Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 86 , Issue 4
Showing 1-16 articles out of 16 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for Creative Work for 2011
  • Hiromi Okamoto
    2013 Volume 86 Issue 4 Pages 397-413
    Published: April 15, 2013
    Released: April 15, 2013
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    Studies on physical and chemical properties of noble metal nanostructures, mainly by near-field optical microscopy and spectroscopy, are described. Near-field optical microscopy provides optical observation methodology with a spatial resolution in nanometer regime beyond the diffraction limit of light. We developed near-field imaging systems equipped with various light sources including ultrashort pulsed lasers, which enables advanced nonlinear and ultrafast near-field measurements as well as conventional near-field imaging. In particular, near-field two-photon excitation imaging was shown to provide a convenient tool to visualize the enhanced optical fields in the vicinities of metal nanostructures. With these methods we demonstrated that nanoscale optical field structures in metal nanostructures can be directly visualized. For single noble metal nanoparticles, such as gold nanorods as typical examples, plasmon standing wave functions were visualized. Ultrafast imaging revealed that sub-picosecond relaxation was reflected on the plasmon wave function images through thermally induced dielectric function changes of the metal. In some cases optical field distribution features arising from the lightning rod effects were observed, depending on the resonance conditions of the incident wavelengths with the plasmon modes. We also found anomalous near-field transmission phenomenon for nanoapertures blocked by nanodisks near the plasmon resonance wavelengths, which arise from the efficient near-field to propagating-field conversion ability of the nanodisks. In assembled nanoparticles, enhanced optical fields at the gap sites between the particles were visualized, which elucidates experimentally the mechanism of surface-enhanced Raman scattering. The characteristic field distributions in many particle assemblies were also observed and analyzed. Through these studies, we established a valuable methodology to investigate optical and spectroscopic properties of metal nanostructures, and the information obtained is available only by optical measurements with high spatial resolution.
    Plasmon standing wave functions and spatial distributions of optical fields were visualized for noble metal nanostructures by near-field optical imaging methods. Characteristic optical features of metal nanostructures were revealed. Fullsize Image
     
The Chemical Society of Japan Award for Creative Work for 2008
  • Atsushi Nakajima
    2013 Volume 86 Issue 4 Pages 414-437
    Published: April 15, 2013
    Released: April 15, 2013
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    Clusters consisting of 10–1000 atoms size-dependently exhibit novel electronic and geometric properties. In particular, composite clusters composed of several elements and/or components provide a promising way for a bottom-up approach for designing functional advanced materials, because the functionality of the composite clusters can be optimized not only by the cluster size but also by their compositions. This account surveys recent investigations of composite clusters focusing on the efforts to create a new functional composite cluster by a fine doping or hybridization based on their size-specific electronic properties. Organometallic clusters and caged clusters are demonstrated as a representative example of designing the functionality of magnetism and electronic state structures. In order to create functional nanomaterials, furthermore, a fine controlling methodology of the soft-landing technique has been developed to fix the composite clusters onto a surface decorated with a self-assembled monolayer. The embedded isolation mechanism on the substrate is discussed form the viewpoint of self-assembly phenomena with the molecular ordering of σ–σ interaction, and also the electronic structures characterized by molecular ordering of π–π interaction is intrinsically revealed by molecular clusters of π-conjugate polyacenes as a model for self-assembled aggregates.
    Composite clusters composed of several elements and/or components provide a promising way for a bottom-up approach for designing functional advanced materials. This account surveys recent investigations of composite clusters focusing on the efforts to create organometallic clusters and caged clusters with the development of a soft-landing technique with a self-assembled monolayer. Self-assembly phenomena are also discussed using molecular clusters of π-conjugate polyacenes. Fullsize Image
     
BCSJ Award Article
  • Tohru Saitoh, Akihiro Arakawa, Masataka Hiraide
    2013 Volume 86 Issue 4 Pages 438-444
    Published: April 15, 2013
    Released: April 15, 2013
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    A thermoresponsive polymer containing highly dense iminodiacetic acid segments was newly designed for the efficient preconcentration of trace metals in water. The polymer was synthesized by the water-soluble carbodiimide-mediated condensation of poly(N-isopropylacrylamide-co-acrylic acid) with polyallylamine and the subsequent conversion of amino groups to iminodiacetic acid. Metal ions in water were collected by adding the thermoresponsive polymer, sodium nitrate, dodecyltrimethylammonium chroride, and buffer components and then heating the resulting solution to form polymer deposits. The use of 0.02% (w/v) thermoresponsive polymer allowed the nearly complete (>99.8%) collection of seven metals (Be, Co, Ni, Cu, Cd, In, and Pb) in the pH range of 6.8–8.3. The polymer deposits were readily collected as a condensed coagulate and dissolved with a small amount of water for the analysis by graphite furnace atomic absorption spectrometry. Because of highly efficient (100-fold) concentration, these metals at pg cm−3–ng cm−3 levels were successfully determined. The precision and accuracy were evaluated by analyzing certified reference water samples.
    The use of a newly designed thermoresponsive polymer having highly dense iminoacitic acid segments allowed nearly complete collection of different metal ions from water for the sensitive determination by graphite furnace atomic absorption spectrometry. Fullsize Image
     
 
  • Ryoichi Fukuda, Masahiro Ehara
    2013 Volume 86 Issue 4 Pages 445-451
    Published: April 15, 2013
    Released: April 15, 2013
    [Advance publication] Released: March 20, 2013
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    The excited electronic states and optical absorption spectra of coronene (C24H12), hexa-peri-hexabenzocoronene (HBC) (C42H18), and circumcoronene (C54H18) were studied using the symmetry-adapted cluster-configuration interaction (SAC-CI) method. For coronene and HBC, the SAC-CI calculations reproduced the experimental spectra well and predicted optically forbidden excited states. For HBC, the symmetry lowering enhanced the intensity of the S2 state that corresponds to the p-band, and the SAC-CI calculation predicted the existence of the second and third optically allowed states around the β-band region near 4.0 eV. For circumcoronene, the SAC-CI calculation predicted a strong absorption of the β-band in the visible light region. The mechanisms of energy splitting for the HOMO–LUMO transition were investigated. Electron correlation was the most important factor for the energy splitting between the lowest and the next-lowest states. Configuration interaction with single excitations (CIS) calculations could not correctly predict the relative energies of these states in coronene and circumcoronene. For HBC, on the other hand, the CIS calculation provided the same energy order as the SAC-CI calculation.
  • Masaki Okada, Kazuyasu Ibuki, Masakatsu Ueno
    2013 Volume 86 Issue 4 Pages 452-463
    Published: April 15, 2013
    Released: April 15, 2013
    [Advance publication] Released: March 20, 2013
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    NMR spin–lattice relaxation times (T1) for nucleus D of D2O in deuterated formamide (FA-d3)–D2O mixtures were measured up to 80 mol % of FA-d3 at 25 °C under pressure up to 196.1 MPa. To discuss the pressure effect on the dynamic behavior of water molecules in the mixtures, the reorientational correlation times (τc) of D2O molecules were estimated from the quadrupole coupling equation. τc monotonously increased with increasing FA-d3 content at all pressures studied. However, τc apparently decreased with increasing pressure until 20 mol % of FA-d3, while over 40 mol % of FA-d3 the pressure coefficient of τc (∂τc/∂P) became positive and larger with increasing FA-d3 content. A negative pressure coefficient would indicate the existence of three-dimensional hydrogen-bonded network structure of water, and a positive one would be ascribed to the strengthening of dipole interactions and hydrogen bonds between FA-d3 and D2O by compression. In order to investigate the pressure effect on the reorientational dynamics of water molecules in detail, we performed molecular dynamics (MD) simulations paying attention to the pressure effect on hydrogen-bonding and dipole interactions.
  • Takao Okazaki, Taisuke Adachi, Toshikazu Kitagawa
    2013 Volume 86 Issue 4 Pages 464-471
    Published: April 15, 2013
    Released: April 15, 2013
    [Advance publication] Released: March 20, 2013
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    Fluoranthene and benzo[k]fluoranthene (3) are nonalternant polyaromatic hydrocarbons. Their derivatives, 3-acetyl, 8-acetyl, 3-nitro, and 3-aminofluoranthenes (4, 5, 7, and 8) were reacted in FSO3H/SO2ClF and the solutions were observed by NMR measurements at low temperatures, which showed the formation of PAH-substituted onium ions. The most deshielded 13C peaks in fluoranthene frames were observed at 155.7 and 148.7 ppm for 4H+, 154.4 ppm for 5H+, 159.1 and 139.6 ppm for 7H+, and 139.7 ppm for 8H+. Distribution of the positive charges were estimated on the basis of changes in 13C NMR chemical shifts between onium ions and their corresponding parent compounds. Only limited delocalization of positive charges into the aromatic rings was found to occur. GIAO-derived NMR chemical shifts calculated by the DFT method were generally consistent with the experimental chemical shifts. DFT calculations suggested that benzo[k]fluoranthene (3) is favored to be protonated at C-3/C-7 positions. GIAO-derived NICS(1)zz were computed to elucidate aromaticity/antiaromaticity, and the results suggested that the five-membered rings are antiaromatic for cations 4H+, 7H+, 8H+, and 3aH+ (3-benzo[k]fluoranthenium ion).
  • Jinghan Zou, Shuhui Yin, Mingxing Guo, Xuesong Xu, Li Che, Lei Li, Hon ...
    2013 Volume 86 Issue 4 Pages 472-478
    Published: April 15, 2013
    Released: April 15, 2013
    [Advance publication] Released: March 20, 2013
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    Using a new 3D adiabatic potential energy surface constructed by Lv et al. (S.-J. Lv, P.-Y. Zhang, K.-L. Han, G.-Z. He, J. Chem. Phys. 2010, 132, 014303), the product polarizations in the reactions H + NeH+/NeD+/NeT+ → H2+/HD+/HT+ + Ne are studied by employing a quasi-classical trajectory method. The distributions of P(θr), P(φr), P(θr, φr) and PDDCSs are calculated at the collision energies of 0.5 and 20 kcal mol−1. The influence of isotope substitution on the product polarization is revealed. The isotopic effect may be attributed to the difference in the mass factor in the title reactions. The noteworthy effect of the potential well on stereodynamics for the title reactions are observed and discussed in the paper.
  • Tomoya Ichino, Yasunori Yoshioka
    2013 Volume 86 Issue 4 Pages 479-491
    Published: April 15, 2013
    Released: April 15, 2013
    [Advance publication] Released: March 20, 2013
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    Based on the structure at 1.9 Å resolved OEC (PDBid=3ARC), geometries and electronic structures of the S0, S1, and S2 states in the Kok cycle have been theoretically investigated by the broken-symmetry B3LYP method. The exchange coupling constants of spins in three states were also estimated. The oxidation states of four manganese atoms at the S0 state are Mn4[III, III, IV, III]. It was found that the hydrogen-bonding patterns of water molecules are influenced by the electronic structure of the CaMn4O5 core. At the S1 state, the oxidation states are Mn4[III, IV, IV, III]. The hydrogen-bonding pattern of the lowest state is similar to that of the higher energy state of the S0 state. The H2O molecule coordinated to the Mn4 atom loses a proton to yield an OH anion. At the S2 state, the oxidation states are Mn4[III, IV, IV, IV]. For S0 → S1 → S2 states, the released electrons have the same direction of spins. Only Mn atoms are oxidized not the substrate (H2O). Our theoretical results are consistent with the observed results.
  • Hiroki Matsubara, Tetsumasa Takaichi, Takanori Takiue, Hajime Tanida, ...
    2013 Volume 86 Issue 4 Pages 492-496
    Published: April 15, 2013
    Released: April 15, 2013
    [Advance publication] Released: March 20, 2013
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    X-ray reflectivity measurements were applied to hexadecane wetting film on aqueous solutions of hexadecyltrimethylammonium bromide (CTAB) and tetradecyltrimethylammonium bromide (TTAB). In both cases, the monolayers in which oil molecules are penetrated from hexadecane droplets into surfactant-adsorbed films were found at room temperature. Upon cooling, they showed first-order freezing transitions, however, it was also confirmed that the structures of freezing films were qualitatively different: hexadecane molecules were frozen together with CTAB to form mixed solid monolayer in CTAB–hexadecane while the frozen hexadecane monolayer wetted mixed liquid monolayer in TTAB–hexadecane.
  • Meysam Najafi, Mohammad Najafi, Houshang Najafi
    2013 Volume 86 Issue 4 Pages 497-509
    Published: April 15, 2013
    Released: April 15, 2013
    [Advance publication] Released: March 20, 2013
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    In this paper, the study of various ortho- and meta-substituted tyrosol derivatives is presented. The reaction enthalpies related to three antioxidant action mechanisms HAT, SET-PT, and SPLET for substituted tyrosols have been calculated using the DFT/B3LYP method in gas phase and water. Calculated results show that electron-withdrawing substituents increase the bond-dissociation enthalpy (BDE), ionization potential (IP), and electron-transfer enthalpy (ETE), while electron-donating ones cause a rise in the proton-dissociation enthalpy (PDE) and proton affinity (PA). In the ortho-position, substituents show larger effect on reaction enthalpies than at the meta-position. In comparison to the gas phase, water attenuates the substituent effect on all reaction enthalpies. In the gas phase, BDEs are lower than PAs and IPs, i.e., HAT represents the thermodynamically preferred pathway. On the other hand, SPLET mechanism represents the thermodynamically favored process in water. Results show that calculated enthalpies can be correlated with Hammett constants (σm) of the substituted tyrosols successfully. Furthermore, calculated IP and PA values for substituted tyrosols show linear dependence on the energy of the highest occupied molecular orbital (EHOMO).
  • Tokiko Murase, Toshitada Yoshihara, Keiichi Yamada, Seiji Tobita
    2013 Volume 86 Issue 4 Pages 510-519
    Published: April 15, 2013
    Released: April 15, 2013
    [Advance publication] Released: March 20, 2013
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    The photophysical properties of protected nonnatural amino acids Boc–L-Dap(7DEAC)–OMe (7DEAC: 7-diethylaminocoumarin) and Boc–L-Dap(C343)–OMe (C343: coumarin 343) were investigated to evaluate the suitability of these amino acids as fluorescent units in peptide-based fluorescent biosensors. The absorption and fluorescence spectra of Boc–L-Dap(7DEAC)–OMe and Boc–L-Dap(C343)–OMe exhibited significant red shifts with increasing solvent polarity. The fluorescence quantum yield and lifetime of Boc–L-Dap(7DEAC)–OMe solutions decreased remarkably with increasing solvent polarity, whereas those of Boc–L-Dap(C343)–OMe were slightly affected by the solvent polarity. Fluorescent peptides H–Dap(7DEAC)–LLA–OMe (1), H–Dap(7DEAC)–KLA–OMe (2), and H–Dap(7DEAC)–ELA–OMe (3) labeled with environment-sensitive 7DEAC were synthesized to examine the interactions of these labeled peptides with lipid membranes and living cells. Neutral 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and anionic 1,2-dimyristoyl-sn-glycero-3-[phospho-rac-(1-glycerol)] (DMPG) liposomes were used to investigate peptide–membrane interactions. Hydrophobic peptide 1 exhibited high affinities to both DMPC and DMPC/DMPG mixed membranes. Of the three peptides, cationic peptide 2 exhibited the strongest affinity to DMPC/DMPG membranes, whereas anionic peptide 3 showed a much lower affinity to DMPC/DMPG membranes. These results could be interpreted based on hydrophobic and electrostatic interactions between the peptides and membranes. Peptide 1 was efficiently internalized into HeLa cells, whereas peptides 2 and 3 showed a much lower intracellular delivery.
  • Fumiya Nikaido, Susumu Inasawa, Yoshiko Tsuji, Yukio Yamaguchi
    2013 Volume 86 Issue 4 Pages 520-525
    Published: April 15, 2013
    Released: April 15, 2013
    [Advance publication] Released: March 20, 2013
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    Previous studies have proposed that silica has micropores or a “gel layer” on its surface; however, previous models of silica dissolution have considered only the top monolayer, and neglected the internal structure of silica. Here, we have developed a dissolution model that takes into account acid dissociation of internal silanol groups. The dissolution rates of silica, the solution pH and the electrophoretic mobilities of the silica particles were measured in basic aqueous media. These parameters were very different depending on the conditions, however all parameters behaved as expected based upon our simple model. In the model, we considered the surface potential and the potential inside the silica particle to quantify the acid dissociation of the top-surface and internal silanols, respectively. The dissolution rates were proportional to the number of top-surface deprotonated silanols, [≡SiO]top. Internal silanol was not directly involved in the dissolution reaction, however acid dissociation of internal silanol must be considered to evaluate [≡SiO]top. Electrophoretic mobilities are discussed to confirm the validity of our model.
  • Tadashi Kawamoto, Minoru Ashizawa, Takehiko Mori
    2013 Volume 86 Issue 4 Pages 526-528
    Published: April 15, 2013
    Released: April 15, 2013
    [Advance publication] Released: March 20, 2013
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    Crystal structure, transport, and magnetic properties of a new organic conductor (ChTM-TTP)2Ag(CN)2, where ChTM-TTP is 2-[4,5-(1,2-cyclohexylenedithio)-1,3-dithiol-2-ylidene]-5-[4,5-bis(methylthio)-1,3-dithiol-2-ylidene]-1,3,4,6-tetrathiapentalene, have been studied. Although the crystal structure is similar to metallic ChTM-TTP conductors, the present compound is a paramagnetic semiconductor even at room temperature, indicating strongly electron correlation.
  • Daolai Sun, Fumiya Sato, Shin-ichi Yamauchi, Yasuhiro Yamada, Satoshi ...
    2013 Volume 86 Issue 4 Pages 529-533
    Published: April 15, 2013
    Released: April 15, 2013
    [Advance publication] Released: March 20, 2013
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    Dimerization of 1,3-butadiene was investigated in a closed batch system under high-pressure conditions. 4-Vinylcyclohexene was mainly produced without using any solvents or catalysts at temperatures of 150–215 °C. The conversion of 1,3-butadiene was significantly dependent on the temperature and pressure. 1,3-Butadiene was converted to 4-vinylcyclohexene at selectivity higher than 90 mol % with by-products of 1,5-cyclooctadiene and 1,2-divinylcyclobutane. Large charges of reactant are efficient in achieving high conversions of 1,3-butadiene. Use of solvents, which dilute the reactant and absorb the reaction heat, is not favorable in the present dimerization of 1,3-butadiene under pressured conditions.
  • Tetsuya Nanba, Tomohiro Chino, Shoichi Masukawa, Junko Uchisawa, Akira ...
    2013 Volume 86 Issue 4 Pages 534-539
    Published: April 15, 2013
    Released: April 15, 2013
    [Advance publication] Released: March 20, 2013
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    We investigated the total oxidation of toluene over Cu/MOx/SiO2 (M = metal) catalysts. Among the metal oxides used to modify the SiO2 support, TiO2 afforded the catalyst with the highest activity. The optimum Cu and TiO2 loadings were 3 and 10 wt %, respectively. Changes in the Cu loading had little influence on the activation energy of the toluene oxidation reaction. Cu/TiO2/SiO2 was more active than Cu/TiO2 because the Cu and TiO2 were more highly dispersed on the SiO2 support of the former. We characterized the Cu species by temperature-programmed reduction with NH3, which showed that in Cu/TiO2/SiO2, Cu2+ was reduced at a lower temperature and Cu+ at a higher temperature than in Cu/TiO2 or Cu/SiO2. That is, the TiO2-modified SiO2 was a good support for Cu because the modification widened the temperature range over which the Cu2+ Cu+ redox cycle occurred.
  • Naoyuki Nishimura, Kazuhiko Maeda, Tsuyoshi Takata, Daling Lu, Jun Kub ...
    2013 Volume 86 Issue 4 Pages 540-546
    Published: April 15, 2013
    Released: April 15, 2013
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    Methods of fabricating photoelectrodes from LaTiO2N particles on fluorine-doped tin oxide (FTO) glasses for photoelectrochemical (PEC) water splitting were studied. Several sizes of LaTiO2N particles were synthesized by the nitridation of oxide precursors of varying particle size under ammonia flow. TiCl4 treatment, which binds particles both to each other and to substrates, was examined. Without TiCl4 treatment, photoelectrodes made from smaller LaTiO2N particles generated a higher photocurrent. On the other hand, photoelectrodes made from larger LaTiO2N particles generated a higher photocurrent with the treatment. The effect of electronic contact between particles on the PEC properties was examined.
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