Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 87 , Issue 11
Showing 1-19 articles out of 19 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for Creative Work for 2011
  • Tomohiro Iwai, Masaya Sawamura
    2014 Volume 87 Issue 11 Pages 1147-1160
    Published: November 15, 2014
    Released: November 15, 2014
    [Advance publication] Released: August 07, 2014
    JOURNALS FREE ACCESS
    Triethynylphosphines with bulky end caps such as triarylsilyl and triarylmethyl groups at alkyne termini have a novel molecular shape presenting a large, deep metal-binding cavity. The hollow-shaped triethynylphosphines functioned as effective ligands in the rhodium-catalyzed hydrosilylation of ketones with triorganosilanes due to the preferential formation of a mono-P-ligated rhodium species. Furthermore, the phosphines displayed remarkable rate enhancement in the gold(I)-catalyzed alkyne cyclization constructing six- to eight-membered ring compounds. It is proposed that the cavity in the ligand forces a nucleophilic center of the acetylenic compounds close to the gold-bound alkyne, making ring-closing anti attack feasible.
    Triethynylphosphines with bulky end caps such as triarylsilyl and triarylmethyl groups at alkyne termini have a novel molecular shape presenting a large, deep metal-binding cavity. The hollow-shaped triethynylphosphines functioned as effective ligands in the rhodium-catalyzed hydrosilylation of ketones with triorganosilanes and the gold(I)-catalyzed alkyne cyclization constructing six- to eight-membered ring compounds. Fullsize Image
     
The Chemical Society of Japan Award for Young Chemists for 2013
  • Yasuhide Inokuma, Makoto Fujita
    2014 Volume 87 Issue 11 Pages 1161-1176
    Published: November 15, 2014
    Released: November 15, 2014
    [Advance publication] Released: August 26, 2014
    JOURNALS FREE ACCESS
    Porous coordination networks have two distinctive characteristics: robust coordination frameworks and fluid pores wherein molecules are mobile. These characteristics allow solution chemistry to be performed in the crystalline state, thus enabling single-crystal X-ray observation of various reactions and host–guest complexation usually observed in solution. From this viewpoint, porous coordination networks can be used as a tool for visualizing solution-based chemical reactions. Using this tool, we have visualized chemical reactions within porous coordination network crystals to elucidate the reaction mechanisms and to determine the molecular structures of the products and intermediates. When the nanospace of porous coordination networks is cleverly designed on the basis of the structures of hollow molecular hosts in solution, solution-like host–guest chemistry is also reproduced in crystals, therefore enabling their visualization by X-ray crystallography. Furthermore, a new method based on crystalline-state host–guest chemistry was developed for the single-crystal X-ray analysis of trace amounts of noncrystalline compounds using porous coordination networks. In this account, we review and discuss the visualization of unique solution-like phenomena by single-crystal X-ray analysis using porous coordination networks as crystalline hosts.
    The robust framework and fluid pores of porous coordination networks allowed solution-like reactions and host–guest chemistry in the crystalline state. Labile reaction intermediates and trace amount of noncrystalline compounds have been visualized by single-crystal X-ray analysis. Fullsize Image
     
BCSJ Award Article
  • Keisei So, Yuki Kitazumi, Osamu Shirai, Kouhei Kurita, Hirofumi Nishih ...
    2014 Volume 87 Issue 11 Pages 1177-1185
    Published: November 15, 2014
    Released: November 15, 2014
    [Advance publication] Released: August 29, 2014
    JOURNALS FREE ACCESS
    Membrane-bound [NiFe]-hydrogenase (MBH) from Hydrogenovibrio marinus is an O2-tolerant enzyme and allows direct-electron-transfer (DET) bioelectrocatalysis for H2-oxidation. MBH is a promising bioelectrocatalyst for bioanode of enzymatic H2–O2 biofuel cells. From the practical viewpoint of electricity production, the H2-depletion near the electrode surface and the oxidative and reversible inactivation called “anaerobic inactivation” of [NiFe]-hydrogenases limit the H2-oxidation at high potentials. We have already proposed a gas-diffusion system to avoid inactivation in our previous study. In this research, we have analyzed the kinetics of the electrochemically induced anaerobic inactivation and the DET bioelectrocatalytic reaction of MBH on electrodes. When the inactivation is considered as a competitive inhibition-like reaction, the maximum value of the apparent Michaelis constant reaches 6.5 mM (at Ketjen Black-modified electrode) as analyzed in our kinetic model. Since the value is larger than the saturated H2-concentration in solution (0.74 mM), we conclude that high-speed H2-supply realized by a gas-diffusion electrode is essential to compete with the inactivation. Furthermore, a gas-diffusion bioanode with MBH can eliminate the H2-depletion near the electrode surface and has reached about 10 mA cm−2 at 0 V (vs. Ag|AgCl|sat. KCl electrode) under quiescent (passive) and H2-atmospheric conditions.
    The illustration of a gas-diffusion-type bioanode with an O2-tolerant [NiFe]-hydrogenase. The high-speed H2-supply for hydrogenase from the gas phase is effective for avoiding the anaerobic inactivation. We have analyzed the kinetic and thermodynamic properties to elucidate the effect. Fullsize Image
     
 
  • Atsushi Suzue, Hisashi Honda, Meiko Kadokura, Susumu Tanaka, Hideyuki ...
    2014 Volume 87 Issue 11 Pages 1186-1194
    Published: November 15, 2014
    Released: November 15, 2014
    [Advance publication] Released: August 01, 2014
    JOURNALS RESTRICTED ACCESS
    We have developed a new cooling material that uses vaporization heat. This system consists of poly(N-isopropylacrylamide) [P(NIPAAm)] and C2H4-permeated mesoporous silica [MCM(C2H4)]. Although the polymer can dissolve in water below ca. 32 °C (above this temperature, it is insoluble in water), 1H nuclear magnetic resonance spectroscopy showed that P(NIPAAm) adsorbed on MCM(C2H4) became water resistant below 32 °C. In addition, this system retained hydrophobic–hydrophilic switching at ca. 32 °C. When this material was used in a house model, the system absorbed water molecules from air during the night (below ca. 32 °C), and the room temperature was decreased by ca. 4 °C when the outside temperature exceeded ca. 32 °C. This system can cool rooms on hot days without using any electrical or human energy.
  • Yoshikazu Ninomiya, Masatoshi Kozaki, Shuichi Suzuki, Keiji Okada
    2014 Volume 87 Issue 11 Pages 1195-1201
    Published: November 15, 2014
    Released: November 15, 2014
    [Advance publication] Released: August 20, 2014
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    An artificial allosteric system composed of a zinc porphyrin moiety as a ligand-binding site, diphenylanthracene moieties as sterically bulky shielding units, and bipyridine terminals as Fe(II) ion-binding sites, was designed, synthesized, and characterized. The allosteric system forms an [Fe(bpy)3]-type complex in the presence of Fe(II) ions and induces a large conformational change in the alkyl side chains and shielding units, in which the anthracene groups would cover both the top and bottom of the porphyrin Zn(II) center. Consequently, the ligand-binding ability of the zinc porphyrin unit was allosterically suppressed. We found that the formation of the Fe(II) complex resulted in a 9.5-fold reduction in the binding constant between the zinc porphyrin and 3,5-bis(3,5-di-tert-butylphenyl)pyridine at 20 °C. Comparisons of entropy and enthalpy changes in the absence and presence of Fe(II) ions led to the conclusion that the allosteric suppression was mainly due to the destabilization of the Zn(II)-coordinated complex owing to the steric repulsion between the ligand and the shielding unit.
  • Mohammad Mehdi Alavianmehr, Sayed Mostafa Hosseini, Jalil Moghadasi, M ...
    2014 Volume 87 Issue 11 Pages 1202-1207
    Published: November 15, 2014
    Released: November 15, 2014
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    This work addresses a revised method of Fowler’s approximation for predicting the surface tension of refrigerant liquids using a Lennard–Jones (LJ) (12–6) model potential. The required LJ parameters were determined from the second virial coefficients. The major finding in this work was that the effective soft-sphere diameters of the studied LJ-like fluids were found to be a function of temperature and the acentric factor (ω). The reliability of the proposed method was determined by comparison with the literature over a temperature range of 85–384 K. From the 296 data points examined for the above-mentioned liquids, the overall average absolute deviation (AAD) was found to be 2.50%. The uncertainty in the surface tension prediction was ±6.85%. Additionally, surface thermodynamic functions, such as the surface entropy (SS) and surface enthalpy (HS), were also computed via our method. The uncertainties were found to be ±8.93% and ±11.64%, respectively. Furthermore, the AADs of the estimated SS and HS values were found to be 7.50% and 4.79%, respectively. Finally, our method was also employed to estimate the critical temperature of some alkanes with an uncertainty equal to ±5.56%.
  • Toratane Munegumi
    2014 Volume 87 Issue 11 Pages 1208-1215
    Published: November 15, 2014
    Released: November 15, 2014
    [Advance publication] Released: August 01, 2014
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    Asparagine is an important amino acid for abiotic polypeptide synthesis. In simulation experiments, it was obtained in 3.0% yield (based on the amount of consumed alanine) from alanine (100 mM) and formamide (200 mM) by contact glow discharge (Harada discharge) onto aqueous solutions. The present results suggest that asparagine could be abiotically synthesized from simple amino acids under possible primitive earth conditions.
  • Sumio Kato, Shinya Akiyama, Masataka Ogasawara, Takashi Wakabayashi, Y ...
    2014 Volume 87 Issue 11 Pages 1216-1223
    Published: November 15, 2014
    Released: November 15, 2014
    JOURNALS RESTRICTED ACCESS
    Pyrochlore-type Ln2Sn2−xZrxO7-supported Rh catalysts were prepared and their catalytic activity for NO reduction by C3H6 was investigated. High NO conversion was achieved with Rh/Ln2Sn2O7 (Ln = La, Nd, and Y) and Nd2SnZrO7 catalysts. The maximum NO conversion declined and the reduction temperature of the oxidized Rh species increased, upon substitution of Sn4+ with Zr4+. H2-TPR and XPS analyses of the catalysts suggested that the decrease in the NO reduction activity of the Rh/Ln2Sn2−xZrxO7 catalysts after aging at 900 °C may be due to diffusion of Rh into the support, decreasing the Rh reducibility.
  • Dinesh Pandey, Seema Kothari
    2014 Volume 87 Issue 11 Pages 1224-1230
    Published: November 15, 2014
    Released: November 15, 2014
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    The oxidation of some alkyl phenyl sulfides by benzimidazolium dichromate (BIDC) in dimethyl sulfoxide, to the corresponding sulfoxides, is first order with respect to BIDC. Michaelis–Menten type kinetics was observed with respect to sulfide. Thermodynamic parameters for the complex formation and activation parameters for the decomposition of the complex were calculated. The reaction is proton-catalyzed and the order is less than one. It appears that the BIDCH+ is the active electrophile. An intermediate of composition sulfide–BIDC–H+ has been envisaged. The high value of negative entropy of activation suggests a cyclic transition state in the rate-determining step. The reaction exhibited negative polar reaction constants and a small degree of steric hindrance. The rate of oxidation of sulfide was determined in 19 organic solvents. An analysis of the solvent effect by Swain’s equation indicated that though both the anion and cation solvating powers of the solvent contribute to the observed solvent effect, the role of cation solvation is major. A mechanism involving the rate-determining oxygen atom transfer in complex, formed by a nucleophilic attack of sulfide-sulfur on BIDCH+ in a rapid pre-equilibrium, is suggested to give corresponding sulfoxide via. a cyclic transition state.
  • Ching-Wen Chiu, Huey-Jen Su, Mei-Chin Lu, Wei-Hsien Wang, Jyh-Horng Sh ...
    2014 Volume 87 Issue 11 Pages 1231-1234
    Published: November 15, 2014
    Released: November 15, 2014
    [Advance publication] Released: July 31, 2014
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    Two new polyacetylenic compounds, callysponynes A (1) and B (2), were isolated from the marine sponge Callyspongia sp. The structures of the new metabolites were elucidated on the basis of their spectroscopic data and comparison of the NMR data with those of known analogues. Moreover, the absolute configuration of 1 was determined by Mosher’s method. Compounds 1 and 2 exhibited cytotoxic activity in vitro against MOLT-4, K-562, and HCT 116 cancer cell lines.
  • Takao Okazaki, Madoka Nakagawa, Toshikazu Kitagawa, Kenneth K. Laali
    2014 Volume 87 Issue 11 Pages 1235-1244
    Published: November 15, 2014
    Released: November 15, 2014
    [Advance publication] Released: July 31, 2014
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    Persistent protonation carbocations generated from hetero-PAHs containing oxygen atoms in their aromatic rings, dibenzo[b,d]furan (5), benzo[b]naphtho[1,2-d]furan (6), benzo[b]naphtho[2,3-d]furan (7), benzo[b]naphtho[2,1-d]furan (8), and dinaphtho[2,1-b:1′,2′-d]furan (9), were directly observed by NMR measurements in superacid. Compound 5 was protonated mainly at C(2) in FSO3H–SbF5 (1:1) or (4:1)/SO2ClF, and 6, 8, and 9 were protonated exclusively at C(5) in CF3SO3H or FSO3H/SO2ClF, whereas 7 was protonated at C(6) and C(11) to give two species in FSO3H/SO2ClF. Surprisingly, compound 5 resists protonation in FSO3H/SO2ClF to show NMR spectra corresponding to that of the intact material. Positive charge delocalization mapping for carbocations based on experimental Δδ13C values indicates limited delocalization in these systems. The chemical shifts and charge delocalization modes derived by DFT calculations agreed with the experimental results.
  • Zun-qi Liu, Yoshiki Ozawa, Atsushi Yagasaki
    2014 Volume 87 Issue 11 Pages 1245-1251
    Published: November 15, 2014
    Released: November 15, 2014
    [Advance publication] Released: August 04, 2014
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    Three oligomeric arylstibonates [H5(p-ClC6H4Sb)16O36]3−, [H4(p-ClC6H4Sb)16O36]4−, and [Na2(p-ClC6H4Sb)12O24(OH)6(H2O)3]4− have been synthesized as tetra-n-butylammonium salts and structurally characterized. The Sb16C16O36 core of the [H5(p-ClC6H4Sb)16O36]3− and [H4(p-ClC6H4Sb)16O36]4− anions is made up from arrays of close-packed O and C atoms and Sb atoms that occupy the octahedral interstices between the close-packed layers. The layers of close-packed O and C atoms are stacked in a sequence ABACA, resulting in an hch packing. The [Na2(p-ClC6H4Sb)12O24(OH)6(H2O)3]4− anion has an “opened-up” δ-Keggin structure.
  • Yasutaka Kuwahara, Wako Kaburagi, Tadahiro Fujitani
    2014 Volume 87 Issue 11 Pages 1252-1254
    Published: November 15, 2014
    Released: November 15, 2014
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    Levulinic acid and its esters, important intermediate chemicals produced from biomass resources, were converted to γ-valerolactone via a catalytic transfer hydrogenation process over silica-supported zirconia catalysts. Silica support with a higher surface area provided highly dispersed active zirconium oxide species, which exhibited superior catalytic activity to the conventional ZrO2 catalyst.
  • Maja C. Milenkovic, Nebojša I. Potkonjak
    2014 Volume 87 Issue 11 Pages 1255-1259
    Published: November 15, 2014
    Released: November 15, 2014
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    The influence of hydroxycinnamic acids (HCA) on the oxy-radical generated system, potassium iodide/hydrogen peroxide, was investigated through the enhancement of triiodide (I3) yield. Caffeic acid, chlorogenic acid, and p-coumaric acid were used as typical representatives of HCA. A linear correlation, with positive slopes, was found between absorption maximum of I3 at 351 nm and HCA concentration in all cases. The magnitude of enhanced I3 production was found to increase in the following order: p-coumaric acid < chlorogenic acid ≤ caffeic acid. A reaction mechanism, which includes negative influence of oxygen-centered free radicals on the I3 yield, was proposed. The enhanced production of I3 by HCA is attributed to their radical scavenging activity. Supported by literature data, results obtained in this study have showed the correlation between radical scavenging activities of HCA and their ability to enhanced I3 generation.
  • Arata Yajima
    2014 Volume 87 Issue 11 Pages 1260-1264
    Published: November 15, 2014
    Released: November 15, 2014
    [Advance publication] Released: August 15, 2014
    JOURNALS OPEN ACCESS
    It is well known that there are nine stereoisomers of inositol that are composed of seven achiral compounds with a pair of enantiomers. However, there is no report regarding larger inositol homologs, contiguously substituted cycloalkane polyols; therefore, the numbers of stereoisomers of such compounds are unknown. This study provides a simple method to calculate the number of stereoisomers of inositol homologs with any carbon number. The established formulae may be useful in attracting novice students to the field of organic chemistry.
  • Losetty Venkatramana, C. Narasimha Rao, Kasibhatta Siva Kumar, Ramesh ...
    2014 Volume 87 Issue 11 Pages 1265-1272
    Published: November 15, 2014
    Released: November 15, 2014
    [Advance publication] Released: August 26, 2014
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    Excess volume and speed of sound data for the ternary mixtures were reported at 303.15 K over the entire composition range for three ternary mixtures containing N-methylcyclohexylamine and toluene as common components and 1-alcohols as third component, namely 1-propanol, 1-butanol, and 1-pentanol. The experimental speed of sound and density of ternary mixtures were used to compute isentropic compressibility (s123) and the quantity Δks123, the difference between measured value and that computed from the constituent binary data. Further, the experimental ternary excess volume data were compared with calculated data obtained by empirical relations proposed by Redlich–Kister, Kohler, Tsao–Smith, and Hwang. The results were analyzed on the basis of intermolecular interactions between component molecules and also in terms of constituent binary data.
  • Minoru Nagashima, Takamasa Tsukamoto, Tetsuya Shimada, Donald A. Tryk, ...
    2014 Volume 87 Issue 11 Pages 1273-1277
    Published: November 15, 2014
    Released: November 15, 2014
    [Advance publication] Released: August 15, 2014
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    Cationic polyfluorinated surfactants (CnF2n+1CONH(CH2)2N+(CH3)2(CH2)15CH3Br; CnF (n = 1–3)) form reversed micelles in organic solvents such as toluene. The reversed micelle formation and their properties were studied by 1H NMR and 19F NMR measurements. The cmc (critical reversed micelle concentration) and the aggregation numbers of reversed micelles formed by fluorinated surfactants were determined. The aggregation numbers of reversed micelles formed by fluorinated surfactant were calculated to be 9–12 in toluene. According to the analysis of NMR longitudinal relaxation time T1, the polyfluorinated reversed micelles were shown to have a very unique microstructure, in which the perfluoroalkyl chains orientate at the interface between organic and water phase, and the mobility of perfluoroalkyl chains in reversed micelles was relatively larger than that of micelles and vesicles. The 19F-T1 values of fluorine nuclei in the terminal trifluoromethyl group of were 750 ± 23, 740 ± 29, and 855 ± 93 ms for C1F, C2F and C3F, respectively.
  • Hui-Yu Fang, Shu-Fen Chiou, Chokkalingam Uvarani, Zih-Hong Wen, Chi-Hs ...
    2014 Volume 87 Issue 11 Pages 1278-1280
    Published: November 15, 2014
    Released: November 15, 2014
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    A new polybrominated indole, 4,5,6-tribromo-2-methylsulfinylindole (1), and eleven known metabolites 212 were isolated from the acetone extract of the red alga Laurencia brongniartii. Structure of the new compound 1 was elucidated by 1D and 2D NMR experiments. Cytotoxic, anti-inflammatory, and antibacterial activities of these sulfur-containing polybromoindoles were evaluated.
  • Mohammad Hossein Fatemi, Kobra Samghani
    2014 Volume 87 Issue 11 Pages 1281-1287
    Published: November 15, 2014
    Released: November 15, 2014
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    In this work, the atmospheric lifetime of 60 halocarbons was estimated from their theoretical derived molecular descriptors by applying quantitative structure–property relationship (QSPR) methodology. The most relevant descriptors selected by stepwise multiple linear regression were used for developing linear and nonlinear models by using multiple linear regression and support vector machine, respectively. Here we show that the support vector machine model is finely capable for predicting the lifetime of halocarbons. The built support vector machine model was assessed by leave one out cross-validation (Q2 = 0.928, SPRESS = 0.479) and Y-randomization test (R2 = 0.222 for 25 trail) as well as external validation test. The developed support vector machine model was used for prediction of the atmospheric lifetime of some halocarbons with lifetimes not reported experimentally.
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