Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 88 , Issue 9
Showing 1-20 articles out of 20 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for Young Chemists for 2013
Accounts for Elements Science
  • Tsukasa Matsuo, Kohei Tamao
    2015 Volume 88 Issue 9 Pages 1201-1220
    Published: September 15, 2015
    Released: September 15, 2015
    JOURNALS FREE ACCESS
    Kinetic stabilization with sterically bulky substituents or ligands has played a pivotal role in exploring a large variety of unsaturated compounds or low-coordinated complexes. This article describes our findings that a series of fused-ring octa-R-substituted s-hydrindacenyl groups (Rind groups), which we developed since 2007, can act as unique protecting groups both in main group chemistry and in transition-metal chemistry. The synthesis, structures, and properties of various types of highly reactive unsaturated and low-coordinated element-organic compounds of Groups 1, 2, 8, 11, and 13–17 featuring the bulky Rind groups are covered.
    A series of fused-ring octa-R-substituted s-hydrindacenyl groups (Rind groups), which we developed since 2007, can act as unique protecting groups both in main group chemistry and in transition-metal chemistry. Fullsize Image
     
BCSJ Award Article
  • Takashi Matsuo, Keita Yamada, Masaya Ishida, Yoshiyuki Miura, Masaru Y ...
    2015 Volume 88 Issue 9 Pages 1221-1229
    Published: September 15, 2015
    Released: September 15, 2015
    [Advance publication] Released: June 08, 2015
    JOURNALS FREE ACCESS
    Caspase-3, an apoptosis-executing enzyme with a dimeric structure, and its zymogen (procaspase-3) are target proteins in cancer chemotherapy using synthetic compounds. Previous work has shown that PAC-1 (1st procaspase-activating compound) affects the activation of procaspase-3 in cancerous cells through the Zn2+-chelation mechanism. However, we found that the compound also enhances the mature caspase-3 activity in the absence of Zn2+. The enhancement of the mature caspase-3 activity by PAC-1 followed a Michaelis–Menten-type saturation dependency with respect to the concentration of the compound. PAC-1 induced the change in the UV–vis spectrum of the mature caspase-3. From these findings, we propose a direct structural interaction of PAC-1 with the protein core. According to a molecular dynamics calculation for the complex of PAC-1 and mature caspase-3, PAC-1 is likely to bind to the interface between the dimeric structure in mature caspase-3. The interactions between PAC-1 and amino acid residues that affect the catalytic activity of mature caspase-3 are suggested. Throughout this work, diverse functions of the apoptosis-inducing compound are disclosed.
    PAC-1, a procaspase-3-activating compound, also enhances the catalytic activity of mature caspase-3. A series of kinetic behaviors and the MD calculation suggest that PAC-1 interacts amino acid residues at the protomer interface of mature caspase-3 to affect the enzyme activity. Fullsize Image
     
 
  • Tohru Wada, Koki Enami, Ryohei Kojima, Tomoki Okada, Yuki Ishikawa, Yu ...
    2015 Volume 88 Issue 9 Pages 1230-1237
    Published: September 15, 2015
    Released: September 15, 2015
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    Platinum complexes with 1,4,7-triazacyclononane (tacn) as facial ligands, [PtIVCl3(tacn)](ClO4), [PtIVCl(bpy)(tacn)](ClO4)3 ([1](ClO4), and [2](ClO4)3, bpy: 2,2′-bipyridine) were prepared, and their hexa-coordinated octahedral structures were determined via single-crystal X-ray analysis. In aqueous solutions containing NaCl as the electrolyte, [2]3+ exhibited a quasi-reversible two-electron redox wave at +0.22 V (vs. SCE) with a large peak separation (ΔE = EpcEpa = 0.28 V). In addition, controlled-potential reduction of [2]3+ at −0.30 V in aqueous solutions containing NaCl afforded [PtII(bpy)(tacn)]2+ ([3]2+), which was then re-oxidized to regenerate [2]3+. X-ray analysis of [3]2+ revealed a tetra-coordinated square-planar structure in which both tacn and bpy were bound to the central Pt as bidentate ligands. The redox potential of this reaction is coupled with dissociation/association of Cl from/to Pt in the solution. MO/DFT calculations indicate that structural changes in tacn promote the reversible two-electron redox reaction between the octahedral Pt(IV) and square planar Pt(II) complexes.
  • Ryuichi Sugimoto, Tomoaki Matsugi
    2015 Volume 88 Issue 9 Pages 1238-1240
    Published: September 15, 2015
    Released: September 15, 2015
    [Advance publication] Released: June 12, 2015
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    Methyl 10-undecenoate treated with 2 equivalents of diisobutylaluminum hydride was quantitatively converted into a 10-undecenoxy aluminum compound, which was successfully utilized for metallocene-catalyzed copolymerization with propylene to produce functional polypropylene with hydroxy groups in its side chains.
  • Yusuke Asakura, Nami Hosaka, Shimon Osada, Taichi Terasawa, Atsushi Sh ...
    2015 Volume 88 Issue 9 Pages 1241-1249
    Published: September 15, 2015
    Released: September 15, 2015
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    Interlayer-condensed materials of protonated layered silicate (magadiite) are synthesized by refluxing in N-methylformamide (NMF) and the subsequent calcination. The obtained materials possess 2–3 times higher surface areas than calcined protonated magadiite, depending on the time of refluxing. NMF molecules in the interlayer spaces are converted to organic substances with higher thermal stability during the refluxing, which is useful for the control of the stacking sequence of silicate layers and for the following interlayer condensation to increase the microporosity. The microporosity of the material obtained by the treatment of protonated magadiite with NMF at r.t. and the subsequent calcination is similar to that of simply calcined protonated magadiite, indicating that the retention of thermally stable substances in the interlayer is critical for the increase in the pore volume and surface area of the derivative from magadiite. The method reported here will stimulate re-estimation of a large number of known layered silicate–organic intercalation compounds as possible candidates for the preparation of porous silica by interlayer condensation.
  • Zewen Xiao, Hechang Lei, Xiao Zhang, Yuanyuan Zhou, Hideo Hosono, Tosh ...
    2015 Volume 88 Issue 9 Pages 1250-1255
    Published: September 15, 2015
    Released: September 15, 2015
    [Advance publication] Released: May 27, 2015
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    Cs2SnI6, a variant of perovskite CsSnI3, is gaining interest as a photovoltaic material. Based on a simple ionic model, it is expected that Cs2SnI6 is composed of Cs+, I, and Sn4+ ions and that the band gap is primarily made of occupied I 5p6 valence band maximum (VBM) and unoccupied Sn4+ 5s conduction band minimum (CBM) similar to SnO2. In this work, we performed density functional theory (DFT) calculations and revealed that the real oxidation state of the Sn ion in Cs2SnI6 is +2 similar to CsSnI3. The +2 oxidation state of Sn originates from 2 ligand holes (L+) in the [SnI6]2− octahedron unit, where the ligand [I6] cluster has the apparent [I66−L+2]4− oxidation state, because the band gap is formed mainly by occupied I 5p VBM and unoccupied I 5p CBM. The +2 oxidation state of Sn and the band gap originate from the intracluster hybridization and stabilized by the strong covalency of the Sn–I bonds.
  • Ayane Watanabe, Osamu Ohno, Maho Morita, Toshiyasu Inuzuka, Kiyotake S ...
    2015 Volume 88 Issue 9 Pages 1256-1264
    Published: September 15, 2015
    Released: September 15, 2015
    [Advance publication] Released: May 28, 2015
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    Novel biselyngbyaside analogs, biselyngbyolide C (1) and biselyngbyasides E (2) and F (3), were isolated from the marine cyanobacterium Lyngbya sp., collected on Ishigaki Island, Japan. The gross structures of 13 were determined by NMR spectral analyses, and their stereochemistries were established based on NOESY spectra and CD data. These compounds inhibited the growth of HeLa and HL60 cells. From the results of an MTT assay, the geometry of the trisubstituted olefin in the side chain and the lack of the sugar moiety were found to be important for the biological activity. In addition, 1 was found to exhibit ER stress- and apoptosis-inducing activities in HeLa cells.
  • Shinsaku Fujita
    2015 Volume 88 Issue 9 Pages 1265-1283
    Published: September 15, 2015
    Released: September 15, 2015
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    Stereoisograms of five types are devised as graphical expressions of the action of an RS-stereoisomeric group on a trigonal pyramidal skeleton. A quadruplet of promolecules (i.e., a reference promolecule, its enantiomer, its RS-diastereomer, and its holantimer) contained in a stereoisogram is counted once as an equivalence class under the action of an RS-stereoisomeric group. An RS-stereoisomeric group is constructed by starting from the point group C3v of a trigonal pyramidal skeleton, where a point group C3v, an RS-permutation group , a ligand-reflection group C3Î are integrated. Fujita’s unit-subduced-cycle-index (USCI) approach for enumeration under point groups is extended to cover enumeration under RS-stereoisomeric groups. The fixed-point-matrix (FPM) method and the partial-cycle-index (PCI) method of the USCI approach are applied to symmetry-itemized and type-itemized enumeration of quadruplets of promolecules under the action of the RS-stereoisomeric group . Theoretical foundations of stereochemical nomenclature are discussed on the basis of Fujita’s stereoisogram approach, where three aspects of absolute configuration are emphasized. Prochirality and pro-RS-stereogenicity are clarified to be conceptually distinct, just as chirality and RS-stereogenicity are conceptually distinct. Young’s tableaux for (pro)chirality and those for (pro-)RS-stereogenicity are compared to demonstrate such conceptual distinctions. It follows that a pair of R/S-stereodescriptors is assigned on the basis of RS-stereogenicity, not of chirality; and a pair of pro-R/pro-S-descriptors is assigned on the basis of pro-RS-stereogenicity, not of prochirality.
  • Hiroaki Tokoyama, Hideo Yamakado, Satoshi Maeda, Koichi Ohno
    2015 Volume 88 Issue 9 Pages 1284-1290
    Published: September 15, 2015
    Released: September 15, 2015
    [Advance publication] Released: June 01, 2015
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    Isomers of benzene (C6H6) have been searched by quantum chemical calculations using the GRRM/SCC-DFTB program. Further optimization at the level of B3LYP/6-311G(d,p) gave 2004 equilibrium structures (EQ). Obtained EQs were assigned as 212 valence isomers, 928 nonvalence isomers, 798 two-component clusters, and 66 three-component clusters. Energies of EQs range from the most stable isomer of benzene to the highest EQ at 1237 kJ mol−1. The low energy region below 380 kJ mol−1 only includes valence isomers. Valence isomers are distributed between 0 and 807 kJ mol−1, while nonvalence isomers are located in the range of 380–1180 kJ mol−1. All of the experimentally known 30 isomers of benzene were searched as valence isomers by the ADDF/SCC-DFTB method. Formally hypervalent molecules including pentacoordinated carbon atoms were discovered among nonvalence isomers.
  • Gamal A. Saleh, Hassan F. Askal, Ibrahim H. Refaat, Fatma A. M. Abdel- ...
    2015 Volume 88 Issue 9 Pages 1291-1300
    Published: September 15, 2015
    Released: September 15, 2015
    [Advance publication] Released: June 04, 2015
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    An electrochemical sensor for acyclovir (ACV) based on polymerization of β-cyclodextrin (β-CD) on electrochemically pretreated pencil graphite electrode (PGE) was built for the first time. A synergistic effect of β-CD was used to construct this sensor for quantification of this important drug. Scanning electron microscope (SEM) images show that polymer of β-CD has been successfully modified on the electrode. Square wave voltammetry (SWV) exhibited two linear dynamic ranges of 5 × 10−8 to 6 × 10−7 M and 1 × 10−6 to 9 × 10−6 M of ACV for its oxidation and the detection limit was found to be as low as 7.59 × 10−9 M of ACV. The parameters affecting ACV oxidation were investigated. The prepared electrodes showed good fabrication reproducibility. The analytical applications of the prepared electrodes were tested by using ACV dosage forms and human urine as a real sample. The SWV analysis has been successfully applied to pharmacokinetic studies of ACV in health human volunteers after oral administration of a single dose of Zovirax suspension (400 mg/5 mL).
  • Kota Yokoyama, Sachiko Matsushita, Takayuki Komatsu, Toshihiro Isobe, ...
    2015 Volume 88 Issue 9 Pages 1301-1307
    Published: September 15, 2015
    Released: September 15, 2015
    [Advance publication] Released: June 02, 2015
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    With the intent of preparing a catalyst support, a hierarchical bimodal mesoporous structure with two types of mesopores (2–50 nm) that would show both high mass transport and high reaction rate was fabricated through a one-pot process using organic monoliths and surfactant micelles. The selectivity and efficiency of a prototypical carbon dioxide (CO2) reduction reaction, namely, the methanation of CO2 on Ni nanoparticles, were increased by the fabricated structure. This catalytic phenomena was discussed using field-emission scanning electron microscopy (FE-SEM), high-angle annular dark-field imaging scanning transmission electron microscopy (STEM), electron energy loss spectroscopy (EELS), N2 adsorption–desorption isotherms, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and inductively coupled optical emission spectrometry (ICP-OES), to observe surface area of the structures, catalyst amount, molecular diffusion efficiency, and CO2 methanation mechanisms. The thermal stability of this hierarchical porous structure in the 823–1273 K temperature range was also examined. Although additional experiments such as the change of the pore size, pore shapes, and the ratio of the larger pores and smaller pores, are required to further discussions, there is a possibility that the hierarchical bimodal mesoporous structure can be a good catalyst support.
  • Keita Omata, Shota Kuwahara, Ryo Hosokawa, Taisei Nishimura, Qing Shen ...
    2015 Volume 88 Issue 9 Pages 1308-1313
    Published: September 15, 2015
    Released: September 15, 2015
    [Advance publication] Released: June 16, 2015
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    A blocking effect on the approach of electron acceptors into a dye/TiO2 electrode in a dye-sensitized solar cell was confirmed by the observation of charge dynamics at the interface when an alkyl-functionalized dye was used. It was found that the density of the adsorbed MK-2 on the TiO2 surface affected the ionic motion in an electrolyte at the interface, and that electron–electrolyte recombination was suppressed with a high density of adsorbed MK-2 molecules, causing prevention of the approach of the redox ions.
  • Hao Zhang, Sai Ba, Sarajane Co Co, Jasmine Yiqin Lee, Juanjuan Guo, Ru ...
    2015 Volume 88 Issue 9 Pages 1314-1316
    Published: September 15, 2015
    Released: September 15, 2015
    [Advance publication] Released: June 11, 2015
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    We have developed an alternative methodology for determining the stabilities of DNA hairpin structures based on a specially designed oligonucleotide template and the T4 DNA ligase. This method was systematically tested by evaluation of DNA hairpin stabilities when varying the loop size and the nature of the loop sequence.
  • Dong Hyun Jo, Chang Hun Lee, Hyunchul Jung, Sunbin Jeon, Sung Hyun Kim
    2015 Volume 88 Issue 9 Pages 1317-1322
    Published: September 15, 2015
    Released: September 15, 2015
    [Advance publication] Released: June 16, 2015
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    Ethylenediamine was grafted onto a polystyrene surface to study the relationship between amine density and amine efficiency. Amine-tethered polystyrene was synthesized in two steps: (1) chloromethylation and (2) amination. The products were characterized by argentometry, N2 physisorption, thermogravimetric analysis, X-ray diffraction, and FT-IR spectroscopy. The amine efficiency declined drastically when the amine density was less than 1 amine molecule per nm2, because formation of ammonium carbamate is difficult under such conditions. A double-functionalization method was introduced to improve the CO2 uptake and amine efficiency of the amine-grafted sorbent by impregnating more amino groups into the porous structure. The combination of grafted and mobile amino groups led to a synergic effect, resulting in a CO2 uptake of up to 20.2 wt % at 30 °C and 1 bar CO2. It was concluded that double-functionalization with tetraethylenepentamine was advantageous for enhancing the amine efficiency, whereas double-functionalization with polyethyleneimine was advantageous for enhancing the cyclic stability of the sorbent.
  • Shinichi Saito, Takanori Ohkubo, Yukari Yamazaki, Tatsuyuki Yokoyama, ...
    2015 Volume 88 Issue 9 Pages 1323-1330
    Published: September 15, 2015
    Released: September 15, 2015
    [Advance publication] Released: June 16, 2015
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    We synthesized a macrocyclic 2,9-dialkyl-1,10-phenanthroline–Cu complex (9) from 1,10-phenanthroline. Compound 9 existed as a dinuclear complex in solid state. In solution, however, the compound existed as a mononuclear complex. Compound 9 mediated the Glaser reaction of an alkyne with a bulky blocking group and the formation of a [2]rotaxane was observed. The reactivity of the 2,9-dialkyl-1,10-phenanthroline–Cu complex (9) was lower than that of a diaryl analogue.
  • Yoichi Okayama, Kazuki Maruhashi, Satoru Tsuji, Atsunori Mori
    2015 Volume 88 Issue 9 Pages 1331-1337
    Published: September 15, 2015
    Released: September 15, 2015
    [Advance publication] Released: June 18, 2015
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    Macrocyclic alkene containing bisimidazole showing molecular asymmetry, which is synthesized by ring-closing metathesis, is subjected to several functional group transformation reactions of the olefin moiety. Syn-addition reactions such as epoxidation, dihydroxylation, and hydrogenation are found to proceed whereas anti-addition does not proceed. Optical resolution of racemic bisimidazole is successfully achieved with a preparative chiral column. Racemization behaviors of bisimidazole derivatives are also studied under several conditions.
  • Taku Shoji, Natsumi Kamata, Akifumi Maruyama, Shunji Ito, Tetsuo Okuji ...
    2015 Volume 88 Issue 9 Pages 1338-1346
    Published: September 15, 2015
    Released: September 15, 2015
    [Advance publication] Released: June 16, 2015
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    Ferrocene-substituted 1,1,4,4-tetracyano-1,3-butadienes (FcTCBDs) connected by arylamine and azobenzene spacers were prepared by the reaction of a variety of alkynes with tetracyanoethylene (TCNE) in a [2 + 2] cycloaddition, followed by retroelectrocyclization of the initially formed [2 + 2] cycloadducts (i.e., cyclobutene derivatives). The characteristic intramolecular charge transfer (ICT) from the donors (ferrocene and arylamine) to the acceptor (TCBD) moieties was investigated by using UV–vis spectroscopy. The redox behaviors of the FcTCBDs were examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their promising redox properties with multi-electron transfer depending on the number of FcTCBD moieties in the molecules. Moreover, significant color changes were observed by visible spectroscopy under the electrochemical reduction conditions.
  • Yoshihito Kunugi, Ayami Mada, Hiroyuki Otsuki, Kazuo Okamoto
    2015 Volume 88 Issue 9 Pages 1347-1349
    Published: September 15, 2015
    Released: September 15, 2015
    [Advance publication] Released: June 18, 2015
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    We synthesized alkyl-substituted phenyl chrysenes as novel solution-processable transistor materials for single crystal organic transistors. All devices displayed typical p-channel characteristics, with the best field-effect mobility of 11.9 cm2 V−1 s−1 belonging to the m-7P-28CR based transistor.
  • Yuichiro Tokoro, Kazuo Tanaka, Yoshiki Chujo
    2015 Volume 88 Issue 9 Pages 1350-1355
    Published: September 15, 2015
    Released: September 15, 2015
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    Benzo[h]quinolyldibenzo[b,f]silepin containing pentacoordinate silicon was incorporated into π-conjugated polymers. Substituent effects were investigated from UV–vis absorption and photoluminescence spectra. The extension of π-conjugation involving pentacoordinate silicon was suggested from the characteristic absorption and emission bands through the polymer chain at meta-positions toward silicon in the silepin rings. The polymers containing the fluorinated silicon showed bathochromic shift compared to that from the methylated silicon-containing polymers. Polymerization at para-positions toward silicon resulted in the formation of short conjugation length. Finally, the emission band from the charge-transfer transition was observed in photoluminescence spectra of the fluorinated polymer.
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