alcohols have shown that the present oxidation reaction consists of fast pre-equilibrium leading to alkoxytetraarylbismuth(V) intermediates (first step) and α-hydrogen abstraction by the aryl ligand attached to the bismuth (second step). The experimental results demonstrate that the electron-deficient aryl ligands enhance the electrophilicity at the bismuth center to put forward the first step and that the bulky ligands destabilize the alkoxybismuth(V) intermediates to accelerate the second step. The newly explored mesityl- and 2,6-xylyltriarylbismuthonium salts have proven to convert primary and secondary alcohols to the corresponding carbonyl compounds with high efficiency under mild conditions. A remarkable steric effect of these oxidants has also been exhibited in the chemoselective oxidation between primary and secondary benzylic alcohols.
  • Hideo Tomioka, Norio Nakane, Jiro Tatsugi
    2008 Volume 81 Issue 12 Pages 1629-1637
    Published: December 15, 2008
    Released: December 12, 2008
    JOURNALS RESTRICTED ACCESS
    The structures, energies, and thermal stabilities of E and Z isomers of a singlet, a triplet, and a quintet states of naphthalene bearing nitrene and carbene units on adjacent (1,2- and 3,2-) positions were examined by DFT methods. For both 1,2- and 3,2-isomers, singlet quinoidal diradicals were predicted to be the ground state with the corresponding triplet state lying slightly higher in energy. The quintet state of the 1,2-isomer was found to lie approximately 30 kcal mol−1 (1 kcal = 4.184 kJ) above the ground state, while that of the 3,2-isomer was predicted to lie only 9 kcal mol−1 above the ground state. This difference is discussed in terms of loss of energy due to aromaticity between the two isomers. Thermal stability of the ground state in terms of ring-opening and -closure reactions indicated that both isomers prefer to decay by the latter process forming naphtho[b]azetes. Attempts to generate and characterize the ground state quionoidal diradical by matrix IR spectroscopic methods in Ar at low temperature all resulted in the detection of the azete.
  • Tsong-Long Hwang, Mei-Ru Lin, Wei-Tse Tsai, Hsiao-Chien Yeh, Wan-Ping ...
    2008 Volume 81 Issue 12 Pages 1638-1646
    Published: December 15, 2008
    Released: December 12, 2008
    JOURNALS RESTRICTED ACCESS
    Six new polyoxygenated briarane-type diterpenoids, briaexcavatins Q–T (14) and robustolides J (5) and K (6), were isolated from a cultured octocoral Briareum excavatum and a sea whip gorgonian coral Ellisella robusta, respectively. The structures of briaranes 16 were established by spectroscopic methods. Briarane 3 exhibited weak cytotoxicity toward CCRF-CEM tumor cells and briaranes 5 and 6 displayed inhibitory effects on superoxide anion generation by human neutrophils.
  • Takashi Hisatomi, Kentaro Teramura, Jun Kubota, Kazunari Domen
    2008 Volume 81 Issue 12 Pages 1647-1656
    Published: December 15, 2008
    Released: December 12, 2008
    JOURNALS RESTRICTED ACCESS
    Physical properties of zinc titanium nitride oxides (ZnxTiOyNz) were studied as a novel photocatalytic material with visible light activity. A series of ZnxTiOyNz having a spinel structure were obtained by nitriding an oxide precursor derived from a polymerized complex method under a high-temperature NH3 flow for various durations. The ZnxTiOyNz spinel obtained was metastable because the Zn in the nitride oxide volatilized during the nitridation process. Both Zn and Ti cations of the ZnxTiOyNz spinel were essentially located in the same cation sites as the inverse spinel phase of Zn2TiO4; Zn species at the octahedral sites were volatilized in preference to those at tetrahedral sites. The bandgap energy of the ZnxTiOyNz spinel decreased as the amount of N species was increased, eventually stabilizing at 2.3 eV.
  • Hirohito Ueno, Norihiko Gokan, Yoshiharu Nakano, Masao Kaneko
    2008 Volume 81 Issue 12 Pages 1657-1662
    Published: December 15, 2008
    Released: December 12, 2008
    JOURNALS RESTRICTED ACCESS
    The effect of bulk natural convection on various chemical processes was investigated in a tight polysaccharide gel reactor composed of a few percent polysaccharide and excess water. It was elucidated that molecular self-diffusion coefficient (D cm2 s−1) in the gel is the same as in liquid water, but bulk natural convection is entirely prohibited making the molecular transport in these gels remarkably slower than in liquid water. Three-dimensional (3D) diffusion of Ru(bpy)32+ in a tight 0.125 wt % agarose gel took place only by molecular self-diffusion since bulk natural convection is prohibited, and the diffusion length agreed well with the theoretical 3-dimensional (3-D) self-diffusion length calculated from D. 2D diffusion of thionine in a polysaccharide gel also agreed well with the theoretical 2-D self-diffusion length showing also the absence of bulk natural convection. The chemical processes in the tight gel reactor in relevance to natural convection effects are discussed in terms of the time scale of the chemical process and the corresponding self-diffusion length of the reactants. For short time scale processes (ns to s) such as photochemical and electrochemical reactions, the process was not affected by bulk natural convection, but for a longer time scale (0.1 to 10 h) the effect of bulk natural convection was large.
  • Nattha Jiravanichanun, Kazuya Yamamoto, Hiroaki Yonemura, Sunao Yamada ...
    2008 Volume 81 Issue 12 Pages 1663-1668
    Published: December 15, 2008
    Released: December 12, 2008
    JOURNALS RESTRICTED ACCESS
    Multilayer hybrid films of imogolite nanofibers and water-soluble poly(p-phenylene) (WS-PPP) were prepared by two assembly methods. Layer-by-layer (LBL) assembly and spin-assembly were applied to fabricate the hybrid films. The deposited amount of WS-PPP per thickness was not significantly different between the two methods. However, the spin-assembly method gave significant orientation of imogolite nanofibers aligned in the radial direction, while imogolite nanofibers were randomly networked in the LBL film. The results suggested that lyotropic mesophase of imogolite and centrifugal and shear forces influenced a self-assembly of imogolite fibers oriented in a force-inducing direction.
  • Rikako Tsukamoto, Masahiro Muraoka, Yoshitsugi Fukushige, Hiromichi Na ...
    2008 Volume 81 Issue 12 Pages 1669-1674
    Published: December 15, 2008
    Released: December 12, 2008
    JOURNALS RESTRICTED ACCESS
    The outer surface of horse spleen apoferritin (HsAFr) was chemically modified by poly(ethylene glycol) (PEG) to prevent bulk precipitation during artificial biomineralization of the cobalt-oxide core (Co3O4) in its cavity. Two kinds of PEGs, with average molecular weights of 2000 and 5000 were covalently attached (PEGylation) on the outer surface of HsAFr and suppressed the bulk precipitation drastically, whereas neither free PEGs nor short PEG (N-{2-[2-(2-methoxyethoxy)ethoxy]ethanoyloxy}succinimide) performed such suppression. The PEGylated HsAFr accommodated fully developed Co3O4 cores and achieved a high yield of homogeneous Co3O4 nanoparticles. Investigation of the early biomineralization stage suggested that [CoIIIO] complex ions were accumulated around the negatively charged outer surface of HsAFr.
  • Mohammad Abul Hasnat, Isao Ishibashi, Kiwako Sato, Ryoko Agui, Tsuyosh ...
    2008 Volume 81 Issue 12 Pages 1675-1680
    Published: December 15, 2008
    Released: December 12, 2008
    JOURNALS RESTRICTED ACCESS
    Electrocatalytic reduction of nitrate ions (NO3) was carried out over Cu–Pd and Cu–Pt bimetallic cathodes, which were deposited on a Nafion-117 H+-conducting polymer membrane. By applying DC current to the membrane–electrode assembly (MEA), H2 evolved on the cathode caused monotonic degradation of NO3 in the cathode compartment. The NO3 reduction proceeded in a consecutive manner and copper increased significantly the catalytic activity for the first step from NO3 to NO2. The Cu–Pd and Cu–Pt cathodes, with 38 and 20 mol % Cu, respectively, exhibited the highest reduction rate. The product selectivity was also dependent on the content of Cu. The Cu–Pd cathode showed a lower selectivity to NO2 and a higher selectivity to NH4+, because the catalytic activity for NO2 reduction is high. The rate of nitrate reduction was increased by supplying CO2, which plays a role of a buffer to keep pH lower than 7 and promotes the reaction, 2NO3+5H2→N2+2OH+4H2O.
feedback
Top