Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 82 , Issue 11
Showing 1-15 articles out of 15 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for Young Chemists for 2008
  • Yasuteru Shigeta
    2009 Volume 82 Issue 11 Pages 1323-1340
    Published: November 15, 2009
    Released: November 10, 2009
    JOURNALS FREE ACCESS
    Recent progress in our theoretical developments and applications where thermal fluctuations and quantum effects are important are reviewed. We first show that motions of a confined atom coupled with a fullerene cage cause large thermal fluctuation of the effective charge on the confined atom and that the fluctuation is sensitive to applied temperature and the number of confined species. Second, two different approaches to treat nuclear quantum effects are discussed. One is non-Born–Oppenheimer (NBO) molecular theory, which is one of an extension of molecular orbital theory for electrons to nuclear motions. This method is suitable to describe static and stationary nuclear (vibrational) states so we apply this method to obtain vibrationally coupled electron density of a protonatable amino acid. We compare the obtained electron density through NBO treatment with conventional calculations. The other approach is referred as to quantum cumulant dynamics (QCD), which is a generalization of quantized Hamiltonian dynamics initially proposed by Prezhdo. This method is applied to vibrational analyses. The ordinary normal mode analysis (NMA) is extended to include quantum degrees of freedom based on QCD formalism, which gives a better description of the vibrational state, where ordinary NMA gives incorrect results. Vibrational frequencies of small molecules by the QCD simulation are compared with those by classical molecular dynamics (MD). It is found that QCD is superior to classical MD in that the results obtained by QCD are in good agreement with those by full quantum treatment. Finally the theoretical background of a real-space grid-based time-dependent density functional theory (RSTDDFT) is explained. This method is applied to solve a NBO problem by using an imaginary time propagator and electron dynamics driven by an off-resonant circularly polarized laser plus in addition to using a real time propagator. For the latter case, we investigate atom-centered dipole moment and induced current and detect the electronic fluctuation in a SiH4 molecule after irradiation.
    Recent progress in theoretical developments and applications, where the thermal fluctuations and quantum effects are important, are reviewed. Particularly, theoretical simulations of QM/MM molecular dynamics, of nuclear quantum effects, of electrons in a molecule driven by circularly polarized laser are shown. Fullsize Image
BCSJ Award Article
  • Hiroyasu Yamaguchi, Takeshi Onji, Hidetaka Ohara, Noriaki Ikeda, Akira ...
    2009 Volume 82 Issue 11 Pages 1341-1346
    Published: November 15, 2009
    Released: November 10, 2009
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    A complex between a monoclonal antibody for porphyrin and zinc–porphyrin was utilized to construct an energy conversion system. Monoclonal antibody 2B6 bound meso-tetrakis(4-carboxyphenyl)porphyrin zinc complex (ZnTCPP) with a dissociation constant of 2.1 × 10−8 M. Upon binding the antibody, the lifetime of the excited triplet state of ZnTCPP increased from 0.5 to 1.2 ms. A stable cationic radical of viologen was obtained by irradiating the solution containing the complex of 2B6 with ZnTCPP, methyl viologen (MV2+), and ethylenediaminetetraacetic acid tetrasodium salt (EDTA-4Na) with light. When colloidal platinum was added as a catalyst, photoinduced hydrogen production was observed upon continuous irradiation of visible light. The estimated turnover number of photoinduced hydrogen evolution was 5.0 × 10−3 s−1. The catalytic activity of the 2B6–ZnTCPP complex on the hydrogen evolution was compared with that of ZnTCPP alone and the complexes of ZnTCPP with fragments of antibody 2B6 (2B6-H and 2B6-L). The heavy chain of antibody 2B6 mainly contributed to the complex formation with ZnTCPP and the resultant hydrogen production, and the whole antibody–ZnTCPP complex led to the efficient hydrogen production.
    A complex between a monoclonal antibody for porphyrin and zinc–porphyrin was utilized to construct an energy conversion system. Hydrogen could be efficiently produced by the whole antibody–porphyrin complex. Fullsize Image
 
  • Hideaki Shirota, Tomotsumi Fujisawa, Hiroki Fukazawa, Keiko Nishikawa
    2009 Volume 82 Issue 11 Pages 1347-1366
    Published: November 15, 2009
    Released: November 10, 2009
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    We have studied the ultrafast dynamics of forty aprotic molecular liquids by femtosecond optical heterodyne-detected Raman-induced Kerr effect spectroscopy. Some physical properties such as shear viscosity, density, and surface tension of the molecular liquids have also been measured. From the Fourier transform Kerr spectra in the frequency range of about 0–200 cm−1, we have found that the first moment of the low-frequency intermolecular vibrational spectrum is moderately correlated with the root of the value of surface tension divided by density. This fact indicates that the microscopic intermolecular interaction is related to the macroscopic physical property of intermolecular force in molecular liquids. On the other hand, a correlation between the first moment of the intermolecular vibrational spectrum and the interaction energy of two identical molecules is almost nonexistent. The difference between the two relations suggests that the many-body interaction effect takes a hand in the intermolecular vibrational dynamics in molecular liquids. We have also found that the shapes of the broad low-frequency vibrational spectra for aromatic molecular liquids show a clearer bimodal feature than those for non-aromatic molecular liquids. Picosecond Kerr transients for most of the molecular liquids are non-exponential. The slowest relaxation time is qualitatively explained by the Stokes–Einstein–Debye model.
  • Takao Tsuneda, Tsuyoshi Hirosawa, Yutaka Nakatsuka, Kimihiko Hirao
    2009 Volume 82 Issue 11 Pages 1367-1371
    Published: November 15, 2009
    Released: November 10, 2009
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    Reproducibilities of d–π bonds were investigated on calculating complexes of first-row transition-metal cation (M+) and benzene (Bz). Calculations were carried out for half-sandwich MBz+ and sandwich MBz2+ complexes with several types of density functional theories (DFTs) and single-configurational wave function theories (WFTs). As a result, it was concluded that electron correlations are required to give the binding energies of d–π bonds even qualitatively, and DFTs would reproduce d–π bonds with quantitative accuracies only if electron correlations and long-range exchange interactions were both taken into consideration in exchange-correlation functionals used. In MBz+ calculations, WFTs fairly underestimated the binding energies for early transition metals (M = Sc–Cr) because of multiconfigurational effects. In contrast, DFTs overestimated them for late transition metals (M = Fe–Cu) due to insufficient long-range interactions in exchange functionals. For MBz2+, DFTs and WFTs gave similar binding energies for MBz2+, although WFTs slightly overestimated them for late transition metals. Furthermore, it was suggested that the experimental binding energies of CrBz2+ and MnBz2+ are probably misestimated.
  • Béla Barabás, Luciano Caglioti, Károly Micskei, G ...
    2009 Volume 82 Issue 11 Pages 1372-1376
    Published: November 15, 2009
    Released: November 10, 2009
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    Statistical distribution of enantiomeric excesses obtained by two sets of parallel experiments of absolute asymmetric synthesis by asymmetric autocatalysis was analyzed. It has been found that experimental data give an excellent fit to a bimodal β distribution formula, where the components are in a golden section ratio. The parameters of this higher order β distribution were found by computer-simulated Pólya urn model experiments. The urn model experiments indicate that the Soai-autocatalysis might operate by three concerted cooperating catalytic cycles. These results may provide also a general model of asymmetric autocatalysis.
  • Jun Yoshida, Shin-ichi Nishikiori, Reiko Kuroda
    2009 Volume 82 Issue 11 Pages 1377-1385
    Published: November 15, 2009
    Released: November 10, 2009
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    Two crystals, [{Co(hfac)2}{Ni(pyterpy)2}][Co(hfac)3]2 (1) and [Co(CNacac)2][Ni(pyterpy)2]SO4·xG (2), composed of 1D cationic coordination polymers were prepared by self-assembly of achiral component metal complexes in solution (hfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dionato, CNacac = 3-cyanopentane-2,4-dionato, pyterpy = 4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine, G = methanol and water). 1 is chiral and spontaneously optically resolved, whereas 2 is achiral. In 1, an alternate linkage of [Co(hfac)2] and [Ni(pyterpy)2]2+ forms a 1D coordination polymer and twisting of the two complexes about the principal axis of the 1D polymer makes the polymer axially chiral. The 1D polymers stack to create two-types of 1D channels, where anionic complexes [Co(hfac)3] are included. One channel contains only Δ-[Co(hfac)3], whereas the other contains an equal amount of Δ- and Λ-[Co(hfac)3]. Therefore, the Δ/Λ ratio of [Co(hfac)3] is 3/1. In the case of 2, 1D coordination polymers are formed by an alternate linkage of [Co(CNacac)2] and [Ni(pyterpy)2]2+. They are chiral due to twisting of one pyridine ring in [Ni(pyterpy)2]2+, however, there are inversion centers in 2. These results demonstrated that axial chirality can be introduced into 1D coordination polymers by twisting the two component metal complexes alternately linked. This method is useful and prospective for preparing chiral coordination polymers from achiral building blocks.
  • Hisashi Shimakoshi, Takeshi Kaieda, Yoshio Hisaeda
    2009 Volume 82 Issue 11 Pages 1386-1392
    Published: November 15, 2009
    Released: November 10, 2009
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    A one-pot synthesis of a new polycationic organo–dicobalt complex having dual cationic alkyl groups as radical sources is reported. The complex was characterized by elemental analysis, UV–vis, 1H NMR, IR, and CSI-mass spectroscopies. CSI-MS afforded intact parent ion peak with labile cobalt–carbon bonds in the complex. The complex was photosensitive, and photocleavage of the cobalt–carbon bonds upon irradiation with visible light produced dual cationic carbon-centered radicals that were detected by EPR spin-trapping. Strong binding of the dicobalt complex with six cationic moieties toward DNA was confirmed by ethidium bromide displacement assays with Kapp = 3.2 × 107 M−1 at 298 K, the value was 100 times that of corresponding monocobalt complex with Kapp = 3.3 × 105 M−1. The dicobalt complex exhibited high ability for single- and double-strand DNA cleavage in comparison with that for the corresponding monocobalt complex under irradiation with visible light.
  • Suntharee Busbongthong, Tomoji Ozeki
    2009 Volume 82 Issue 11 Pages 1393-1397
    Published: November 15, 2009
    Released: November 10, 2009
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    Crystals of (CH3NH3)3[PW12O40]·2H2O (1), [(CH3)2NH2]3[PW12O40] (2), and [(CH3)3NH]3[PW12O40] (3) exhibit a similar packing of cations and anions, although they crystallize into different space group types, namely , , and , respectively. Their structures were interpreted in terms of supergroup–subgroup relationships, revealing that the basic arrangements of cations and anions are primarily dominated by electrostatic interactions on which hydrogen bonds exert influences.
  • Shin-ichi Takekuma, Kenji Fukuda, Toshie Minematsu, Hideko Takekuma
    2009 Volume 82 Issue 11 Pages 1398-1408
    Published: November 15, 2009
    Released: November 10, 2009
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    Wittig reactions of (E)-4-(4-methoxyphenyldiazenyl)benzaldehyde and (E)-4-[4-(dimethylamino)phenyldiazenyl]benzaldehyde with (3-guaiazulenylmethyl)triphenylphosphonium bromide in ethanol in the presence of sodium ethoxide at 25 °C for 24 h under argon give only E forms (E)-4-{(E)-4-[2-(3-guaiazulenyl)vinyl]phenyldiazenyl}methoxybenzene and (E)-N,N-dimethyl-4-{(E)-4-[2-(3-guaiazulenyl)vinyl]phenyldiazenyl}aniline in 71 and 73% yields. Comparative studies on spectroscopic properties and crystal structures of the two new extended π-electron systems with those of structurally related (and delocalized) π-electron systems (3-guaiazulenyl)[(E)-4-(4-methoxyphenyldiazenyl)phenyl]methylium ion and {(E)-4-[4-(dimethylamino)phenyldiazenyl]phenyl}(3-guaiazulenyl)methylium ion compounds are reported. Similarly, Wittig reaction of (E)-diphenyldiazene-4,4′-dicarbaldehyde with the same reagent under the same reaction conditions as the above affords only E forms (E)-4-{(E)-4-[2-(3-guaiazulenyl)vinyl]phenyldiazenyl}benzaldehyde and (E)-bis{(E)-4-[2-(3-guaiazulenyl)vinyl]phenyl}diazene in 7 and 24% yields. Furthermore, reaction of guaiazulene (=7-isopropyl-1,4-dimethylazulene) with (E)-diphenyldiazene-4,4′-dicarbaldehyde in methanol in the presence of hexafluorophosphoric acid at 25 °C for 30 min provides (E)-diphenyldiazene-4,4′-bis(3-guaiazulenylmethylium) bis(hexafluorophosphate) in 46% yield which upon reduction with NaBH4 in a mixed solvent of ethanol and acetonitrile at 25 °C for 30 min gives (E)-bis[4-(3-guaiazulenylmethyl)phenyl]diazene in 88% yield. Comparative studies of spectroscopic properties of a new extended π-electron system (E)-bis{(E)-4-[2-(3-guaiazulenyl)vinyl]phenyl}diazene with those of a new delocalized π-electron system (E)-diphenyldiazene-4,4′-bis(3-guaiazulenylmethylium) bis(hexafluorophosphate) are documented.
  • Maria Carmelita Z. Kasuya, Mami Tojino, Shinya Nakano, Mamoru Mizuno, ...
    2009 Volume 82 Issue 11 Pages 1409-1415
    Published: November 15, 2009
    Released: November 10, 2009
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    A series of fluorous-tagged saccharide primers with different contents of fluorous atoms was synthesized and introduced into mouse melanoma B16 cells. The primers did not affect cell morphology and viability at a concentration of 50 µM. The numerous fluorine atoms did not pose a steric barrier to primer assimilation into cells and did not affect cellular-enzyme-catalyzed glycosylation. The lactoside primers were sialylated to afford GM3-type oligosaccharide. On the other hand, the GlcNAc primers were galactosylated to afford a lactosamine derivative that was further sialylated by cellular enzymes to afford a sialylated lactosamine.
  • Kenji Kobayashi, Yuto Kita, Motoyuki Shigeiwa, Satoru Imamura, Shuuich ...
    2009 Volume 82 Issue 11 Pages 1416-1425
    Published: November 15, 2009
    Released: November 10, 2009
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    Differentially functionalized hexakis( p-substituted-phenylethynyl)benzene and hexakis[4-( p-substituted-styryl)phenylethynyl]benzene derivatives with various (D6h, D3h, D2h, and C2v) symmetries were synthesized by Sonogashira cross-coupling reactions. The optical properties of this starburst-type π-conjugated system were investigated. Among them, hexakis[4-( p-dioctylaminostyryl)phenylethynyl]benzene (5) showed the largest two-photon absorption cross-section of δ = 818 GM at 800 nm, which was determined by open aperture Z-scan with 120 fs laser pulses in toluene solution.
  • Ping-Jyun Sung, Su-Hui Wang, Michael Y. Chiang, Yin-Di Su, Yu-Chia Cha ...
    2009 Volume 82 Issue 11 Pages 1426-1432
    Published: November 15, 2009
    Released: November 10, 2009
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    Four briarane-type diterpenoids, including two new chlorinated metabolites, fragilides F (1) and G (2), along with two known compounds, junceellonoid D (3) and juncin Z (4), were isolated from the gorgonian coral Junceella fragilis. The structures of new briaranes 1 and 2 were elucidated by spectral data analysis and the absolute configuration of 1 was directly determined by a single-crystal X-ray diffraction analysis. The relationships between proton chemical shifts and conformations of the methylenecyclohexane ring in briaranes possessing a C-11/20 carbon–carbon double bond are described. Briarane 4 was found to exhibit significant cytotoxicity toward the CCRF-CEM tumor cells.
  • Tatsuya Wada, Yuto Sumida, Azusa Kondoh, Hideki Yorimitsu, Koichiro Os ...
    2009 Volume 82 Issue 11 Pages 1433-1435
    Published: November 15, 2009
    Released: November 10, 2009
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    Radical addition of bromotrichloromethane to 2-ethynyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane takes place in the presence of a radical initiator in refluxing benzene. Perfluoroalkyl iodides undergo similar addition reactions. The addition reactions proceed in an anti fashion. The corresponding 1-halo-1-alkenylboronic esters are useful intermediates that undergo cross-coupling reactions.
  • Tomohito Kameda, Takashi Yamazaki, Toshiaki Yoshioka
    2009 Volume 82 Issue 11 Pages 1436-1440
    Published: November 15, 2009
    Released: November 10, 2009
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    Mg–Al layered double hydroxide intercalated with 2,7-naphthalene disulfonate ion (2,7-NDS·Mg–Al LDH) was prepared by coprecipitation and was found to selectively take up aromatic compounds from aqueous solutions. The amount of material absorbed by 2,7-NDS·Mg–Al LDH depends on the electron-donating or -withdrawing properties of the functional groups on the molecules to be absorbed. The absorption mechanism is dependent on π–π stacking interactions between the aromatic ring of the molecules to be absorbed and the naphthalene moiety of 2,7-NDS2−.
  • Kingo Uchida, Hibiki Sumino, Yumiko Shimobayashi, Yousuke Ushiogi, Ats ...
    2009 Volume 82 Issue 11 Pages 1441-1446
    Published: November 15, 2009
    Released: November 10, 2009
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    A bis(2-thienyl)perfluorocyclopentene having methoxy groups at both reactive carbon atoms was synthesized and the quantum yields of cyclization and cycloreversion reactions were found to be 0.29 and 0.27, respectively. Usual bis(3-thienyl)perfluorocyclopentenes with methoxy groups at both reactive carbon atoms show much lower cycloreversion quantum yields. The unusual large yield was explained by theoretical methods. Additionally the compound did not show any coloration in crystalline state upon UV irradiation, even though the distance between both reactive carbon atoms is less than 4 Å. The reason was discussed by using the crystallographic data.
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