Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 81 , Issue 2
Showing 1-18 articles out of 18 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for 2004
  • Tadayuki Imanaka
    2008 Volume 81 Issue 2 Pages 171-182
    Published: February 15, 2008
    Released: February 12, 2008
    JOURNALS FREE ACCESS
    I reflect on some of our studies on the hyperthermophilic archaeon, Thermococcus kodakaraensis KOD1 and its enzymes. The strain can grow at temperatures up to 100 °C, and also represents one of the simplest forms of life. As expected, all enzymes, DNA, and cytoplasmic membrane displayed remarkable thermostability, and we have determined some of the basic principles that govern this feature. To our delight, many of the enzymes exhibited unique biochemical properties and novel structures not found in mesophilic proteins. Here, I will focus on some enzymes whose three-dimensional structures are characteristic of thermostable enzymes. I will also add some examples on the stabilization of DNA and cytoplasmic membrane.
    We isolated the hyperthermophilic archaeon, Thermococcus kodakaraensis KOD1, which can grow at temperatures up to the boiling point. As expected, all enzymes, DNA, and cytoplasmic membrane displayed remarkable thermostability, and we have determined some of the basic principles that govern this feature. Fullsize Image
The Chemical Society of Japan Award for Young Chemists for 2006
  • Moritoshi Sato
    2008 Volume 81 Issue 2 Pages 183-192
    Published: February 15, 2008
    Released: February 12, 2008
    JOURNALS FREE ACCESS
    Fluorescence imaging could be the most powerful technique available for observing spatial and temporal dynamics of molecular processes in living cells, if fluorescent indicators for the relevant molecular processes become available. Therefore, we have been developing fluorescent indicators for a variety of cellular signaling processes, including second messengers and protein phosphorylation reactions. Using the indicators, we have visualized spatial and temporal dynamics of these molecular events in single living cells. The present fluorescent indicators are becoming an indispensable tool for understanding the complex mechanism of the signal transduction in living cells and for screening pharmaceuticals that inhibit or promote molecular processes in the cell.
    Our research on the development of novel methods are reviewed that allowed us to visualize spatial and temporal dynamics of key molecular processes in living cells. Fullsize Image
BCSJ Award Article
  • Shinsaku Fujita
    2008 Volume 81 Issue 2 Pages 193-219
    Published: February 15, 2008
    Released: February 12, 2008
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    Monosubstituted alkanes as stereoisomers have been counted combinatorially by regarding them as nested planted promolecules, where the resulting numbers have been itemized with respect to carbon content (k), to the number of asymmetric carbons (l), as well as to the number of pseudoasymmetric carbons (m). To accomplish such itemization, the definitions of RS-stereogenic centers, asymmetric centers, and pseudoasymmetric centers have been discussed in detail. Each itemized number has been obtained as the coefficient of the term xkylzm appearing in a respective generating function, which has been derived by following Fujita’s proligand method (S. Fujita, Theor. Chem. Acc. 2005, 113, 73; 2005, 113, 80; S. Fujita, Theor. Chem. Acc. 2006, 115, 37). The itemized values up to carbon content 30 have been listed in tabular forms, which are distinctively concerned with achiral stereoisomers, chiral stereoisomers, and constitutional isomers (graphs).
    Monosubstituted alkanes are combinatorially enumerated, where the stereoisomer numbers are itemized with respect to carbon content, the number of asymmetric centers (*), and the number of pseudoasymmetric centers (†). Fullsize Image
 
  • Jalil Moghadasi, Mohammad Mehdi Papari, Delara Mohammad-Aghaie, Antoni ...
    2008 Volume 81 Issue 2 Pages 220-234
    Published: February 15, 2008
    Released: February 12, 2008
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    In previous work, we have correlated the dilute gas transport properties of alternative refrigerant mixtures. The purpose of this theoretical study was to obtain, using two-iterative inversion of the corresponding states of viscosity, effective and isotropic pair potential energies for a group of refrigerants: methane, ethane, propane, butane, R22, R123, R124, R134a, R152a, R32, and R143a. Employing the inverted pair potential energies, the Chapman–Enskog scheme could be used reasonably well to reproduce transport properties, except the thermal conductivity. The thermal conductivity was determined using the Huber scheme, wherein the use of the inverted pair potential energies is discussed at length. In the wide temperature range of 200K<T<1000K, the accuracies of the calculated viscosities, self-diffusion coefficients, and thermal conductivities were 2%, 4%, and 8% (at most 10%), respectively.
  • Hirotoshi Mori, Eisaku Miyoshi
    2008 Volume 81 Issue 2 Pages 235-240
    Published: February 15, 2008
    Released: February 12, 2008
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    The possibility for photon-mode memory writing of [{Co(Hbim)(C6H4O2)(NH3)2}2] (Hbim = 2,2′-biimidazole) is examined from results obtained by spin–orbit complete active space configuration interaction (SO-CASCI) calculations. The spin-crossover phenomenon in the proton–electron-coupled complex monomer [Co(Hbim)(C6H4O2)(NH3)2] is a key process in memory writing to the complex dimer. We found a possibility of an efficient spin-crossover in the monomer. UV (ca. 300 nm) irradiation of the monomer 1A′ state leads to a spin-crossover into the high-spin 5A′ state. The back photoreaction from the 5A′ to 1A′ state is also possible with vis (ca. 600–700 nm) excitation. In these spin-crossover and back spin-crossover reactions, the intermediate triplet states, 13A″ and 23A″, are found to participate.
  • Jun-ichi Aihara
    2008 Volume 81 Issue 2 Pages 241-247
    Published: February 15, 2008
    Released: February 12, 2008
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    Aromaticity has been viewed as multidimensional, because different scales of aromaticity sometimes make different predictions as to the aromaticity of a polycyclic π-system. Our graph theory of aromaticity and ring-current diamagnetism enables us to interpret magnetic scales of aromaticity in terms of aromatic stabilization energy (ASE). We have now no reason to regard any magnetic scale of aromaticity as a scale orthogonal to the energetic ones. Aromaticity is one-dimensional in this sense and should in principle be described in terms of ASE. Other scales of aromaticity, such as geometric ones, must likewise reflect ASE to varying extents, although it is not easy to interpret them analytically in energetic terms.
  • Isao Kanesaka, Eiji Mitsuhashi
    2008 Volume 81 Issue 2 Pages 248-253
    Published: February 15, 2008
    Released: February 12, 2008
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    Infrared spectra of formamide are wholly simulated for the in-plane modes on the basis of a damped oscillator model, where force constants and intensity parameters and damping constants defined in every Cartesian displacement coordinate are simultaneously adjusted. Band constants evaluated from the damped oscillator model are compared with those observed. The present analysis reveals the relation in band widths among all vibrational modes, in other words, the origin of band widths. Large values of the damping constant on H in the NH2 group result from inter-molecular interactions, i.e., hydrogen bonds. Unexpected results of the damping constants on O, C, and N are discussed with van der Waals forces and intra-molecular interactions.
  • Katsuhiro Tamura, Toshio Watanabe, Takayoshi Ishimoto, Hiroaki Umeda, ...
    2008 Volume 81 Issue 2 Pages 254-256
    Published: February 15, 2008
    Released: February 12, 2008
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    FMO-MO (Molecular orbitals (MOs) of the fragment MO (FMO) method) for (−)-epicatechin gallate were calculated to examine the dependency of the accuracy on the fragmentation patterns and on the basis set, and the results were compared to those obtained using conventional MO calculations. Results also show that the FMO-MO can be used as the initial guess in self-consistent field calculations.
  • Gamal Abdel-Hafeez Mostafa, Atef Mohammed Homoda
    2008 Volume 81 Issue 2 Pages 257-261
    Published: February 15, 2008
    Released: February 12, 2008
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    The construction and general performance characteristics of two novel potentiometric membrane sensors responsive to bismuth are described. The sensors are based on the use of ion-association complexes of tetraiodobismate(III) (TIB) anion with polyoxyethylene(10) octyl phenyl ether (1) and tris(1,10-phenanthroline)iron(II) (2) as exchange sites in a carbon paste matrix. The sensors show fast, stable, and near-Nernstian response for the mono-charged anion of tetraiodobismate(III) over the concentration range 1×10−3–1×10−6 mol dm−3 at 25 °C over the pH range 4.0–9.0 and 3.0–8.0 with an anionic slope of 51.5±0.5 and 53.0±0.4 per concentration decade for tetraiodobismate(III)-1 and -2 (sensor-1 and sensor-2), respectively. The lower detection limit was 4×10−6 and 2×10−6 mol dm−3 with a response time of 20–40 s for sensor-1 and sensor-2 in the same order. The selectivity coefficients for bismuth relative to a number of interfering anions and iodide complexes of some metal ions were investigated. Direct potentiometric determination of 1–200 μg cm−3 of bismuth in aqueous solution showed an average recovery of 98.4% and a mean relative standard deviation of 1.5% at 80.0 μg cm−3. The determination of bismuth(III) in suppositories and ointment dosage form in the present study was comparable with the British pharmacopoeia method.
  • Nanhai Singh, Bandana Singh
    2008 Volume 81 Issue 2 Pages 262-267
    Published: February 15, 2008
    Released: February 12, 2008
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    Heterobimetallic ion-pair complexes of the type [M(bpy)3][M′(cdc)2] (M = Fe2+, Co2+, and Ni2+; M′ = Ni2+ and Cu2+; bpy = 2,2′-bipyridine, cdc2− = cyanoiminomethanedithiolate (C2N2S22−)) have been synthesized by reacting a solution of K2[M′(cdc)2] with [M(bpy)3]X2 (X = Cl and SO42−) in equimolar ratio. These complexes have been characterized by elemental analysis, solution conductance, and magnetic susceptibility measurements, IR, 1H and 13C NMR, ESR, and UV–visible spectroscopies and pressed pellet conductivity technique. Three of these salts show behavior of semiconductors in the 295–443 K temperature range while the remaining are insulators. The lowering of the ν(C≡N) frequency in I2-doped products of these complexes as compared to the parent complexes clearly reveals interaction of the C≡N group of the ligand cdc2− resulting in decrease in ν(C≡N) bond order and in turn partial reduction of I2. The I2-doped products of the majority of the complexes show enhanced room-temperature conductivity and exhibit semiconducting behavior.
  • Takeshi Kawasaki, Chihiro Kachi-Terajima, Toshiaki Saito, Takafumi Kit ...
    2008 Volume 81 Issue 2 Pages 268-273
    Published: February 15, 2008
    Released: February 12, 2008
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    Two novel 3D network coordination polymers {Mn(L)2[Ag(CN)2]2}{Mn(H2O)2[Ag(CN)2]2} (L = 4-CNpy (1) or py-4-aldoxime (2)) (4-CNpy = 4-cyanopyridine; py-4-aldoxime = pyridine-4-aldoxime) were synthesized and characterized by using single-crystal X-ray analysis and magnetic measurements. Both complexes have two distinct octahedral manganese atoms, Mn(1) and Mn(2), linked by a [Ag(CN)2] unit. The pyridine ring of two Ls coordinate at the apical positions of Mn(1). On the other hand, at the apical positions of Mn(2), two H2O are coordinated. The apical axis of Mn(1) is not parallel to the apical axis of Mn(2). Therefore, {Mn[Ag(CN)2]2} networks in 1 and 2 are distorted and form three-dimensional (3D) frameworks. There are large channels in the 3D networks; however, triple interpenetration was found in 1 and 2. From the temperature dependence of magnetic susceptibility, there is very weak antiferromagnetic interaction between the Mn atoms bridged by a [Ag(CN)2] unit in 1 and 2.
  • Naoya Hosoda, Yoshihiro Iogawa, Yuichi Shimada, Masatoshi Asami
    2008 Volume 81 Issue 2 Pages 274-277
    Published: February 15, 2008
    Released: February 12, 2008
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    Catalytic asymmetric borane reduction of prochiral ketones was examined in the presence of (S)-2-(anilinomethyl)pyrrolidine. Chiral secondary alcohols were obtained with moderate to high enantiomeric excesses (up to 96% ee).
  • Nobuhiro Ito, Hiroyoshi Esaki, Tsuneaki Maesawa, Eikoh Imamiya, Tomohi ...
    2008 Volume 81 Issue 2 Pages 278-286
    Published: February 15, 2008
    Released: February 12, 2008
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    An effective and applicable deuteration method for aromatic rings using Pt/C–D2O–H2 system was established. Especially, phenol was fully deuterated even at room temperature, and other electron-rich aromatic nuclei were efficiently deuterated under mild conditions. The scope and limitations of the presence method and its application to the synthesis of deuterium-labeled biologically active compounds and deuterium-labeled building blocks for practical multi-gram scale syntheses are reported.
  • Shigeo Yasuda, Hideki Yorimitsu, Koichiro Oshima
    2008 Volume 81 Issue 2 Pages 287-290
    Published: February 15, 2008
    Released: February 12, 2008
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    Vanadium(III) chloride catalyzed cross-coupling reactions of alkyl halides with arylmagnesium bromides. Various arylmagnesium bromides, except for an ortho-substituted arylmagnesium reagent, could be used for the reaction. Among alkyl halides tested, cyclohexyl halides and primary alkyl halides were good substrates. The reactions likely proceed via carbon-centered radical intermediates.
  • Takeshi Matsumoto, Takamasa Otsuki, Yoshimi Sueishi, Shunzo Yamamoto
    2008 Volume 81 Issue 2 Pages 291-297
    Published: February 15, 2008
    Released: February 12, 2008
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    The kinetics of the hydride-transfer reaction between methylene blue (MB) and reduced nicotinamide–adenine dinucleotide (NADH) were studied in basic buffer solutions containing anionic surfactants (sodium dodecyl sulfate (SDS), sodium decyl sulfate (SDES), and sodium tetradecyl sulfate (STS)) under oxygen-saturated conditions. Initially, the absorbance of MB at 666 nm decreased with SDES concentration, but increased gradually near and above the cmc. The observed first-order rate constant (kobsd) decreased gradually at first, more steeply with increasing SDES concentration and then reached to a small value and became constant. The changes in the absorbance of MB and the observed rate constant were explained by changes in the form of MB in the solution with increasing SDES concentration. The concentration of SDES can be divided into four regions, in connection with the changes in the absorbance and the observed rate constant. The profiles of the changes in the absorbance of MB and the apparent rate constant for SDS and STS with surfactant concentrations were very similar to those for SDES.
  • Hideaki Uchida, Ko Yasumoto, Akinori Nishigami, Jerry A. Zweigenbaum, ...
    2008 Volume 81 Issue 2 Pages 298-300
    Published: February 15, 2008
    Released: February 12, 2008
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    Daphnia kairomones induce morphological change to green alga. An active compound (8-methylnonyl sulfate), which was originally isolated and determined from Daphnia pulex body, was identified from a cultured medium of Daphnia magna by time-of-flight liquid chromatography/mass spectrometry with electrospray ionization after concentration by the Methylene Blue method.
  • Sadayuki Matsuda
    2008 Volume 81 Issue 2 Pages 301-303
    Published: February 15, 2008
    Released: February 12, 2008
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    The effects of metal ion binding to pig brain S-100 proteins on the hydrophobicity of their cysteine (Cys) residues were examined using the fluorescent thiol reagent, N-(1-anilinonaphthyl-4)maleimide (ANM). The hydrophobicity order was Ca2+/S-100 < K+/S-100 < Mg2+/S-100 < S-100 < Zn2+/S-100.
  • Kazuki Iguchi, Yoshiaki Sugihara, Juzo Nakayama
    2008 Volume 81 Issue 2 Pages 304-306
    Published: February 15, 2008
    Released: February 12, 2008
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    Sterically congested compounds, such as 6,7-di-t-butyl-1,4-naphthoquinone, 2,3,6,7-tetra-t-butylanthraquinone, and 2,3,6,7-tetra-t-butylanthracene, were synthesized via a Diels–Alder reaction involving 3,4-di-t-butylthiophene 1-oxide as the key step.
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