Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 88 , Issue 5
Showing 1-18 articles out of 18 articles from the selected issue
Accounts for Nanospace Materials
  • Zhehao Huang, Shunai Che
    2015 Volume 88 Issue 5 Pages 617-632
    Published: May 15, 2015
    Released: May 15, 2015
    [Advance publication] Released: January 19, 2015
    JOURNALS FREE ACCESS
    This account describes our recent advances on the fabrication of mesoporous/mesostructured silica materials through the co-structure-directing route. This route establishes critical interactions between the head groups of templates and co-structure-directing agent (CSDA) to form highly ordered mesostructures and well-defined morphologies. Three particular approaches are described based on the different kinds of templates: anionic surfactants, cationic surfactants, and biomolecules (DNA and peptides). Notably, because of the pairing effect between templates and CSDA, the functional groups can be arranged regularly in the surface of the mesopores. Moreover, the applications and future perspective of mesoporous materials synthesized through co-structure-directing route are briefly described.
    Due to the favorable interactions introduced by co-structure-directing route, mesoporous and mesostructured silica materials with diverse structures and morphologies were synthesized by using anionic surfactants, cationic surfactants, and biomolecules. This method also provides a simple way to functionalize the materials. Fullsize Image
     
Accounts
  • Yoshiki Chujo, Kazuo Tanaka
    2015 Volume 88 Issue 5 Pages 633-643
    Published: May 15, 2015
    Released: May 15, 2015
    JOURNALS FREE ACCESS
    The concept and representative examples of “element-block polymers” are described. A structural unit consisting of various groups of elements is called an “element-block.” In this review, unique properties of “element-block polymers” composed of organoboron complexes, o-carboranes, and polyhedral oligomeric silsesquioxanes as typical examples of element blocks are illustrated. The design and synthesis of new element-blocks and development of methods forming higher-order structures for realizing the desired functions based on a bottom-up approach are explained.
    The concept and representative examples of “element-block polymers” are described. A structural unit consisting of various groups of elements is called as “element-block.” In this review, unique properties of “element-block polymers” composed of organoboron complexes, o-carboranes, and polyhedral oligomeric silsesquioxanes as typical examples of element blocks are illustrated. The design and synthesis of new element-blocks and development of methods forming higher-order structures for realizing desired functions based on a bottom-up approach are explained. Fullsize Image
     
BCSJ Award Article
  • Haruna Shimizu, Hulin Tai, Kaori Saito, Tomokazu Shibata, Masashi Kino ...
    2015 Volume 88 Issue 5 Pages 644-652
    Published: May 15, 2015
    Released: May 15, 2015
    [Advance publication] Released: February 10, 2015
    JOURNALS FREE ACCESS
    The molecular structure and heme electronic structure of a complex (heme–(d(TTAGGGT))4 complex) between heme and a parallel G-quadruplex DNA formed from heptanucleotide d(TTAGGGT), i.e., (d(TTAGGGT))4, have been characterized using 1H NMR. The study demonstrated that the heme is accommodated between G6 and T7 of the G-quadruplex DNA to form a 1:1 complex between the heme and DNA. The spin state of the heme Fe3+ of the heme(Fe3+)–(d(TTAGGGT))4 complex exhibited a characteristic pH-dependent change from a high spin (HS) state, i.e., S = 5/2, at low pH to a thermal spin equilibrium between the HS and low spin state (LS), i.e., S = 1/2, at high pH, with a midpoint at the pH value of 8.9 ± 0.2. The pH-dependent spin state change of the heme(Fe3+)–(d(TTAGGGT))4 complex was similar to that of metmyoglobin (T. M. McGrath and G. N. La Mar, Biochim. Biophys. Acta, 1978, 534, 99–111), demonstrating that these two systems are highly alike in terms of the heme environment. This finding provides novel insights as to the design of the heme–DNA complexes that exhibit catalytic activities similar to those of hemoproteins.
    Heme (iron–porphyrin complex) and a parallel G-quadruplex DNA assembled from d(TTAGGGT) form a 1:1 complex through stacking of the heme between G6 and T7 of the DNA. Fullsize Image
     
 
  • Hiroaki Imoto, Katsuya Ishida, Ai Sasaki, Yasuyuki Irie, Hideaki Ito, ...
    2015 Volume 88 Issue 5 Pages 653-656
    Published: May 15, 2015
    Released: May 15, 2015
    [Advance publication] Released: February 04, 2015
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    Mixture of octa(3-aminopropyl) polyhedral oligomeric silsesquioxane (POSS-NH2) and tetrachloroauric(III) acid under basic condition spontaneously produced gold nanoparticles (AuNPs). The amino groups reduced Au(III) cation to Au(0) and interacted with the surface of AuNPs; POSS-NH2 worked as a reductant and a stabilizer at once. Sodium hydroxide partially hydrolyzed Si–O bonds of polyhedoral oligomeric silsesquioxane (POSS) to generate SiO species, which stabilized AuNPs via electrostatic interparticle repulsion to avoid aggregation. Addition of hydrochloric acid neutralized the amino groups of POSS-NH2, and generated NH3+ interacted with SiO to form aggregates. That is, pH-responsive AuNPs were prepared through the facile method.
  • Yoshiteru Hosaka, Noriya Ichikawa, Takashi Saito, Mitsutaka Haruta, Ko ...
    2015 Volume 88 Issue 5 Pages 657-661
    Published: May 15, 2015
    Released: May 15, 2015
    [Advance publication] Released: February 05, 2015
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    A new double perovskite Ca2FeMnO6 with a layered arrangement of Mn4+ and the unusually high-valence Fe4+ was obtained by oxidizing the precursor brownmillerite Ca2FeMnO5 with ozone at 200 °C. This low-temperature topotactic reaction kept the layered cation arrangement of the brownmillerite but oxidized Mn3+ to Mn4+ and Fe3+ to Fe4+. The crystal structure with a P21/c space group was revealed by detailed structure analysis with neutron powder diffraction data, and the layered arrangement of the cations was confirmed in an STEM-EELS elemental mapping image. The fully oxidized chemical composition was also confirmed by thermogravimetric analysis. Even with the two-dimensional layered arrangement, the instability of the unusually high-valence Fe4+ in Ca2FeMnO6, like that of the Fe4+ in the perovskites CaFeO3 and CaCu3Fe4O12 with three-dimensional arrangements of Fe4+, was relieved by charge disproportionation (2Fe4+ → Fe3+ + Fe5+) at a low temperature.
  • Abdolhamid Bamoniri, Naimeh Moshtael-Arani
    2015 Volume 88 Issue 5 Pages 662-672
    Published: May 15, 2015
    Released: May 15, 2015
    [Advance publication] Released: January 22, 2015
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    A new type of green heterogeneous solid acid was prepared by the immobilization of BF3·Et2O on the surface of Fe3O4@SiO2 core–shell nanocomposite (Fe3O4@SiO2–BF3) and characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), vibrating sample magnetometer (VSM), field emission scanning electron microscope (FE-SEM), energy-dispersive X-ray (EDS), and transmission electron microscope (TEM). The activity of this super solid acid was probed through the synthesis of aryl diazonium salts as the starting reactant and then, their diazo coupling with aldehyde phenylhydrazones for formation of formazan derivatives in a solvent-free medium at room temperature. This clean and environmentally benign methodology has advantages such as: no need for corrosive and toxic liquid acids, solvents, or buffer solutions, room temperature reaction, high yields, and short reaction times. In addition, long-term stability of aryl diazonium salts supported on the surface of Fe3O4@SiO2–BF3 magnetic nanoparticles (MNPs) at room temperature was one of the most important results of this procedure.
  • Haruka Yamada, Takahiro Hayashi, Toyonobu Usuki
    2015 Volume 88 Issue 5 Pages 673-683
    Published: May 15, 2015
    Released: May 15, 2015
    [Advance publication] Released: January 27, 2015
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    Desmosine, a COPD biomarker and elastin crosslinker, is a tetrasubstituted pyridinium amino acid. In this paper, the total synthesis of desmosine is described utilizing stepwise and regioselective palladium-catalyzed Sonogashira cross-coupling reactions of trihalopyridines and terminal alkynes as key steps. The 13-step synthesis starting from 4-hydroxypyridine was achieved in 11% overall yield.
  • Maryam Massah Bidgoli, Mohsen Mohsennia, Farhad Akbari Boroumand
    2015 Volume 88 Issue 5 Pages 684-689
    Published: May 15, 2015
    Released: May 15, 2015
    [Advance publication] Released: February 03, 2015
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    Carboxylated graphene oxide–CdS nanocomposite (GO-COOH-CdS) was successfully prepared by a facile mixing method in tetrahydrofuran (THF) and used to fabricate photovoltaic devices. The as-prepared nanocomposite was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The XRD analysis further confirmed that CdS nanoparticles have been effectively intercalated into the GO-COOH stacks. The prepared GO-COOH-CdS nanocomposite has been applied for fabrication of hybrid bulk heterojunction photovoltaic devices by using the poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) as an electron donor in two different weight ratios with GO-COOH-CdS nanocomposite, as an electron acceptor. The effective electron transfer from MEH-PPV to GO-COOH-CdS was confirmed by the significant photoluminescence (PL) quenching of MEH-PPV. According to the obtained results, the photovoltaic devices based on conjugated polymer-GO-COOH-CdS have the potential to open up new production technologies for hybrid bulk heterojunction solar cells based on GO–semiconductor composites.
  • Yoshihide Tokunou, Kazuhito Hashimoto, Akihiro Okamoto
    2015 Volume 88 Issue 5 Pages 690-692
    Published: May 15, 2015
    Released: May 15, 2015
    [Advance publication] Released: February 05, 2015
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    Periplasmic pH (pHp) was monitored by an in vivo assay that was developed for Shewanella oneidensis MR-1 based on the outer membrane permeability of a biosynthesized flavin molecule. The pHp data obtained by this method suggest that proton motive force is not generated during anaerobic respiration associated with either intracellular fumarate reduction or extracellular electron transport to electrodes.
  • Hiroaki Imoto, Shigeyoshi Suzuki, Kensuke Naka
    2015 Volume 88 Issue 5 Pages 693-697
    Published: May 15, 2015
    Released: May 15, 2015
    [Advance publication] Released: February 10, 2015
    JOURNALS RESTRICTED ACCESS
    Octa(3-aminopropyl) polyhedral oligomeric silsesquioxane (POSS-NH2), adopting a rigid cubic structure, have been employed as a stabilizer for gold nanoparticles (AuNPs). The AuNPs possessing POSS-NH2 were stable enough to tolerate evaporation by incubating for 24 h after the preparation. Changing molar ratio of POSS-NH2 controlled the size of particle aggregates. In addition, the affinity of the AuNPs to organic solvents was changed via Michael addition with methyl acrylate to the amino groups on POSS-NH2. Redispersibility, aggregation control, and surface modification were successfully achieved with POSS-NH2 as a multifunctional single molecule.
  • Saori Takeda, Hiroka Yamada, Shunpei Takezawa, Isao Yoshikawa, Hidetak ...
    2015 Volume 88 Issue 5 Pages 698-705
    Published: May 15, 2015
    Released: May 15, 2015
    [Advance publication] Released: February 18, 2015
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    A series of hexanuclear zinc complexes was prepared using a triarylmethane (TAM)-based ligand. Depending on the alkyl chains at the peripheral position of the complex, the complexes crystallized as needles, octahedral crystals, or both. A needle crystal consisting of molecular columns in which P- and M-forms of propeller-shaped complexes were alternately stacked. Octahedral crystals had an enantiomeric cubic system. All crystals were photooxidized under UV irradiation to yield the corresponding TAM dyes with characteristic absorption (ca. 540 nm) and emission (ca. 600 nm) spectra. The crystals with the columnar packing structure exhibited linearly polarized emission, while the crystals with the cubic system did not show noticeable dichroism in either absorption or emission. The differences in photophysical properties among the complexes with various alkanoic groups were interpreted in terms of the spatial arrangement of the TAM dye molecules in the crystals.
  • Hanieh Malekzadeh, Mohammad H. Fatemi
    2015 Volume 88 Issue 5 Pages 706-712
    Published: May 15, 2015
    Released: May 15, 2015
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    Multivariate curve resolution (MCR) methods are proposed to improve the analysis of volatile components of an Iranian rice sample (Domsiah) by headspace sampling coupled to gas chromatography-mass spectrometry. A total of 31 components was identified using similarity searches between mass spectra and mass spectrometry database. Then extended multivariate curve resolution-alternating least squares (MCR-ALS) by applying proper constraints is used to obtain pure elution and mass spectral profiles for the components present in each peak cluster. The resolved components were identified by similarity searches using the NIST mass database and their percentage were calculated for qualitative and quantitative analysis, respectively. The number of identified components was extended to 82 by applying the MCR-ALS techniques. The main identified volatile chemicals that were found in an Iranian rice sample (Domsiah) were; nonanal (18.22%), hexanal (14.33%), 2-benzoyl-6,7-dimethoxy-4-methylidene-2H-1,3-benzothiazine (7.81%), epilophodione (7.023%), and 1-methyl-4-(1-methylethenyl)cyclohexene (6.61%).
  • Chitoshi Kitamura, Sining Li, Munenori Takehara, Yoshinori Inoue, Kats ...
    2015 Volume 88 Issue 5 Pages 713-715
    Published: May 15, 2015
    Released: May 15, 2015
    [Advance publication] Released: February 16, 2015
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    Recrystallization of 1,4-dipropoxy-9,10-anthraquinone from hexane solution afforded two polymorphs: red prisms and yellow needles. X-ray crystallographic analyses revealed that the molecular arrangement was an anti-parallel orientation for red solids and a slipped-parallel orientation for yellow solids. The difference in solid-state color was analyzed by TD-DFT calculations of their multimers.
  • Naoya Okada, Ryohei Eto, Emi Horiguchi-Babamoto, Takashi Kobayashi, Hi ...
    2015 Volume 88 Issue 5 Pages 716-721
    Published: May 15, 2015
    Released: May 15, 2015
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    Optical properties of three crystal modifications of 5-t-butyl-2,3-dicyano-6-[4-(dimethylamino)styryl]pyrazine having different color appearances were measured and interpreted on the basis of crystal structure analysis. Two of the three modifications exhibited a bathochromic spectral shift both in absorption and fluorescence compared with those in a toluene solution of the dye. The crystal structure analysis revealed that a two-dimensional brick-wall structure is formed in both modifications. In contrast, the third modification showed a hypsochromic absorption shift with a large bathochromic fluorescence shift. The crystal structure of this modification was characterized by a one-dimensional stacked molecular column. The optical characteristics of the three modifications were qualitatively interpreted in terms of excitonic intermolecular interaction on the basis of their crystal structures.
  • Samira Naghdi, Babak Jaleh, Ali Ehsani
    2015 Volume 88 Issue 5 Pages 722-728
    Published: May 15, 2015
    Released: May 15, 2015
    [Advance publication] Released: February 18, 2015
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    In the present work, graphene oxide (GO) was deposited on aluminum (Al) by cathodic electrophoretic deposition (EPD). The effects of low thermal annealing (50–200 °C) on hydrophobicity of Al–GO samples were investigated by water contact angle (WCA) measurement. The reduction of GO is confirmed by X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDAX). The results of EDAX showed that the oxygen/carbon atomic ratio decreased after reduction and this has been confirmed by XPS analysis. The corrosion activity of GO-coated Al samples (Al–GO) was investigated using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. The surface morphological characterization of bare Al and Al–reduced GO (samples after thermal annealing) was carried out by scanning electron microscopy (SEM) before and after immersion in sodium chloride (NaCl) solution. It was shown that bare samples were damaged after 10 days of immersion in 3.5% NaCl solution and cracks and pits developed during the immersion period. However, GO-coated samples were undamaged after immersion in NaCl solution.
  • Osamu Hayashida, Keiko Kojima
    2015 Volume 88 Issue 5 Pages 729-735
    Published: May 15, 2015
    Released: May 15, 2015
    [Advance publication] Released: February 20, 2015
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    Reduction-responsive cyclophane dimer 2 having a disulfide linkage derived from an L-cystine residue was synthesized. Complex formation of 2 with anionic guests such as 6-p-toluidinonaphthalene-2-sulfonate (TNS) and 6-anilinonaphthalene-2-sulfonate (2,6-ANS) were proven by fluorescence titration experiments. The evaluated 1:1 binding constants (K) of 2 with TNS and 2,6-ANS were calculated to be 7.6 × 104 and 5.5 × 104 M−1, respectively. These binding affinities were increased 11- and 13-fold in comparison with those of a corresponding monocyclic cyclophane 3, respectively. Reduction of disulfide bond of 2 by dithiothreitol (DTT) gave the corresponding monocyclic cyclophanes having less guest-binding affinity. Consequently, such a DTT treatment promotes release of guest molecules entrapped by 2 to the bulk aqueous media.
  • Tomoyuki Tajima, Takuya Nishihama, Shogo Miyake, Nobuhiro Takahashi, Y ...
    2015 Volume 88 Issue 5 Pages 736-745
    Published: May 15, 2015
    Released: May 15, 2015
    [Advance publication] Released: February 23, 2015
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    (Terthiophene)4–poly(amidoamine)–C60 pentad 8a and (terthiophene)2–poly(amidoamine)–C60 triad 8b have been synthesized with the aim of developing novel precursors for photoinduced polymerization. The electrochemical oxidation of pentad 8a by repetitive cyclic voltammogram scans gave a polymeric 8a film on a FTO electrode, which showed electrochemical activity and photoelectric response. When a monomer film of 8 on FTO was irradiated with visible light, the photoinduced polymerization of the terthiophene moiety was observed. The photoanodic features of an electropolymerized film of 8a on a FTO (poly-8aelectro/FTO) and 8a/FTO were investigated regarding photocurrent response to light irradiation. The photocurrent of a photopolymerized 8a film on a FTO (poly-8aphoto/FTO) electrode formed by photoreaction of 8a/FTO, is approximately 6 times greater than that of the 8a/FTO electrode.
  • Toshiyuki Masui, Tomoya Kamata, Nashito Fukuhara, Nobuhito Imanaka
    2015 Volume 88 Issue 5 Pages 746-751
    Published: May 15, 2015
    Released: May 15, 2015
    [Advance publication] Released: February 25, 2015
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    1 wt % Pt/11 wt % (Co1−xCux)3O4−δ/16 wt % Ce0.62Zr0.20Sn0.18O2.0/γ-Al2O3 catalysts were prepared to realize complete combustion of toluene at lower temperatures than that of a 1 wt % Pt/11 wt % Co3O4/16 wt % Ce0.62Zr0.20Sn0.18O2.0/γ-Al2O3 catalyst previously reported by our group without increasing the amount of platinum. Addition of copper into the Co3O4 lattice was effective to facilitate oxygen release and storage, and thereby, the toluene oxidation activity was enhanced. The highest activity for the combustion of toluene was observed using a 1 wt % Pt/13 wt % (Co0.97Cu0.03)3O4−δ/16 wt % Ce0.62Zr0.20Sn0.18O2.0/γ-Al2O3 catalyst, and despite a smaller platinum loading in the present catalyst, toluene was completely oxidized to carbon dioxide and water vapor at the lower temperature of 140 °C compared to that (160 °C) using 1 wt % Pt/11 wt % Co3O4/16 wt % Ce0.62Zr0.20Sn0.18O2.0/γ-Al2O3.
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