Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
最新号
選択された号の論文の17件中1~17を表示しています
 
Account/Review for Materials Innovation
Award Account
  • Takane Imaoka, Kimihisa Yamamoto
    2019 年 92 巻 5 号 p. 941-948
    発行日: 2019/05/15
    公開日: 2019/05/15
    ジャーナル 認証あり

    Metal clusters composed of several to several tens of atoms, in general, can be regarded as molecules rather than small nanoparticles. That is, a cluster bearing a different number of atoms is a “different molecule” showing different properties. Therefore, at least ultraprecision control of the size at the one-atom level is a requirement to study and fully utilize clusters. Although these substances sometimes exhibit exceptionally high catalytic activity relative to nanoparticles, highly demanding synthesis is obstructing their application. In this account, we will explain the progress of cluster supported catalyst synthesis technology in recent years and the possibility of large-scale precision synthesis.

    Metal clusters composed of several to several tens of atoms, in general, can be regarded as molecules rather than small nanoparticles. These substances sometimes exhibit exceptionally high catalytic activity relative to nanoparticles. However, ultra-high precision at atomic-level is required for their performance. In this account, we will show the latest wet-chemical synthesis of cluster-supported catalysts that allows large-scale preparation with precise control of the atomicity. Fullsize Image
     
 
  • Hitoshi Watarai, Ziyu Chen
    2019 年 92 巻 5 号 p. 949-951
    発行日: 2019/05/15
    公開日: 2019/05/15
    ジャーナル 認証あり

    Magnetic field induced Sagnac interference was observed for the COOH modified iron oxide magnetic nanoparticles (MNPs) dispersed in water. The effect of cationic surfactants showing agglomeration and deagglomeration of the MNPs was clearly detected by the phase shift due to the magnetic orientation of MNPs. The observed phase shifts were discussed by using Langevin parameters.

  • Takuma Igari, Kana Imamura, Kenta Yasumura, Tomoki Iwasa, Kazuki Sakak ...
    2019 年 92 巻 5 号 p. 952-960
    発行日: 2019/05/15
    公開日: 2019/05/15
    ジャーナル 認証あり

    Techniques for selective deposition of conductive inks, in particular metal nano-particulate inks, by using self-assembling monolayers (SAMs) mostly involve control of wettability with highly hydrophobic compounds. In this work, we focused on electrostatic interaction of metal nano-particles and investigated the influence of functional groups on the substrate upon selective deposition of metal nanoparticles. Surface modifiers bearing four kinds of functional groups (-OH, -NH2, -SH, -COOH) protected by a photodegradable 2-nitrobenzyl ester were synthesized and used to form SAMs on an indium tin oxide-coated glass substrate. UV-irradiation through a photomask generated the respective functional group in exposed regions. High-quality patterning of aqueous Au nano-particulate ink, which is negatively charged, was successfully achieved by spin coating onto amine-bearing SAMs. These results suggest the feasibility of micro-scale patterning based on electrostatic interaction between Au nano-particles and free amino groups introduced onto the substrate by photoirradiation-induced deprotection of surface-modifying agents.

  • Jin Yeong Yun, Ahran Kim, Suh Mi Hwang, Dongju Yun, Hyojin Lee, Ki-Tae ...
    2019 年 92 巻 5 号 p. 961-966
    発行日: 2019/05/15
    公開日: 2019/05/15
    ジャーナル 認証あり

    A novel selective and sensitive chemosensor, (E)-1-((((1H-benzo[d]imidazol-2-yl)methyl)imino)methyl)naphthalen-2-ol (BIN), was developed for fluorescence detection of Zn2+. The compound BIN acts as a fluorescent “turn-on” detector for Zn2+. The limit of detection (2.26 µM) for zinc ion is well below the WHO standard (76.0 µM). Probe BIN can be chemically reversible with ethylenediaminetetraacetic acid (EDTA). The binding mechanism of BIN with zinc ion was demonstrated by fluorescence, UV-visible, electrospray ionization mass spectroscopy, 1H NMR titration and calculations. Importantly, probe BIN could be applied to determine zinc ion in water samples and living zebrafish.

  • Naoya Morohashi, Yutaka Kato, Sahoko Sumida, Yu Kurusu, Tetsutaro Hatt ...
    2019 年 92 巻 5 号 p. 967-972
    発行日: 2019/05/15
    公開日: 2019/05/15
    ジャーナル 認証あり

    p-tert-Butylcalix[4]arenediphosphonic acid (L) extracts Zr(IV) and Hf(IV) from aqueous HCl, H2SO4, and H3PO4. In the extraction from aqueous HCl of different concentrations, the percentage of extraction (E%) of Hf(IV) decreases notably with an increase in acid concentration (96% at 0.5 M HCl and 12% at 7 M HCl), whereas the E% of Zr(IV) remains at a moderate level (90% at 0.5 M HCl and ∼60% at 7 M HCl). Thus, selective extraction of Zr(IV) over Hf(IV) is achieved from high-concentration HCl solutions. The separation factor (SZr) reaches 24 when using two molar equiv of L to Zr(IV) at 7 M HCl. Mechanistic studies indicate that L extracts Zr(IV) from high-concentration HCl solutions by a solvation mechanism by forming a 1:1 complex, LZrCl4. Back extraction of Zr(IV) proceeds quantitatively by treating the organic phase with 5 M H3PO4 after the extraction of Zr(IV).

  • Hidemitsu Uno, Misaki Ishiwata, Kota Muramatsu, Masayoshi Takase, Shig ...
    2019 年 92 巻 5 号 p. 973-981
    発行日: 2019/05/15
    公開日: 2019/05/15
    ジャーナル 認証あり

    1,3-Dihydrothieno[3,4-a]- and 1,3,8,10-tetrahydrodithieno[3,4-a;3′4′-m]-HPHACs were prepared by the successive SNAr reactions of hexafluorobenzene with 1,3-dihydrothieno[3,4-c]pyrrole and 3,4-dihexylpyrrole followed by Scholl oxidation. Oxidation of 1,3-dihydrothieno-fused HPHACs with excess amounts of iodine at room temperature quantitatively gave the corresponding dication bis(triiodide)s. Further dehydrogenative oxidation of the dicationic species with iodine giving a thieno[3,4-a]HPHAC dication was achieved at a higher temperature by removing hydrogen iodide generated during the reaction. Neutral species of thieno[3,4-a]HPHAC could not be isolated.

  • Takatoshi Nohara, Toshiki Sawada, Hiroshi Tanaka, Takeshi Serizawa
    2019 年 92 巻 5 号 p. 982-988
    発行日: 2019/05/15
    公開日: 2019/05/15
    ジャーナル 認証あり

    2D nanomaterials with atomic-/molecular-level thickness are of great interest due to their unique physicochemical and functional properties derived from their planar morphologies. In vitro enzymatic synthesis of cellulose oligomers is an attractive approach for crafting 2D cellulose assemblies with tailored surface functionality. In this study, the templated synthesis of gold nanoparticles (AuNPs) was demonstrated on surface-aminated 2D cellulose assemblies prepared via enzymatic reaction. Gold precursor effectively adsorbed to the surface amino groups and was subsequently reduced for AuNP production via lateral diffusion-based nucleation and subsequent growth processes on the assemblies. The immobilized AuNPs on the assemblies showed high catalytic activities toward a model hydrogenation reaction. The cellulose-based 2D nanomaterials with molecularly designable surface functionality open a new avenue for controlled synthesis and immobilization of inorganic nanoparticles.

  • Satoshi Wada, Hiroaki Imoto, Kensuke Naka
    2019 年 92 巻 5 号 p. 989-994
    発行日: 2019/05/15
    公開日: 2019/05/15
    ジャーナル 認証あり

    Incompletely condensed polyhedral oligomeric silsesquioxanes (IC-POSS) are promising building blocks for the development of organic-inorganic hybrid materials. Pd-catalyzed arylation of heptaphenyl IC-POSS has been developed to introduce various substituents on to the open moieties without using highly moisture-sensitive chlorosilane derivatives. The substituents drastically affected the thermal behavior of the corresponding IC-POSSs. The obtained IC-POSSs were well dispersed in poly(methyl methacrylate) (PMMA) matrices to tune the thermal and optical properties of their composite films.

  • Naoki Zenmyo, Hiroki Tokumaru, Shohei Uchinomiya, Hirokazu Fuchida, Sh ...
    2019 年 92 巻 5 号 p. 995-1000
    発行日: 2019/05/15
    公開日: 2019/05/15
    ジャーナル 認証あり

    Chemical labeling of proteins with synthetic molecular probes offers the possibility to probe the functions of proteins of interest in living cells. However, the methods for covalently labeling targeted proteins using complementary peptide tag-probe pairs are still limited, irrespective of the versatility of such pairs in biological research. Herein, we report the new CysHis tag-Ni(II) probe pair for the specific covalent labeling of proteins. A broad-range evaluation of the reactivity profiles of the probe and the CysHis peptide tag afforded a tag-probe pair with an optimized and high labeling selectivity and reactivity. In particular, the labeling specificity of this pair was notably improved compared to the previously reported one. This pair was successfully utilized for the fluorescence imaging of membrane proteins on the surfaces of living cells, demonstrating its potential utility in biological research.

BCSJ Award Article
 
  • Ko Takase, Keiichi Noguchi, Koji Nakano
    2019 年 92 巻 5 号 p. 1008-1017
    発行日: 2019/05/15
    公開日: 2019/05/15
    ジャーナル 認証あり

    The pyrrole-containing chiral spiro π-conjugated compounds were successfully synthesized from 10,10′-spirobi[indeno[1,2-b][1]benzothiophene] 5,5-dioxide and 5,5,5′,5′-tetraoxide via a sequential inter/intramolecular nucleophilic aromatic substitution with arylamines. The enantiopure ones were also prepared from the enantiopure substrates. UV-vis absorption and photoluminescence spectroscopies and theoretical calculations revealed that the replacement of thiophene unit(s) of 10,10′-spirobi[indeno[1,2-b][1]benzothiophene] with pyrrole unit(s) has a great impact on photophysical properties. The pyrrole-containing chiral spiro π-conjugated compounds exhibited circularly polarized luminescence with a relatively large dissymmetry factor.

feedback
Top