Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 82 , Issue 4
Showing 1-17 articles out of 17 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for 2006
  • Yasuhiro Aoyama
    2009 Volume 82 Issue 4 Pages 419-438
    Published: April 15, 2009
    Released: April 11, 2009
    JOURNALS FREE ACCESS
    In this account is described an outline of research the author has conducted over the last 35 years. Depending on the type of molecular assemblies dealt with, the whole work is divided into four parts, i.e., small host–guest systems in organic media, infinite solid systems, huge but finite nano systems in aqueous media, and manipulated biological systems. The essence of the host–guest systems (Section 2) is molecular recognition based on convergent multiple interactions involving O–H···O hydrogen bonds, where sugar binding and detailed thermodynamic analysis of multipoint recognition may be taken as highlights. A couple of new fields arise from the host–guest chemistry by paradigm shift. One is in the direction of multiple interactions, from convergent to divergent. Section 3 thus concerns molecular alignment control in crystals using orthogonal aromatic triad and diad building blocks. Catalysis by microporous metallo-organic frameworks as organic zeolites is also described. The other shift in paradigm is in the media, from organic to aqueous, and also in the significance of sugar binding, from sugars as a guest to sugars as a probe. Section 4 is devoted to the highly adhesive (hydrogen bonding) nature of glycocluster compounds and their micelle-like aggregates, focusing on the formation of glycoviruses and glycoviral gene delivery. With DNA and RNA manipulation techniques in hand, we became interested in in-cell gene sensing and transcription monitoring. The latest activity in this area is shown in Section 5. The entire work is design-based. The author, who is soon retiring from Kyoto University, now has mixed feelings about this apparently natural approach, as briefly referred to in the Closing Remark (Section 6).
    In this account is reviewed the outline of the author's research work over the last 35 years, covering small host–guest systems in apolar organic media, infinite solid systems, huge but finite nano systems in aqueous media, and manipulated biological systems. Fullsize Image
BCSJ Award Article
  • Kazuhiro Fukada, Nobuhiro Miki
    2009 Volume 82 Issue 4 Pages 439-445
    Published: April 15, 2009
    Released: April 11, 2009
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    Effects of 1:1 electrolytes (LiCl, NaCl, NaBr, KCl, RbCl, and NH4Cl) on the stacked multilamellar structure of phosphatidylcholine–water systems below the acyl-chain melting temperature were examined by means of small-angle X-ray scattering and differential scanning calorimetry. For the ternary DPPC–salt–water system at 20 °C, the lamellar repeating distance, D, jumped from 64 to 72 Å at certain thresholds of electrolyte concentration; 4.0, 2.1, and 1.4 mol kg−1 when LiCl, NaCl, or KCl were added, respectively. The temperature-dependent D jump from 72 to 64 Å at 20 °C was also confirmed for DPPC in 2.1 mol kg−1 NaCl accompanying the small latent heat of ca. 0.033 J g−1. For the DMPC–NaCl–water system at 5 °C, the salt-induced D jump, at a threshold NaCl concentration of 1.2 mol kg−1, was also observed. A triangular phase diagram of DPPC–NaCl–water at 20 °C was constructed based on X-ray scattering data. It was confirmed that the DPPC–NaCl–water system had a three-phase coexisting region, i.e., two lamellar phases with different repeating distances of 64 or 72 Å, respectively, and the NaCl bulk solution. Some qualitative aspects are discussed concerning the interpretation of the phase separation into the two different lamellar phases based on the lipid–monovalent ion interactions.
    A new phase transition of DPPC bilayers accompanied by a jump in lamellar repeating distance (D) was found for the first time by adding a large amount of 1:1 electrolyte in aqueous medium. Fullsize Image
  • Setodeh Bagheri, Hossein Roohi
    2009 Volume 82 Issue 4 Pages 446-452
    Published: March 15, 2009
    Released: April 11, 2009
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    The proton transfer in 2-thioxoimidazolidin-4-one (1,3-IM) via two keto/enol and thione/thiol intramolecular mechanisms was investigated by using DFT (B3LYP) and ab initio (MP2) methods in the gas phase. A conspicuous consistency was found between results of B3LYP and MP2 calculations. The change in structural parameters for direct keto/enol tautomerization is greater than thione/thiol transformation on going from ground state to transition state. At both level of calculations, the computed energy barrier for direct and water-assisted keto/enol tautomerization is higher than the corresponding thione/thiol. The energy barriers for direct proton-transfer tautomerization reactions are significantly greater than H2O-assisted tautomerization. The NBO results show that the change of electronic charge of hydrogens involved in migration in direct proton transfer is much greater than in the water-assisted mechanism.
  • Afzal Shah, Rumana Qureshi, Asad Muhammad Khan, Farzana Latif Ansari, ...
    2009 Volume 82 Issue 4 Pages 453-457
    Published: April 15, 2009
    Released: April 11, 2009
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    This paper reports that how the variation in peak current, absorbance, and viscosity of ferrocenyl chalcone (FC), chemically named as 1-ferrocenyl-3-(4-nitrophenyl)-2-propen-1-one, in 10% aqueous DMF upon addition of DNA can be used to probe the mode of interaction and binding parameters. Binding constant (K = 5.17 (±0.25) × 103 M−1), binding site size (s = 1.08 ± 0.05 bp) and diffusion coefficient of the free (Df = 5.22 × 10−7 cm2 s−1) and DNA bound drug (Db = 4.39 × 10−8 cm2 s−1) were determined from voltammetric data. The binding constant (K = 4.91 (±0.20) × 103 M−1) was also obtained from UV–vis absorption titration. Gibbs energy change (ΔG = −RT ln K) of −21.18 kJ mol−1 at 25 °C indicated the spontaneity of the binding interaction. The experimental results revealed intercalation of FC into DNA as the dominant mode of interaction. Furthermore, the radii of the free and DNA-bound drug were determined from viscosity measurements.
  • Tomotaka Iihoshi, Tetsuya Sato, Masaaki Towatari, Naohide Matsumoto, M ...
    2009 Volume 82 Issue 4 Pages 458-466
    Published: April 15, 2009
    Released: April 11, 2009
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    Copper(II) complexes with tridentate ligands H2LR (R = H, 2-Me, and 5-Me) derived from 1:1 condensation products of DL-phenylalanine and imidazole-4-carbaldehyde derivatives (imidazole-4-carbaldehyde, 2-methylimidazole-4-carbaldehyde, and 5-methylimidazole-4-carbaldehyde), [CuClHLH] (1), [CuClHL2-Me] (2), [CuClHL5-Me]·MeOH (3), [CuBrHLH] (4a and 4b), and [CuBrHL2-Me] (5), were prepared. Two types of crystals in the reaction vessel, 4a and 4b, were obtained in the reaction between CuBr2 and H2LH. Their assembled structures were determined by single-crystal analysis. Except for 4b, the complexes assumed a homochiral chain structure constructed by intrachain imidazole–carboxylato hydrogen bonds between the adjacent two molecules, and the adjacent chains are linked by interchain Cu–X (X = Cl or Br) interactions. 3 exhibited a shorter interchain Cu–X distance and crystallized in the acentrosymmetric space group C2221 representing a spontaneous resolution (conglomerate), while 1, 2, 4a, and 5 gave a stacking of the adjacent chains with opposite chiralities to give racemic crystals. 4b assumed a homochiral chain structure constructed by a coordination bond between a copper(II) ion and an oxygen atom of the carboxyl group of the adjacent complex. A zinc(II) complex, [ZnClHLH] (6), showed a similar racemic crystal to that of 4b.
  • Tetsuya Yoshida, Masaaki Towatari, Tetsuya Sato, Naohide Matsumoto, Na ...
    2009 Volume 82 Issue 4 Pages 467-471
    Published: April 15, 2009
    Released: April 11, 2009
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    A mononuclear copper(II) complex, [2-ethoxy-6-{[3-(2-methyl-4-imidazolylmethyleneamino)propyl]iminomethyl}phenolato]copper(II) perchlorate [CuHL]ClO4 and its deprotonated complex at the imidazole moiety, [CuL]n, were prepared. The structure of [CuHL]ClO4 consists of a cation [CuHL]+ exhibiting a four-coordinated square-planar geometry and an anion ClO4, while [CuL]n assumes an imidazolato-bridged zigzag-chain structure, in which the copper(II) ion is coordinated by the imidazolato nitrogen atom of the adjacent molecule with Cu–N = 2.258(5) Å and the two adjacent CuL units assumes a perpendicular orientation. The temperature-dependent magnetic susceptibilities from 2.0 to 300 K and field-dependent magnetization at 2.0 K demonstrate that [CuHL]ClO4 is a magnetically isolated copper(II) molecule while [CuL]n is a ferromagnetic chain. The magnetic susceptibility data of [CuL]n were analyzed by Baker’s model based on H = −2JΣSAjSAj+1 for chain of equally spaced copper(II) ions to give the best-fit parameters of g = 2.08 and J = +0.63 cm−1.
  • Koji Machitani, Yoshio Nakahara, Keiichi Kimura
    2009 Volume 82 Issue 4 Pages 472-474
    Published: April 15, 2009
    Released: April 11, 2009
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    The fluorescence properties of a Eu3+ complex with a tetraazamacrocyclic derivative bearing a spirobenzopyran and three carboxymethyl moieties were investigated. The enhanced fluorescence of Eu3+, which proved that the spirobenzopyran moiety worked as an antenna for the sensitization, was controlled photochemically.
  • Takayoshi Itoh, Jiro Tatsugi, Hideo Tomioka
    2009 Volume 82 Issue 4 Pages 475-481
    Published: April 15, 2009
    Released: April 11, 2009
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    Photolysis of indan-1,2,3-trion (1a), benzo[b]furan-2,3-dione (1b), and N-methylisatin (1c) in argon matrix either with or without oxygen at 10 K was investigated by IR spectroscopy in combination with DFT calculations. The results indicate that while 1a and 1b gave the products mixture as a result of α-cleavage, followed by decarbonylation, 1c was rather photostable under similar conditions. However, when the irradiation was carried out in argon matrix doped with 20% oxygen, 1c decomposed much more efficiently than that in argon matrix and cyclic diacyl peroxide presumably formed by trapping of initial diradical originating from α-cleavage by molecular oxygen was detected. Similar irradiation of 1b also gave cyclic diacyl peroxide along with photodecarbonylation products, but irradiation of 1a in oxygen-doped matrix produced not only cyclic diacyl peroxide but also products as a result of oxidation of photodecarbonylation product. The present observation reveals that photolysis of ketones in oxygen-doped matrix at low temperature provides useful information concerning the reactivities of ketones toward α-cleavage.
  • Yuka Kawashita, Juichi Yanagi, Tatsuo Fujii, Masahiko Hayashi
    2009 Volume 82 Issue 4 Pages 482-488
    Published: April 15, 2009
    Released: April 11, 2009
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    Nineteen activated carbons, including sixteen tailor-made and three commercially available ones, were employed to investigate their role in the one-pot synthesis of 2-arylbenzazoles starting from 2-aminophenol, 1,2-diaminobenzene, or 2-aminobenzenethiol, and aldehyde via oxidative cyclization of intermediate phenolic Schiff base promoted by the activated carbon–molecular oxygen system. Tailor-made activated carbons were prepared from wood, coconut shell, and coal by the steam activation method or the chemical activation method. All activated carbons were characterized to clarify their properties, such as metal contaminants, specific surface area, porosity, and surface functionality. After examining their effects on reactivity in the oxidative aromatization, we found that the essential role of activated carbon in this oxidation system is concerned not with metal contaminants, specific surface area, pore volume, mean pore diameter, and surface oxygen groups evolving as CO2 at 900 °C but with surface oxygen groups evolving as CO during heating at 900 °C, such as carbonyl groups on the surface of activated carbon. Additionally, in the synthesis of 2-arylbenzoxazole, it was found that activated carbon would also promote the cyclization of the intermediate Schiff base.
  • Koichi Tanaka, Hidehiro Itoh, Aki Nakashima, Dominik Wójcik, Zo ...
    2009 Volume 82 Issue 4 Pages 489-493
    Published: April 15, 2009
    Released: April 11, 2009
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    Some inclusion crystals of phosphonium salts with aromatic alcohols showed thermally reversible photochromism in the solid state. Corresponding to the color development, ESR signals appeared in the inclusion crystals. The crystal structures of the inclusion crystals were determined by X-ray analysis.
  • Kazuo Mukai, Aya Ouchi, Akiko Mitarai, Keishi Ohara, Chihiro Matsuoka
    2009 Volume 82 Issue 4 Pages 494-503
    Published: April 15, 2009
    Released: April 11, 2009
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    In order to understand the dynamics of antioxidant actions of vitamin E (α-, β-, γ-, and δ-tocopherols, TocH) in biological systems, kinetic study of the formation and decay reactions of vitamin E radicals (α-, β-, γ-, and δ-tocopheroxyls, Toc) has been performed in organic solvents, using stopped-flow spectrophotometry. By mixing α-, β-, γ-, and δ-TocH with aryloxyl radical (ArO) in ethanol, the peaks of the UV–vis absorption due to α-, β-, γ-, and δ-Toc radical appeared rapidly at ca. 430–340 nm, showed maxima, and then decayed gradually. The second-order rate constants (kf and 2kd) for the formation and decay (that is, bimolecular disproportionation) reactions of α-Toc were determined by comparing the observed curves with the simulation ones obtained by the numerical calculation of differential equations related to the above reactions. From the results, the wavelengths of absorption maxima (λmaxi) and molar extinction coefficients (εi) (i = 1–4) of the optical spectra were determined for α-Toc radical. Notable solvent effects have been observed for the reaction rates (kf and 2kd) and absorption spectra (λmaxi and εi) of α-Toc radical. The scheme of the formation and decay reactions of α-, β-, γ-, and δ-Toc radicals has been discussed based on the results obtained.
  • Shinji Kurose, Kunishige Kataoka, Naoya Shinohara, Yuko Miura, Maiko T ...
    2009 Volume 82 Issue 4 Pages 504-508
    Published: April 15, 2009
    Released: April 11, 2009
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    Replacement of Met510, the axial ligand to the type I Cu in a cuprous oxidase CueO, with Leu afforded the three-coordinated type I Cu, while Gln, Ala, and Thr mutations led to the replacement of the thioether ligand with oxygen ligands (amide carbonyl group and water), and characteristic properties of absorption, circular dichroism, and electron paramagnetic resonance spectra of a variety of Met510 mutants were correlated with the changes in redox potential and enzyme activities.
  • Atsushi Kamiouji, Keiji Hashimoto, Hiroshi Kominami, Seishiro Ito
    2009 Volume 82 Issue 4 Pages 509-513
    Published: April 15, 2009
    Released: April 11, 2009
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    Saponification of methyl dodecanoate with an aqueous sodium hydroxide solution in the absence and presence of alcohols was studied using a tubular reactor made of silicone tube to elucidate effects of alcohol addition on the saponification. The reaction rates of saponification were accelerated significantly when alcohols were dissolved in methyl dodecanoate and the rates were increased in the order: without alcohol << ethanol < propanol < butanol. The rates in all cases obeyed the Nernst diffusion rate equation, and the values of apparent diffusion constant, ka, that were determined from the slope of Nernst plots were increased in the above order, indicating that diffusion of sodium ion in the aqueous solution into the mixture of methyl dodecanoate and alcohol was much easier than that to methyl dodecanoate without alcohol. The values of ka increased with increase in the amount of butanol both in the tubular reactor and in a beaker (batch system). The thickness of the diffusion layer, δ, decreased with increase in the amount of butanol in the saponification in the tubular reactor, suggesting that the increase in ka in the saponification in the presence of butanol in the tubular reactor can be explained by decrease in values of δ.
  • Akihide Iwase, Kenji Saito, Akihiko Kudo
    2009 Volume 82 Issue 4 Pages 514-518
    Published: April 15, 2009
    Released: April 11, 2009
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    NiO/NaNbO3 (BG: 3.5 eV) showed photocatalytic activity for water splitting into H2 and O2 under UV irradiation. When NaMO3 (M: Nb and Ta) was codoped with iridium ions and alkaline earth metal ions or lanthanum ions, a new visible-light absorption band was observed in addition to the band gap absorption band of the host material. The codopants of alkaline earth metal and lanthanum ions contributed to maintaining the charge balance and forming of fine crystals of the NaMO3 powder. These NaNbO3 and NaTaO3 codoped with iridium ions and alkaline earth metal ions or lanthanum ions showed photocatalytic activities for H2 or O2 evolution from an aqueous solution containing a sacrificial reagent under visible light irradiation.
  • Kenta Tojo, Tatsuya Arisawa, Yoshio Aoki, Daiyo Terunuma
    2009 Volume 82 Issue 4 Pages 519-527
    Published: April 15, 2009
    Released: April 11, 2009
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    Chiral dopants with a spiro structure for nematic liquid crystals were synthesized from optically active 3,3′-(4H,4′H)-spirobi(2H-naphtho[1,2-b]pyran)-6,6′-dicarboxylic acid, and their helical twisting power (HTP) values were evaluated. Chiral dopants having the S configuration induced minus helices in the host nematic liquid crystals. It was found that the novel ester-linked spiro chiral dopants exhibited large molar HTP values. In particular, a chiral dopant with two pyrimidine structures in the side chain moiety showed the highest molar HTP value of 62.1 µm−1 mol−1 kg. In contrast, ether-linked chiral dopants showed relatively small molar HTP values.
  • Kiyonori Ogisu, Kazuhiro Takanabe, Daling Lu, Masaki Saruyama, Takahir ...
    2009 Volume 82 Issue 4 Pages 528-535
    Published: April 15, 2009
    Released: April 11, 2009
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    Uniformly sized CdS nanoparticles exhibiting quantum size effect have been synthesized as a suspension in hexane solution containing oleic acid and 9-octadecenylamine as protective ligands. Our study focuses on utilizing the intrinsic optical property of the nanoparticles for photocatalytic H2 evolution and photoelectrochemical reaction by immobilizing oxide substrate and removing protective ligands. Immobilized CdS nanoparticles on TiO2 were found to maintain their original particle size and optical property after impregnation and removal of the protective ligands by oxidative heat treatment and/or alkali treatment. The photocatalytic H2 evolution rates in Na2S–Na2SO3 solution under visible light were strongly affected by the CdS particle size (quantum size effect), CdS loading amount, and TiO2 surface area. High photoanodic current was observed for CdS/TiO2 sprayed on a fluoride-doped tin oxide (FTO) electrode, functioning as an n-type semiconductor. The knowledge acquired in this study can be extended for further development in the field of nanoparticle materials covered with protective ligands.
  • Yasunobu Tagami, Takashi Matsufuji, Hajime Ikigai, Takayuki Narita, Yu ...
    2009 Volume 82 Issue 4 Pages 536-538
    Published: April 15, 2009
    Released: April 11, 2009
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    We investigated the aggregation state of a mixed monolayer of 1,2-dimyristoyl-sn-glycero-3-phospholine and cholesterol at different surface pressures by AFM. AFM images revealed a nanoscopically separated structure despite a macroscopic homogenization of the monolayer under compression.
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