Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 83 , Issue 6
Showing 1-19 articles out of 19 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for Creative Work for 2006
  • Masayoshi Nishiura, Zhaomin Hou
    2010 Volume 83 Issue 6 Pages 595-608
    Published: June 15, 2010
    Released: June 15, 2010
    [Advance publication] Released: May 28, 2010
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    This article describes our recent studies on the synthesis and chemistry of mono(cyclopentadienyl)-ligated rare earth metal alkyl and hydride complexes. The half-sandwich mono- and dialkyl rare earth metal complexes are prepared either by alkane elimination reactions between trialkyl rare earth complexes and the neutral cyclopentadiene derivatives or by metathetical reactions of rare earth trichlorides with the alkali metal salts of the corresponding ligands. The reaction of the dialkyl complexes with an equivalent of a borate compound such as [Ph3C][B(C6F5)4] or [PhNMe2H][B(C6F5)4] generates easily the corresponding cationic monoalkyl species, which serve as excellent catalysts for the polymerization and copolymerization of a variety of olefins to yield a new family of polymer materials that show novel properties but are difficult to prepare by other catalysts. The half-sandwich monoalkyl rare earth complexes bearing the silylene-linked cyclopentadienyl–arylamido ligands act as excellent catalysts for the catalytic dimerization of terminal alkynes, cross coupling of terminal alkynes with isocyanides, and the catalytic addition of terminal alkyne C–H, amine N–H, and phosphine P–H bonds to carbodiimides. The hydrogenolysis of the dialkyl rare earth complexes with H2 affords a new class of polynuclear rare earth metal polyhydride complexes, which show unique features in both structure and reactivity.
    This article describes our recent studies on the synthesis and chemistry of mono(cyclopentadienyl)-ligated rare earth metal alkyl and hydride complexes, many of which show unique activity and selectivity in olefin polymerization and other chemical transformations. Fullsize Image
The Chemical Society of Japan Award for Young Chemists for 2006
  • Michito Yoshizawa, Makoto Fujita
    2010 Volume 83 Issue 6 Pages 609-618
    Published: June 15, 2010
    Released: June 15, 2010
    [Advance publication] Released: May 28, 2010
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    This account recounts the application of self-assembled coordination hosts as molecular tools and the development of unusual chemical reactions and interactions generated within their cavities. Starting from the simple molecular recognition of guest molecules, coordination hosts have been used to accelerate reaction rates, endow regio- and stereoselectivity, and create unique reactions in their nanometer-sized cavities. Coordination hosts were also used to develop a new, practical method for constructing discrete stacks of aromatic molecules with unique electronic and magnetic properties.
    This account recounts the development of our self-assembled coordination hosts as molecular tools and describes their application toward creating unusual chemical properties, reactions, interactions, and phenomena in the nanometer-sized cavities. Fullsize Image
BCSJ Award Article
  • Akira Yada, Tomoya Yukawa, Hiroaki Idei, Yoshiaki Nakao, Tamejiro Hiya ...
    2010 Volume 83 Issue 6 Pages 619-634
    Published: June 15, 2010
    Released: June 15, 2010
    [Advance publication] Released: May 20, 2010
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    Nickel/Lewis acid dual catalysis is found to effect the carbocyanation reaction of alkynes using acetonitrile and substituted acetonitriles to give a range of variously substituted acrylonitriles. The addition of propionitrile across alkynes is also demonstrated briefly to give the corresponding ethylcyanation products in good yields, whereas the reaction of butyronitrile gives significant amounts of hydrocyanation products due possibly to β-hydride elimination of a propylnickel intermediate. The reaction of optically active α-phenylpropionitrile suggests a reaction mechanism that involves oxidative addition of a C–CN bond with retention of its absolute configuration.
    Nickel/Lewis acid dual catalysis is found to effect the carbocyanation reaction of alkynes using acetonitrile and substituted acetonitriles to give a range of variously substituted acrylonitriles in a highly regio- and stereoselective manner. Fullsize Image
 
  • Satoru Hamaya, Hiroyuki Fukui
    2010 Volume 83 Issue 6 Pages 635-642
    Published: June 15, 2010
    Released: June 15, 2010
    [Advance publication] Released: May 20, 2010
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    A formulism for four-component Dirac–Hartree–Fock perturbation theory using the restricted magnetic balance (RMB) condition with gauge-including atomic orbitals (GIAOs) is derived at an ab initio level. In this formulation, the zeroth-order Dirac–Hartree–Fock equations are subject only to the usual restricted kinetic balance (RKB) condition, while the external field-dependent RMB condition is introduced in the calculation of the first-order magnetically perturbed orbitals. The magnetic shielding can be divided into a paramagnetic part and a diamagnetic part, as for nonrelativistic (NR) shielding. The present theory is applied to the calculation of hydrogen halide and molecular halogen shieldings.
  • Toshio Takenaka, Anatoly A. Zinchenko, Kenichi Yoshikawa, Shizuaki Mur ...
    2010 Volume 83 Issue 6 Pages 643-650
    Published: June 15, 2010
    Released: June 15, 2010
    [Advance publication] Released: May 28, 2010
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    The compaction of gene-size T4 DNA induced by the action of silica nanoparticles (10–100 nm diameter), the surfaces of which were modified to various degrees by a 3-aminopropylsilyl groups, was monitored by a fluorescent microscope in an aqueous solution. It was found that DNA compaction was facilitated by mono- and divalent cations such as Na+, K+, Mg2+, and Ca2+. This promotion by cations was the result of charge-neutralization of DNA and was more remarkable in compaction by histone-size nanoparticles (10 nm) than in that by larger ones (>15 nm). Divalent metal ions were more effective at promoting compaction due to their greater charge-neutralizing character, but a quaternary diammonium derivative of 1,3-propanediamine deactivated DNA compaction by 10-nm nanoparticles. Although metal ions binding to DNA can reduce electrostatic tension on DNA and provide flexibility to create a DNA loop with a small diameter, such ammonium dication does not make DNA sufficiently flexible.
  • Hiro-Fumi Okabayashi, Ken-Ichi Izawa, Akiko Sumiya, Julian Eastoe, Cha ...
    2010 Volume 83 Issue 6 Pages 651-659
    Published: June 15, 2010
    Released: June 15, 2010
    [Advance publication] Released: May 28, 2010
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    The IR spectra in the 1300–1450 cm−1 region, which reflect the CH and CH2 deformation vibrational modes of the succinate skeleton, have been investigated in detail for sodium dialkylsulfonates (alkyl groups: ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, n-octyl, n-decyl, and n-dodecyl) and sodium 1,2-bis(2-ethylhexyl)sulfosuccinate (sodium 1,2-bis(2-ethylhexyloxycarbonyl)ethanesulfonate) (AOT). The results have provided clear evidence that two configurations, arising from the difference in the torsion angles of the succinate skeleton, are preferentially stabilized in aqueous solution as well as in the solid state, depending upon the concentration. Thus, the IR spectra of this region can be used as a powerful tool for elucidation of the mechanism of the disorder–order transition in aggregate systems of AOT or its homologs at the molecular level.
  • Keiko Takano, Nobuaki Koga, Toshio Matsushita, Kenro Hashimoto, Haruo ...
    2010 Volume 83 Issue 6 Pages 660-666
    Published: June 15, 2010
    Released: June 15, 2010
    [Advance publication] Released: May 20, 2010
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    Quantum Chemistry Literature Data Base (QCLDB, http://qcldb2.ims.ac.jp) is a database of those papers published after 1978 which treat only ab initio calculations of atomic and molecular electronic structures. From about thirty core journals they are collected, surveyed, and given proper tags revealing the content and essence by theoretical and computational chemists. Those theoretical works even without reporting any computational results are also collected which are judged to have significant relevance to ab initio calculations, while no semiempirical calculations are included. QCLDB has been maintained by Quantum Chemistry Data Base Group (QCDBG). QCLDB provides information not only to chemists but also to both theoretical and experimental scientists, who want to know the state of the art theoretical aspects of chemical substances and materials. Although the last version, “QCLDB I,” has been sustained and utilized steadily for almost a quarter century up to the end of 20th century, new circumstances related to the internet facility imposed re-construction of QCLDB I on QCDBG. A policy of the academic database of references has been established. The policy emphasizes that there should be a balance between data collection as research itself and utility for users. According to the policy, an unprecedented hybrid and highly academic database, QCLDB II, has been constructed and is open to all scientists via the work site.
  • Masatsugu Taneda, Daisuke Maeda, Hisashi Shimakoshi, Masaaki Abe, Yosh ...
    2010 Volume 83 Issue 6 Pages 667-671
    Published: June 15, 2010
    Released: June 15, 2010
    [Advance publication] Released: May 28, 2010
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    2,7,12,17-Tetra-n-propylporphycenatodihalotin(IV) complexes ([Sn(TPrPc)X2], X = F, Cl, and Br) were synthesized and their photophysical properties were investigated. These complexes exhibit strong absorptions in the red region (600–630 nm). Strong quenching was observed during the fluorescence emission of the dibromotin(IV) complex, which is caused by an intramolecular heavy-atom effect. The complexes emit NIR phosphorescence in 1-iodopropane at room temperature and the intensity of the emission of the dibromotin(IV) complex is found to be smaller than that of the dichlorotin(IV) complex. The quantum efficiency (ΦΔ) of generation of singlet oxygen using the dibromotin(IV) complex is the highest among the porphycenatotin(IV) complexes (ΦΔ = 0.79). Photooxidation of 1,3-diphenylisobenzofuran catalyzed by the complexes upon irradiation with red light (over 600 nm) was studied and a rapid oxidation of the substrate was observed when using the dibromotin(IV) complex.
  • Yurngdong Jahng, A. F. M. Motiur Rahman
    2010 Volume 83 Issue 6 Pages 672-677
    Published: June 15, 2010
    Released: June 15, 2010
    [Advance publication] Released: May 28, 2010
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    A series of 2,2′-di(heteroaryl)-9,9′-spirobifluorenes were prepared by employing Friedländer reaction of 2,2′-diacetyl-9,9′-spirodifluorene with a series of ortho-aminoarenecarbaldehydes. The compound 2,2′-di(benzo[b]-1,10-phenanthrolin-2-yl)-9,9′-spirofluorene (4e) showed a green light emission at 500 nm upon the excitation of the absorption at 374 nm while 2,2′-di(benzo[h]quinolin-2-yl)-9,9′-spirofluorene (4c), 2,2′-di(1,10-phenanthrolin-2-yl)-9,9′-spirofluorene (4d), 2-(benzo[h]quinolin-2-yl)-2′-(benzo[b]-1,10-phenanthrolin-2-yl)-9,9′-spirofluorene (4g), and 2-(1,10-phenanthrolin-2-yl)-2′-(benzo[b]-1,10-phenanthrolin-2-yl)-9,9′-spirofluorene (4h) showed emissions at 413, 465, 442, and 442 nm upon excitation of the absorption at 370, 362, 370, and 363 nm, respectively, thus having potential for OLED applications.
  • Chiung-Yao Huang, Jui-Hsin Su, Yung-Chun Liu, Zhi-Hong Wen, Chi-Hsin H ...
    2010 Volume 83 Issue 6 Pages 678-682
    Published: June 15, 2010
    Released: June 15, 2010
    [Advance publication] Released: May 28, 2010
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    Two new natural products, the oppositane-type sesquiterpenoids leptocladolins A and B (1 and 2), along with two known compounds 1β-hydroxy-6α-acetoxyeudesm-4(15)-ene (3) and 1β,6α-dihydroxyeudesm-4(15)-ene (4) were obtained from a Formosan soft coral Sinularia leptoclados. The relative structures of 1 and 3 were confirmed by X-ray diffraction analysis. The absolute structures of 1 and 3 were determined by the Mosher’s method. It was found that 4 significantly inhibited the upregulation of pro-inflammatory iNOS protein in LPS-stimulated RAW264.7 macrophage cells.
  • Junichi Taira, Satoshi Osada, Ryo Hayashi, Toshihisa Ueda, Masoud Jelo ...
    2010 Volume 83 Issue 6 Pages 683-688
    Published: June 15, 2010
    Released: June 15, 2010
    [Advance publication] Released: May 28, 2010
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    Several ion channel forming cyclic peptides have been reported over the past two decades and various ion conducting mechanisms have been proposed. In this article, we report on amino acid substitutions in cyclic hexapeptides and their effects on the ion conducting properties of these peptides. Cyclic hexapeptides, cyclo(Pro–Xxx–Yyy)2, containing two Pro residues, were used as the main framework. The substitution is performed at the Xxx positions with cationic/hydrophilic Lys or hydrophobic Leu. Yyy positions were substituted with D-Phe, D-Ala, or Gly. The peptides which were absent Lys residues showed ion conducting profiles with clear transitions of electric currents, whereas the peptides containing Lys residues tended to exhibit spiky or burst-like profiles. These profiles were altered single state profiles by the protection of ε-amino groups with aromatic protecting groups. The protected analogs exhibited significant decrease in ion conductance. These results indicated that peptides containing Lys conduct ions without forming ring stacked tube-like structure. Ion channel properties were also affected by conformational changes of the cyclic peptides induced by substitution of the Yyy positions. Enhancement of intramolecular β-turn structures of cyclic peptides tended to decrease their ion conductance values.
  • Doddakunche S. Prasanna, Chandagirikoppal V. Kavitha, Kambappa Vinaya, ...
    2010 Volume 83 Issue 6 Pages 689-697
    Published: June 15, 2010
    Released: June 15, 2010
    [Advance publication] Released: May 28, 2010
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    Heterocyclic urea derivatives play an important role as anticancer agents because of their good inhibitory activity against receptor tyrosine kinases (RTKs), raf kinases, protein tyrosine kinases (PTKs), and NADH oxidase, which play critical roles in many aspects of tumorigenesis. Benzothiazole moiety constitutes an important scaffold of drugs, possessing several pharmacological functions, mainly the anticancer activity. Based on these interesting properties of benzothiazoles and urea moiety to obtain new biologically active agents, we synthesized a series of novel 1-((S)-2-amino-4,5,6,7-tetrahydrobenzo[d]thiazol-6-yl)-3-(substituted phenyl)urea derivatives and evaluated for their efficacy as antileukemic agents against two human leukemic cell lines (K562 and Reh). These compounds showed good and moderate cytotoxic effect to cancer cell lines tested. Compounds with electron-withdrawing chloro and fluoro substituents on phenyl ring showed good activity and compounds with electron-donating methoxy group showed moderate activity. Compound with electron-withdrawing dichloro substitution on phenyl ring of aryl urea showed good activity. Further, lactate dehydrogenase (LDH) assay, flow cytometric analysis of annexin V-FITC/propidium iodide (PI) double staining and DNA fragmentation studies showed that compound with dichloro substitution on phenyl ring of aryl urea can induce apoptosis.
  • Habib Firouzabadi, Nasser Iranpoor, Mohammad Abbasi
    2010 Volume 83 Issue 6 Pages 698-702
    Published: June 15, 2010
    Released: June 15, 2010
    [Advance publication] Released: June 03, 2010
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    A novel one-pot odourless synthesis of symmetrical disulfides from their corresponding halides in aqueous media using thiourea and MnO2 in the presence of NaHCO3 or Na2CO3 catalyzed by micellar solution of sodium dodecyl sulfate (SDS) is described. By this method, primary, allylic and benzylic halides were converted into their corresponding disulfides in high yields.
  • Beena G. Singh, Partha P. Bag, Fumio Kumakura, Michio Iwaoka, K. Indir ...
    2010 Volume 83 Issue 6 Pages 703-708
    Published: June 15, 2010
    Released: June 15, 2010
    [Advance publication] Released: May 28, 2010
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    Selenocystine (CysSeSeCys), a diselenide, exhibits glutathione peroxidase (GPx) activity, where it catalyses the reduction of hydroperoxides using a thiol co-factor. To understand the relative reactivity of the two substrates, enzyme kinetic parameters, i.e., the turnover number (kcat) and the relative reactivity parameters toward thiol (φG) and hydroperoxide (φH), were determined by applying Dalziel kinetics for a bi-substrate model in the presence of hydrogen peroxide (H2O2), t-butyl hydroperoxide, or α-cumyl hydroperoxide and glutathione or dithiothreitol (DTTred). The intermediates formed during the reaction of CysSeSeCys with H2O2 and DTTred were characterized by 77Se NMR spectroscopy. Ab initio calculation at HF/6-31G(d) indicated that the reactions with H2O2 are exothermic, while those with DTTred are endothermic. Based on these studies, the GPx activity of CysSeSeCys is likely to be initiated by the reaction with hydroperoxide and in the catalytic cycle, the reaction with thiol is the rate-determining step.
  • Masaki Matsui, Tomoki Fujita, Yasuhiro Kubota, Kazumasa Funabiki, Hide ...
    2010 Volume 83 Issue 6 Pages 709-711
    Published: June 15, 2010
    Released: June 15, 2010
    [Advance publication] Released: May 28, 2010
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    D149 ethyl ester molecules are arranged in a “herringbone” fashion. Cyclopentane, phenylene, and one of the phenyl moieties surround a planar π-conjugated chromophore to weaken π–π stacking between the molecules arranged in parallel.
  • Yoko Seki, Makoto Ogawa
    2010 Volume 83 Issue 6 Pages 712-715
    Published: June 15, 2010
    Released: June 15, 2010
    [Advance publication] Released: May 28, 2010
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    The adsorption of 2-phenylphenol onto organically pillared clays (a natural montmorillonite and a synthetic saponite) was investigated. Organoammonium salts used for the clay modification were trimethylphenylammonium bromide, 3-(trifluoromethyl)phenyltrimethylammonium bromide, and neostigmine bromide. All the organically pillared clays adsorbed 2-phenylphenol from water. The adsorbed amount of 2-phenylphenol was smaller as the cation-exchange capacity of host was larger, showing possible pore volume engineering.
  • Yoshitomo Okamura, Norio Ishii, Takashi Nogami, Takayuki Ishida
    2010 Volume 83 Issue 6 Pages 716-725
    Published: June 15, 2010
    Released: June 15, 2010
    [Advance publication] Released: May 28, 2010
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    Several metal–radical alternating chains ([Co(hfac)2(CnPNN)]) were prepared, and their crystal structures and magnetic properties were systematically studied, where CnPNN stands for a phenylnitronyl nitroxide ligand having a linear Cn alkoxy group at the ortho or para position. X-ray crystal structure analysis was successfully performed for [Co(hfac)2(p-C5PNN)] (p-5). The chain structure is similar to those of the known p-butoxy and o-ethoxy derivatives. Compound p-5 showed a very large coercive field of 51 kOe (4.1 MA m−1) and a saturation magnetization of 9.7 × 103 erg Oe−1 mol−1 at 6 K. o-Propoxy and o-pentoxy derivatives also exhibited large coercive fields of 50–54 kOe at 5–6 K. The activation energies of magnetization reorientation for the present compounds were estimated to be as large as 290–360 K from Arrhenius analysis using ac susceptibility data. In a temperature range of ca. 10–40 K, all of the present compounds behaved as very soft magnets, as indicated by no hysteresis in the ferromagnetic MH curves. We propose a mechanism for the drastic soft–hard switch. The hard character grows immediately after freezing of the spin dynamics owing to the strong magnetic anisotropy.
  • Ju Yeon Woo, Young Soo Kang, Byung Kyu Kim
    2010 Volume 83 Issue 6 Pages 726-731
    Published: June 15, 2010
    Released: June 15, 2010
    [Advance publication] Released: May 28, 2010
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    The grating formation dynamics, SEM images, diffraction efficiency, and electrooptical properties of transmission grating of holographic polymer dispersed liquid crystals (HPDLCs) have been investigated by incorporating three different types of monofunctional reactive diluents into the host polymer matrices. A gradual increase of real time diffraction efficiency, a decrease of LC droplet size, and an increase of diffraction efficiency of the composite film were obtained with the addition of epoxy acrylate monomers due to the increased viscosity of polymer/LC mixtures leading to decreased droplet coalescence. In addition, epoxy acrylate monomers induced decreased volume shrinkage according to their ring structure with bulky group. Driving voltage increased with the addition of epoxy monomers whereas rise time and decay time decreased as a result of the decreased LC droplet size. At an optimum composition of epoxy monomer, a minimum switching voltage of 6 V µm−1 and rise time of 0.15 ms and a decay time of 18.05 ms were respectively obtained.
  • Ryoji Shibuya, Masa-aki Ohshima, Hideki Kurokawa, Hiroshi Miura
    2010 Volume 83 Issue 6 Pages 732-734
    Published: June 15, 2010
    Released: June 15, 2010
    [Advance publication] Released: May 28, 2010
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    The influence of calcination temperatures on the dispersion of Ir/SiO2 catalysts has been studied. At low calcination temperatures, the chloride precursor was dispersed on the silica surface and formed highly dispersed Ir/SiO2 catalysts upon reduction. At high calcination temperatures, the formation of IrO2 was confirmed, which resulted in low dispersion after reduction.
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