2021/11/27 更新

写真a

カネコ タカシ
金子 隆司
KANEKO Takashi
所属
教育研究院 自然科学系 生産デザイン工学系列 教授
自然科学研究科 材料生産システム専攻 素材生産科学 教授
工学部 工学科 教授
職名
教授
外部リンク

学位

  • 博士(工学) ( 1995年3月   早稲田大学 )

研究分野

  • ナノテク・材料 / 高分子化学

  • ナノテク・材料 / ナノ構造化学

経歴(researchmap)

  • 新潟大学   自然科学研究科 材料生産システム専攻 素材生産科学   教授

    2011年4月 - 現在

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  • 新潟大学   工学部 化学システム工学科   教授

    2011年4月 - 現在

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  • 新潟大学   超域研究機構   教授

    2005年9月 - 2011年3月

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  • 新潟大学   超域研究機構   助手

    2003年4月 - 2005年8月

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  • 新潟大学   工学部 化学システム工学科   助手

    1998年4月 - 2005年8月

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  • 新潟大学   自然科学研究科   助手

    1995年4月 - 1998年3月

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  • 早稲田大学   日本学術振興会特別研究員

    1992年4月 - 1995年3月

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▶ 全件表示

経歴

  • 新潟大学   自然科学研究科 材料生産システム専攻 素材生産科学   教授

    2011年4月 - 現在

  • 新潟大学   化学システム工学科   教授

    2011年4月 - 現在

  • 新潟大学   超域研究機構   教授

    2005年9月 - 2011年3月

  • 新潟大学   超域研究機構   助手

    2003年4月 - 2005年8月

  • 新潟大学   化学システム工学科   助手

    1998年4月 - 2005年8月

  • 新潟大学   自然科学研究科   助手

    1995年4月 - 1998年3月

▶ 全件表示

学歴

  • 早稲田大学   理工学研究科   応用化学専攻

    - 1995年3月

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    国名: 日本国

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  • 早稲田大学   理工学研究科   応用化学専攻

    - 1992年3月

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    国名: 日本国

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  • 早稲田大学   理工学部   応用化学科

    1986年4月 - 1990年3月

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    国名: 日本国

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所属学協会

 

論文

  • Macromolecular Design for Oxygen/Nitrogen Permselective Membranes—Top-Performing Polymers in 2020—

    Jianjun Wang, Zhichun Shi, Yu Zang, Hongge Jia, Masahiro Teraguchi, Takashi Kaneko, Toshiki Aoki

    Polymers   13 ( 17 )   3012 - 3012   2021年9月

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    掲載種別:研究論文(学術雑誌)   出版者・発行元:MDPI AG  

    Oxygen/nitrogen permselective membranes play particularly important roles in fundamental scientific studies and in a number of applications in industrial chemistry, but have not yet fulfilled their full potential. Organic polymers are the main materials used for such membranes because of the possibility of using sophisticated techniques of precise molecular design and their ready processability for making thin and large self-supporting membranes. However, since the difference in the properties of oxygen and nitrogen gas molecules is quite small, for example, their kinetic diameters are 3.46 Å and 3.64 Å, respectively, the architectures of the membrane macromolecules should be designed precisely. It has been reported often that oxygen permeability (PO2) and oxygen permselectivity (α = PO2/PN2) have trade-off relationships for symmetric membranes made from pure polymers. Some empirical upper bound lines have been reported in (ln α − ln PO2) plots since Robeson reported an upper bound line in 1991 for the first time. The main purpose of this review is to discuss suitable macromolecular structures that produce excellent oxygen/nitrogen permselective membranes. For this purpose, we first searched extensively and intensively for papers which had reported α and PO2 values through symmetric dense membranes from pure polymers. Then, we examined the chemical structures of the polymers showing the top performances in (ln α − ln PO2) plots, using their aged performances. Furthermore, we also explored progress in the molecular design in this field by comparing the best polymers reported by 2013 and those subsequently found up to now (2020) because of the rapid outstanding growth in this period. Finally, we discussed how to improve α and PO2 simultaneously on the basis of reported results using not only symmetric membranes of pure organic polymers but also composite asymmetric membranes containing various additives.

    DOI: 10.3390/polym13173012

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  • Synthesis and Oxygen Permeation of Novel Alternating Copolymers Containing Disiloxane and Imido Groups by Hydrosilylation Polyaddition

    Chenxi Xu, Masahiro Teraguchi, Takashi Kaneko, Toshiki Aoki

    Chemistry Letters   50 ( 9 )   1617 - 1619   2021年9月

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    掲載種別:研究論文(学術雑誌)   出版者・発行元:The Chemical Society of Japan  

    DOI: 10.1246/cl.210306

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  • Highly Efficient Absolute Optical Resolution with Circularly Polarized Light via Two Serial Enantioselective Reactions of Acetylene Monomers Bearing a Racemic Substituent

    Yanan Tang, Lijia Liu, Junpei Suzuki, Masahiro Teraguchi, Takashi Kaneko, Toshiki Aoki

    Chemistry Letters   50 ( 9 )   1688 - 1690   2021年9月

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    掲載種別:研究論文(学術雑誌)   出版者・発行元:The Chemical Society of Japan  

    DOI: 10.1246/cl.210341

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  • Improved oxygen permeation of a multi-stranded network two-dimensional polymer synthesized by three-step polymerizations of a novel monomer bearing three different polymerizable groups followed by photoexfoliation

    Kehan Cheng, Masahiro Teraguchi, Takashi Kaneko, Toshiki Aoki

    Polymer   228   123857 - 123857   2021年7月

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    掲載種別:研究論文(学術雑誌)   出版者・発行元:Elsevier BV  

    DOI: 10.1016/j.polymer.2021.123857

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  • Improvement of oxygen permselectivity of a rigid helical polyphenylacetylene: Effect of flexible groups, degree of polymerization, composites, thickness, orientation, and network formation

    Jia Shi, Yuka Kimura, Shohei Takeda, Chenxi Xu, Kazuki Shoji, Masahiro Teraguchi, Takashi Kaneko, Toshiki Aoki

    Polymer   228   123900 - 123900   2021年7月

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    掲載種別:研究論文(学術雑誌)   出版者・発行元:Elsevier BV  

    DOI: 10.1016/j.polymer.2021.123900

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  • Synthesis of Cis-Cisoid or Cis-Transoid Poly(Phenyl-Acetylene)s Having One or Two Carbamate Groups as Oxygen Permeation Membrane Materials

    Yu Zang, Yinghui Lun, Masahiro Teraguchi, Takashi Kaneko, Hongge Jia, Fengjuan Miao, Xunhai Zhang, Toshiki Aoki

    Membranes   10 ( 9 )   199 - 199   2020年8月

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    掲載種別:研究論文(学術雑誌)   出版者・発行元:MDPI AG  

    Three new phenylacetylene monomers having one or two carbamate groups were synthesized and polymerized by using (Rh(norbornadiene)Cl)2 as an initiator. The resulting polymers had very high average molecular weights (Mw) of 1.4–4.8 × 106, with different solubility and membrane-forming abilities. The polymer having two carbamate groups and no hydroxy groups in the monomer unit showed the best solubility and membrane-forming ability among the three polymers. In addition, the oxygen permeability coefficient of the membrane was more than 135 times higher than that of a polymer having no carbamate groups and two hydroxy groups in the monomer unit with maintaining similar oxygen permselectivity. A better performance in membrane-forming ability and oxygen permeability may be caused by a more extended and flexible cis-transoid conformation and lower polarity. On the other hand, the other two new polymers having one carbamate group and two hydroxy groups in the monomer unit showed lower performances in membrane-forming abilities and oxygen permeabilities. It may be caused by a very tight cis-cisoid conformation, which was maintained by intramolecular hydrogen bonds.

    DOI: 10.3390/membranes10090199

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  • Synthesis and Permselectivity of a Soluble Two-Dimensional Macromolecular Sheet by Solid–Solid Interfacial Polycondensation Followed by Chemical Exfoliation 査読

    Yanqing Qu, Xiaoyu Du, Kehan Cheng, Yu Zang, Liang Xu, Ken-ichi Shinohara, Masahiro Teraguchi, Takashi Kaneko, Toshiki Aoki

    ACS Materials Letters   1121 - 1128   2020年8月

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    掲載種別:研究論文(学術雑誌)   出版者・発行元:American Chemical Society (ACS)  

    DOI: 10.1021/acsmaterialslett.0c00178

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  • Synthesis of Well-Defined Chiral Oligopinanylsiloxane Graft Copoly(phenylacetylene)s Using the Macromonomer Method and Their Enantioselective Permeability 査読

    Yu Zang, Toshiki Aoki, Masahiro Teraguchi, Takashi Kaneko, Liqun Ma, Hongge Jia, Fengjuan Miao

    ACS Applied Polymer Materials   2 ( 2 )   853 - 861   2020年2月

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    掲載種別:研究論文(学術雑誌)   出版者・発行元:American Chemical Society (ACS)  

    DOI: 10.1021/acsapm.9b01111

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  • Synthesis, in-situ membrane preparation, and good gas permselectivity of insoluble poly(substituted acetylene)s loosely cross-linked with short and soft siloxane and silanol linkages 査読

    Jianjun Wang, Toshiki Aoki, Takashi Kaneko, Masahiro Teraguchi

    Polymer   187   122081 - 122081   2020年1月

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    掲載種別:研究論文(学術雑誌)   出版者・発行元:Elsevier BV  

    DOI: 10.1016/j.polymer.2019.122081

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  • Helix-sense-selective polymerization of 3,5-bis(hydroxymethyl)phenylacetylene rigidly bearing galvinoxyl residues and their chiroptical properties 査読

    Zhichun Shi, Jianjun Wang, Masahiro Teraguchi, Toshiki Aoki, Takashi Kaneko

    Polymers   11 ( 11 )   1877   2019年11月

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    掲載種別:研究論文(学術雑誌)  

    © 2019 by the authors. Four kinds of newly synthesized achiral phenylacetylenes bearing a phenylhydrogalvinoxyl residue at 4-position were polymerized by using a chiral rhodium catalyst system, [Rh(nbd)B(C6H5)4] or [Rh(nbd)Cl]2 catalysts in the presence of chiral (R)-(+)- or (S)-(-)-1-phenylethylamine ((R)- or (S)-PEA) cocatalysts. Poly(m-HGDHPA) and poly(m-HGTHPA) in THF showed Cotton signals at the absorption regions of the main chain and hydrogalvinoxyl in the circular dichroism (CD) spectra. It indicated that excess of one-handed helical polyacetylene backbone was induced by helix-sense-selective polymerization (HSSP) under the asymmetric conditions despite the achiral monomer, and the hydrogalvinoxyl moieties were also arranged to form one-handed helical structure. However, there was no Cotton effect for poly(p-HGDHPA) and poly(p-HGTHPA) because the intramolecular hydrogen bonding did not act well to stabilize the helical conformation. The hydrogalvinoxyl units of poly(m-HGDHPA) and poly(m-HGTHPA) were converted to the corresponding galvinoxyl radicals after treatment with PbO2. In the CD spectra of the polyradicals, the Cotton effects decreased depending on their static stability of helical conformation, suggesting that reversal conformation of the polymer chain arose.

    DOI: 10.3390/polym11111877

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  • Antiparallel Arrangement of 2,7-Substituted 9,10-Bis(phenylethynyl)anthracene Assisted by Hydrogen Bonding of Terminal Units 査読

    Takashi Kaneko, Yosuke Araki, Ken ichi Shinohara, Masahiro Teraguchi, Toshiki Aoki

    Bulletin of the Chemical Society of Japan   92 ( 10 )   1672 - 1678   2019年10月

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    © 2019 The Chemical Society of Japan. 2,7-Substituted 9,10-bis(phenylethynyl)anthracenes with bulky phenol residues were synthesized and investigated for their antiparallel molecular arrangement. UV-vis absorption and photoluminescence properties and molecular mechanics calculation indicate that they formed an antiparallel π-π stacked dimer, which was strongly associated by hydrogen bonding and π-π interaction. This strongly associated dimer structure was supported by AFM images of specimens prepared on mica by spin casting dilute chloroform/hexane (2/8 v/v) solution. However, the absence of intradimer hydrogen bonding resulted in the offset stacking, which was confirmed from the single crystal X-ray analysis.

    DOI: 10.1246/bcsj.20190156

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  • Synthesis of a Novel AB Block Copolyaceylene Consisting of a Dynamic Cis-transoidal Racemic Helical Sequence and a Static Cis-cisoidal One-handed Helical Sequence 査読

    Yin Guanwu, Suzuki Junpei, Aoki Toshiki, Teraguchi Masahiro, Kaneko Takashi

    CHEMISTRY LETTERS   48 ( 6 )   506 - 509   2019年6月

  • New Synthetic Methods of Novel Nanoporous Polycondensates and Excellent Oxygen Permselectivity of Their Composite Membranes 査読

    Zang Yu, Aoki Toshiki, Teraguchi Masahiro, Kaneko Takashi, Jia Hongge, Ma Liqun, Miao Fengjuan

    NANOMATERIALS   9 ( 6 )   2019年6月

  • Simultaneous improvement of permeability and selectivity in enantioselective permeation through solid chiral membranes from a newly synthesized one-handed helical polyphenylacetylene with aldehyde pendant groups by enantioselective reaction 査読

    Zang Yu, Qu Yanqing, Aoki Toshiki, Teraguchi Masahiro, Kaneko Takashi, Jia Hongge, Ma Liqun, Miao Fengjuan

    POLYMER   171   45 - 49   2019年5月

  • Helix-Sense-Selective Polymerization of Phenylacetylenes Having a Porphyrin and a Zinc-Porphyrin Group: One-Handed Helical Arrangement of Porphyrin Pendants 査読

    Teraguchi Masahiro, Nahata Nobuyuki, Nishimura Takahiro, Aoki Toshiki, Kaneko Takashi

    POLYMERS   11 ( 2 )   2019年2月

  • Synthesis and oxygen permeability of novel graft copolymers consisting of a polyphenylacetylene backbone and long oligosiloxane grafts from phenylacetylene-type macromonomers 査読

    Zang Yu, Aoki Toshiki, Kaneko Takashi, Teraguchi Masahiro, Ma Liqun, Jia Hongge, Miao Fengjuan

    POLYMER   156   66 - 70   2018年11月

  • Enhanced performances of enantioselective permeation through one-handed helical polymer membranes by enantioselective imine exchange reaction with permeants and by partially decomposed reaction of the membrane 査読

    Qu Yanqing, Aoki Toshiki, Teraguchi Masahiro, Kaneko Takashi

    POLYMER   156   39 - 43   2018年11月

  • Synthesis and Ultrahigh Oxygen Permeability of Silicon-containing cis-cisoidal Poly(substituted phenylacetylene)s 査読

    Xu Chenxi, Aoki Toshiki, Ma Liqun, Jia Hongge, Teraguchi Masahiro, Kaneko Takashi

    CHEMISTRY LETTERS   47 ( 10 )   1314 - 1317   2018年10月

  • Chiral teletransmission in the cis-cisoidal sequence of copoly(substituted acetylene)s by multiple stage solvent exchange of the copolymer solution through a membrane 査読

    Lijia Liu, Yuanyuan Gu, Yudan Wang, Toshiki Aoki, Guan Wang, Takeshi Kaneko, Masahiro Teraguchi

    Polymer   154   253 - 257   2018年10月

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    © 2018 Elsevier Ltd Copoly(4-dodecyloxyl-3,5-dihydroxymethyl-phenylacetylene/p-pinanyldimethylsilylphenylacetylene) (copoly(1/2)) consist of both the cis-cisoidal sequence of achiral 4-dodecyloxyl-3,5-dihydroxymethyl-phenylacetylene (1) and cis-transoidal sequence of chiral p-pinanyldimethylsilylphenylacetylene (2). The reactivity ratios of 1 and 2 in the copolymerization were estimited as r 1 = 1.49 and r 2 = 0.50, respectively. By replacing THF (a good solvent) of copoly(1/2) solution with methanol (a poor solvent) gradually by concentration-driven permeation through a membrane for several times, stepwise increase in the CD intensity at 308 nm arisen from the cis-cisoidal main-chain was observed. The local chirality in chiral 2 units was successfully transmitted to the cis-cisoidal sequence of achiral 1. Even when the molar ratio of 1/2 reaches 50, this method of the multiple-stage-solvent-exchange is still effective for transmitting the local chirality in 2 to the cis-cisoidal sequence 1 in the copolymer. Directly adding methanol to the copoly(1/2)'s solution and annealing of copoly(1/2) in THF/methanol could not realize this chiral teletransmission. Hence, this new method of the multiple stage solvent exchange in the copolymer solution through a membrane is suitable and efficient to realize the efficient chirality transmission and amplification in the cis-cisoidal polyacetylene.

    DOI: 10.1016/j.polymer.2018.09.023

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  • Synthesis and oxygen permeation of novel well-defined homopoly(phenylacetylene)s with different sizes and shapes of oligosiloxanyl side groups 査読

    Yu Zang, Toshiki Aoki, Kazuki Shoji, Masahiro Teraguchi, Takashi Kaneko, Liqun Ma, Hongge Jia, Fengjuan Miao

    Journal of Membrane Science   561   26 - 38   2018年9月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:Elsevier B.V.  

    Six new silicon-containing phenylacetylenes having short oligosiloxane substituents with different sizes and shapes have been synthesized. Homopolymerization of the monomers yielded the corresponding homopoly(substituted phenylacetylene)s with high molecular weights and good solubility. These comb-shaped homopolymers gave self-standing membranes whose PO2 and PO2 /PN2 could be measured. We discuss the effect of the chemical structures on their membrane performances together with the other seven related polymers we synthesized before and commercially available cross-linked polydimethylsiloxane (PDMS). While the homopolymers with linear oligodimethylsiloxanes (ODMS) show very high PO2 values which are higher than PDMS, the homopolymers with branched ODMS show high PO2 /PN2 values which are close to that of poly(phenylacetylene) (poly(PA)) and, in addition, had ten times higher PO2 than poly(PA). Introduction of the branched spherical ODMS substituents increases PO2 without any drop of PO2 /PN2 and introduction of the linear ODMS substituents increases PO2 largely which is higher than that of PDMS. It was found that the chemical structures, i.e., the shapes of the ODMS substituents were more important than that of composition for determining their performance as oxygen permselective membrane materials. In conclusion, oxygen permeation could be tuned by changing sizes and shapes of the ODMS side groups.

    DOI: 10.1016/j.memsci.2018.04.031

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  • Ultrahigh oxygen permeability of chemically-modified membranes of novel (co) polyacetylenes having a photodegradative backbone and crosslinkable side chains 査読

    Zhang Mingyu, Aoki Toshiki, Liu Lijia, Wang Jianjun, Teraguchi Masahiro, Kaneko Takashi

    POLYMER   149   117 - 123   2018年8月

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    掲載種別:研究論文(学術雑誌)  

    DOI: 10.1016/j.polymer.2018.06.075

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  • Synthesis of soluble oligsiloxane-end-capped hyperbranched polyazomethine and their application to CO2/N-2 separation membranes 査読

    Xu Liang, Lei Tianyang, Jing Boyu, Zang Yu, Miao Fengjuan, Aoki Toshiki, Teraguchi Masahiro, Kaneko Takashi

    DESIGNED MONOMERS AND POLYMERS   21 ( 1 )   99 - 104   2018年5月

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    掲載種別:研究論文(学術雑誌)  

    DOI: 10.1080/15685551.2018.1472720

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  • Solvent-tuned dual emission of a helical poly[3,5-bis(hydroxymethyl)phenylacetylene] connected with a π-conjugated chromophore 査読

    Zhichun Shi, Giseop Kwak, Young-Jae Jin, Masahiro Teraguchi, Toshiki Aoki, Takashi Kaneko

    Polymer Journal   50 ( 7 )   1 - 5   2018年3月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:Nature Publishing Group  

    For THF solutions of an optically active helical poly[3,5-bis(hydroxymethyl)phenylacetylene] derivative bearing a biphenyl group, photoexcitation of the terphenyl moiety at 300 nm led to photoluminescence at 390 nm. On the other hand, the photoluminescence resulting from excitation at 280 nm caused dual emission at 310 and 390 nm, whose intensities were tuned by the polar-solvent stimuli which induced the collapse of the intramolecular stack structure of the side groups, and the change in the emission wavelength accompanied disappearance of the optical activity.

    DOI: 10.1038/s41428-018-0045-7

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  • Fluorescence emission and image patterning from selective photocyclic aromatization of cis–cisoid helical poly(phenylacetylene)s in situ in a film via top-down photodegradation 査読

    Young-Jae Jin, Hyosang Park, Chang-Lyoul Lee, Masahiro Teraguchi, Takashi Kaneko, Toshiki Aoki, Giseop Kwak

    Dyes and Pigments   149   444 - 448   2018年2月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:Elsevier Ltd  

    Selective photocyclic aromatization (SCAT) of cis–cisoid helical poly(phenylacetylene) derivatives was investigated during the in situ photodegradation in a film. An infrared absorption peak appeared at ∼1700 cm−1 owing to the overtone vibration of the 1,3,5-trisubstituted benzene and the peak at 1060 cm−1 due to the cis C=C bending of the main chain decreased, indicating occurrence of SCAT. Simultaneously, the polymer film became emissive in visible region during SCAT. The fluorescence (FL) quantum efficiency was approximately 0.92% in the film and not so much high relative to usual fluorophores. The FL emission disappeared in an instant when the decomposition product dissolved in a solvent. The FL lifetime of the polymer film increased with photodegradation. These all indicated the occurrence of excimer emission. A finely resolved FL image pattern was readily obtained using a photomask.

    DOI: 10.1016/j.dyepig.2017.10.035

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  • Synthesis of Two Well-Defined Quadruple-Stranded Copolymers having Two Kinds of Backbones by Postpolymerization of a Helical Template Polymer 査読

    Yu Zang, Toshiki Aoki, Hiroyoki Tanagi, Kana Matsui, Masahiro Teraguchi, Takashi Kaneko, Liqun Ma, Hongge Jia, Ken-Ichi Shinohara

    Macromolecular Rapid Communications   39 ( 4 )   2018年2月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:Wiley-VCH Verlag  

    A brand new, soluble quadruple-stranded copolymer is synthesized by using a self-template polymer from a new monomer. In addition, another very unique quadruple-stranded copolymer having a π−π stacking supramolecular polymer main chain is synthesized by selective photocyclic aromatization of the quadruple-stranded copolymer. The two quadruple-stranded copolymers gave self-standing membranes.

    DOI: 10.1002/marc.201700556

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  • A New Analysis Method for Quantitative Determination of Triads of Copoly(substituted acetylene) Backbones by Highly Selective Photocyclic Aromatization 査読

    Guanwu Yin, Nennei Nagaoka, Lijia Liu, Toshiki Aoki, Masahiro Teraguchi, Takashi Kaneko

    CHEMISTRY LETTERS   46 ( 11 )   1608 - 1611   2017年11月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    Since highly selective photocyclic aromatization (SCAT) of poly(substituted acetylene) s yields quantitatively the corresponding 1,3,5-trisubstituted benzene derivatives, the SCAT products were applied for quantitative determination of microstructures of copoly(substituted acetylene) s by NMR (nuclear magnetic resonance). By this SCAT-NMR method for two copolymers of two different types of substituted acetylenes, quantitative analysis for microstructures, i. e., triad distributions and compositions, have been achieved successfully under mild conditions, although they could not be obtained from the NMR of the original copolymers because of their broad and overlapped peaks.

    DOI: 10.1246/cl.170697

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  • Transformer of Achiral Amounts to Chirality: Double Reversal of Enantioselectivity Using a Single Cocatalyst in Asymmetric Polymerization 査読

    Guanwu Yin, Geng Zhang, Toshiki Aoki, Masahiro Teraguchi, Takashi Kaneko, Jesus Rodriguez Castanon, Masashi Shiotsuki, Fumio Sanda

    MACROMOLECULES   50 ( 19 )   7468 - 7474   2017年10月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    Chiral compounds play a vital role in our lives because we are made up of chiral polymers. A strict rule of chirality synthesis is "to obtain one enantiomer of a new chiral product, one enantiomer of a chiral source is needed". If two enantiomers can be synthesized using a single chiral compound, we can both break the above rule and open up a more efficient route to useful chiral materials using a cheaper chiral source. Here we report the first example of double reversals of enantioselectivity in catalytic asymmetric polymerization of achiral monomers using a single isomer of simple chiral compounds as cocatalyst. Furthermore, we achieved this by changing only one achiral condition, that is, the amount of the chiral cocatalyst, without any other changes in the polymerization conditions. As a result, we easily and directly synthesized (+)- or (-)-polymer using a single chiral compound as a cocatalyst.

    DOI: 10.1021/acs.macromol.7b01671

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  • Oxygen permselectivities through supramolecular polymer membranes prepared by highly selective photocyclic aromatization of poly(substituted acetylene) 査読

    Guanwu Yin, Eri Ohtaka, Toshiki Aoki, Jianjun Wang, Masahiro Teraguchi, Takashi Kaneko

    POLYMER   127   232 - 235   2017年10月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ELSEVIER SCI LTD  

    In order to estimate oxygen permselectivities through a supramolecular polymer membrane for the first time, we prepared three kinds of composite membranes consisting of a supramolecular polymer membrane and a conventional organic polymer membrane. Supramolecular polymer membranes were prepared by using highly selective photocyclic aromatization of poly(substituted acetylene)s. It was found that the supramolecular polymer membrane had oxygen permselectivity (alpha = P-O2/P-N2) around three in spite of its low molecular weight. (C) 2017 Published by Elsevier Ltd.

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  • Subnanoporous Highly Oxygen Permselective Membranes from Poly(conjugated hyperbranched macromonomer)s Synthesized by One-Pot Simultaneous Two-Mode Homopolymerization of 1,3-Bis(silyl)phenylacetylene Using a Single Rh Catalytic System: Control of Their Structures and Permselectivities 査読

    Jianjun Wang, Jun Li, Toshiki Aoki, Takashi Kaneko, Masahiro Teraguch, Zhichun Shi, Hongge Jia

    MACROMOLECULES   50 ( 18 )   7121 - 7136   2017年9月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    Novel well-defined complex,polymers, polymers of acetylene type macronionomers having silylene-vinylene-phenylene-ethynylene hyper-branches, investigated as a new class of subnanoporous oxygen permselective membrane materials, were synthesized very easily by one-pot Simultaneous two-mode homopolymerization of a single monomer with a single catalyst. For this "simultaneous polymerization" we synthesized AB(2)-type monomers (1,3-bis(dimethylsilyl)phenylacetylenes) containing one terminal triple bond and two Si-H groups. The resulting poly(hyperbrancIed mactornonomer)s had high molecular weights, low densities, high solubility, and good self-membrane forming ability. They had higher oxygen permselectivities (a = P-O2/P-N2) than any other reported polymers having similar oxygen permeabilities (P-O2). These excellent polymer membranes could be obtained only by the simultaneous polymerization. In the one-pot simultaneous polymerization, the two different modes of polymerizations, i.e., addition polymerization of the triple bond and polyaddition of the triple bond and two SiH groups in the single monomer, occurred simultaneously by using one catalytic system, i.e., [Rh(norbornadiene)Cl](2)/various amines. The ratio of the branches (RB), i.e., the addition polymerization and the polyaddition, could be controlled by changing the amine cocatalysts. Their oxygen permselectivities could be adjusted by controlling the polymer structures including RB.

    DOI: 10.1021/acs.macromol.7b01458

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  • Oxygen Permselectivities of Novel Multi-bridged Copolymers Synthesized by Imine Metathesis between N-Imines and C-Imines in the Pendant Groups of Two Poly(substituted acetylene)s 査読

    Yinghui Lun, Yu Zang, Toshiki Aoki, Masahiro Teraguchi, Takashi Kaneko

    CHEMISTRY LETTERS   46 ( 3 )   401 - 404   2017年3月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    New types of multi-bridged copolymers were designed and examined as oxygen permselective membrane materials. The multi-bridged copolymers were synthesized by imine metathesis reactions between N-imine (synthetic equivalent of amine)containing poly(substituted acetylene)s and C-imine (synthetic equivalent of aldehyde)-containing poly(substituted acetylene) s in the membrane state. The resulting copolymers maintained good self-membrane forming ability. The introduction of multibridge structures enhanced both oxygen permselectivities and oxygen permeabilities simultaneously.

    DOI: 10.1246/cl.161104

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  • Helix-Sense-Selective Polymerization of Achiral Phenylacetylenes and Unique Properties of the Resulting Cis-cisoidal Polymers 査読

    Lijia Liu, Yu Zang, Hongge Jia, Toshiki Aoki, Takashi Kaneko, Shingo Hadano, Masahiro Teraguchi, Mari Miyata, Geng Zhang, Takeshi Namikoshi

    POLYMER REVIEWS   57 ( 1 )   89 - 118   2017年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:TAYLOR & FRANCIS INC  

    One of the authors discovered helix-sense-selective polymerization (HSSP) of an achiral substituted phenylacetylene which has two hydroxymethyl groups and a relatively hydrophobic substituent by using a chiral catalytic system in 2003. The one-handed helicity is stable and static in nonpolar solvents because it is maintained by intramolecular hydrogen bonds. Since the resulting polymer has extremely tight helicity in its main chain, it shows many interesting and unusual properties including highly selective photocyclic aromatization (SCAT). In this review, the discovery and development of the HSSP and SCAT reactions, and the properties and application of the resulting polymers prepared by HSSP and the resulting supramolecular polymers prepared by SCAT will be examined.

    DOI: 10.1080/15583724.2016.1160930

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  • Fluorescence emission enhancement of poly(phenylacetylene) via thermal annealing 査読

    Young-Jae Jin, Hyojin Kim, Dong-Yeon Hwang, Masahiro Teraguchi, Takashi Kaneko, Toshiki Aoki, Giseop Kwak

    MOLECULAR CRYSTALS AND LIQUID CRYSTALS   645 ( 1 )   50 - 57   2017年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:TAYLOR & FRANCIS LTD  

    Both cis- and trans-rich poly[p-(trimethylsilyl)phenylacetylene]s (PTM-SPAs) were synthesized using [Rh(norbornadiene)Cl](2)-TEA (TEA: triethylamine) and WCl6-Ph4Sn as catalysts, respectively. The Rh-based cis-rich polymer exhibited a remarkable fluorescence (FL) emission enhancement after thermal annealing (heating at 200 degrees C in N-2 atmosphere for 1 min), while the pristine polymer was almost entirely non-emissive. NMR and Raman spectroscopic studies clarified the occurrence of irreversible cis-trans isomerization under thermal annealing and suggested that the FL emission increased with an increase in the trans content of PTMSPA. Computer simulations of 12-mer model compounds clarified that the FL emission is a result of intramolecular excimers formed from side-on -stacking of phenyl groups, which is possible only along the backbone of the trans-based polymer.

    DOI: 10.1080/15421406.2016.1277910

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  • Synthesis of One-Handed Helical Block Copoly(substituted acetylene)s Consisting of Dynamic cis-transoidal and Static cis-cisoidal Block: Chiral Teleinduction in Helix-Sense-Selective Polymerization Using a Chiral Living Polymer as an Initiator 査読

    Lijia Liu, Geng Zhang, Toshiki Aoki, Yudan Wang, Takashi Kaneko, Masahiro Teraguchi, Chunhong Zhang, Hongxing Dong

    ACS MACRO LETTERS   5 ( 12 )   1381 - 1385   2016年12月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    By using a living one-handed helical cis-transoidal poly(chiral substituted phenylacetylene) as a polymer initiator (poly(I-n)), helix-sense-selective polymerization (HSSP) of an achiral phenylacetylene 2 having two hydroxy groups successfully afforded a diblock copoly(phenylacetylene) (copoly(I-n/2(m))) consisting of a dynamic one-handed helical cis-transoidal block and a static one-handed helical cis-cisoidal block. The formation of the diblock structure was confirmed by consumption of the chiral initiator, appearance of characteristic CD indicating the one handed helical cis-cisoidal block, and occurrence of the selective photocylic aromatization reaction in the cis-cisoidal block. Therefore, HSSP has been achieved by using the chiral alkenyl groups in the initiator as a chiral source for the first time. In addition, since the HSSP was achieved in spite of the long distance between the chiral initiation site and the propagating site, chiral teleinduction through the rigid and static one-handed helical cis-cisoidal block based on domino effects was confirmed.

    DOI: 10.1021/acsmacrolett.6b00809

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  • Synthesis and oxygen permselectivity of copoly(substituted acetylene)s with bulky fused polycyclic aliphatic groups 査読

    Hongge Jia, Jian Luo, Toshiki Aoki, Lijia Liu, Yu Zang, Yinghui Lun, Masahiro Teraguchi, Takashi Kaneko

    POLYMER   99   695 - 703   2016年9月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ELSEVIER SCI LTD  

    We synthesized six phenylacetylenes (RCOPAs, RSOPAs, and RSPAs) having a bulky fused polycyclic aliphatic group, which is adamantyl(Ad), pinanyl(Pi), or cholesteryl(Ch) via oxycarbonyl (CO) or oxydimethylsilyl( SO), and the other two phenylacetylenes having less or non-bulky substituents, i.e., menthyloxycarbonylphenylacetylene (MtCOPA) or ethoxydimethylsilylphenylacetylene (EtSOPA) (Et = Ethyl). The new monomers were polymerized and copolymerized with p-trimethylsilylphenylacetylene (SPA) by using catalyst [ Rh(nbd)Cl](2) (nbd = 2,5-norbornadiene) in trimethylamine to give soluble high molecular-weight polymers in relatively good yields. The resulting copolymers were fabricated to self-supporting membranes which had enough strength for separation membranes by solution casting method. As a result, we can discuss the relationship between bulky chemical structures and permeation behavior systematically for the first time. Oxygen permselectivities (PO2/PN2) of copolyRSOPAs having the bulky fused polycyclic aliphatic groups such as Ad and Pi were higher than those of copolyEtSOPAs. PO2/PN2 values of copolyRCOPAs were higher than those of polyRSOPAs when they had the same content of the identical bulky groups. The rigid spacer was effective for enhancing PO2/PN2. Among copolyRCOPAs with bulky fused polycyclic aliphatic groups, the copolymers with spherical substituents such as Pi and Ad groups showed higher PO2/PN2 values than those with a planer substituent i.e., Ch groups. PO2 values of copolyRSOPAs and copolyRCOPAs were 130-220 and 50-90 barrer, respectively. The flexible silyloxy spacers in RSOPAs were effective in enhancing their PO2 values. (C) 2016 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/j.polymer.2016.07.023

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  • Novel Isolated, L-Amino Acid-Ligated Rhodium Catalysts that Induce Highly Helix-Sense-Selective Polymerization of an Achiral 3,4,5-Trisubstituted Phenylacetylene 査読

    Hongge Jia, Yongqiang Shi, Liqun Ma, Xuan Gao, Yazhen Wang, Yu Zang, Jijun Peng, Toshiki Aoki, Masahiro Teraguchi, Takashi Kaneko, Toshio Masuda

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   54 ( 15 )   2346 - 2351   2016年8月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:WILEY-BLACKWELL  

    Two novel chiral well-defined rhodium complexes, Rh(cod)(L-Phe) (cod=1,5-cyclooctadiene, Phe=phenylalanine) and Rh(cod)(L-Val) (Val=valine) were synthesized, isolated by recrystallization, and characterized. The helix-senseselective polymerization (HSSP) of an achiral 3,4,5-trisubstituted phenylacetylene, p-dodecyloxy-m, m-dihydroxyphenylacetylene (DoDHPA) was examined by using the two Rh complexes as catalysts. These catalysts provided high molecular weight polymers (M-w 28 x 10(4)-45 x 10(4)) in about 40%-85% yields. The resulting polymers exhibited a bisignated CD signal at about 300 nm and a broad signal around 470 nm, indicating that they have preferential one-handed helical structure. The present catalysts achieved larger molar ellipticity up to [theta](310) = 13.0 x 10(4) deg cm(2)/dmol than those with binary chiral catalytic systems, [Rh(cod)Cl](2)/(L-phenylalaninol), [Rh(cod)Cl](2)/(L-valinol), and [Rh(nbd)Cl](2)/(R)-PEA. All these results manifest that the present, well-defined Rh complexes serve as excellent catalysts for the HSSP of DoDHPA. (C) 2016 Wiley Periodicals, Inc.

    DOI: 10.1002/pola.28106

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  • Highly Selective Photocyclic Aromatization (SCAT)-GPC Method for Quantitative Determination of Microstructures of Copoly(substituted acetylenes) Backbone 査読

    Guanwu Yin, Lijia Liu, Toshiki Aoki, Takeshi Namikoshi, Masahiro Teraguchi, Takashi Kaneko

    CHEMISTRY LETTERS   45 ( 7 )   813 - 815   2016年7月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    Highly selective photocyclic aromatization (SCAT) of poly(substituted acetylene)s, which can quantitatively yield the corresponding 1,3,5-trisubstituted benzene derivative, was applied to quantitative determination of the microstructures of copoly(substituted acetylene)s. By GPC analysis of the SCAT products of the copolymers of two substituted acetylenes having substituents whose molecular weights were greatly different, some clear information regarding the microstructures, such as sequence (triad) distribution and composition, which could not be obtained from NMR because of their broad peaks, could be obtained successfully under a mild condition.

    DOI: 10.1246/cl.160357

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  • Highly Emissive, Optically Active Poly(diphenylacetylene) Having a Bulky Chiral Side Group 査読

    Hyojin Kim, Kyo-Un Seo, Young-Jae Jin, Chang-Lyoul Lee, Masahiro Teraguchi, Takashi Kaneko, Toshiki Aoki, Giseop Kwak

    ACS MACRO LETTERS   5 ( 5 )   622 - 625   2016年5月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    A highly emissive, optically active poly(diphenylacetylene) derivative, NpSi*-PDPA, was synthesized by introducing a bulky chiral pendant group into the polymer chain. NpSi*-PDPA exists in a glassy state having a highly disordered and amorphous structure. Hence, the fractional free volume is quite high, i.e., 0.29. NpSi*-PDPA emits a green light in solution and a yellow light in film. This polymer is quite emissive, as the photoluminescence (PL) quantum yield is 56.1% in solution and 6.2% in film, and the PL lifetime is relatively long, 1.71 ns in solution and 1.05 ns in film. NpSi*PDPA shows the strongest circular dichroism (CD) signal at 384 nm, with a magnitude of circular polarization (g(CD)) of 0.90 x 10(-3) and an optical rotation of 110 degrees (4.30 X 10(-3) g mL(-1), in CHCl3). The CD intensity is significantly increased by annealing at 80 degrees C, reaching an equilibrium at g(CD) of 7.10 X 10(-3) after 72 h.

    DOI: 10.1021/acsmacrolett.6b00184

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  • Asymmetric Restriction of Intramolecular Rotation in Chiral Solvents 査読

    Young-Jae Jin, Hyojin Kim, Jong Jin Kim, Nam Ho Heo, Jong Won Shin, Masahiro Teraguchi, Takashi Kaneko, Toshiki Aoki, Giseop Kwak

    CRYSTAL GROWTH & DESIGN   16 ( 5 )   2804 - 2809   2016年5月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    Commercially available molecular rotor (MR) compounds were recrystallized using chiral monoterpenes as solvents. The resulting crystals exhibited large circular dichroism signals with opposing signs according to the handedness of the chiral solvent used. X-ray crystallographic analysis showed that the chirality originated from asymmetric restriction of intramolecular rotation in the crystals. The crystals were also highly emissive due to restricted bond rotation, while solutions of the materials were almost nonemissive. The solvent-to-MR chirality transfer approach to. crystallization discussed herein should be a convenient, universal way to obtain highly emissive chiral crystals.

    DOI: 10.1021/acs.cgd.6b00128

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  • High Oxygen Permselectivity through a Membrane from Novel Soluble Imido-bridged Ladder Polysiloxane 査読

    Shuangping Xu, Toshiki Aoki, Masahiro Teraguchi, Takashi Kaneko

    CHEMISTRY LETTERS   45 ( 4 )   424 - 426   2016年4月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    A novel soluble well-defined ladder polysiloxane bridged by imido linkages having a high molecular weight was successfully synthesized via the corresponding supramolecular intermediate and was fabricated to a very flexible self-standing membrane. The membrane showed a better oxygen permselectivity than conventional linear polyorganosiloxanes. We directly observed the effect of the regular molecular-sized pores formed by the ladder structure on the oxygen permselectivity for the first time. This is the first report on gas permeability thorough a well-characterized ladder polymer.

    DOI: 10.1246/cl.151196

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  • Influence of a hydrodynamic environment on chain rigidity, liquid crystallinity, absorptivity, and photoluminescence of hydrogen-bonding-assisted helical poly(phenylacetylene) 査読

    Young-Jae Jin, Hyojin Kim, Mari Miyata, Guanwu Yin, Takashi Kaneko, Masahiro Teraguchi, Toshiki Aoki, Giseop Kwak

    RSC ADVANCES   6 ( 43 )   36661 - 36666   2016年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ROYAL SOC CHEMISTRY  

    The chain rigidity, liquid crystallinity, absorptivity, and photoluminescence of a helical poly(phenylacetylene) derivative varied significantly depending on the solvent employed, owing to the conformational changes caused by the formation or destruction of intramolecular hydrogen bonds. The polymer chains were rigid and liquid crystalline when dissolved in such non-solvents as toluene and THF to show lower absorptivity and intramolecular excimer emission while the same polymer chains became flexible in piperidine having a high hydrogen-bonding acceptor strength to exhibit strong absorption in the visible region and the emission was significantly quenched.

    DOI: 10.1039/c6ra01940d

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  • Highly Efficient Helix-sense-selective Polymerization of an Achiral Phenylacetylene Having a Bulky Group 査読

    Yanqing Qu, Yu Zang, Mingyu Zhang, Toshiki Aoki, Masahiro Teraguchi, Takashi Kaneko, Liqun Ma, Hongge Jia

    CHEMISTRY LETTERS   44 ( 12 )   1777 - 1779   2015年12月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    A novel achiral phenylacetylene having a bulky t-butyl group was synthesized and polymerized by a chiral catalytic system containing [Rh(nbd)Cl](2) (nbd: norbomadiene) and chiral amines to yield a one-handed helical polymer having a much higher g value than polymers with no bulky groups. Highly efficient helix-sense-selective polymerization has been achieved using a bulky monomer and a less bulky chiral cocatalyst.

    DOI: 10.1246/cl.150863

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  • Quantitative Introduction of Perfluoroalkyl Groups to Poly(diphenylacetylene) Membranes via Three-step Membrane Reaction Including Click Reaction and Their Gas Permeability 査読

    Takashi Sato, Masahiro Teraguchi, Motohiro Kiuchi, Takashi Kaneko, Toshiki Aoki

    CHEMISTRY LETTERS   44 ( 12 )   1679 - 1681   2015年12月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    Poly(diphenylacetylene) membranes having perfluoroalkyl groups were quantitatively synthesized via a three-step membrane reaction, that is, desilylation (the 1st step), Williamson reaction (the 2nd step), and Click reaction (the 3rd step). The conversions of the all reactions were confirmed by IR. spectra and elemental analysis. Even though the reactions were carried out in membrane state, the conversions were fairly high. These high conversions are attributed to high swelling property of poly(diphenylacetylenes), including the extremely large fractional free volume. The gas permeability and thermal property of the perfluoroalkylated poly(diphenylacetylene) membranes were investigated. Polymer reactions are a very useful and powerful

    DOI: 10.1246/cl.150841

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  • Helical Conformation Stability of Poly[3,5-bis(hydroxymethyl)phenylacetylene]s Depending on the Length of Their Rigid and Linear pi-Conjugated Side Groups 査読

    Zhichun Shi, Masahiro Teraguchi, Toshiki Aoki, Takashi Kaneko

    CHEMISTRY LETTERS   44 ( 10 )   1413 - 1415   2015年10月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    We synthesized new 3,5-bis(hydroxymethyl)phenylacetylene (HPA) monomers connected with a rigid and linear pi-conjugated oligomer. The monomers were successfully polymerized with a rhodium catalyst [Rh(nbd)Cl](2) in the presence of chiral PEA to give the corresponding polymers. Helix-sense-selective polymerization proceeded for DBHPA. CD, UV, and WAXS spectroscopic studies revealed that the intramolecular hydrogen bonds of the polymers contributed to the stabilization of their helical conformation but the stability depended on the length of the rigid and linear pi-conjugated side group.

    DOI: 10.1246/cl.150616

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  • Synthesis of a Fluorine-Containing Cis-Cisoidal One-Handed Helical Polyphenylacetylene and Application of Highly Selective Photocyclic Aromatization Product on Oxygen Permselective Membrane 査読

    Yu Zang, Guanwu Yin, Toshiki Aoki, Masahiro Teraguchi, Takashi Kaneko, Liqun Ma, Hongge Jia

    CHIRALITY   27 ( 8 )   459 - 463   2015年8月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:WILEY  

    A novel phenylacetylene monomer having a perfluorinated alkyl group (M-F) was synthesized and polymerized in a chiral catalytic system to yield a one-handed helical polymer. The ability and efficiency of the chiral induction of the fluorine-containing monomer in the helix-sense-selective polymerization (HSSP) was much higher than those of a monomer having the corresponding alkyl group (M-H) we reported before. The resulting polymer P-F showed cis-cisoidal one-handed helical conformation, and was suitable for highly selective photocyclic aromatization (SCAT) to give a 2D surface modifier (T-F). Oxygen permselectivity through a base polymer membrane was highly enhanced from 1.83 to 2.36 by adding a small amount (1-5wt%) of the 2D surface modifier T-F. The improvement was thought to be caused by improvement of solution selectivity on the membrane surface which the 2D surface modifier effectively covered. Chirality 27:459-463, 2015. (c) 2015 Wiley Periodicals, Inc.

    DOI: 10.1002/chir.22441

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  • A Helical Polyphenylacetylene Having Amino Alcohol Moieties Without Chiral Side Groups as a Chiral Ligand for the Asymmetric Addition of Diethylzinc to Benzaldehyde 査読

    Lijia Liu, Qing Long, Toshiki Aoki, Geng Zhang, Takashi Kaneko, Masahiro Teraguchi, Chunhong Zhang, Yudan Wang

    CHIRALITY   27 ( 8 )   454 - 458   2015年8月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:WILEY-BLACKWELL  

    One-handed helical polyphenylacetylenes having achiral amino alcohol moieties, but no chiral side groups, were synthesized by the helix-sense-selective copolymerization of an achiral phenylacetylene having an amino alcohol side group with a phenylacetylene having two hydroxyl groups. Since the resulting helical copolymers were successfully utilized as chiral ligands for the enantioselective alkylation of benzaldehyde with diethylzinc, we can conclude that the main-chain chirality based on the one-handed helical conformation is useful for the chiral catalysis of an asymmetric reaction for the first time. The enantioselectivities of the reaction were controlled by the optical purities of the helical polymer ligands. In addition, the polymer ligands could be easily recovered by precipitation after the reaction. Chirality 27:454-458, 2015. (c) 2015 Wiley Periodicals, Inc.

    DOI: 10.1002/chir.22455

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  • Helix-sense-selective Polymerization of Achiral Phenylacetylenes by Using One-handed Helical Poly(phenylacetylene)s as Chiral Cocatalysts Prepared by Helix-sense-selective Polymerization of Achiral Phenylacetylenes 査読

    Geng Zhang, Lijia Liu, Toshiki Aoki, Masahiro Teraguchi, Takashi Kaneko

    CHEMISTRY LETTERS   44 ( 3 )   318 - 320   2015年3月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    We found that the helix-sense-selective polymerization (HSSP) of achiral phenylacetylenes having two hydroxy groups was realized by using one-handed helical poly(phenylacetylene)s as chiral cocatalysts prepared by HSSP of the same or similar achiral phenylacetylenes having two hydroxy groups. In other words, the chirality caused only by the one-handed helical backbone was found to be able to work as a cocatalyst in the chiral catalytic system. In addition, the efficiency of the chiral induction was high and almost the same as that of the HSSP by using enatiomerically pure phenylethylamine as a cocatalyst.

    DOI: 10.1246/cl.141079

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  • A Chiral Supramolecular Polymer Membrane with no Chiral Substituents by Highly Selective Photocyclic Aromatization of a One-Handed Helical Cis-cisoidal Polyphenylacetylene 査読

    Lijia Liu, Qing Long, Toshiki Aoki, Takeshi Namikoshi, Yunosuke Abe, Mari Miyata, Masahiro Teraguchi, Takashi Kaneko, Yudan Wang, Chunhong Zhang

    MACROMOLECULAR CHEMISTRY AND PHYSICS   216 ( 5 )   530 - 537   2015年3月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:WILEY-V C H VERLAG GMBH  

    A one-handed helical cis-cisoidal polyphenylacetylene (P) is successfully synthesized by an asymmetric-induced polymerization of a chiral-substituted phenylacetylene having two hydroxymethyl groups. Quantitative photocyclic aromatization of P in a membrane-state followed by in situ removal of the chiral substituents affords a one-handed helical supramolecular polymer membrane of the corresponding cyclic trimer (T) with no chiral substituents. The original one-handed helicity of the precursor P is successfully transmitted to the resulting supramolecular helicity of de-T. Both the hydrogen bonds and the pi-pi stacking are thought to contribute to the retention of the chirality during the two-step reaction in the membrane state.

    DOI: 10.1002/macp.201400526

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  • Selective Polymerization of Dimethylsilylphenylacetylene and the Gas Permselectivity of the Resulting Polymer Membranes 査読

    Jun Li, Jianjun Wang, Toshiki Aoki, Takashi Kaneko, Masahiro Teraguchi

    CHEMISTRY LETTERS   44 ( 2 )   182 - 184   2015年2月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    Three types of homopolymerizations of p-(dimethylsilyl)-phenylacetylene (HSPA) having a terminal triple bond and a Si-H group were selectively carried out by using three kinds of polymerization catalysts. Among them poly(HSPA) synthesized by addition polymerization of its triple bond using [Rh(nbd)Cl](2) (nbd: norbornadiene)/phenylethylamine (PEA) showed a good membrane forming ability. The copolymerizations of HSPA with p-(trimethylsilyl)phenylacetylene (SPA) were carried out using [Rh(nbd)Cl](2)/PEA and the resulting copolymers were fabricated to self-supporting membranes. These membranes, including the homopolymer of HSPA, showed higher permselectivities for oxygen and carbon dioxide over nitrogen than those of poly(SPA). Incorporation of HSPA unit to poly(SPA) effectively enhanced its permselectivities with only small decrease in its permeability.

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  • Two-Dimensional and Related Polymers: Concepts, Synthesis, and their Potential Application as Separation Membrane Materials 査読

    Yu Zang, Toshiki Aoki, Masahiro Teraguchi, Takashi Kaneko, Liqun Ma, Hongge Jia

    POLYMER REVIEWS   55 ( 1 )   57 - 89   2015年1月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:TAYLOR & FRANCIS INC  

    Although two-dimensional polymers (2DPs) and related materials are very attractive subjects for research because they are expected to function as ideal gas separation membrane materials, we need to answer some basic questions about them. For example, "Why are they not a common or popular topic, especially in textbooks?"; "How can they be synthesized?"; and "Whatever are 2DPs? and "How can we define 2DPs?" In this review, we try to answer these questions. First, the significance of 2DP as molecular-sieving membrane materials is explained in Section 1. Second, the definitions and classifications are proposed that take into account their first-order and high-order structures in Section 2. Third, syntheses and function of a few real 2DPs and many related polymers described in the literature are reviewed, including such materials as covalent organic frameworks(COFs), carbonized molecular sieving membranes(CMSMs), polymers of intrinsic porosity(PIM), and our recent results on the synthesis and function of 2DPs and related polymers in Sections 3 and 4. Finally, in Section 5 we evaluate the two-dimensional (2D) characters of 2DPs described in Section 3 using some 2D characteristic values defined in Section 2, and the future of 2DPs is discussed in Section 6.

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  • Synthesis and oxygen permeation of novel polymers of phenylacetylenes having two hydroxyl groups via different lengths of spacers 査読

    Yu Zang, Toshiki Aoki, Masahiro Teraguchi, Takashi Kaneko, Liqun Ma, Hongge Jia

    POLYMER   56 ( SI )   199 - 206   2015年1月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ELSEVIER SCI LTD  

    Three novel phenylacetylenes having two hydroxyl groups via different kinds of spacers between the two hydroxyl groups and benzyl group were synthesized and polymerized. Two of the resulting polymers having oxyalkylene spacers between the hydroxyl group and benzyl group had good membrane forming ability, relatively high oxygen permselectivity and high oxygen permeability. By introducing the oxyalkylene spacers, the membrane forming abilities and oxygen permselectivity were enhanced. Oxygen permselectivity (P-O2/P-N2 = 2.67) of the polymer membrane having the longest spacers was higher than that (2.19) of polymer without any spacers. It may be because the columnar content and then defects decreased when the cis-cisoid conformation was changed to cis-transoid conformation. In addition, by decreasing the columnar content of the membrane from the polymer without any spacers, which could be controlled by conditions in membrane preparation, the membrane forming ability and oxygen permselectivity were effectively enhanced (from 2.19 to 2.61) without any drop of oxygen permeability. (C) 2014 Elsevier Ltd. All rights reserved.

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  • Catalytic helix-sense-selective polymerisation of achiral substituted acetylenes containing bulky pi-conjugated planar substituents yielding soluble and statically stable one-handed helical polymers 査読

    Y. Zang, X. Wang, W. Zhang, T. Aoki, M. Teraguchi, T. Kaneko, L. Ma, H. Jia

    RSC ADVANCES   5 ( 129 )   106819 - 106823   2015年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ROYAL SOC CHEMISTRY  

    Helix-sense-selective polymerisation of three new achiral substituted acetylenes containing two bulky pi-conjugated planar substituents via imino groups by using catalytic amounts of a chiral source yielded soluble and statically stable one-handed helical polymers which were stabilized by intramolecular steric hindrance.

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  • Helix-sense-selective Degradation of Poly[4-dodecyloxy-3,5-bis(hydroxymethyl)phenylacetylene] by Selective Photocyclic Aromatization (SCAT) Using Circularly Polarized Light (CPL) 査読

    Mari Miyata, Masahiro Teraguchi, Hiromichi Endo, Takashi Kaneko, Toshiki Aoki

    CHEMISTRY LETTERS   43 ( 9 )   1476 - 1477   2014年9月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    Helix-sense-selective photodegaradation of poly[4-dodecyloxy-3,5-bis(hydroxymethyl)phenylacetylene] (poly(DoDHPA)) in membrane state was achieved by selective photocyclic aromatization (SCAT) using single-handed circularly polarized light (CPL). This is the first example of kinetic optical resolution of helical polymers by using CPL.

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  • Synthesis of Poly(1,2-phenyleneethynylene-1,2-phenylenevinylene) Bearing Phenol Residues and Forming Ability of the Folded Helical Conformation 査読

    Takashi Kaneko, Yuta Togashi, Masahiro Teraguchi, Toshiki Aoki

    CHEMISTRY LETTERS   43 ( 8 )   1219 - 1221   2014年8月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    5,4'-Bis(3,5-di-tert-buty1-4-acetoxypheny1)-2-ethynyl-2'-iodo-stilbene was synthesized and polymerized by the Sonogashira reaction to give the corresponding regioregular head-totail poly(1,2-phenyleneethynylene-1,2-phenylenevinylene). The polymer was converted to the corresponding hydroxy polymer after complete elimination of the protecting acetyl group by treatment with an alkaline solution. It was found that the folded helical conformation was preferred for the polymer containing the poly(1,2-phenylenevinylene) structure upon addition of methanol to the chloroform solution owing to the solvophobic interaction.

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  • Synthesis of sequential poly(1,3-phenyleneethynylene)-based polyradicals and through-space antiferromagnetic interaction of their solid state 査読

    Takashi Kaneko, Kyohei Iwamura, Ryo Nishikawa, Masahiro Teraguchi, Toshiki Aoki

    POLYMER   55 ( 5 )   1097 - 1102   2014年3月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ELSEVIER SCI LTD  

    Some 1,3-PPE-based polyradicals with pendent phenoxy radicals whose repeating unit consisted of four 1,3-phenyleneethynylene units were synthesized via polymerization between monomers and trimeric monomers in the presence of the Pd(PPh3)(4) complex catalysts. The ESR spectra of the polyradicals in dichloromethane showed unimodal broad signals. For the solid samples which were prepared from the dichloromethane solution by evaporating the solvent and by drying in vacuo, the signal intensity decreased with broadening of peak-to-peak line-width (Delta H-pp). However, the ESR spectra almost recover to the initial intensity and shapes due to redissolving in dichloromethane. In particular, the decrease of doubly integrating the ESR signal (I-ESR) was more remarkable for the polyradical bearing galvinoxyl and phenoxyl residues than others. This behavior suggests that strong antiferromagnetic interaction partially arose for the polyradical. (C) 2014 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/j.polymer.2014.01.019

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  • Facile synthesis of five 2D surface modifiers by highly selective photocyclic aromatization and efficient enhancement of oxygen permselectivities of three polymer membranes by surface modification using a small amount of the 2D surface modifiers 査読

    Jianjun Wang, Yu Zang, Guanwu Yin, Toshiki Aoki, Hiroyuki Urita, Ken Taguwa, Lijia Liu, Takeshi Namikoshi, Masahiro Teraguchi, Takashi Kaneko, Liqun Ma, Hongge Jia

    POLYMER   55 ( 6 )   1384 - 1396   2014年3月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ELSEVIER SCI LTD  

    A facile synthesis of novel five 2D (planar) surface modifiers having a triphenylbenzene derivatives as a 2D structure has been achieved by the highly selective photocyclic aromatization reaction. Efficient enhancement of oxygen permselectivities through the three polymer membranes has been achieved by adding a small amount (< 5.0 wt%) of the 20 surface modifiers. Among the five 2D surface modifiers, a modifier compound having oligoethylene oxide groups showed the best performance for the enhancement. These improvements were thought to be caused mainly by improvement of the solution selectivity on the membrane surface where the 2D surface modifiers were accumulated. In some of the surface-modified blend membranes, their plots in the P-O2(-alpha) graph were over or close to the upper boundary line by Robeson in 1991. Since all the membranes containing the 2D surface modifiers showed better permselectivities than the corresponding substrate membranes, it is very promising for the future. (C) 2013 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/j.polymer.2013.11.046

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  • Synthesis and Enantioselective Permeability of One-handed Helical Multihydroxy Poly(phenylacetylene) Membrane by In Situ Removal of the Original Chiral Substituents 査読

    Lijia Liu, Kazuomi Mottate, Toshiki Aoki, Takashi Kaneko, Masahiro Teraguchi

    CHEMISTRY LETTERS   43 ( 2 )   237 - 239   2014年2月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    An insoluble chiral membrane of one-handed helical multihydroxy poly(phenylacetylene) without the coexistence of any other chiral moieties has been synthesized by in situ complete removal of a one-handed helical poly(phenylacetylene) having multihydroxymethyl groups and chiral pinanyl groups in each polymeric unit in the membrane state. Although the enantiopermselectivity was decreased, the permeability increased four times by removing the chiral groups. In comparison with the corresponding poly(phenylacetylene) having no hydroxymethyl groups and chiral pinanyl groups, the loss of enantiopermselectivity was much lower. It is believed that the multihydroxy groups could maintain the main-chain chirality or enhanced interaction with permeant.

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  • 堅い平面板状イミノ置換基を有する新規置換アセチレンのらせん選択重合と生成光学活性高分子の定量的膜反応 査読

    宮田 真理, 勝然 勇也, 青木 俊樹, 寺口 昌宏, 金子 隆司

    高分子論文集   71 ( 8 )   372 - 381   2014年

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    記述言語:日本語   掲載種別:研究論文(学術雑誌)  

    著者らのグループは以前置換アセチレンのらせん選択重合(HSSP)とその生成ポリマーの高選択光環化芳香族化分解(SCAT)を報告してきた。本論文では反応性基としてイミノ置換基を有する新規置換アセチレンの合成を行い、このHSSPとSCATへの適合性を調べた。

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  • Facile Synthesis of an Amphiphilic 1,3,5-Trisubstituted Benzene as a Novel Surface Modifier by Selective Photocyclic Aromatization and Efficient Improvement of Oxygen Permselectivity by the Addition of the Surface Modifier 査読

    Jianjun Wang, Toshiki Aoki, Lijia Liu, Takeshi Namikoshi, Masahiro Teraguchi, Takashi Kaneko

    CHEMISTRY LETTERS   42 ( 9 )   1090 - 1092   2013年9月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    An amphiphilic 1,3,5-trisubstituted benzene as a new 2D surface modifier (T-EO) which has six hydroxy groups and three oligoethylene groups was successfully and easily synthesized by selective photocyclic aromatization in high conversion and selectivity for the first time. We prepared four kinds of blend membranes based on PVA or poly(trimethylsilylphenylacetylene) (poly(SPA)) containing the new amphiphilic cyclic trimer (T-EO) or the corresponding polymer (P-EO), that is, T-EO/PVA, P-EO/PVA, and T-EO/poly(SPA) membranes prepared by conventional solvent casting method (Method 1) and T-EO/poly(SPA) membranes prepared by a new solvent casting method (Method 11). T-EO/PVA membranes by Method I and T-EO/poly(SPA) membranes by Method II showed better performance in oxygen permeation than P-EO/PVA membranes by Method I and T-EO/poly(SPA) membranes by Method I, respectively. A PVA-based membrane containing 1.0 wt % T-EO showed the best performance, that is, the alpha became twice that of the original PVA membrane without any decrease in P-O2. The ideal improvement may be caused by effective surface modification by T-EO.

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  • Helix-sense-selective Polymerization of 3,5-Bis(hydroxymethyl)phenylacetylene Connected with a Rigid and pi-Conjugated Substituent 査読

    Zhichun Shi, Yoshinori Murayama, Takashi Kaneko, Masahiro Teraguchi, Toshiki Aoki

    CHEMISTRY LETTERS   42 ( 9 )   1087 - 1089   2013年9月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    An achiral 3,5-bis(hydroxymethyl)phenylacetylene connected with a rigid and pi-conjugated substituent was polymerized using a rhodium (Rh) complex catalyst in the presence of chiral 1-phenylethylamines. The circular dichroism (CD) spectra of the polymers indicated that an excess of one-handed helical polyacetylene backbone was induced by helix-sense-selective polymerization under the asymmetric conditions despite the achiral monomer. The split-type-induced CD signals at 300 nm were attributed to the chromophore including the conjugated side group since the signal appeared at a longer wavelength than the poly[3,5-bis(hydroxymethyl)phenylacetylene] without conjugated substituent.

    DOI: 10.1246/cl.130339

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  • Flexible self-supporting supramolecular polymeric membranes consisting of 1,3,5-trisubstituted benzene derivatives synthesized by highly selective photocyclic aromatization of helical poly(phenylacetylene)s in the membrane state 査読

    Mari Miyata, Takeshi Namikoshi, Lijia Liu, Yu Zang, Toshiki Aoki, Yunosuke Abe, Yoshiyuki Oniyama, Toyokazu Tsutsuba, Masahiro Teraguchi, Takashi Kaneko

    Polymer (United Kingdom)   54 ( 17 )   4431 - 4435   2013年8月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    It has been achieved to obtain flexible self-supporting supramolecular polymeric membranes consisting of only 1,3,5-trisubstituted benzene derivatives prepared by highly selective photocyclic aromatization of the corresponding poly (substituted phenylacetylene)s having a columnar structure. The flexibilities of the self-supporting supramolecular polymeric membranes were enhanced by introducing hydroxyl groups or phenylene groups to the starting polymers (monomers). There were two reasons for the enhanced strength: 1) introduction of intercolumnar hydrogen bonds and 2) enhancement of the degree of intracolumnar stackings. This strength depended on the structure of the starting polymers which functioned as a template. © 2013 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/j.polymer.2013.05.063

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  • Chiral Amplification during Asymmetric-Induced Copolymerization of Phenylacetylenes with Tight Cis-Cisoidal Main Chains 査読

    Lijia Liu, Kazuomi Mottate, Geng Zhang, Toshiki Aoki, Takashi Kaneko, Masahiro Teraguchi

    MACROMOLECULAR RAPID COMMUNICATIONS   34 ( 14 )   1140 - 1144   2013年7月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:WILEY-V C H VERLAG GMBH  

    A novel phenylacetylene (1) having two hydroxyl groups and a chiral pinanyl group together with the other three related phenylacetylenes has been synthesized and (co)polymerized by using an achiral catalytic system. Among the four monomers, only 1 is suitable to the asymmetric-induced polymerization (AIP). Chiral amplification phenomenon is only observed in the copolymerization of 1 with an achiral phenylacetylene having two hydroxyl groups (3). The tight helical cis-cisoidal main chain formed by making intramolecular hydrogen bonds between the hydroxyl groups in the copoly(1/3) enhances the efficiency of chiral induction and as a result chiral amplification phenomenon is observed during the copolymerization.

    DOI: 10.1002/marc.201300318

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  • Excellent oxygen permselectivity of fluorine-containing poly(trimethylsilyldiphenylacetylene)s prepared by direct alkylation of perfluorodecyl groups in membrane state 査読

    Takashi Sato, Naoki Yoshida, Akihiro Ishida, Masahiro Teraguchi, Toshiki Aoki, Takashi Kaneko

    Polymer (United Kingdom)   54 ( 9 )   2231 - 2234   2013年4月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    Two poly(trimethylsilyldiphenylacetylene) membranes containing different contents of fluorine-containing groups were prepared by direct perfluorodecylation of poly(trimethylsilyldiphenylacetylene) (poly 1) in the membrane state using different ratios of (perfluorodecyl)phenyliodonium triflates to the phenyl groups in the polymer. The resulting perfluorodecylated poly(trimethylsilyldiphenylacetylene) (poly 2a and poly 2b) membranes were self-standing and tough. The two membranes showed better performance in oxygen permselectivity compared with all the membranes reported by many researchers. The performance (PO2 &gt
    103 barrer and α = PO 2/PN2 = 2.9) of the poly 2a membrane having a lower content of the fluorine groups located on the upper boundary line reported by Robeson in 2008. The poly 2b membrane having a higher content of the fluorine groups was one of the polymers having the highest PO2 values (PO 2 &gt
    104 barrer) in all the polymers reported.

    DOI: 10.1016/j.polymer.2013.03.008

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  • Folding-Induced Through-Space Magnetic Interaction of Poly(1,3-phenyleneethynylene)-Based Polyradicals 査読

    Takashi Kaneko, Hiromasa Abe, Masahiro Teraguchi, Toshiki Aoki

    MACROMOLECULES   46 ( 7 )   2583 - 2589   2013年4月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    We synthesized poly(1,3-phenyleneethynylene)s bearing galvinoxyl moieties. The absorption ratio of the anion form in 1 M KOH methanol solution between 309 and 294 nm (A(309)/A(294)) decreased with increasing degree of polymerization. The wide-angle X-ray scattering of the powder, which was prepared by precipitation in dilute hydrochloric acid solution from the anion form in 1 M KOH methanol solution, showed a crystalline peak at 2 theta = 28 degrees. Polymers in which the chiral diethynyl-1,1'-binaphthyl moiety was inserted into the poly(1,3-phenyleneethynylene) chain were synthesized, and clear Cotton effects were observed in the absorption region of the galvinoxyl anion chromophore in the CD spectra taken in 1 M KOH-MeOH solution, indicating an excess of one-handed folded helical conformation. A relatively strong antiferromagnetic interaction was observed for the polyradicals prepared by precipitating the anionic form from alkaline methanol solution accompanied with oxidation using aqueous K3Fe(CN)(6) solution. These observations suggest that the relatively strong antiferromagnetic interaction of the polyradicals was caused by the close packing between galvinoxyl radicals induced by the formation of the folded helical structure.

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  • Helix-sense-selective Polymerization of Achiral Acetylene Monomer Catalyzed by Rh Zwitterionic Complexes with Tethered Chiral Amino and Ether Groups 査読

    Naoya Onishi, Toshiki Aoki, Takashi Kaneko, Masahiro Teraguchi, Natsuhiro Sano, Toshio Masuda, Masashi Shiotsuki, Fumio Sanda

    CHEMISTRY LETTERS   42 ( 3 )   278 - 280   2013年3月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    Zwitterionic rhodium (Rh) complexes with tethered chiral amino and ether groups were synthesized by the reaction of [(C2H4)(2)RhCl](2) with the 2,5-norbornadiene tether, (CH2)(4)R [2: R = (R)-NHCH(CH3)Ph, 3: (R)-OCH(CH3)Ph], followed by exchange of Cl with BPh4. The resultant Rh complexes, 2 and 3, catalyzed the polymerization of 4-dodecyloxy-3,5-bis(hydroxymethyl)phenylacetylene (1) to afford polymers [poly(1)s] with number-average molecular weights of 16000 and 82000, respectively. The poly(1)s showed clear circular dichroism resulting from their polyacetylene backbones, which indicates the formation of predominantly one-handed helical structures.

    DOI: 10.1246/cl.2013.278

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  • Living-like helix-sense-selective polymerization of an achiral substituted acetylene having bulky substituents 査読

    Yu Zang, Kazuki Nakao, Hiroki Yotsuyanagi, Toshiki Aoki, Takeshi Namikoshi, Toyokazu Tsutsuba, Masahiro Teraguchi, Takashi Kaneko

    POLYMER   54 ( 7 )   1729 - 1733   2013年3月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ELSEVIER SCI LTD  

    By using a new achiral phenylacetylene having bulky substituents as a monomer, living-like helix-sense-selective polymerization (HSSP) has been achieved. This is the first example of the HSSP of substituted acetylenes where the degree of polymerization was controlled. The resulting one-handed helical living polymer initiated polymerization of a second monomer to successfully yield a block copolymer. (C) 2013 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/j.polymer.2013.02.009

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  • Top-down preparation of self-supporting supramolecular polymeric membranes using highly selective photocyclic aromatization of cis-cisoid helical poly(phenylacetylene)s in the membrane state 査読

    Lijia Liu, Takeshi Namikoshi, Yu Zang, Toshiki Aoki, Shingo Hadano, Yunosuke Abe, Ikuya Wasuzu, Toyokazu Tsutsuba, Masahiro Teraguchi, Takashi Kaneko

    Journal of the American Chemical Society   135 ( 2 )   602 - 605   2013年1月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    A novel, highly selective photocyclic aromatization (SCAT) of π-conjugated polymers from phenylacetylene having two hydroxyl groups to exclusively yield a 1,3,5-trisubstituted benzene derivative was developed, and its success was confirmed by 1H NMR, GPC, and TOF-MS. The SCAT reaction has many unique characteristics. (1) It is a quantitative reaction: it gave only the corresponding cyclic trimer, i.e., a 1,3,5-trisubstituted benzene derivative, quantitatively (100%). No byproducts were produced under the best conditions. (2) It is an intramolecular reaction: it occurred between three adjacent monomer units in one macromolecule. (3) It is a stereospecific and topochemical or template reaction: the reactivity strongly depended on the configuration and conformation of the starting polymer substrates. (4) It is a photoreaction: high selectivity (100%) was observed only by the use of visible light irradiation, not by heating. (5) It is a solid-state reaction: high selectivity (100%) was observed only in the solid state, not in solution. In addition, (6) the resulting cyclic trimers could form a self-supporting membrane, despite their low molecular weights. This new approach resulted in a new class of supramolecular polymers consisting of a 1,3,5-trisubstituted benzene derivative, numbers of which were linearly linked by hydrogen bonds and stacked benzene derivatives. Since SCAT has such high selectivities and is useful for the preparation of a self-supporting supramolecular polymer membrane, many applications can be expected. © 2012 American Chemical Society.

    DOI: 10.1021/ja3113214

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  • Helix-sense-selective polymerization of substituted acetylenes by using an isolated rh chiral initiator with an amino acid ligand 査読

    Yu Zang, Tomoyuki Ohishi, Toshiki Aoki, Masahiro Teraguchi, Takashi Kaneko

    Chemistry Letters   42 ( 4 )   430 - 432   2013年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    Helix-sense-selective polymerization (HSSP) of substituted acetylenes by using an isolated chiral Rh initiator with an amino acid ligand has been achieved. The sense of the helix of the main chain of the resulting polymer was controlled by the sign of the chirality of the ligand. The isolated initiator needed less of the chiral ligand and gave polymers having a higher value than the two component chiral initiator systems we reported previously. The resulting polymers had a higher Mw. © 2013 The Chemical Society of Japan.

    DOI: 10.1246/cl.121295

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  • Two modes of asymmetric polymerization of phenylacetylenes having an L-amino alcohol residue and two hydroxy groups 査読

    Hongge Jia, Jun Li, Yu Zang, Toshiki Aoki, Masahiro Teraguchi, Takashi Kaneko

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   50 ( 24 )   5134 - 5143   2012年12月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:WILEY-BLACKWELL  

    Four novel chiral phenylacetylenes having an L-amino alcohol residue and two hydroxymethyl groups were synthesized and polymerized by an achiral catalyst ((nbd)Rh+[?6-(C6H5)B-(C6H5)3]) or a chiral catalytic system ([Rh(nbd)Cl]2/(S)- or (R)-phenylethylamine ((S)- or (R)-PEA)). The two resulting polymers having an L-valinol or L-phenylalaninol residue showed Cotton effects at wavelengths around 430 nm. This observation indicated that they had an excess of one-handed helical backbones. Positive and negative Cotton effects were observed only for the polymers having an L-valinol residue produced by using (R)- and (S)-PEA as a cocatalyst, respectively, although the monomer had the same chirality. Even when the achiral catalyst was used, the two resulting polymers having an L-valinol or L-phenylalaninol residue showed Cotton effects despite the long distance between the chiral groups and the main chain. We have found the first example of a new type of chiral monomer, that is, a chiral phenylacetylene monomer having an L-amino alcohol residue and two hydroxy groups that was suitable for both modes of asymmetric polymerization, that is, the helix-sense-selective polymerization (HSSP) with the chiral catalytic system and the asymmetric-induced polymerization (AIP) with the achiral catalyst. The other two monomers having L-alaninol and L-tyrosinol were found to be unsuitable to neither HSSP nor AIP because of their polymers' low solubility. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

    DOI: 10.1002/pola.26346

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  • Helix-Sense-Selective Polymerization of Achiral Phenylacetylenes with Two N-Alkylamide Groups to Generate the One-Handed Helical Polymers Stabilized by Intramolecular Hydrogen Bonds 査読

    Masahiro Teraguchi, Daisuke Tanioka, Takashi Kaneko, Toshiki Aoki

    ACS MACRO LETTERS   1 ( 11 )   1258 - 1261   2012年11月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    In this study, we investigated the helix-sense-selective polymerizations of newly synthesized achiral phenylacetylenes having two N-alkylamide groups, such as 3,5-bis(dodecylamide)phenylacetylene (DAPA), 3,5-bis(octylamide)phenylacetylene (OAPA), and 3,5-bis(butylamide)phenylacetylene (BAPA), by using a chiral rhodium catalyst system ([Rh(nbd)Cl](2)-(R)-(+)-1-phenylethylamine [(R)-PEA]). Poly(BAPA) was insoluble in any solvents. On the other hand, poly(DAPA) and poly(OAPA) were soluble in toluene, THF, and CHCl3, and the obtained polymers showed intense circular dichroism signals at the absorption region of the main chain in the UVvis region. This result suggested those polymers were present in helical conformations with an excess of one-handed screw sense. The chiral helix structures of the formed polymers were stable in toluene at room temperature for a long time because of intramolecular hydrogen bonds. This result is the second example about polyacetylenes with one-handed helical conformation stabilized by intramolecular hydrogen bonds.

    DOI: 10.1021/mz300309c

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  • Enhanced Gas Permselectivity of Copoly(Hyperbranched Macromonomer) Synthesized by One-pot Simultaneous Copolymerization of Dimethylsilyl-containing Phenylacetylenes 査読

    Jun Li, Jianjun Wang, Yu Zang, Toshiki Aoki, Takashi Kaneko, Masahiro Teraguchi

    CHEMISTRY LETTERS   41 ( 11 )   1462 - 1464   2012年11月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    Copoly(hyperbranched macromonomer)s, i.e., poly(phenylacetylene)s having many branches were synthesized by one-pot simultaneous copolymerization of two kinds of dimethylsilyl-phenylacetylenes. Membranes from the copoly(hyperbranched macromonomer)s having several kinds of branches showed higher permselectivities for oxygen and carbon dioxide over nitrogen than those of the corresponding copoly(hyperbranched macromonomer)s without any branches. In particular, the copoly(hyperbranched macromonomer)s having long and rigid branches had both the advantages of poly(phenylacetylene)s and poly(dendron)s. In summary, copoly(hyperbranched macromonomer)s showing good performance as gas-separation membranes were synthesized very easily by the one-pot simultaneous polymerization method. To our knowledge, this is the first synthesis of such complex copolymers showing good performance as gas-separation membranes.

    DOI: 10.1246/cl.2012.1462

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  • Synthesis of stable and soluble one-handed helical poly(substituted acetylene)s without chiral pendant groups via polymer reaction in membrane state 査読

    Yunosuke Abe, Toshiki Aoki, Hongge Jia, Shingo Hadano, Takeshi Namikoshi, Yuriko Kakihana, Lijia Liu, Yu Zang, Masahiro Teraguchi, Takashi Kaneko

    POLYMER   53 ( 11 )   2129 - 2133   2012年5月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ELSEVIER SCI LTD  

    A soluble and stable one-handed helical conjugated polymer without the coexistence of any other chiral moieties was successfully synthesized by asymmetric-induced polymerization of a chiral monomer having two hydroxyl groups followed by desubstitution of the chiral groups in a solid membrane state. The reason for the success was the polymer reaction was carried out in the membrane state. This is an alternative method to obtain such a unique chiral polymer which was obtained only by the helix-sense-selective polymerization (HSSP) we reported before. In addition the efficiency of the chiral induction was higher than that of the HSSP. It is interesting that the "Membrane state" acted like as if a protecting group. (C) 2012 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/j.polymer.2012.03.022

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  • Transformation from preformed racemic helical poly(phenylacetylene)s to the enantioenriched helical polymers by chiral solvation, followed by removal of the chiral solvents 査読

    Takashi Kaneko, Xiaoyun Liang, Atsuko Kawami, Masayuki Sato, Takeshi Namikoshi, Masahiro Teraguchi, Toshiki Aoki

    POLYMER JOURNAL   44 ( 4 )   327 - 333   2012年4月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:NATURE PUBLISHING GROUP  

    Homochiral or enantioenriched helical polymers are essential for investigating the relationship between chirality of helical structures and their performance in the design of various optically active functional polymers. We have succeeded in obtaining the helical poly(phenylacetylene)s poly(1)-poly(6) possessing no chiral moieties, except for helicity; the enantioenriched helical sense of these polymers was induced by transformation in chiral solvents, followed by removal of the chiral solvents, even if the interaction between the chiral molecule and the polymer was weak such as solvent-solute interaction. In particular, the newly synthesized poly(6) retained the induced helical sense even in an achiral solvent. Polymer Journal (2012) 44, 327-333; doi:10.1038/pj.2011.144; published online 18 January 2012

    DOI: 10.1038/pj.2011.144

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  • Chiral Teleinduction in Asymmetric Polymerization of 3,5-Bis(hydroxymethyl)phenylacetylene Having a Chiral Group via a Very Long and Rigid Spacer at 4-Position 査読

    Yunosuke Abe, Toshiki Aoki, Hongge Jia, Shingo Hadano, Takeshi Namikoshi, Yuriko Kakihana, Lijia Liu, Yu Zang, Masahiro Teraguchi, Takashi Kaneko

    CHEMISTRY LETTERS   41 ( 3 )   244 - 246   2012年3月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    A new polymer prepared by polymerization of 3,5-bis(hydroxymethyl)phenylacetylene having a chiral menthyl group via a very long and rigid spacer by an achiral rhodium complex with triethylamine as an initiator showed strong CD absorptions assigned to the main chain in spite of the long distance (23 angstrom) between the chiral group and the polymerizing group in the monomer. This distance is the longest to the best of our knowledge. In addition, switching between the two chiralities of the resulting polymer was realized in the CD spectrum.

    DOI: 10.1246/cl.2012.244

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  • Helix-sense-selective polymerization of chiral or achiral silicon-containing phenylacetylenes 査読

    Liu Lijia, Zang Yu, Jia Hongge, Teraguchi Masahiro, Kaneko Takashi, Aoki Toshiki

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   243   2012年3月

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    記述言語:英語   出版者・発行元:AMER CHEMICAL SOC  

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  • Asymmetric-induced polymerization and polymer reaction of the resulting one-handed helical polymer membranes 査読

    Yunosuke Abe, Takeshi Namikoshi, Yu Zang, Masahiro Teraguchi, Takashi Kaneko, Toshiki Aoki

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   243   2012年3月

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    記述言語:英語   出版者・発行元:AMER CHEMICAL SOC  

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  • Helix-sense-selective polymerization of achiral phenylacetylenes and selective cyclicaromatization of the resulting cis-cisoidal poly(phenylacetylene)s 査読

    Yu Zang, Yunosuke Abe, Lijia Liu, Takeshi Namikoshi, Tomoyuki Ohishi, Ikuya Wasuzu, Kazutomo Kikuchi, Masahiro Teraguchi, Takashi Kaneko, Toshiki Aoki

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   243   2012年3月

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    記述言語:英語   出版者・発行元:AMER CHEMICAL SOC  

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  • Synthesis of Stable and Soluble One-Handed Helical Homopoly(substituted acetylene)s without the Coexistence of Any Other Chiral Moieties via Two-Step Polymer Reactions in Membrane State: Molecular Design of the Starting Monomer 査読

    Yunosuke Abe, Toshiki Aoki, Hongge Jia, Shingo Hadano, Takeshi Namikoshi, Yuriko Kakihana, Lijia Liu, Yu Zang, Masahiro Teraguchi, Takashi Kaneko

    MOLECULES   17 ( 1 )   433 - 451   2012年1月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:MDPI AG  

    A soluble and stable one-handed helical poly(substituted phenylacetylene) without the coexistence of any other chiral moieties was successfully synthesized by asymmetric-induced polymerization of a chiral monomer followed by two-step polymer reactions in membrane state: (1) removing the chiral groups (desubstitution); and (2) introduction of achiral long alkyl groups at the same position as the desubstitution to enhance the solubility of the resulting one-handed helical polymer (resubstitution). The starting chiral monomer should have four characteristic substituents: (i) a chiral group bonded to an easily hydrolyzed spacer group; (ii) two hydroxyl groups; (iii) a long rigid hydrophobic spacer between the chiral group and the polymerizing group; (iv) a long achiral group near the chiral group. As spacer group a carbonate ester was selected. The two hydroxyl groups formed intramolecular hydrogen bonds stabilizing a one-handed helical structure in solution before and after the two-step polymer reactions in membrane state. The rigid long hydrophobic spacer, a phenylethynylphenyl group, enhanced the solubility of the starting polymer, and realized effective chiral induction from the chiral side groups to the main chain in the asymmetric-induced polymerization. The long alkyl group near the chiral group avoided shrinkage of the membrane and kept the reactivity of resubstitution in membrane state after removing the chiral groups. The g value (g = ([theta]/3,300)/epsilon) for the CD signal assigned to the main chain in the obtained final polymer was almost the same as that of the starting polymer in spite of the absence of any other chiral moieties. Moreover, since the one-handed helical structure was maintained by the intramolecular hydrogen bonds in a solution, direct observation of the one-handed helicity of the final homopolymer has been realized in CD for the solution for the first time.

    DOI: 10.3390/molecules17010433

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  • Polymerization of Phenylacetylene-Based Monodendrons with Alkoxy Peripheral Groups and Oxygen/Nitrogen Permeation Behavior of Their Membranes 査読

    Takashi Kaneko, Kazuaki Sato, Yoshihiko Uchiya, Masahiro Teraguchi, Toshiki Aoki

    INTERNATIONAL JOURNAL OF POLYMER SCIENCE   974204 - 974204   2012年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:HINDAWI PUBLISHING CORPORATION  

    Monodendron monomers with alkoxy peripheral groups were synthesized, and the focal point of monodendrons, terminal acetylene, was polymerized with rhodium catalyst to yield corresponding polydendrons with a high molecular weight. The polydendrons were soluble in common organic solvents and readily formed membranes. Oxygen permselectivity was improved in the polydendrons with a space-persistent dendritic crowd. It was found that the well-defined dendritic and rod-like structure of the polydendrons was useful for permselective membrane.

    DOI: 10.1155/2012/974204

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  • Pseudo helix-sense-selective polymerisation of achiral substituted acetylenes 査読

    Yu Zang, Toshiki Aoki, Lijia Liu, Yunosuke Abe, Yuriko Kakihana, Masahiro Teraguchi, Takashi Kaneko

    CHEMICAL COMMUNICATIONS   48 ( 39 )   4761 - 4763   2012年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ROYAL SOC CHEMISTRY  

    Pseudo helix-sense-selective polymerisation of a wide range of achiral substituted acetylenes having dynamic covalent bonds has been realised to yield static one-handed helical polymers without any other chiral moieties.

    DOI: 10.1039/c2cc00030j

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  • Advanced Polymer Particles 査読

    Eri Yoshida, Takashi Kaneko, Toshifumi Satoh, Yusuf Menceloglu, Atsuyoshi Nakayama

    INTERNATIONAL JOURNAL OF POLYMER SCIENCE   168412 - 168412   2012年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:HINDAWI PUBLISHING CORPORATION  

    様々な分野で応用が期待されるミクロおよびナノサイズのポリマー粒子の最近の進展について解説している。

    DOI: 10.1155/2012/168412

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  • Reversible Photogeneration of a Stable Chiral Radical-Pair from a Fast Photochromic Molecule 査読

    Sayaka Hatano, Kana Fujita, Nobuyuki Tamaoki, Takashi Kaneko, Takuya Nakashima, Masanobu Naito, Tsuyoshi Kawai, Jiro Abe

    JOURNAL OF PHYSICAL CHEMISTRY LETTERS   2 ( 21 )   2680 - 2682   2011年11月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    The photochromic naphthalene-bridged imidazole dimer containing a naphthyl moiety that tethers two triarylimidazole units shows instantaneous coloration upon exposure to UV light and rapid fading in the dark. In this work, we demonstrate the formation of a stable chiral radical-pair that exhibits no photoracemization even by repeated photochromic cycles. The photogenerated radical-pair from the imidazole dimer exhibits the Cotton effect in the visible light region, indicating the retention of the enantiomeric conformation of the radical-pair. This result suggests that the chirality resulting from the binaphthyl moiety induces exciton coupling between the two radical chromophores by through-space interaction.

    DOI: 10.1021/jz2012935

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  • Synthesis and Function of Chiral π-Conjugated Polymers from Phenylacetylenes 査読

    Toshiki Aoki, Takashi Kaneko, Masahiro Teraguchi

    Polymeric Chiral Catalyst Design and Chiral Polymer Synthesis   423 - 455   2011年6月

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    記述言語:英語   掲載種別:論文集(書籍)内論文   出版者・発行元:John Wiley and Sons  

    DOI: 10.1002/9781118063965.ch15

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  • Enantioselective Pervaporation through Membranes from Poly(1,3-phenyleneethynylene)-based One-handed Helical Foldamer and Unfoldamer 査読

    Makoto Inoue, Masahiro Teraguchi, Toshiki Aoki, Takeshi Namikoshi, Edy Marwanta, Takashi Kaneko

    CHEMISTRY LETTERS   40 ( 4 )   384 - 386   2011年4月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    We synthesized two kinds of poly(1,3-phenyleneethynylenes), one has (+)-menthoxycarbonyl groups at all repeating units and the other has (+)-menthoxycarbonyl groups and n-dodecyloxy groups alternately. Self-supporting membranes could be obtained easily by solvent casting. Enantioselective permeations of the polymers were investigated by pervaporation of 2-butanol. Enantioselective permeabilities of the membrane consisting of one-handed helical foldamer and unfoldamer were clarified.

    DOI: 10.1246/cl.2011.384

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  • 教育GP「使えない『つもり学習』からの脱却」化学系のデザイン科目実施事例 査読

    清水 忠明, 兒玉 竜也, 木村 勇雄, 吉田 雅典, 金子 隆司, 寺口 昌宏

    工学教育   59 ( 1 )   74 - 78   2011年3月

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    記述言語:日本語   掲載種別:研究論文(学術雑誌)  

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  • New Achiral Phenylacetylene Monomers Having an Oligosiloxanyl Group Most Suitable for Helix-Sense-Selective Polymerization and for Obtaining Good Optical Resolution Membrane Materials 査読

    Lijia Liu, Yu Zang, Shingo Hadano, Toshiki Aoki, Masahiro Teraguchi, Takashi Kaneko, Takeshi Namikoshi

    MACROMOLECULES   43 ( 22 )   9268 - 9276   2010年11月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    To develop new phenylacetylene monomers more suitable for helix-sense selective polymerization (HSSP) we reported previously and to improve the efficiency of the HSSP and membrane performance of the resulting polymers, novel phenylacetylenes having a flexible oligosiloxanyl group (SnBDHPA) together with the other related three series of monomers were synthesized and polymerized by using a chiral catalytic system and enantioselectivity in permeation of the membranes from the resulting chiral polymers were examined SnBDHPA was the most suitable for the HSSP and the CD absorptions (G values) of poly (SnBDHPA) were stronger and more stable than those of the corresponding polymers having rigid alkyl groups The polymers could be fabricated to flexible self supporting membranes by using solvent casting method In addition, enantioselectivity in permeation of one of poly(SnBDHPA) membranes was much higher than that of a poly(phenylacetylene) membrane having alkyl groups This was because the polymers having oligosiloxane groups had high regularity of structures, i e, chemical structures of the macromolecules such as one handedness and high order structures such as columnar contents in the membranes, and the membranes were flexible and had almost no defects These good properties as optical resolution membrane materials were caused by flexibility, hydrophobicity, and bulkiness of the oligosiloxane chains S3BDHPA having a trisiloxanyl group was found to be the best monomer for the HSSP and for obtaining good optical resolution membrane materials

    DOI: 10.1021/ma101999k

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  • Three Mechanisms of Asymmetric Polymerization of Phenylacetylenes Having an L-Amino Ether Residue and Two Hydroxy Groups 査読

    Hongge Jia, Masahiro Teraguchi, Toshiki Aoki, Yunosuke Abe, Takashi Kaneko, Shingo Hadano, Takeshi Namikoshi, Tomoyuki Ohishi

    MACROMOLECULES   43 ( 20 )   8353 - 8362   2010年10月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    Three novel chiral phenylacetylenes having in octyloxyethanolamine residue derived from a L-aminoalcohol and two hydroxymethyl groups were synthesized and polymerized by two achiral catalysts ((nbd)Rh(+)[eta(6)-(C(6)H(5))B(-)(C(6)H(5))(3)] and [Rh(nbd)Cl](2)/triethylamine (TEA)) and a chiral catalytic system ([Rh(nbc)Cl](2)/(S)- or (R)-phenylethylamine ((S)- or (R())-PEA)). All of the resulting polymers showed Cotton effects at wavelengths around 430 nm. This observation indicated that they had an excess of one-handed helical backbones. Positive and negative Cotton effects were observed for the polymers having an L-valinol residue produced by using (S)- and (R)-PEA as it cocatalyst, respectively, although the monomers had the same chirality. The two polymers having in L-aliminol or L-phenylalaninol residues obtained by using (S)- and (R)-PEA as a cocatalyst showed CD absorptions with identical signs. Therefore, we found that the chiral monomer having an L-valinol residue was suitable for both modes of asymmetric polymerization, that is, helix-sense-selective polymerization (HSSP) with the chiral catalytic system and asymmetric-induced polymerization (AIP) with the achiral catalysts. However, the other two monomers having an L-alaninol or L-phenylalaninol residue were not suitable for HSSP because the helix sense could not be controlled by the chirality of PEA. To explain the unexpected behaviors in the asymmetric polymerizations of the two chiral monomers having a chiral bidentate ligand, a novel third mechanism of asymmetric polymerization, that is, self-helix-sense-selective polymerization (SHSSP), is proposed in this Article. This Article discusses the contribution of the three mechanisms (AIP, HSSP, and SHSSP) in asymmetric polymerizations of the three monomers.

    DOI: 10.1021/ma101424x

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  • Synthesis and helix-sense-selective polymerization of a novel phenylacetylene having a trisiloxanyl group and two hydroxyl groups and enantioselective permeability of the resulting chiral polymeric membrane: Effect of the trisiloxanyl group on the polymerization and enantioselective permeability 査読

    Lijia Liu, Yoshiyuki Oniyama, Yu Zang, Shingo Hadano, Toshiki Aoki, Masahiro Teraguchi, Takashi Kaneko, Takeshi Namikoshi, Edy Marwanta

    POLYMER   51 ( 12 )   2460 - 2464   2010年5月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ELSEVIER SCI LTD  

    To develop a new phenylacetylene monomer suitable for helix-sense-selective polymerization (HSSP) we reported previously and to improve the efficiency of the HSSP and membrane performance of the resulting polymer, a novel phenylacetylene having a trisiloxanyl group (S3BDHPA) was synthesized and polymerized by using a chiral catalytic system and enantioselectivity in permeation of its membrane was examined. S3BDHPA was suitable for the HSSP and the CD absorption of poly(S3BDHPA) was stronger and more stable than that of the corresponding polymer having no siloxanyl groups. In addition, enantioselectivity in permeation of poly(S3BDHPA) was much higher than that of a polymer membrane having no siloxanyl groups. They are thought to be caused by the flexibility and hydrophobicity of the trisiloxane groups. (C) 2010 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/j.polymer.2010.04.030

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  • Optically active helical structure and magnetic interaction of poly(phenylacetylene)-based polyradicals 査読

    Takashi Kaneko, Hiroo Katagiri, Yasuhiro Umeda, Takeshi Namikoshi, Edy Marwanta, Masahiro Teraguchi, Toshiki Aoki

    POLYHEDRON   28 ( 9-10 )   1927 - 1929   2009年6月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:PERGAMON-ELSEVIER SCIENCE LTD  

    We synthesized optically active polyradicals possessing an excess of one-handed helical backbone by helix-sense-selective polymerization (HSSP) of achiral monomers which was promoted by rhodium complex catalyst in the presence of (R)- or (S)-1-phenylethylamine. The monomer, which had two hydroxy groups and a hydrogalvinoxyl unit, gave the corresponding polymer with an optically active helical conformation stabilized by intramolecular hydrogen bonding. The chemical oxidation of the polymer yielded the corresponding optically active helical polyradical with high spin concentration. The static magnetic susceptibility of the chiral polyradical was measured using a SQUID magnetometer. We have found that the stronger antiferromagnetic interaction was observed for the polyradical synthesized by HSSP in comparison with the polyradical via polymerization in the presence of racemic phenylethylamine. (C) 2008 Elsevier Ltd. All rights reserved

    DOI: 10.1016/j.poly.2008.10.067

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  • Synthesis of an optically active poly(aryleneethynylene) bearing galvinoxyl residues and its chiroptical and magnetic properties 査読

    Takashi Kaneko, Hiromasa Abe, Takeshi Namikoshi, Edy Marwanta, Masahiro Teraguchi, Toshiki Aoki

    SYNTHETIC METALS   159 ( 9-10 )   864 - 867   2009年5月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ELSEVIER SCIENCE SA  

    We synthesized an optically active poly(binaphthyl-6,6'-diylethynylene-1,3-phenyleneethynylene) with pendant galvinoxyl residues. The hydrogalvinoxyl precursor polymer was given by polymerization of (1,3-diiodophenyl)hydrogalvinoxyl and 6,6'-diethynyl-2,2'-dihexyloxybinaphthyl using Pd(PPh(3))(4) catalyst (M(w) = 4.6 x 10(4), M(w)/M(n) = 30). The polymer yielded the corresponding polyradical with high spin concentration by treatment of the polymer solution with PbO(2). In the CD spectra of the polymer and polyradical taken in various solutions, clear Cotton effects were observed in the absorption region of the binaphthyl chromophore, while no Cotton effect was observed in that of the galvinoxyl chromophore. On the other hand, in the MCD, Faraday effects were observed in the absorption region of the backbone and galvinoxyl chromophore. The static magnetic susceptibility of the chiral polyradical was measured using a SQUID magnetometer, and showed weak antiferromagnetic interaction. (C) 2009 Elsevier B.V. All rights reserved.

    DOI: 10.1016/j.synthmet.2009.01.042

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  • Helix-Sense-Selective Polymerization of Achiral Bis(hydroxymethyl)phenylacetylenes Bearing Alkyl Groups of Different Lengths 招待 査読

    Shingo Hadano, Takuya Kishimoto, Tomonori Hattori, Daisuke Tanioka, Masahiro Teraguchi, Toshiki Aoki, Takashi Kaneko, Takeshi Namikoshi, Edy Marwanta

    MACROMOLECULAR CHEMISTRY AND PHYSICS   210 ( 9 )   718 - 727   2009年5月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:WILEY-V C H VERLAG GMBH  

    4-Alkyloxy-3,5-bis(hydroxymethyl)phenylacetylenes with eight types of alkyl groups were synthesized and polymerized with a chiral catalytic system. We found that the length of the alkyl groups played a very important role in achieving helix-sense-selective polymerization. Five helix-sense-selective polymerizations were achieved resulting in polymers with alkyl groups whose chain length was longer than six. We think that the longer-chain alkyl groups prevented the polymers from becoming insoluble by forming intermolecular hydrogen bonds between the hydroxyl groups, and stabilized their one-handed helical structure by promoting the formation of intramolecular hydrogen bonds.

    DOI: 10.1002/macp.200800594

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  • Synthesis of poly(1,3-phenyleneethynylenes) membranes having one-handed helical conformation without any chiral side groups by in-situ desubstitution of D-menthoxy groups 査読

    Makoto Inoue, Masahiro Teraguchi, Toshiki Aoki, Shingo Hadano, Takeshi Namikoshi, Edy Marwanta, Takashi Kaneko

    SYNTHETIC METALS   159 ( 9-10 )   854 - 858   2009年5月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ELSEVIER SCIENCE SA  

    In this study, we synthesized four chiral helical poly(phenyleneethynylenes) having optically active menthoxycarbonyl groups and desubstituted the chiral groups in membrane state. Polycondensations of (+)-menthyl 3,5-diethynylbenzoate with (+)-menthyl 3,5-diiodobenzoate, 1,2-diiodobenzenen, 1,3-diiodobenzene, and 1,4-diiodobenzene using PdCl(2)(PPh(3))(2)-PPh(3)-Cul were afforded helical polymers in good yields (named as PMtMt, o-PMtH, m-PMtH, and p-PMtH, respectively). Among them, PMtMt in a mixture of chloroform/benzene showed the largest Cotton effect in absorption region and gave self-supporting membrane by solvent-casting method. PMtMt membrane also showed a Cotton signal similar to that observed in solution. Desubstitution of PMtMt proceeded quantitatively by immersing the membrane into alkaline solution at room temperature for 3 days. The desubstituted PMtMt membrane showed circular dichroism (CD) signals similar shape to that of the original membrane in the UV region in despite of the polymer having no chiral moieties except for helical conformation. This is the first example of synthesis of chiral helical poly(phenyleneethynylenes) without the coexistence of any other chiral moieties. (C) 2009 Elsevier B.V. All rights reserved.

    DOI: 10.1016/j.synthmet.2009.01.038

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  • Phenyleneethynylene Macrocycle-Fused Phenylacetylene Monomers: Synthesis and Polymerization 招待 査読

    Takashi Kaneko, Takahiro Horie, Shinji Matsumoto, Masahiro Teraguchi, Toshiki Aoki

    MACROMOLECULAR CHEMISTRY AND PHYSICS   210 ( 1 )   22 - 36   2009年1月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:WILEY-V C H VERLAG GMBH  

    Phenyleneethynylene macrocycle-substituted acetylenes were synthesized by repetition of the Sonogashira coupling reaction, and the elimination reaction of the terminal acetylene protecting group. The monomers were polymerized with a rhodium catalyst, [Rh(nbd)Cl](2), at the terminal acetylene unit, and the polymerization mixtures were purified by precipitating into methanol to yield the corresponding poly(phenylacetylene) derivatives as yellow-red powders, which had a high degree of polymerization ((DP) over bar approximate to 500) in spite of their steric bulkiness. The trimethylsilyl and pentamethyldisiloxanyl groups of polymers improved their solubility, and the polymers were soluble in common organic solvents, such as toluene, chloroform and tetrahydrofuran.

    DOI: 10.1002/macp.200800429

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  • Two Modes of Asymmetric Polymerization of Phenylacetylene Having a L-Valinol Residue and Two Hydroxy Groups 査読

    Hongge Jia, Masahiro Teraguchi, Toshiki Aoki, Yunosuke Abe, Takashi Kaneko, Shingo Hadano, Takeshi Namikoshi, Edy Marwanta

    MACROMOLECULES   42 ( 1 )   17 - 19   2009年1月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    L-バリノール残基と二つのヒドロキシメチル基を有する光学活性なフェニルアセチレン誘導体を合成し、キラル触媒系でのらせん選択重合と光学活性基に誘導された不斉誘起重合の両方が可能であることを明らかにした。

    DOI: 10.1021/ma802313z

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  • Copper(I) iodide accelerates catalytic activation in rhodium complex-catalyzed helix-sense-selective polymerization of achiral phenylacetylene monomers 査読

    Hiroo Katagiri, Takashi Kaneko, Masahiro Teraguchi, Toshiki Aoki

    CHEMISTRY LETTERS   37 ( 4 )   390 - 391   2008年4月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    Achiral phenylacetylene monomers were polymerized using a rhodium (Rh) complex catalyst in the presence of (S)1-phenylethylamine. Addition of copper(I) iodide (CuI) into the catalytic system improved the polymer yield. The monomer, which had two hydroxy groups and a hydrogalvinoxyl unit, gave the corresponding polymer with an optically active helical conformation stabilized by intramolecular hydrogen bonding. The chemical oxidation of the polymer yielded the corresponding optically active helical polyradical with high spin concentration.

    DOI: 10.1246/cl.2008.390

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  • Helix-sense-selective polymerization of trimethylsilyl or siloxanyl group containing monomer

    Liu Lijia, Masahiro Teraguchi, Takeshi Namikoshi, Edy Marwanta, Takashi Kaneko, Toshiki Aoki

    2008 Niigata-Inha Joint Symposium on Advanced Polymeric Materials   6   2008年

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    記述言語:英語   掲載種別:研究論文(国際会議プロシーディングス)  

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  • Function of one-handed helical backbone of polyphenylacetylenes 招待

    Toshiki Aoki, Masahiro Teraguchi, Takashi Kaneko

    The 5th International Symposium on Advanced Materials in Asia-Pacific Rim (5th ISAMAP)   2008年

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    記述言語:英語   掲載種別:研究論文(国際会議プロシーディングス)  

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  • Synthesis and Properties of Chiral Polyphenylacetylenes Having their Chiral Structures Only in the Backbone 招待

    Toshiki Aoki, Masahiro Teraguchi, Takashi Kaneko

    International Symposium on Polymer Chemistry (PC'2008, Hefei)   2008年

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    記述言語:英語   掲載種別:研究論文(国際会議プロシーディングス)  

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  • Synthesis of Chiral Helical Poly(phenyleneethynylene) Membranes by Desubstitution of Chiral Group /2008 Niigata-Inha Joint Symposium on Advanced Polymeric Materials

    Makoto Inoue, Masahiro Teraguchi, Takeshi Namikoshi, Edy Marwanta, Takashi Kaneko, Toshiki Aoki

    2008 Niigata-Inha Joint Symposium on Advanced Polymeric Materials   3   2008年

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    記述言語:英語   掲載種別:研究論文(国際会議プロシーディングス)  

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  • Helix-sense tunability induced by achiral diene ligands in the chiral catalytic system for the helix-sense-selective polymerization of achiral and bulky phenylacetylene monomers 査読

    Takashi Kaneko, Yasuhiro Umeda, Honge Jia, Shingo Hadano, Masahiro Teraguchi, Toshiki Aoki

    MACROMOLECULES   40 ( 20 )   7098 - 7102   2007年10月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    Helix-sense-selective polymerization of {4-[(3,5-di-tert-butyl-4-hydroxyphenyl)(3,5-di-tert-butyl-4-oxo-cyclohexa-2,5-dienylidene)methyl]phenyl}acetylene (abbreviated as (4-ethynylphenyl)hydrogalvinoxyl) was promoted by [Rh(cod)Cl](2) and [Rh(nbd)Cl](2) catalyst in the presence of (R)-(+)-1-phenylethylamine or (S)-(-)-1-phenylethylamine (PEA). The [Rh(cod)C](2) Catalyst system gave red polymers whose CD spectra showed the stronger Cotton effect though the yield (2-3%) and molecular weight (M-n = (1.1 - 1.4) x 10(4)) were lower than those of polymers obtained by [Rh(nbd)Cl](2). Moreover, we investigated the effect of bulkiness of the catalyst, cocatalyst, and monomer on helix-sense-selective polymerization of (4-ethynylphenyl)hydrogalvinoxyl in the presence of (R)-PEA. The CD patterns of polymers obtained by [Rh(nbd)Cl](2) and [Rh(cod)Cl](2) were nearly mirror image of each other, except for the magnitudes of the signals in spite of the same chiral condition, i.e., in the presence of (R)-PEA. That is, [Rh(nbd)Cl](2) and [Rh(cod)Cl](2) catalysts generated P-helix and M-helix, respectively. This is a novel result, since the control of helix sense is usually achieved by enantiomeric moieties of catalysts or initiators for the helix-sense-selective polymerization.

    DOI: 10.1021/ma0713963

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  • Efficient charge transport through a metal oxide semiconductor in the nanocomposite film with tris(2,2 '-bipyridine)ruthenium(II) 査読

    Koji Sone, Masahiro Teraguchi, Takashi Kaneko, Toshiki Aoki, Masayuki Yagi

    JOURNAL OF PHYSICAL CHEMISTRY C   111 ( 31 )   11636 - 11641   2007年8月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    A nanocomposite film of tungsten trioxide (WO3) and [Ru(bpy)(3)](2+) (bpy = 2,2'-bipyridine) (denoted as Ru-WO3) was prepared from an aqueous colloidal triad solution containing peroxotungstic acid, [Ru(bpy)(3)](2+), and poly(sodium 4-styrenesulfonate) by an electrodeposition technique. The electrochemical features of the Ru-WO3 film were investigated using cyclic voltammetry (CV) and potential-step chronoamperospectrometry (PSCAS) techniques, compared with those in a [Ru(bpy)(3)](2+)/Nafion (Ru-Nf) film. PSCAS data spectrophotometrically showed that Ru-II is completely oxidized for 0.3 s in the Ru-WO3 film, in contrast to the corresponding reaction completed for 30 s in the Ru-Nf film. The apparent diffusion coefficient (D-app = (0.1-1.1) x 10(-7) cm(2) s(-1)) for charge transport (CT) by a Ru-II/Ru-III redox in the Ru-WO3 film was higher than that (2.4 x 10(-10) cm(2) s(-1)) in the Ru-Nf film by 2 or 3 orders of magnitude. Activation energy (E-a) for CT (14.1 kJ mol(-1)) for the Ru-WO3 film was 3.5 times lower than that (E-a = 49.8 kJ mol(-1)) for the Ru-Nf film. The lower E-a could be responsible for the faster CT in the Ru-WO3 film than the Ru-Nf film. D-app in the Ru-WO3 film increased linearly with an increase of the final applied potential (E-f) for PSCAS from 1.2 to 1.5 V vs SCE and saturated above E-f = 1.5 V. The mechanism for CT in the Ru-WO3 film is proposed, in which electrons are injected from [Ru(bpy)(3)](2+) into the conduction band (CB) of WO3 and go through there to a collector electrode.

    DOI: 10.1021/jp073020x

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  • Electrochemical and photosensitized redox reactions of a Prussian blue film layered on a WO3/[Ru(bpy)(3)](2+)/polymer hybrid film 査読

    Koji Sone, Masahiro Teraguchi, Takashi Kaneko, Toshiki Aoki, Masayuki Yagi

    CHEMPHYSCHEM   8 ( 9 )   1357 - 1362   2007年6月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:WILEY-V C H VERLAG GMBH  

    A hybrid film of WO3/tris(2,2'-bipyridine)ruthenium(II) ([Ru(bpy)(3])(2+)) /poly(sodium 4-styrenesulfonote) (PSS) (denoted as a WRP hybrid film) was prepared as a base layer on an indium tin oxide electrode substrate by cathodic electrodeposition from a colloidal ternary solution containing peroxotungstic acid, [Ru(bpy)(3)](2+), and PSS. Prussian blue, Fe-4(III)[Fe-II(CN)(6)](3) (Fe-II-Fe-III) was cathodically electrodeposited on the WRP hybrid film from a Berlin brown (Fe-II-Fe-III) colloidal solution to give a WRP/Fe-II-Fe-III biloyer film. Spectrocyclic voltammetry measurement of the WRP/ Fe-II-Fe-III bilayer film reveals that Prussian white (Fe-II-Fe-III) is oxidized to Fe-II-Fe-III by electrogenerated Ru-III, and Fe-II-Fe-III is re-reduced to Fe-II-Fe-III by electrogenerated HxWO3. Visible-light irradiation of the WRP hybrid film generates a small photocurrent (approximate to 8 nA cm(-2)) at 0.4 V of an applied potential, whereas irradiation of the WRP/Fe-II-Fe-III bilayer film (Fe-II-Fe-III is electrochemically reduced to the Fe-II-Fe-III state) significantly generates a steady photoonodic current of 2.0-1.1 mu A cm(-2) under the some conditions, thus demonstrating that the photoanodic current is produced by the layered Fe-II-Fe-III film. The photoaction spectrum of the bilayer film reveals that the photoanodic current is based on the photoexcitation of [Ru(bpy)(3)](2+). The photogeneration of Fe-II-Fe-III from Fe-II-Fe-III is shown by the absorption spectral change of the bilayer film on irradiation. These results corroborate the notion that Fe-II-Fe-III is oxidized by photogenerated Ru-III to generate Fe-II-Fe-III. However, the rote of photogenerotion of Fe-II-Fe-III is slow, which could be ascribed to the fast back electron transfer (ET) from WO3 to Ru-III, comparable with the forward ET from Fe-II-Fe-III to Ru-III. The fast back ET could be a crucial problem for the [Ru(bpy)(3)](2+)-sensitized reaction in the hybrid film.

    DOI: 10.1002/cphc.200700192

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  • Synthesis of an optically active helical poly(1,3-phenyleneethynylene) bearing stable radicals and its chiroptical and magnetic properties 査読

    Takashi Kaneko, Shota Yoshimoto, Shingo Hadano, Masahiro Teraguchi, Toshiki Aoki

    POLYHEDRON   26 ( 9-11 )   1825 - 1829   2007年6月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:PERGAMON-ELSEVIER SCIENCE LTD  

    We synthesized an optically active helical poly(1,3-phenyleneethynylene) with pendant galvinoxyl residues and dimethyl(10-(1S)pinanyl)silyl groups. The hydrogalvinoxyl precursor polymer was given by polymerization of (1,3-diiodophenyl)hydrogalvinoxyl and 1,3-diethynyl-5-[dimethyl(10-(1S)-pinanyl)silyl]benzene using Pd(PPh3)(4) catalyst (M-w = 1.7 x 10(5), M-w/M-n = 3.7). In the CD spectrum taken in ethyl acetate solution, clear Cotton effects were observed in the absorption region of the backbone and hydrogalvinoxyl chromophore, indicating an excess of one-handed helical foldamer conformation. The polymer yielded the corresponding polyradical with high spin concentration by treatment of the polymer solution with PbO2. The Cotton effects appeared in CD spectra of the polymer and polyradical by addition of methanol to the chloroform solution, although the Cotton effects were hardly observed in chloroform. On the other hand, in the MCD spectra of the polymer and polyradical taken in chloroform solution, Faraday effects were observed in the absorption region of the backbone and galvinoxyl chromophore. The static magnetic susceptibility of the chiral polyradical was measured using a SQUID magnetometer, and showed the antiferromagnetic interaction. (c) 2006 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/j.poly.2006.09.104

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  • Enantioselective permeability through membranes from a poly(substituted phenylacetylene) having a chiral helical backbone and achiral bidentate ligands as pendant groups 査読

    Shingo Hadano, Masahiro Teraguchi, Takashi Kaneko, Toshiki Aoki

    CHEMISTRY LETTERS   36 ( 2 )   220 - 221   2007年2月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    A chiral helical poly(phenylacetylene) bearing N-(2-hydoroxyethyl)aminomethyl groups as ligand sites was synthesized by helix-sense-selective polymerization. In the obtained polymeric membrane, the ligands could complex with Cu2+. In permeation of aqueous solution of racemic phenylalanine, enantioselectivity in permeation through the Cu2+ complexing membrane was about 3 times higher than that of the original membrane.

    DOI: 10.1246/cl.2007.220

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  • Synthesis and Helix-Sense-Selective Copolymerization of Disiloxane Containing Monomer 査読

    Liu Lijia, Hadano Shingo, Hoshi Yuya, Teraguchi Masahiro, Kaneko Takashi, Aoki Toshiki

    Proceedings of International Symposium on Fusion Technology 2006-2007 at Niigata   P-3   2007年

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    記述言語:英語   掲載種別:研究論文(国際会議プロシーディングス)  

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  • Helix-sense-selective copolymerization of phenylacetylene having two silanol groups and chemical fixation of ladder chiral double helical structure of the resulting copolymer

    Shingo Hadano, Kazuo Futamata, Masahiro Teraguchi, Toshiki Aoki, Takashi Kaneko

    International Symposiumon Fusion Tech 2006-2007   41   2007年

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    記述言語:英語   掲載種別:研究論文(国際会議プロシーディングス)  

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  • Electrochemical and photosensitized redox reactions of a Prussian blue film layered on a WO3 / tris(2,2'-bipyridine)ruthenium(II) / polymer hybrid film

    Koji Sone, Masahiro Teraguchi, Takashi Kaneko, Toshiki Aoki, Masayuki Yagi

    International Symposiumon Fusion Tech 2006-2007   38   2007年

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    記述言語:英語   掲載種別:研究論文(国際会議プロシーディングス)  

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  • Synthesis of optically active helical polyacetylenes bearing stable radicals via helix-sense-selective polymerization

    Takashi Kaneko, Yasuhiro Umeda, Shingo Hadano, Masahiro Teraguchi, Toshiki Aoki

    International Symposiumon Fusion Tech 2006-2007   40   2007年

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    記述言語:英語   掲載種別:研究論文(国際会議プロシーディングス)  

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  • Synthesis of poly(phenylacetylene)-based polydendrons consisting of a phenyleneethynylene repeating unit, and oxygen/nitrogen permeation behavior of their membranes 査読

    T Kaneko, K Yamamoto, M Asano, M Teraguchi, T Aoki

    JOURNAL OF MEMBRANE SCIENCE   278 ( 1-2 )   365 - 372   2006年7月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ELSEVIER SCIENCE BV  

    Monodendrons consisting of m-linked phenyleneethynylene repeating unit with trimethylsilyl-, pentamethyldisiloxanyl- and nonamethyltetrasiloxanyl-peripheral groups were synthesized using the convergent approach. The focal point of monodendrons, terminal acetylene, was polymerized with rhodium catalyst to yield corresponding polydendrons with a high molecular weight. The polydendrons were solubile in common organic solvents, and readily formed membranes. Oxygen permselectivity was improved in the polydendrons with a space-persistent dendritic crowd. It was found that the well-defined dendritic and rod-like structure of the polydendrons was useful for pemselective membrane. Oxygen permselectivity was increased in polydendrons with a trimethylsilyl group compared to the corresponding zero generation poly(phenylacetylene) derivatives. (c) 2005 Elsevier B.V. All rights reserved.

    DOI: 10.1016/j.memsci.2005.11.023

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  • Synthesis of functional pi-conjugated polymers from aromatic acetylenes 査読

    Toshiki Aoki, Takashi Kaneko, Masahiro Teraguchi

    POLYMER   47 ( 14 )   4867 - 4892   2006年6月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ELSEVIER SCI LTD  

    Because of their unique structures and properties, pi-conjugated polymers have attracted the attention of scientists and engineers. The authors have studied the synthesis of two kinds of pi-conjugated poly(aromatic acetylene)s, i.e. poly(arylacetylene)s and poly(aryleneethynylene)s with the aim of obtaining new polymers having novel functions or higher performances. This review mainly concerns the authors' results, as follows: first, we describe the synthesis and properties of achiral poly (aryl acetylene) s, containing trimethylsilyl groups, oligodimethylsiloxanyl groups, dendritic groups, and glavinoxyl groups, for application as oxygen permselective, membrane materials. Their self-membrane-forming abilities and high oxygen permeabilities are presented. Second, the synthesis by asymmetric-induced polymerization of chiral poly(arylacetylene)s having both a main-chain chirality and chiral pendant groups and their application as optical resolution membranes are described. Third, two new synthetic methods for preparing chiral helical poly (phenyl acetylene) s without the coexistence of any other chiral moieties are presented. One is helix-sense-selective addition polymerization and the other is in situ removal of chiral pendant groups from membranes of poly(arylacetylene)s that also contain a main-chain chirality. The chiral helical poly(arylacetylene)s were tested as optical resolution membranes. The chiral and achiral poly(arylacetylene)s were synthesized by addition polymerization using metathesis catalysts or rhodium complexes. Finally, the synthesis of regiospecific poly(aryleneethynylene)s bearing stable radicals by the polycondensation of bromoethynylanthracene derivatives using a Pd(0) complex is described. The magnetization and the static magnetic susceptibility of the polyradicals are explained. (c) 2006 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/j.polymer.2006.04.047

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  • Analysis and regulation of unusual adsorption of phthalocyanine zinc(II) into a Nafion film as investigated by UV-vis spectroscopic techniques 査読

    T Kuwabara, M Teraguchi, T Kaneko, T Aoki, M Yagi

    JOURNAL OF PHYSICAL CHEMISTRY B   109 ( 44 )   21202 - 21208   2005年11月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    Phthalocyanine zinc(II) (ZnPc) was found to be adsorbed well into a Nafion (Nf) film. The kinetic analysis suggested that the adsorption of ZnPc into the Nf film is controlled by its diffusion in the Nf film with a diffusion coefficient of D = 1.9 x 10(-6) cm(2) s(-1) that is higher than those (10(-9)-10(-12) cm(2) s(-1)) of cationic redox molecules in the Nf film by 3-6 orders of magnitude. The adsorption isothermal was analyzed by a Brunauer-Emmett-Teller (BET) equation suggesting multilayer adsorption of ZnPc into the film. The BET analysis provided the amount of ZnPc for monolayer adsorption (w(m) = 1.50 x 10(-7) mol cm(-2)), from which the effective area for the ZnPc adsorption was estimated to be larger by a factor of 1.7 x 103 than the Nf film area (1.0 cm(2)). The absorption spectra of a Nf film adsorbing ZnPc ((Nf/ZnPc)(ads) film) exhibited two broad absorption bands at 385 and 680-750 nm without any structural features, which is significantly different from the absorption spectra of either ZnPc solution in DMF or a (Nf/ZnPc)(mix) film prepared from a DMF solution containing Nf and ZnPc by solvent evaporation. This is ascribed to the formation of a ZnPc aggregate in the (Nf/ZnPC)(ads) film. Photoluminescence data for the (Nf/ZnPc)(mix) film suggested the presence of a ZnPc monomer and dimer at equilibrium in the film with a concentration of 0.1 M and that energy transfer occurs from the monomer to the dimer in excitation of the monomer (at A x = 609 nm) to yield emission from the dimer. By contrast, photoluminescence data for the (Nf/ZnPc)(ads) film suggested that the excited ZnPc is self-quenched significantly by the formation of the ZnPc aggregate in the film. The lesser electroactivity of ZnPc in the (Nf/ZnPc)(ads) film compared with that in the (Nf/ZnPc)(mix) film could be ascribable to more difficult diffusion of ZnPc in the former film due to the formation of the ZnPc aggregate. The adsorption of ZnPc into the Nf film was significantly regulated by simple pretreatments of the Nf film such as immersion in solvents and storage under solvent vapors. The regulation was explained by controlled physical and chemical properties of a channel for mass and ion transport that is formed by sulfonate groups, countercations, and solvent molecules in the Nf film.

    DOI: 10.1021/jp052218j

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  • Assignment of helical sense for poly(phenylacetylene) bearing achiral galvinoxyl chromophore synthesized by helix-sense-selective polymerization 査読

    T Kaneko, Y Umeda, T Yamamoto, M Teraguchi, T Aoki

    MACROMOLECULES   38 ( 23 )   9420 - 9426   2005年11月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    {4-[(3,5-Di-tert-butyl-4-hydroxyphenyl)(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)methyl] phenyl}acetylene (abbreviated as (4-ethynylphenyl)hydrogalvinoxyl) was polymerized using [Rh(norbornadiene)Cl](2) catalyst in the presence of (R)-1-phenylethylamine or (S)-1-phenylethylamine to give red polymers. The circular dichroism (CD) spectra of polymers indicated that an excess of one-handed helical polyacetylene backbone was induced by helix-sense-selective polymerization under the asymmetric condition despite the achiral monomer. Results show that the CD signal intensity depends on temperature and decreases reversibly with increasing temperature, although the energy difference between the right-handed and left-handed conformations of each other is almost zero. The sign of the CD signal in the absorption region (420 nm) of the hydrogalvinoxyl chromophore, which was calculated from the polymer geometry, suggests that the excess of right-handed helix was induced by polymerization in the presence of (R)-1-phenylethylamine.

    DOI: 10.1021/ma050864a

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  • Synthesis and magnetic characterization of monodisoerse oligo(9, 10-anthryleneethynylene)-based polyradicals with two pendant stable phenoxyls in one anthracene skeleton 査読

    T Kaneko, A Onuma, H Ito, M Teraguchi, T Aoki

    POLYHEDRON   24 ( 16-17 )   2544 - 2549   2005年11月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:PERGAMON-ELSEVIER SCIENCE LTD  

    We synthesized monodisperse oligo(9,10-anthryleneethynylene)s with pendant phenol residues at the 2- and 7-positions. The absorption maxima of oligomers shifted to longer wavelength with the degree of polymerization, suggesting a developed pi-conjugation correlated with the chain length. The static magnetic susceptibility of the dimeric radical was measured using a SQUID magnetometer, and the 2J (J: spin coupling constant through the dianthrylacetylene unit) value of the dimeric radical was 34 cm(-1), which agreed with the 2J value of the corresponding 2-substituted dimeric radical (31 cm(-1)). These large 2J values of the dimeric radicals can be explained from less steric hindrance between the side chain radicals and the backbone. (c) 2005 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/j.polt.2005.03.127

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  • Synthesis of chiral helical poly(hydroxyl-containing phenylacetylene) membranes by in-situ depinanylsilylation and their enantioselective permeabilities 査読

    M Teraguchi, K Mottate, SY Kim, T Aoki, T Kaneko, S Hadano, T Masuda

    MACROMOLECULES   38 ( 15 )   6367 - 6373   2005年7月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    Two new chiral helical poly(hydroxyl-containing phenylacetylene) membranes without the coexistence of any other chiral moieties were prepared in the following manner: (1) synthesis and homo-or copolymerization of two new chiral pinanylsiloxy-containing phenylacetylenes, (2) preparation of self-supporting membranes from the (co)poly(chiral pinanylsiloxy-containing phenylacetylene)s by a solvent-casting technique, and (3) depinanylsilylation of the preformed polymer membranes in situ. Complete depinanylsilylation was successfully achieved by treating with trifluoroacetic acid. The resulting membranes exhibited circular dichroism despite the absence of the chiral substituents, a fact indicating that the main chains of the polymers retained their chiral helicity. This is the first method to synthesizing such chiral poly(phenylacetylene) membranes. Since the membranes maintained their self-supporting properties, we were able to use them as enantioselective separation membranes in the permeation of an aqueous solution of a racemate. As a result, the importance of the contribution of the chiral main chain on enantioselective permeation was directly confirmed for the first time. In addition, since some of the depinanylsilylated membranes were insoluble in organic solvents, we could use them as an separation membrane for a toluene solution of a racemate.

    DOI: 10.1021/ma0500898z

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  • Helix-sense-selective polymerization of a phenylacetylene bearing an achiral and bulky galvinoxyl moiety 査読

    Y Umeda, T Kaneko, M Teraguchi, T Aoki

    CHEMISTRY LETTERS   34 ( 6 )   854 - 855   2005年6月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    An achiral and bulky phenylacetylene monomer, (4-ethynyl-phenyl)hydrogalvinoxyl), was polymerized using [Rh(nbd)Cl](2) (nbd = 2,5-norbornadiene) catalyst in chiral phenylethylamine. The circular dichroism (CD) spectra of the obtained polymers indicated that an excess of one-handed helical polyacetylene backbone was induced by helix-sense-selective polymerization despite the achiral monomer.

    DOI: 10.1246/cl.2005.854

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  • Preparation of chiral polystyrene monoliths by utilizing W/O emulsion polymerization and their optical resolution ability 査読

    M Teraguchi, M Ohtake, H Inoue, A Yoshida, T Aoki, T Kaneko, K Yamanaka

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   43 ( 11 )   2348 - 2357   2005年6月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:JOHN WILEY & SONS INC  

    We synthesized two kinds of chiral polystyrene-based monoliths, which are macroporous gel with continuous open-celled monolith structure. Thus, two chiral styrene monomers, (-)-p-[dimethyl(10-pinanyl)silyl] styrene ((-)-PSSt) and (-)-p-(menthoxycarbonyl)styrene ((-)-MtSt]), were prepared and subjected to water-in-oil emulsion polymerization in the presence of divinylbenzene and AIBN. The macroporous structure of the obtained monoliths was directly confirmed by SEM observation. The obtained monoliths showed an optical resolution ability. That is, in the enantioselective adsorption using trans-stilbene oxide, poly[(-)-PSSt] monolith and poly[(-)-MtSt] monoliths preferentially adsorbed (SS)-isomer [poly[(-)-PSStl monolith: α((S,S)) = 1.49 (0.25 wt % acetone solution); poly[(-)-MtSt] monolith: α((S,S)) = 1.39 (0.25 wt % toluene solution)]. Depinanylsilylation of the poly[(-)-PSStl monolith and removal of menthyl groups from the poly[(-)-MtSt] monolith were achieved by acid-catalyzed. scission of the Si-C bond and base-catalyzed hydrolysis, respectively. In addition, de-poly[(-)-PSSt] and de-poly[(-)-MtSt] showed enantioselectivity ((SS)-isomer preferentially absorbed) in adsorption using trans-stilbene oxide in spite of the absence of chiral substituents in the monoliths. © 2005 Wiley Periodicals, Inc.

    DOI: 10.1002/pola.20645

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  • New macromolecular architectures for permselective membranes - Gas permselective membranes from dendrimers and enantioselectively permeable membranes from one-handed helical polymers 査読

    T Aoki, T Kaneko

    POLYMER JOURNAL   37 ( 10 )   717 - 735   2005年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:SOC POLYMER SCIENCE JAPAN  

    Chemistry of macromolecular architecture is one of the fastest growing branches of polymer chemistry. The present review describes macromolecular architectures for permselective membranes relating their structures and permselectivity, and is focused on dendrimers for gas permselective membranes and one-handed helical polymer membranes for enantioselectively permeable membranes (optical resolution). The first part of this review described the three kinds of permselective membranes prepared from pure polydendrons or dendronized polymers having self-membrane-forming ability by us, and from another polymer and dendrimers or hyperbranched polymers as a crosslinker, and from another supporting membrane and dendrimers as a modifier. The membranes from polydendrons showed better oxygen permselectivities than those of conventional polymer membranes. In the second part, three kinds of enantioselectively permeable membranes reported by many researchers, i.e., chiral carriers-containing composite membranes, membranes based on chiral HPLC stationary phase polymers, and chiral molecular imprinting membranes, are reviewed briefly. In particular, the detail of our macromolecular designs of one-handed helical poly(substituted acetylene)s as materials for enantioselectively permeable membranes is discussed as the fourth category. When the content of the chiral groups was higher, the permselectivity was enhanced. The one-handed helical backbones were found to be effective for enantioselective permeation. It was also shown that the disadvantage of this method, i.e., low permeation rate was improved by using thinner membranes. In addition, enantioselectively permeable membranes are classified from the view point of their permeation mechanisms.

    DOI: 10.1295/polymj.37.717

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  • 連続細孔構造を有するモノリス型多孔質イオン交換樹脂によるイオン交換挙動の改良 査読

    井上 洋, 山中弘次, 吉田晃子, 中村 彰, 青木俊樹, 寺口昌宏, 金子隆司

    高分子論文集   62 ( 1 )   7 - 16   2005年

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    記述言語:日本語   掲載種別:研究論文(学術雑誌)  

    前報で合成した連続気泡構造を持つモノリス状カチオンおよびアニオン交換樹脂のイオン交換能を改良した。モノリス状交換樹脂のイオン交換帯長さは従来の粒子型イオン交換樹脂の3分の1まで短縮できた。

    DOI: 10.1295/koron.62.7

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  • Role of chiral amine cocatalysts in the helix-sense-selective polymerization of a phenylacetylene using a catalytic system 査読

    T Sato, T Aoki, M Teraguchi, T Kaneko, SY Kim

    POLYMER   45 ( 24 )   8109 - 8114   2004年11月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ELSEVIER SCI LTD  

    We have examined the role of the chiral amine cocatalyst in the recently discovered helix-sense-selective polymerization of a phenylacetylene using a catalytic system consisting of an achiral rhodium complex ([Rh(norbornadiene)Cl](2)) as the catalyst and a chiral amine as the cocatalyst. Several chiral amines were effective for the polymerization reaction and their effectiveness depended on their bulkmess and coordination ability to rhodium. The sense selectivity of the polymerization increased with the concentration of the chiral amines. To discuss the structure of the true active species in the catalytic system, we have synthesized a new chiral rhodium complex having two chiral amines as ligands ([Rh (norbomadiene) (chiral amine)(2)]+BF4-). The isolated chiral complex also catalyzed the helix-senses-elective polymerization. These findings suggest that a chiral rhodium complex having two chiral amines may be the true active species when using the catalytic system consisting of [Rh(norbornadiene)Cl](2) and a chiral amine. (C) 2004 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/j.polymer.2004.09.046

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  • Synthesis of chiral helical poly[p-(oligopinanylsiloxanyl)phenylacetylene]s and enantioselective permeability of their membranes 査読

    T Aoki, T Fukuda, KI Shinohara, T Kaneko, M Teraguchi, M Yagi

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   42 ( 18 )   4502 - 4517   2004年9月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:JOHN WILEY & SONS INC  

    To develop better polymeric materials for optical-resolution membranes, we synthesized nine chiral phenylacetylenes containing pinanyl groups. We used them to investigate the effects of chemical structures, including the number and position of the chiral groups in the monomers, on the induction of chirality in the main chain during polymerization and on the degree of enantioselectivity in the permeation of the polymeric membranes. The monomers included six new chiral p-(oligomethylpinanylsiloxanyl)phenylacetylenes. The homopolymerizations of these nine monomers with a Rh complex produced high-molecular-weight polymers (molecular weight = 10(5)-10(6)). Of the five polymers with a chiral pinanyl group at the 1-position of each oligosiloxanyl group, all except for two polymers showed high molar ellipticity in the main-chain region in the circular dichroism spectra. This finding indicated that these polymers had a chiral helical main chain. The membranes fabricated from all the polymers synthesized in this study were high-quality, except for two polymers. All these membranes showed enantioselective permeabilities for two amino acids and an alcohol. The membranes from the polymers with a chiral helical backbone, a high content of pinanyl groups, no oligodimethylsiloxane moieties, or a combination of these showed good enantioselectivities ( = 1.7-640) in permeation. We propose that the sense of the main-chain helicity determined the selectivity. (C) 2004 Wiley Periodicals, Inc.

    DOI: 10.1002/pola.20356

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  • Synthesis and cation exchange properties of a new porous cation exchange resin having an open-celled monolith structure 査読

    H Inoue, K Yamanaka, A Yoshida, T Aoki, M Teraguchi, T Kaneko

    POLYMER   45 ( 1 )   3 - 7   2004年1月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ELSEVIER SCI LTD  

    We succeeded in introducing cation exchange groups quantitatively into a porous resin having an open-celled monolith structure. The resulting new cation exchange resin had the following advantages compared with conventional ion exchange resins having a bead structure. First, it was easier to pack it in a column. Second, the ion exchange rate of the new cation exchange resin was much higher than that of the conventional ion exchange resins, and the ion exchange band length of the new resin was smaller than that of the conventional ones. In addition, the electric conductivity was about five times higher than that of the conventional ones, although they had similar ion exchange capacities. These unique properties of the new cation exchange resin were caused by the quantitative introduction of ion exchange groups into the resin having the open-celled monolith structure. (C) 2003 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/j.polymer.2003.10.097

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  • 連続細孔構造を有するモノリス型多孔質イオン交換樹脂の合成とイオン交換特性 査読

    井上 洋, 山中弘次, 吉田晃子, 青木俊樹, 金子隆司, 寺口昌宏

    高分子論文集   61 ( 5 )   301 - 309   2004年

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    記述言語:日本語   掲載種別:研究論文(学術雑誌)  

    連続気泡構造を持つモノリス状カチオン交換樹脂を合成し、そのイオン交換能について従来の粒子型イオン交換樹脂にはない特徴を見出した。モノリス状イオン交換樹脂は高分子反応により定量的にアニオン交換基を導入することで合成した。イオン交換速度の向上し、動的イオン交換挙動がより均一かつ迅速になり、さらに電気伝導度が大きな値を示した。

    DOI: 10.1295/koron.61.301

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  • Enantioselective permeation through membranes of chiral helical polymers prepared by depinanylsilylation of poly(diphenylacetylene) with a high content of the pinanylsilyl group 査読

    M Teraguchi, J Suzuki, T Kaneko, T Aoki, T Masuda

    MACROMOLECULES   36 ( 26 )   9694 - 9697   2003年12月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    光学活性なピナニルジメチルシリル基を1つまたは2つ有するジフェニルアセチレンの共重合によりピナニル基を多く含むポリ(ジフェニルアセチレン)の高重合体を収率良く合成した。これらのキャスト膜を酸処理することで脱ピナニルシリル化し、光学活性な分子空孔を有する膜を調製した。光学活性な分子空孔を有する膜が不斉認識能を示すことが明らかとなった。

    DOI: 10.1021/ma035493h

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  • Entropy effect on physical displacement of redox molecules in a naflon film as studied by double potential-step chronoabsorptometry 査読

    M Yagi, M Takahashi, M Teraguchi, T Kaneko, T Aoki

    JOURNAL OF PHYSICAL CHEMISTRY B   107 ( 46 )   12662 - 12667   2003年11月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    Charge transport (CT) in a Nafion film incorporating [(NH3)(5)Ru(mu-pz)Ru(NH3)(5)](4+) ([Ru-II-Ru-II](4+); pz = pyrazine) was studied using a double potential-step chronoabsorptometry (DPSCA) technique. The oxidative CT by [Ru-II-Ru-II](4+)/[Ru-II-Ru-III](5+) (in a potential step from -0.2 to 0.3 V; first step) was compared with that by [Ru-II-Ru-III](5+)/[Ru-III-Ru-III](6+) (in a successive potential step from 0.3 to 0.7 V; second step). The predominant CTs by a physical displacement mechanism of the complexes were suggested for both of the steps. However, the rate constant of the CT for the first step was 5.2 time higher than that for the second step at 25 degreesC. The results on CT kinetics and dynamics revealed that the CTs in both of the steps are entropy-controlled in the activation at room temperature. The DeltaH(double dagger) (12 kJ mol(-1)) for the physical displacement in the second step was lower than that (24 kJ mol(-1)) for the first step, showing that the physical displacement for the second step is enthalpically favorable compared with that for the first step. The corresponding DeltaS(double dagger) (-234 J K-1 mol(-1)) for the second step is lower than that (DeltaS(double dagger) = -184 J K-1 mol(-1)) for the first step, making the physical displacement for the second step more entropically difficult than that for the first step. The entropy effect on the physical displacement was discussed on the basis of the interaction of the complexes with Nafion and reorganization of the solvent (water) molecule involved in the process. The DeltaS(double dagger) for the physical displacement of redox complexes in the film decreased with the positive charge of the complexes, suggesting that the highly positive-charged complex is entropically unfavorable for physical displacement, presumably due to higher degree of solvation of the complex and the sulfonate groups in their dissociation.

    DOI: 10.1021/jp036146c

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  • A poly(9, 10-anthryleneethynylene)-based polyradical designed to be a ladder-like ferromagnetic spin coupling network 査読

    T Kaneko, T Makino, H Miyaji, A Onuma, M Teraguchi, T Aoki

    POLYHEDRON   22 ( 14-17 )   1845 - 1850   2003年7月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:PERGAMON-ELSEVIER SCIENCE LTD  

    We synthesized monomers of poly(9,10-anthryieneethynylene)s which were anthracene derivatives substituted with one or two phenol residues at the P-position. The monomers were polymerized by Pd(0) catalyst to give the corresponding precursor polymer with (M) over bar (n) approximate to 5 X 10(3). The polyradicals were synthesized by oxidation of the hydroxyl group. The magnetization plots of the polyradicals showed that the average ground state spin quantum number of the polyradical with two pendant phenoxyls in one anthracene unit (S = 5/2) became larger than that of the polyradical with one pendant phenoxyl (S = 2/2) at the same spin concentration (spin cone.;approximate to 0.35 spin/phenoxyl unit). The statistical simulation of the ground spin states supported that this behavior was caused by ladder-like spin coupling network of the polyradical with two pendant phenoxyls in one anthracene unit. (C) 2003 Elsevier Science Ltd. All rights reserved.

    DOI: 10.1016/S0277-5387(03)00251-1

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  • Helix-sense-selective polymerization of phenylacetylene having two hydroxy groups using a chiral catalytic system 査読

    T Aoki, T Kaneko, N Maruyama, A Sumi, M Takahashi, T Sato, M Teraguchi

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   125 ( 21 )   6346 - 6347   2003年5月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    キラル触媒系を用いた水酸基を二つ持つアキラルなフェニルアセチレンのらせん選択重合に初めて成功した。水酸基を持たないモノマーから得られたポリマーおよび極性溶媒中でCDシグナルが観測されないことから、水酸基による分子内水素結合で安定化されたらせんであると結論した。

    DOI: 10.1021/ja021233o

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  • Ladder-like Ferromagnetic Spin Coupling Network on a π-Conjugated Pendant Polyradical 査読

    Takashi Kaneko, Takahisa Makino, Hiroshi Miyaji, Masahiro Teraguchi, Toshiki Aoki, Makoto Miyasaka, Hiroyuki Nishide

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   125 ( 12 )   3554 - 3557   2003年3月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    2,7-位に3,5-ジ-t-ブチル-4-アセトキシフェニル基を持つブロモエチニルアントラセンモノマーを合成し、パラジウム0価錯体触媒を用いた自己重縮合を経て重合度約6の頭尾結合が制御されたポリラジカルを得た。ESRスペクトルからは主鎖骨格へのスピン密度分布が観測された。SQUID磁気測定により得られた大きなスピン量子数(S=5/2)から、スピン欠陥が存在するにもかかわらず、ラダー状のスピン結合構造により大きな磁気的相互作用が分子全体におよぶことを明らかにした。

    DOI: 10.1021/ja026929w

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  • Synthesis of a Pendant Polyradical with a New π-Conjugated Polymer Backbone Containing an Anthracene Skeleton and Its Ferromagnetic Spin Coupling 査読

    Takashi Kaneko, Takayuki Matsubara, Toshiki Aoki

    CHEMISTRY OF MATERIALS   14 ( 9 )   3898 - 3906   2002年9月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    3,5-ジ-t-ブチル-4-アセトキシフェニル基を持つブロモエチニルアントラセンモノマーを合成し、これをパラジウム0価錯体触媒を用いて自己重縮合することで、重合度4〜6の頭尾結合が制御されたポリマーを得た。ESRスペクトルからは主鎖骨格へのスピン密度分布が観測され、トルエングラス中ではg=4に3重項状態のスペクトルが認められた。SQUID磁気測定からはペンダントラジカルとしては非常に大きな強磁性的相互作用 (J = 39 cm<sup>-1</sup>)を示すことが明らかとなった。

    DOI: 10.1021/cm020317t

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  • Helical Chirality of π-Conjugated Main-Chain Induced by Polymerization of Phenylacetylene with Chiral Bulky Pinanyl Groups: Effects of the Flexible Spacer and Polymerization Catalyst 査読

    Ken-ichi Shinohara, Toshiki Aoki, Takashi Kaneko

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   40 ( 11 )   1689 - 1697   2002年6月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    かさ高い光学活性基であるピナニルシリル基を持つフェニルアセチレンを重合すると主鎖に不斉が誘起されることを見いだした。この不斉誘起は光学活性基と重合官能基とのスペーサーの長さおよび用いる開始剤に影響を受けることが分かった。また、このポリマーよりの膜は優れた光学分割性能を示した。

    DOI: 10.1002/pola.10253

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  • Synthesis and stable high oxygen permeability of poly(diphenylacetylene)s with two or three trimethylsilyl groups 査読

    G Kwak, T Aoki, T Kaneko

    POLYMER   43 ( 5 )   1705 - 1709   2002年3月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ELSEVIER SCI LTD  

    We synthesized two new poly(diphenylacetylene)s having two or three trimethylsilyl groups and found these membranes having extremely high oxygen permeabilities of more than 1000 barrers which are of the same order as that for poly[1-(trimethylsilyl)-1-propyne]. Whereas oxygen permeability of poly[1-(trimethylsilyl)-1-propyne] was reported to decrease largely with time, these high oxygen permeabilities were stable for several months. These membranes also showed ethanol permselectivities because of their hydrophobicity, It was found that the introduction of two or three trimethylsilyl groups to poly(diphenylacetylene) was very effective for obtaining stable high oxygen permeable and ethanol permselective membranes. (C) 2002 Elsevier Science Ltd. All rights reserved.

    DOI: 10.1016/S0032-3861(01)00739-X

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  • Pervaporation of nonaqueous ethanol azeotropes through interpenetrating polymer network membranes prepared from poly(4-vinylpyridine) and poly(vinyl alcohol) 査読

    E Oikawa, K Nozawa, T Kaneko, T Aoki

    JOURNAL OF APPLIED POLYMER SCIENCE   82 ( 11 )   2729 - 2738   2001年12月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:JOHN WILEY & SONS INC  

    Highly hydrophilic interpenetrating polymer network (IPN) membranes were prepared from a mixture system of poly(4-vinylpyridine) (P4VP) and poly(vinyl alcohol) (PVA) by quaternizing crosslinking of P4VP with 1,4-dibromobutane (DBB) and simultaneous crosslinking of PVA with hexamethylene diisocyanate (HMDI). The membrane performance in pervaporation (PV) for the azeotropic mixture of ethanol with a less polar organic liquid (chloroform, benzene, carbon tetrachloride, and cyclohexane) was investigated. The strength of these IPN membranes was higher than that of the cellulose acetate membrane and depended on the membrane composition. All the membranes were ethanol permselective for the azeotropic feeds and equimolar mixture feeds as well. Only the swelling degree Q of the membrane, among several physicochemical factors, showed a relationship with the separation performance for the four feeds; a lower value of Q generally corresponded to a higher separation factor and smaller permeability. The membrane composition, which exhibited an optimum membrane performance, was examined in detail for some membranes. Both the separation factor for sorption and that for diffusion far exceeded unity, but the latter was greater in most cases than was the former and dominated the overall separation. (C) 2001 John Wiley & Sons, Inc.

    DOI: 10.1002/app.2125

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  • Poly(9,10-anthryleneethynylene)-based polyradicals with pendant phenoxyls 査読

    T Kaneko, T Makino, G Sato, T Aoki

    POLYHEDRON   20 ( 11-14 )   1291 - 1296   2001年5月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:PERGAMON-ELSEVIER SCIENCE LTD  

    We synthesized monomers of poly(9,10-anthryleneethynylene)s which were anthracene derivatives substituted with one or two phenol residues at the beta -position which would receive less steric hindrance from the poly(9,10-anthryleneethynylene) backbone. The monomers were polymerized by Pd(0) catalyst to give the corresponding precursor polymer with (M) over bar (W) similar to 10(4). The polyradicals were synthesized by oxidation of the hydroxyl group. The clearer hyperfine structure of the corresponding monomeric radicals suggested that the polyradicals probably also involved an effectively delocalized spin density distribution into the anthryleneethynylene skeleton. Diradical models for the poly(9, 10-anthryleneethynylene)-based polyradicals were also synthesized, and the magnetic properties of diradicals suggested defect insensitive strong ferromagnetic spin coupling of the corresponding polyradicals. (C) 2001 Elsevier Science Ltd. All rights reserved.

    DOI: 10.1016/S0277-5387(01)00608-8

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  • Syntheses and enantioselective recognition of chiral poly(phenyleneethynylene)s bearing bulky optically active menthyl groups 査読

    K Shinohara, T Aoki, T Kaneko, E Oikawa

    POLYMER   42 ( 1 )   351 - 355   2001年1月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ELSEVIER SCI LTD  

    Two optically active poly(menthoxycarbonylphenyleneethynylene)s were synthesized by polycondensation using a palladium-copper catalyst system. All polymers showed Cotton effects in the absorption region of the main chain, implying that chirality is induced to the main chain. Moreover, these chiral polymers showed the enantioselective recognition ability for chiral menthol in the circular dichroism (CD) spectra. (C) 2000 Elsevier Science Ltd. All rights reserved.

    DOI: 10.1016/S0032-3861(00)00391-8

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  • Polymerization of phenylacetylene-based monodendrons and structure of the corresponding polydendrons 査読

    T Kaneko, M Asano, K Yamamoto, T Aoki

    POLYMER JOURNAL   33 ( 11 )   879 - 890   2001年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:SOC POLYMER SCIENCE JAPAN  

    Monodendrons consisting of in-linked phenyleneethynylene repeating unit with trimethylsilyl-, pentamethyldisiloxanyl-, and nonamethyltetrasiloxanyl- peripheral groups were synthesized using the convergent approach. The focal point of monodendrons, terminal acetylene, was polymerized with Rh catalyst to give the corresponding polydendrons with a high molecular weight, e.g., (M) over bar (w) = 2.8 x 10(6) ((DP) over bar = 2.8 x 10(3)). The polydendrons showed good solubility in common organic solvents, and good membrane forming ability. Since we obserbed high ratio of a peak at delta 5.8-6.0, assignable to cis proton of poly(phenyl acetylene) main-chain, in H-1 NMR of the polydendrons, the polydendrons were found to be cis-rich polymer. The visible absorption maxima (lambda(max)) of the polydendrons significantly increased due to effect of the bulky substituents at in-position in comparison with the corresponding zero generation of poly(phenylacetylene) derivatives having no substituents at in-position. The wide angle X-Ray scattering of the polymers suggested the pseudohexagonal lattice of rod-like molecules. The interplanar d spacing increased with increasing generation or size of the peripheral silyl group.

    DOI: 10.1295/polymj.33.879

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  • Synthesis of galvinoxyl unit-containing derivatives of poly(phenylacetylene) and polystyrene, and oxygen permeation behavior of their membranes 査読

    T Kaneko, T Yamamoto, H Tatsumi, T Aoki, E Oikawa

    POLYMER   41 ( 12 )   4437 - 4444   2000年6月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ELSEVIER SCI LTD  

    Poly(phenylacetylene) and polystyrene which contain galvinoxyl and trimethylsilyl units were synthesized by copolymerization of the corresponding monomers or polymer reaction of the corresponding methyl benzoate polymers with [3,5-di-tert-butyl-4-(trimethylsiloxy)-phenyl]lithium. The copolymers obtained from (4-trimethylsilyl)phenylacetylene and (4-ethynylphenyl)hydrogalvinoxyl using [Rh(norbornadiene)Cl](2) catalyst had very high molecular weights. On the contrary, the copolymers of (4-trimethylsilyl)styrene and methyl 4-vinylbenzoate nearly completely reacted with [3,5-di-tert-butyl-4-(trimethylsiloxy)phenyl]lithium to give the corresponding galvinoxyl-copolymers with high molecular weights. The hydrogalvinoxyl could be fabricated to self-supporting membranes. We succeeded in obtaining such stable polyradical membranes that the initial spin concentration was maintained for a few days. The oxygen permselectivity (alpha = P-O2/P-N2) increased and the oxygen permeability (P-O2) decreased as galvinoxyl units increased, owing to the rigid character of galvinoxyl moiety. (C) 2000 Elsevier Science Ltd. All rights reserved.

    DOI: 10.1016/S0032-3861(99)00693-X

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  • Charge propagation in a polymer membrane incorporating zinc(II) phthalocyanine as studied by spectroelectrochemical techniques 査読

    M Yagi, H Fukiya, T Kaneko, T Aoki, E Oikawa, M Kaneko

    JOURNAL OF ELECTROANALYTICAL CHEMISTRY   481 ( 1 )   69 - 75   2000年1月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ELSEVIER SCIENCE SA  

    Charge transport in a Nafion(R) membrane incorporating zinc(II) phthalocyanine (ZnPc) was studied using spectrocyclic voltammetry (SCV) and potential-step chronocoulospectrometry (PSCCS) techniques. The visible absorption spectra of the membrane depended on the ZnPc concentration in the membrane, showing the formation of the ZnPc dimer. The equilibrium constant between the monomer and dimer of ZnPc in the membrane was calculated as 75 M-1. Tt was found that the charge transport occurs by two processes; the first process was considered to be the charge injection from the electrode to the ZnPc present in close proximity to the electrode, and the second one, bulk charge transport in the membrane. The apparent rate constant for the presumed charge injection was estimated as 1.6 x 10(-2) s(-1). The bulk charge transport in the membrane was analyzed as a combination of a physical displacement of ZnPc and charge hopping between them considering the equilibrium between the monomer and dimer of ZnPc. This analysis shows that the charge transport takes place by physical displacement of the ZnPc monomer and not by charge hopping, and that the contribution of the dimer to the charge transport is negligible. The first order rate constant (k(p)) of the physical displacement of the ZnPc monomer was estimated as 3.3 x 10(-3) s(-1). The saturated fraction of the oxidized ZnPc in the membrane decreased with the ZnPc concentration in the membrane because of the bulk charge transfer decreased by the formation of the ZnPc dimer. (C) 2000 Elsevier Science S.A. All rights reserved.

    DOI: 10.1016/S0022-0728(99)00488-X

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  • Polydendrons and polymacrocycles with phenyleneethynylene repeating unit 査読

    Takashi Kaneko, Takahiro Horie, Motohiro Asano, Shinji Matsumoto, Kazuto Yamamoto, Toshiki Aoki, Eizo Oikawa

    Polymers for Advanced Technologies   11 ( 8-12 )   685 - 691   2000年

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    記述言語:英語   掲載種別:研究論文(国際会議プロシーディングス)   出版者・発行元:John Wiley & Sons Ltd  

    We synthesized monodendrons and macrocyclic compounds consisting of phenyleneethynylene repeating units, which have a precisely defined three-dimensional structure. They have a terminal acetylene group, and were successfully polymerized with a rhodium catalyst to give the corresponding polydendrons and polymacrocycles with high molecular weight in spite of their bulky dendritic and macrocyclic residue. The polydendrons and polymacrocycles with a high degree of polymerization have good membrane-forming ability, and were available for oxygen-permselective membrane. Copyright (C) 2000 John Wiley and Sons, Ltd.

    DOI: 10.1002/1099-1581(200008/12)11:8/12<685::AID-PAT20>3.0.CO;2-7

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  • フェニルアセチレンユニットで分岐したモノデンドロンの重合 査読

    金子隆司, 堀江貴洋, 青木俊樹, 及川栄蔵

    高分子論文集   57 ( 10 )   672 - 677   2000年

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    記述言語:日本語   掲載種別:研究論文(学術雑誌)  

    t-ブチル基が導入されたフェニルアセチレン誘導体と4-(3,5-ジブロモフェニル)-2-メチル-3-ブチン-2-オールから第一世代のモノデンドロンマクロモノマーを合成した。焦点部のフェニルアセチレンをロジウム錯体触媒で重合することで、高分子量のポリデンドロンが合成できた。H NMR,紫外可視スペクトルから、共役系の発達したシス−トランソイダル主鎖構造を持つことが明らかとなった。

    DOI: 10.1295/koron.57.672

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  • Synthesis of an optically active poly(phenylacetylene) bearing galvinoxyl radicals for magnetic materials 査読

    T Kaneko, T Yamamoto, T Aoki, E Oikawa

    CHEMISTRY LETTERS   28 ( 7 )   623 - 624   1999年7月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    An optically active polyradical was first synthesized by copolymerization of (4-ethynylphenyl)hydrogalvinoxyl and chiral acetylene monomer using Rh-catalyst. The circular dichroism spectrum of the polyradical showed a Cotton effect indicating the, exess of one-handed helix backbone and the induced chirality of side-chain galvinoxyl units. Intermoleculer antiferromagnetic interaction observed for the polyradical was larger than that of the corresponding polyradical without excess of one-handed helix.

    DOI: 10.1246/cl.1999.623

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  • Synthesis and properties of polymers from disubstituted acetylenes with chiral pinanyl groups 査読

    T Aoki, Y Kobayashi, T Kaneko, E Oikawa, Y Yamamura, Y Fujita, M Teraguchi, R Nomura, T Masuda

    MACROMOLECULES   32 ( 1 )   79 - 85   1999年1月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    Disubstituted acetylenes with chiral pinanyl groups, (-)-1-{4-[dimethyl(10-pinanyl)silyl]phenyl)-2-phenylacetylene (1), (-)-1-{3-[dimethyl(10-pinanyl)silyl]phenyl}-2-phenylacetylene(2), (-)-1-{4-[dimethyl(10-pinanyl)silyl]phenyl}-1-propyne (3), and (-)-1-chloro-2-(4-[dimethyl( 10-pinanyl)silyl]phenyl)acetylene (4), polymerized with NbCl5-, TaCl5-, or MoCl5-based catalysts to give high molecular weight polymers in good yields. Poly(1) and poly(a) showed intense circular dichroism (CD) effects in the UV-vis region and large optical rotations, which suggests that these polymers exist in helical conformations with an excess of one-handed screw sense. No significant decrease in the magnitude of CD effects of poly(1) and poly(a) with increasing temperature indicated the relatively high stability of their helical conformations. On the other hand, the intensities of CDs of poly(3) and poly(4) were approximately 1/10 those of poly(1) and poly(a), which means that introduction of two aromatic side groups into the repeating unit is favorable for the induction of helical conformation to disubstituted acetylene polymers. The free-standing membranes of poly(1), poly(a), and poly(3) exhibited characteristic properties as gas-permeable and optical resolution membranes.

    DOI: 10.1021/ma9810969

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  • Polymerization of (p-vinylphenyl)hydrogalvinoxyl and formation of a stable polyradical derivative 査読

    T Kaneko, H Tatsumi, T Aoki, E Oikawa, H Yoshiki, N Yoshioka, E Tsuchida, H Nishide

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   37 ( 2 )   189 - 198   1999年1月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:JOHN WILEY & SONS INC  

    4-[(3,5-Di-tert-butyl-4-hydroxyphenyl)(3 2,5-di-tert-butyl-4-oxo-cyclohexa-2,5-dienylidene)methyl]styrene (abbreviated as (p-vinylphenyl)hydrogalvinoxyl) was polymerized using AIBN as an initiator to give a bright yellow polymer with &lt;(M)over bar (w)&gt; = 3.2 x 10(4). The polymer was oxidized to give the corresponding polyradical derivative, whose spin concentration could be increased up to about 70 mol % depending on oxidative conditions. ESR signal line-width in the solid state was greatly increased below 200 K for the polyradical with a high spin concentration (&gt; 50 mol %). The magnetization and magnetic susceptibility indicated weak antiferromagnetic interaction among the radical sites. (C) 1999 John Wiley & Sons, Inc.

    DOI: 10.1002/(SICI)1099-0518(19990115)37:2<189::AID-POLA9>3.3.CO;2-Q

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  • π-Conjugated Polyradicals Containing Anthracene Skeleton in the Backbone Chain 査読

    Takashi Kaneko, Takayuki Matsubara, Toshiki Aoki, Eizo Oikawa

    MOLECULAR CRYSTALS AND LIQUID CRYSTALS   334   221 - 228   1999年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    3,5-ジ-t-ブチル-4-アセトキシフェニル基を持つブロモエチニルアントラセンモノマーを合成し、これをパラジウム0価錯体触媒を用いて自己重縮合することで、重合度12の頭尾結合が制御されたポリマーを得た。このポリラジカルのSQUID磁気測定からは平均スピン量子数が1/2を超える強磁性的な相互作用が明らかとなった。

    DOI: 10.1080/10587259908023320

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  • Pervaporation and solute separation through semi-interpenetrating and interpenetrating polymer network membranes prepared from poly(4-vinylpyridine) and poly(glycidyl methacrylate) 査読

    E Oikawa, H Tatsumi, C Takano, T Kaneko, T Aoki

    JOURNAL OF APPLIED POLYMER SCIENCE   69 ( 10 )   1953 - 1963   1998年9月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:JOHN WILEY & SONS INC  

    Semi-interpenetrating (SPN) and interpenetrating polymer network( IPN) membranes were prepared from a mixture system of poly( 4-vinylpyridine) (P4VP) and poly(glycidyl methacrylate) (PGMA) by quaternizing crosslinking of P4VP with 1,4-dibromobutane (DBB) and by simultaneous crosslinking of P4VP with DBB and PGMA with tetraethylenepentamine (TEPA), respectively. The difference between SPN and IPN was demonstrated by IR, tensile strength, and dimension stability. The membrane performance in pervaporation (PV) for ethanol-water mixtures and reverse osmosis (RO) was investigated. The polymer mixture of 1 : 1 on a monomer base with 30 mol % DBB on the 4VP unit and 5.6-7.5 mol % (8-10 wt %) TEPA on the GMA unit gave an optimum membrane performance. Those crosslinked membranes were stronger than was the cellulose acetate membrane, mostly owing to the PGMA chains, and exhibited a high separation factor for the azeotropic feed in PV. IPN membranes generally showed a performance higher than that of the SPN ones. An attempt to improve the product rate was made by the addition of a water-soluble polymer to the membrane on casting. The separation factor for solubility in the membrane at the feed side dominated the overall separation factor, particularly for feeds of`higher ethanol concentrations. (C) 1998 John Wiley & Sons, Inc.

    DOI: 10.1002/(SICI)1097-4628(19980906)69:10<1953::AID-APP7>3.0.CO;2-D

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  • Polydendron: Polymerization of dendritic phenylacetylene monomers 査読

    T Kaneko, T Horie, M Asano, T Aoki, E Oikawa

    MACROMOLECULES   30 ( 10 )   3118 - 3121   1997年5月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    フェニルアセチレンを繰り返し単位とするモノデンドロンを合成し、末端アセチレンをロジウム錯体触媒で重合した。側鎖にかさ高い置換基を持つにも関わらず重合は進行し、重合条件により重合度数千におよぶポリデンドロンが得られた。中心核を高分子鎖にすることで棒状あるいは太い線状の構造体を構築し、デンドリマーの特徴を持ったまま高分子特有の性質を賦与した。

    DOI: 10.1021/ma9616975

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  • Enantioselective permeation of racemates through a solid (+)-poly{2-[dimethyl(10-pinanyl)silyl]norbornadiene} membrane 査読

    T Aoki, M Ohshima, KI Shinohara, T Kaneko, E Oikawa

    POLYMER   38 ( 1 )   235 - 238   1997年1月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ELSEVIER SCI LTD  

    A novel norbornadiene polymer having optically active pinanyl groups in the pendant groups was synthesized as an optical resolution membrane material. The resulting polymer membrane showed highly enantioselective permeability for racemic propranolol used as a medicine. The permeability of tryptophan was much higher than that of a (+)-poly{1-[dimethyl(10-pinanyl)silyl]-1-propyne} membrane we reported previously. Copyright (C) 1996 Elsevier Science Ltd.

    DOI: 10.1016/S0032-3861(96)00630-1

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  • Detection of the site of an enantioselective interaction between chiral polypinanylsilane and a hydrophobic enantiomer by use of circular dichroism 査読

    K Shinohara, T Aoki, T Kaneko, E Oikawa

    CHEMISTRY LETTERS   1997 ( 4 )   361 - 362   1997年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    Since optically active poly(methylpinanylsilane) synthesized by Na-mediated polycondensation of the corresponding dichlorosilane showed an Cotton effect at the UV region of Si sigma-Si sigma* transition of the main chain in the circular dichroism (CD) spectrum, the main chain was found to have a chirality. The Cotton bands in the presence of the (+)-isomer of a hydrophobic compound were different from those in the presence of the (-)-isomer. Therefore, this polymer was found to have an ability of the enantioselective recognition. On the other hand, a hydrophilic compound did not affect the CD band. These findings indicate that the recognition was caused mainly by hydrophobic diastereomeric interaction between the chiral compound and the chiral main chain in this polymer.

    DOI: 10.1246/cl.1997.361

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  • FT Pulsed ESR/ESTN (Electron Spin Transient Nutation) Spectroscopy Applied to High-Spin Systems; Direct Evidence of the First High-Spin Polymer as Models for Organic Ferro- and Superpara-Magnets 査読

    Takeji Takui, Kazunobu Sato, Daisuke Shiomi, Koichi Itoh, Takashi Kaneko, Eishun Tsuchida, Hiroyuki Nishide

    Bulletin of Magnetic Resonance   18 ( 1-2 )   21 - 29   1996年12月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    アモルファスなスピン配列の混合体である一次元高スピンポリラジカルについて、パルスESRを用いたESTN法により、各々のスピン配列種のスピン量子数について分離観測した。少なくとも、S=1以上の成分が混合して存在していることが明らかとなった。

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  • Poly(phenylenevinylene)-attached phenoxyl radicals: Ferromagnetic interaction through planarized and pi-conjugated skeletons 査読

    H Nishide, T Kaneko, T Nii, K Katoh, E Tsuchida, PM Lahti

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   118 ( 40 )   9695 - 9704   1996年10月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    Chemically stable poly[2-(3,5-di-tert-butyl-4-oxyphenyl)-1,4(p)-phenylenevinylene], poly[4-(3,5-di-tert-butyl-4-oxyphenyl)-1,3(m)-phenylenevinylene], and poly[4-(3,5-di-tert-butyl-4-oxyphenyl)-1,2(o)-phenylenevinylene] were synthesized via the polymerization of 4-bromo-2-(3,5-di-tert-butyl-4-acetoxyphenyl)styrene, 5-bromo-2-(3,5-di-tert-butyl-4-acetoxyphenyl) styrene, and 2-bromo-4-(3,5-di-tert-butyl-4-acetoxyphenyl) styrene, respectively, using a palladium catalyst. The o- and p-polyradicals, even with their spin concentration of 0.6 spin/unit, displayed S values of 4/2 to 5/2 (S = 5/2 for the o-polyradical with a degree of polymerization of 17 and a spin concentration of 0.68), while the m-polyradical has a singlet ground state. A long-range intramolecular through-bond ferromagnetic exchange interaction was realized between the pendant unpaired electrons for the o- and p-polyradicals, in accordance with theoretical predictions based on the molecular connectivity. The average value of the exchange coupling constant for the o-polyradical, 2 (J) over bar = 48 +/- 6 cm(-1), was larger than 2 (J) over bar = 32 +/- 2 cm(-1) for the p-polyradical, while they were almost coincident with or much larger than the exchange coupling constants for the corresponding diradical model compounds. Both force field calculations and spectroscopic results indicated a less hindered steric structure with a planarized pi-conjugated skeleton for the o-polyradical.

    DOI: 10.1021/ja961721u

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  • Enantioselective permeation of various racemates through an optically active poly{1-[dimethyl(10-pinanyl)silyl]-1-propyne} membrane 査読

    T Aoki, K Shinohara, T Kaneko, E Oikawa

    MACROMOLECULES   29 ( 12 )   4192 - 4198   1996年6月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    Optical resolution of various racemates such as (+/-)-tryptophan and (+/-)-1,3-butanediol was achieved by permeation through a self-supporting membrane of (+)-poly{1-[dimethyl(10-pinanyl)silyl]-1-propyne} [(+)-poly(DPSP)] prepared by homopolymerization of (-)-1-[dimethyl(10-pinanyl)silyl]-1-propyne [(-)-DPSP]. Almost complete optical resolution (% ee of the permeate = 81-100% ee) was achieved at an initial period of concentration-driven permeation, and stable permeation with moderate permselectivity (% ee of the permeate = 12-54% ee) continued for more than 600 h. In addition, by permeation of vapor permeant such as evapomeation and pervaporation, higher permeation rates were attained maintaining high enantioselectivity. The sign of the enantiomer that predominantly permeated through a (+)-poly(DPSP) membrane was opposite to that through a (-)-poly(DPSP) membrane. In the permeation through a (+)-poly(DPSP) membrane of a solute or a solvent having a high affinity for (+)-poly(DPSP) and in the permeation through a membrane from the copolymer of (-)-DPSP with a small amount of 1-(trimethylsilyl)-1-propyne, their enantioselectivities were much lower. These findings suggest that the permeating route surrounding chiral pinanyl groups in a (+)-poly(DPSP) membrane that can enantioselectively separate various racemates was easily deformed by using a solute or solvent having a high affinity for (+)-poly(DPSP) or by removing a small amount of pinanyl groups.

    DOI: 10.1021/ma9517254

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  • Synthesis of and ferromagnetic coupling in poly(phenylenevinylene)s bearing built-in t-butyl nitroxides 査読

    H Nishide, T Kaneko, S Toriu, Y Kuzumaki, E Tsuchida

    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN   69 ( 2 )   499 - 508   1996年2月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    Poly[[2- or 4-[N-t-butyl-N-(triethylsiloxy- or t-butyldimethylsiloxy)amino]-1,4- or 1,2-phenylene]vinylene] was synthesized by polymerizing 4- or 2-bromo-2- or 4-[N-t-butyl-N- (triethylsiloxy- or t-butyldimethylsiloxy)amino] styrene with a palladium catalyst, respectively. They were deprotected and chemically oxidized to yield poly(1,4- or 1,2-phenylenevinylene)s bearing a 2- or 4-substituted built-in nitroxide radical. The polyradicals were chemically stable, and their spin concentration was increased to 0.8 spin/unit. A SQUID measurement which included the corresponding diradicals and triradicals indicated that a partial, but strong, intramolecular ferromagnetic coupling was established through the conjugated backbone, despite a spin defect in the side radical moiety, for the poly(1,2-phenylenevinylene) bearing 4-substituted built-in nitroxide radical.

    DOI: 10.1246/bcsj.69.499

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  • UPS study of poly(phenylenevinylene)s substituted with hexyloxy, phenoxy, and nitroxy residues 査読

    T Kaneko, E Ito, K Seki, E Tsuchida, H Nishide

    POLYMER JOURNAL   28 ( 2 )   182 - 184   1996年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:SOC POLYMER SCIENCE JAPAN  

    2,6-ジ-t-ブチルフェノール、t-ブチルニトロキシドなどが置換されたオリゴおよびポリ(フェニレンビニレン)誘導体の紫外光電子スペクトルを測定した。側鎖の立体効果によらず共平面性は維持され、イオン化ポテンシャルとバンドギャップの相関は置換基の構造に依存した。対応するポリラジカルでは大きなイオン化ポテンシャルの増大は認められず、共役系は維持されていた。

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  • FT pulsed ESR/electron spin transient nutation (ESTN) spectroscopy applied to high-spin systems in solids; Direct evidence of a topologically controlled high-spin polymer as models for quasi 1D organic ferro- and superpara-magnets 査読

    T Takui, K Sato, D Shiomi, K Itoh, T Kaneko, E Tsuchida, H Nishide

    MOLECULAR CRYSTALS AND LIQUID CRYSTALS SCIENCE AND TECHNOLOGY SECTION A-MOLECULAR CRYSTALS AND LIQUID CRYSTALS   278   A155 - A176   1996年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:GORDON BREACH SCI PUBL LTD  

    FT Pulsed ESR/Electron Spin Transient Nutation(ESTN) Spectroscopy has been, for the first time, extended to amorphous and powder states of materials. Recently, organic high-spin polymers and clusters have emerged. With the increasing molecular spin quantum number S and molecular weight of the polymers, cw ESR spectroscopy manifests its inherent disadvantages in discriminating high spins from S=1/2 and in determining the S's for the complex mixture of various spin assemblages. An electron spin transient nutation (ESTN) method based on pulsed ESR spectroscopy has been for the first time applied to a quasi 1D neutral high-spin polymers (A) as one of the most complex amorphous spin assemblages, identifying that the first neutral high-spin polymer A is comprised of high-spin assemblages characterized by the even S's greater than 1/2. The molecular quantum spin number S have been identified up to S=4, showing direct evidence of the occurrence of a high-spin polymer with a pi-topologically controlled spin polarization. Eelectron spin transient nutation spectroscopy is facile and useful method for the exclusive identification of S and ESR transitions even for the cases of apparently vanishing fine-structure splittings and for spin systems with residual fine-structure terms in the spin Hamiltonian Fundamental bases for the transient nutation method are described, emphasizing inherent advantages in the nutation spectroscopy from the methodological viewpoint. The salient feature of multiple-quantum nutations have been disclosed in this work.

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  • FERROMAGNETIC SPIN COUPLING OF TERT-BUTYLNITROXIDE DIRADICALS THROUGH A CONJUGATED OLIGO(1,2-PHENYLENEVINYLENE)-COUPLER 査読

    T KANEKO, S TORIU, E TSUCHIDA, H NISHIDE, D YAMAKI, G MARUTA, K YAMAGUCHI

    CHEMISTRY LETTERS   24 ( 6 )   421 - 422   1995年6月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    Ferromagnetic spin coupling of the tert-butylnitroxide diradicals connected to the oligo(1,2-phenylenevinylene)-skeleton was studied to relate with their pi-conjugated electronic structure. The spin coupling constant (J) determined from their magnetic susceptibility increased with the degree of oligomerization in the conjugated skeleton and was reduced in response to the conjugated but spacing phenylenevinylene unit. These 2J values qualitatively agreed with the semiempirically calculated ones.

    DOI: 10.1246/cl.1995.421

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  • Synthesis of π-Conjugated Polyradicals with Poly(phenylenevinylene) Skeleton and Their Molecular Magnetism

    Takashi Kaneko

    1995年2月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    ポリアセチレンあるいはポリ(フェニレンビニレン)を主鎖骨格として、対応するラジカル前駆体モノマーを特定の有機金属触媒で重合し、ラジカルの置換位置と連結様式が一定の構造明確なポリフェノキシおよびポリニトロキシラジカルを合成した。高分子鎖内での電子状態、スピン相関および磁気的性質を分光法および磁気測定により解析し、有機高分子で強磁性体を設計するための一つの手順を明らかにしている。

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  • THROUGH-BOND AND LONG-RANGE FERROMAGNETIC SPIN ALIGNMENT IN A PI-CONJUGATED POLYRADICAL WITH A POLY(PHENYLENEVINYLENE) SKELETON 査読

    H NISHIDE, T KANEKO, T NII, K KATOH, E TSUCHIDA, K YAMAGUCHI

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   117 ( 1 )   548 - 549   1995年1月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    2,6-ジ-t-ブチルフェノキシルを置換したポリ(1,4-および1,2-フェニレンビニレン)を合成し、電子状態と磁気的性質について分子構造と関連させて議論した。磁化測定値のBrilouin関数へのフィッティングでは、平均スピン量子数はS=4/2を超え、構造明確なポリラジカル高分子としては前例のない高いスピン多重度を実現できた。

    DOI: 10.1021/ja00106a070

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  • Electrochemical study of the nitroxyl radical derivatives built in the π‐conjugated poly(phenylenevinylene) skeleton 査読

    Shuichi Toriu, Takashi Kaneko, Hiroyuki Nishide, Eishun Tsuchida

    Polymers for Advanced Technologies   6 ( 11 )   707 - 710   1995年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    The electrochemical oxidation and reduction of the stable neutral nitroxyl radical gave the oxoaminium salt and hydroxylamine or nitroxyl anion, respectively. The electrochemical behavior of the N‐butylnitroxyl radicals or N‐butylhydroxylamines built in to various phenylenevinylene species were discussed in connection with its developed π‐conjugated structure based on cyclic voltammetric measurements. The aromatic nitroxyl radical showed two pairs of oxidation–reduction waves, but the acidic proton (hydroxylamine) changed its cathodic peak to a broad one with a shift to the anodic side. The π‐conjugated poly(phenylenevinylene) backbone and mobile proton of the hydroxylamine unstabilized the nitroxyl radical by retaining the energy gap. Copyright © 1995 John Wiley &amp
    Sons, Ltd.

    DOI: 10.1002/pat.1995.220061105

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  • π-Conjugated Polyradicals with Poly(phenylenevinylene) Skeleton and Their Through-Bond and Long-Range Interaction 査読

    Hiroyuki Nishide, Takashi Kaneko, Shuichi Toriu, Kohya Katoh, Masahiro Takahashi, Eishun Tsuchida, Kizashi Yamaguchi

    MOLECULAR CRYSTALS AND LIQUID CRYSTALS   271   A131 - A138   1995年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    2,6-ジ-t-ブチルフェノキシルあるいはt-ブチルニトロキシドを置換したポリ(1,4-および1,2-フェニレンビニレン)での強磁性的相互作用の大きさが、ESR超微細構造から見積もられるスピン分極の大きさに対応することを明らかにした。ESRスペクトル超微細構造からは主鎖-側鎖間の立体障害の小さいポリ(1,2-フェニレンビニレン)においてより広がったスピン密度分布を示した。

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  • Poly[(N-oxyamino) and (oxyphenyl)phenylenevinylene]s: Magnetically coupled polyradicals in the chain 査読

    T Kaneko, S Toriu, T Nii, E Tsuchida, H Nishide

    MOLECULAR CRYSTALS AND LIQUID CRYSTALS SCIENCE AND TECHNOLOGY SECTION A-MOLECULAR CRYSTALS AND LIQUID CRYSTALS   271   A153 - A160   1995年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:GORDON BREACH SCI PUBL LTD  

    Poly(phenylenevinylene)s with built-in radical groups are expected to show magnetic interaction caused by spin polarization and/or coplanarity of the pi-conjugated chain. Diradical models for the poly(phenylenevinylene)-based polyradicals were synthesized, and the magnetic properties were discussed based on ESR spectra and magnetic measurement. Magnetization and magnetic susceptibilities of the polyradicals, tert-butylnitroxyl- and 2,6-di-tert-butylphenoxyl-substituted poly(1,2- or 1,4-phenylenevinylene), indicated the occurrence of ferromagnetic interaction corresponding to these oligomeric diradicals.

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  • New aspects of high-spin chemistry 査読

    K Itoh, T Takui, Y Teki, K Sato, D Shiomi, T Kinoshita, T Nakamura, T Momose, T Shida, T Okuno, A Izuoka, T Sugawara, T Kaneko, E Tsuchida, H Nishide

    MOLECULAR CRYSTALS AND LIQUID CRYSTALS SCIENCE AND TECHNOLOGY SECTION A-MOLECULAR CRYSTALS AND LIQUID CRYSTALS   271   129 - 146   1995年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:GORDON BREACH SCI PUBL LTD  

    As a novel high-spin molecule, a through-bond spin-frustrated organic molecule 4, 4', 4 ''-trisdiphenylmethyleneamine (TDMA) and its anion and cation was studied by cw-ESR spectroscopy. TDMA is a spin frustrated system composed of three S=1 units coupled antiferromagnetically. This molecule was shown to have a triplet ground-state which is asymmetrical in its exchange interaction as well as its molecular conformation. The TDMA ions were generated at low temperature via successive radiolysis and photolysis of its diazo precursor. It was shown that the ground states of the anion and cation are quartet and sextet, respectively. This means that upon ionization the ground state changed from the intermediate-spin state of TDMA to the high-spin state of the ions, showing the interrelation between spin alignment and excess charge in a molecular field. On the other hand, in order to identify and discriminate the spin multiplicities of complicated spin assemblages in amorphous materials, we have developed electron spin transient nutation spectroscopy based on FT pulsed ESR and applied it to a pseudo one-dimensional high-spin polymer with effective spin S greater than or equal to 2.

    DOI: 10.1080/10587259508034046

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  • FT pulsed ESR/electron spin transient nutation spectroscopy in the study of molecular based magnetism: Applications to high-spin polymers and ferromagnetic materials 査読

    T Takui, K Sato, D Shiomi, K Itoh, T Kaneko, E Tsuchida, H Nishide

    MOLECULAR CRYSTALS AND LIQUID CRYSTALS SCIENCE AND TECHNOLOGY SECTION A-MOLECULAR CRYSTALS AND LIQUID CRYSTALS   271   191 - 212   1995年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:GORDON BREACH SCI PUBL LTD  

    Recently, organic high-spin polymers and clusters have been emerging. With the increasing effective molecular spin quantum number S and molecular weight of the polymers, however, cw ESR spectroscopy manifests its inherent disadvantages in discriminating high spins from S=1/2 and in determining the S's for the complex mixture of various spin assemblages. An electron spin transient nutation method based on pulsed ESR spectroscopy has been for the first time applied to a quasi 1D high-spin polymer as one of the most complex amorphous spin assemblages, identifying that the polymer is comprised of high-spin assemblages with the S's greater than two. It can be concluded that electron spin transient nutation spectroscopy is a facile and useful method for the exclusive identification of S and ESR transitions even for the cases of apparently vanishing fine-structure splittings and for spin systems with residual fine-structure terms in the spin Hamiltonian. Fundamental bases for the transient nutation method are described, emphasizing inherent advantages in the nutation spectroscopy from the methodological viewpoint. The salient features of multiple-quantum nutations have been disclosed in this work.

    DOI: 10.1080/10587259508034052

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  • FT Pulsed EPR/Transient Quantum Spin Nutation Spectroscopy Applied to Inorganic High-Spin Systems and a High-Spin Polymer as Models for Organic Ferromagnets 査読

    Kazunobu Sato, Daisuke Shiomi, Takeji Takui, Koichi Itoh, Takashi Kaneko, Eishun Tsuchida, Hiroyuki Nishide

    Journal of Spectroscopical Society of Japan   43   280 - 291   1994年12月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    ポリ[4-(3,5-ジ-t-ブチル-4-オキシフェニル)-1,2-フェニレンビニレン]についてパルスESRの電子スピン緩和nutation法によりポリラジカルのスピン多重度を概算した。スピン量子数としては、S&gt;4/2の成分に相当するシグナルが観測された。

    DOI: 10.5111/bunkou.43.280

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  • POLY(PHENYLENEVINYLENE) BEARING BUILT-IN TERT-BUTYLNITROXIDE - A POLYRADICAL FERROMAGNETICALLY COUPLED IN THE INTRACHAIN 査読

    T KANEKO, S TORIU, Y KUZUMAKI, H NISHIDE, E TSUCHIDA

    CHEMISTRY LETTERS   23 ( 11 )   2135 - 2138   1994年11月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

    Poly(1,4- or 1,2-phenylenevinylene)s bearing a 2- or 4-substituted nitroxide radical were synthesized by polymerizing [bromo[N-tert-butyl-N-(trialkylsiloxy)amino]]-styrenes with a palladium catalyst. The polyradicals were chemically stable, and their ESR and SQUID measurements indicated an intramolecular and through-bond ferromagnetic coupling.

    DOI: 10.1246/cl.1994.2135

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  • SEMIEMPIRICAL INVESTIGATION OF STILBENE-LINKED DIRADICALS AND MAGNETIC STUDY OF THEIR BIS(N-TERT-BUTYLNITROXIDE) VARIANTS 査読

    N YOSHIOKA, PM LAHTI, T KANEKO, Y KUZUMAKI, E TSUCHIDA, H NISHIDE

    JOURNAL OF ORGANIC CHEMISTRY   59 ( 15 )   4272 - 4280   1994年7月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    The electronic states of open-shell stilbene diradicals were st;hied. Previously used semiempirical MO-CI methods were applied to stilbenes having dimethylene, dioxyl, and dinitroxide centers in o,o'-, o,m'-, o,p'-, m,m'-, m,p'-, and p,p'-substitution patterns, and the various singlet-triplet energy gaps were computed to predict qualitative ground state spin multiplicities. Singlet and triplet spin states were essentially degenerate in the m,m'-isomers of disjoint connectivity, while nondisjoint o,m'- and m,p'-isomers had triplet computed ground states. Nitroxide-based diradicals showed considerably smaller computational exchange coupling energies than did other diradical models studied. As a tests of these computations, stilbenes with two N-tert-butyl nitroxide groups at the o,m'-, m,m'-, and m,p'-positions were prepared, and their magnetic properties were studied by ESR and-magnetic susceptibility measurements. The m,m'- and m,p'-isomers were found experimentally to have singlet and triplet ground states, respectively, in accord with the qualitative computed predictions.

    DOI: 10.1021/jo00094a046

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  • MAGNETIC CHARACTERIZATION AND COMPUTATIONAL MODELING OF POLY(PHENYLACETYLENE)S BEARING STABLE RADICAL GROUPS 査読

    H NISHIDE, T KANEKO, M IGARASHI, E TSUCHIDA, N YOSHIOKA, PM LAHTI

    MACROMOLECULES   27 ( 11 )   3082 - 3086   1994年5月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    The magnetic properties of poly(phenylacetylene)s with radical groups at the paraposition, poly[(3,5-di-tert-butyl-4-oxyphenyl)acetylene] (1),poly[[4-[(3,5-di-tert-butyl-4-oxyphenyl)(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dien-1-ylidene)methyl]phenyl]acetylene] (2), and poly[[4-(N-tert-butyl-N-oxyamino)phenyl]acetylene] (3), were studied with a SQUID magnetometer. The magnetization and magnetic susceptibility indicated unexpected antiferromagnetic interactions between the radical sites. The exchange interaction observed in these conjugated polyradicals was discussed in connection with their computationally modeled structures.

    DOI: 10.1021/ma00089a027

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  • メタクリル酸樹脂のカルシウム吸着能とエナメル質吸着性 査読

    藤森行雄, 金子隆司, 西出宏之, 土田英俊

    高分子論文集   51 ( 1 )   1 - 4   1994年

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    記述言語:日本語   掲載種別:研究論文(学術雑誌)  

    カンファーキノンとジメチルアミノエチルメタクリレートを重合開始剤としてメタクリル酸を可視光重合した。得られたポリメタクリル酸樹脂は、カルシウムイオンをLangmuir式に従って強固に吸着し(結合平衡定数10&lt;sup&gt;4&lt;/sup&gt; l/mol)、歯質のカルシウムとも結合して、エナメル質を良好に吸着した。

    DOI: 10.1295/koron.51.1

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  • Polyacetylene Derivatives with Chain-Sided Phenoxy and Galvinoxyl Radicals 査読

    Hiroyuki Nishide, Takashi Kaneko, Ritsuko Gotoh, Eishun Tsuchida

    Molecular Crystals and Liquid Crystals Science and Technology. Section A. Molecular Crystals and Liquid Crystals   233 ( 1 )   89 - 95   1993年9月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    Polyacetylene derivatives bearing chain-sided, Π-conjugated and bult-in phenoxy radicals were synthesized. They were soluble in common solvents and gave a transparent thin-film. ESR indicated partial derealization of the unpaired electron generated in the chain-sided group into the main chain. But any ferromagnetic interaction between the spins could not be observed. © 1993, Taylor &amp
    Francis Group, LLC. All rights reserved.

    DOI: 10.1080/10587259308054950

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  • Poly(Phenylvinylene) and Poly(Phenylene-Vinylene) with Nitroxide Radicals 査読

    Hiroyuki Nishide, Takashi Kaneko, Yoshihiro Kuzumaki, Naoki Yoshioka, Eishun Tsuchida

    Molecular Crystals and Liquid Crystals Science and Technology. Section A. Molecular Crystals and Liquid Crystals   232 ( 1 )   143 - 150   1993年8月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    Poly(phenylvinylene) and poly(phenylenevinylene) with tear-butyInitroxide as a built-in radical group were synthesized. Precursor polymers were obtained by the polymerization of the corresponding acetylene and styrene derivatives by Rh and Pd catalysts. They were soluble in common soivents and their chemical Oxidation under moderate condition gave the corresponding polyradicals. © 1993, Taylor &amp
    Francis Group, LLC. All rights reserved.

    DOI: 10.1080/10587259308035708

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  • POLY[[4-(N-TERT-BUTYL-N-HYDROXYAMINO)PHENYL]ACETYLENE] AND THE MAGNETIC PROPERTY OF ITS RADICAL DERIVATIVE 査読

    H NISHIDE, T KANEKO, N YOSHIOKA, H AKIYAMA, M IGARASHI, E TSUCHIDA

    MACROMOLECULES   26 ( 17 )   4567 - 4571   1993年8月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    [4-(N-tert-Butyl-N-hydroxyamino)phenyllacetylene (7) was synthesized and polymerized to yield a solvent-soluble polyacetylene: poly[[4-(N-tert-butyl-N-hydroxyamino)phenyl]acetylene] (8). Oxidation of the polymer gave its radical derivative: the ESR spectrum showed a broad signal only in the DELTAm(s) = +/-1 region, and magnetic measurement with a SQUID magnetometer revealed an antiferromagnetic through-space interaction.

    DOI: 10.1021/ma00069a023

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  • POLY(PHENYLVINYLENE) AND POLY(PHENYLENEVINYLENE) WITH NITROXIDE RADICALS 査読

    H NISHIDE, T KANEKO, Y KUZUMAKI, N YOSHIOKA, E TSUCHIDA

    MOLECULAR CRYSTALS AND LIQUID CRYSTALS   232   143 - 150   1993年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:TAYLOR & FRANCIS LTD  

    Abstract Poly(phenylvinylene) and poly(phenylenevinylene) with tert-butylnitroxide as a built-in radical group were synthesized. Precursor polymers were obtained by the polymerization of the corresponding acetylene and styrene derivatives by Rh and Pd catalysts. They were soluble in common solvents and their chemical oxidation under moderate condition gave the corresponding polyradicals.

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  • 光重合型歯科用高分子でのラジカルの発生機構と硬化特性 査読

    藤森行雄, 金子隆司, 西出宏之, 土田英俊

    高分子論文集   50 ( 6 )   485 - 488   1993年

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    記述言語:日本語   掲載種別:研究論文(学術雑誌)  

    カンファーキノンとジメチルアミノエチルメタクリレートは光重合型歯科用レジンに重合開始剤として応用されている。カンファーキノンおよび各種アミンの存在下におけるメチルメタクリレートの重合をモデル系として、光照射によるカンファーキノンのカルボニル基とラジカルの減少率がポリマーの収率に依存すること、大気中の酸素により開始反応が阻害されることを明らかにした。

    DOI: 10.1295/koron.50.485

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  • POLY[(P-ETHYNYLPHENYL)HYDROGALVINOXYL] AND ITS POLYRADICAL DERIVATIVE WITH HIGH-SPIN CONCENTRATION 査読

    N YOSHIOKA, H NISHIDE, T KANEKO, H YOSHIKI, E TSUCHIDA

    MACROMOLECULES   25 ( 15 )   3838 - 3842   1992年7月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    [4-[(3,5-Di-tert-butyl-4-hydroxyphenyl)(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dien-1-ylidene)methyl]phenyl]acetylene (6), was synthesized and polymerized to yield a solvent-soluble polyacetylene poly[[4-[(3,5-di-tert-butyl-4-hydroxyphenyl)(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dien-1-ylidene)methyl]phenyl]acetylene] (5a). The polymer gave its polyradical derivative 5b through the chemical oxidation with active PbO2. 5b was stable, whose spin concentration could be increased up to 4.8 x 10(23) spins per molar monomer unit. ESR analysis indicated localization of unpaired electrons in the galvinoxyl residue. ESR analysis also suggested an exchange-narrowing and interpolymer dipole-dipole interaction.

    DOI: 10.1021/ma00041a003

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  • Polymerization and photoinitiation behavior in the light‐cured dental composite resins 査読

    Yukio Fujimori, Takashi Kaneko, Takahiko Kaku, Naoki Yoshioka, Hiroyuki Nishide, Eishun Tsuchida

    Polymers for Advanced Technologies   3 ( 8 )   437 - 441   1992年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    The polymerization behavior and photoinitiation process in the visible light‐cured dental composite resins were studied using ESR and IR spectroscopies. The concentration of methacryl propagating radical corresponded to the transmittance of irradiated light. While the radical was stable and long‐lived in the cured resin, its concentration quickly decreased in the oral cavity due to the ventilation of atmospheric oxygen accompanied by respiration. Camphorquinone radical in the presence of tertiary amine easily initiated the radical polymerization. A decrease in monomer consumption was explained by the inhibition effect of oxygen in the photoinitiation process. Post‐curing by the residual radical proceeded effectively in the deeper part of the resin. Copyright © 1992 John Wiley &amp
    Sons, Ltd.

    DOI: 10.1002/pat.1992.220030804

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  • SYNTHESIS AND MAGNETIC-PROPERTIES OF CONJUGATED STABLE POLYRADICALS 査読

    H NISHIDE, N YOSHIOKA, T KAKU, T KANEKO, M YAMAZAKI, E TSUCHIDA

    JOURNAL OF MACROMOLECULAR SCIENCE-CHEMISTRY   A28 ( 11-12 )   1177 - 1187   1991年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:MARCEL DEKKER INC  

    Synthesis and magnetic properties of pi-conjugated stable polyradicals bearing a polyacetylene backbone are described. 2,6-Di-tert-butyl-4-ethynylphenol (8) and 4-ethynylphenylhydrogalvinoxyl (9) are polymerized with W, Mo chloride or Rh complex to yield their polyacetylene derivatives with molecular weight of ca. 10(4), while 2-ethynylphenalenone (10) gives only its oligomer. The polymers are soluble in common solvents and converted to the corresponding conjugated polyradicals via heterogeneous chemical oxidation using PbO2 or alkaline K3Fe(CN)6. The polyradicals with extremely high spin concentration (up to 4.8 x 10(23) spins/monomer mol) are obtained by regulating the oxidative conditions. The polyradicals are quite stable in solution and even in the solid state because of resonance stabilization and/or a steric effect of the substituents. Magnetic interactions between the unpaired spins in the conjugated stable polyradicals are discussed.

    DOI: 10.1080/00222339108054091

    Web of Science

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  • UPS SPECTRA OF THE POLYACETYLENE DERIVATIVES CARRYING STABLE RADICAL SUBSTITUENTS 査読

    N YOSHIOKA, H NISHIDE, T KAKU, T KANEKO, E TSUCHIDA, S NARIOKA, K SEKI

    POLYMER JOURNAL   23 ( 7 )   921 - 924   1991年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:SOC POLYMER SCIENCE JAPAN  

    2,6-ジ-t-ブチルフェノール、フェニルヒドロガルビノキシルのようなかさ高い置換基を有するポリアセチレン誘導体の紫外光電子スペクトルから、側鎖の立体効果により共役長がポリ(フェニルアセチレン)に比べ増大することを明らかにした。対応するポリラジカルでは、キノイド構造の生成により共役系が切断された。

    DOI: 10.1295/polymj.23.921

    Web of Science

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  • POLY(PARA-ETHYNYLPHENYL)GALVINOXYL - FORMATION OF A NEW CONJUGATED POLYRADICAL WITH AN EXTRAORDINARILY HIGH-SPIN CONCENTRATION 査読

    H NISHIDE, N YOSHIOKA, T KANEKO, E TSUCHIDA

    MACROMOLECULES   23 ( 20 )   4487 - 4488   1990年10月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    フェニルヒドロガルビノキシル残基を有するポリアセチレンモノマーをロジウム錯体触媒で重合することで分子量数万のポリマーを合成した。このポリマーの水酸基を化学的に酸化することで、ユニットあたり0.8を超えるスピン濃度をもつポリラジカルの合成に成功した。

    DOI: 10.1021/ma00222a028

    Web of Science

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▶ 全件表示

書籍等出版物

  • Polymeric Chiral Catalyst Design and Chiral Polymer Synthesis

    Toshiki Aoki, Takashi Kaneko, Masahiro Teraguchi( 担当: 共著 ,  範囲: Chapter 15, pp.423-455, 共同研究につき分担部分抽出不可能)

    Wiley  2011年9月 

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    総ページ数:497   担当ページ:423-455   記述言語:英語 著書種別:学術書

    Shinichi Itsuno Ed.,Chapter 15 "Synthesis and Function of Chiral π-Conjugated Polymers from Phenylacetylenes" pp.423-455

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  • 次世代共役ポリマーの超階層制御と革新機能

    金子隆司( 担当: 共著 ,  範囲: 第II編, 第8章, pp 164-170)

    シーエムシー出版  2009年1月 

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    総ページ数:445   担当ページ:164-170   記述言語:日本語 著書種別:学術書

    赤木和夫監修、第II編、第8章「キラル共役ポリラジカルの合成と磁性・不斉光学機能」164-170頁 片巻き優先のらせん構造を有するポリラジカルを合成する方法として、安定ラジカル構造を有するモノマーと光学活性基を有するモノマーとの共重合、キラル触媒を用いたアキラルモノマーのらせん選択重合、光学不活性ポリマーの光学活性溶媒中でのらせん誘起について解説した。また、その磁気的性質に関してらせん構造との相関ついても言及した。

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  • 化学便覧応用化学編第6版II

    金子隆司( 担当: 共著 ,  範囲: 20.3.5, pp1094-1097)

    丸善  2003年1月 

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    総ページ数:1709   担当ページ:1094-1097   記述言語:日本語 著書種別:学術書

    日本化学会編、20.3.5「磁性高分子」1094-1097頁 磁性高分子の定義を述べると共に、その代表たる共役ポリラジカルについて、その構造および合成方法から分類した。また、磁性高分子の磁気的性質に関して重要な因子である重合度、スピン濃度、および立体構造とスピン分極構造について解説した。ポリラジカルの次元拡張など発展の方向性および材料としての応用の可能性についても解説した。

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  • Magnetic Properties of Organic Materials

    Hiroyuki Nishide, Takashi Kaneko( 担当: 共著 ,  範囲: Pendant and π-Conjugated Organic Polyradicals)

    marcel dekker, inc.  1999年5月 

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    総ページ数:728   担当ページ:285-303   記述言語:英語 著書種別:学術書

    Lahti, P. M.編、279巻、第14章「Pendant and π-Conjugated Organic Polyradicals」285-303頁 共役高分子の側鎖に規則的に安定ラジカルユニットが導入された、ラジカルペンダント型共役ポリラジカルについて、その合成法および構造と磁気的相互作用の関係について、ポリ(フェニルアセチレン)およびポリ(フェニレンビニレン)骨格を中心としてまとめた。

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  • Magnetism: A Supramolecular Function

    Takeji Takui, Kazunobu Sato, Daisuke Shiomi, Koichi Itoh, Takashi Kaneko, Eishun Tsuchida, Hiroyuki Nishide( 担当: 共著 ,  範囲: FT Pulsed ESR/ESTN(Electron Spin Transient Nutation) Spectroscopy Applied to High-Spin Systems)

    Kluwer Academic Publishers  1996年12月 

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    総ページ数:672   担当ページ:249-280   記述言語:英語 著書種別:学術書

    Kahn, O.編、484巻「FT Pulsed ESR/ESTN(Electron Spin Transient Nutation) Spectroscopy Applied to High-Spin Systems」 249-280頁 パルスESRを用いた電子スピン緩和nutation法 (Electron Spin Transient Nutation)についての応用例を示した。アモルファスなスピン配列の混合体など、複数のスピン量子数を考慮する系においても解析可能であることも示した。

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MISC

  • 進化し続ける高分子酸素分離膜 査読

    青木俊樹, 金子隆司, 寺口昌宏

    化学   74 ( 10 )   66 - 67   2019年10月

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    記述言語:日本語   掲載種別:記事・総説・解説・論説等(学術雑誌)  

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  • 2Dポリマーの合成と分子ふるい膜への利用

    藏 雨, 青木 俊樹, 寺口 昌宏, 金子 隆司

    膜   39 ( 3 )   118 - 131   2014年3月

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    記述言語:日本語   掲載種別:記事・総説・解説・論説等(学術雑誌)   出版者・発行元:日本膜学会  

    2Dポリマーは水素、酸素、窒素、二酸化炭素など気体小分子を分離するための理想的分子篩膜として興味が持たれている。しかしながら2Dポリマーには解決すべき多くの疑問点や問題点が残されている。本総説では、2Dポリマーを定義づけしつつ例示するとともに、分子篩膜との関連について説明した。

    DOI: 10.5360/membrane.39.118

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  • らせん選択重合体膜の光トポケミカル超分子膜化

    浪越毅, 波多野慎悟, 寺口昌宏, 金子隆司, 青木俊樹

    化学工業   61 ( 11 )   846 - 854   2010年11月

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    記述言語:日本語   掲載種別:記事・総説・解説・論説等(学術雑誌)   出版者・発行元:化学工業社  

    著者らによる光学活性基置換アセチレンのらせん不斉誘起重合の発見と展開を述べた。また、キラル触媒系によるアキラル置換アセチレンのらせん選択重合および置換アセチレン高分子の分離膜素材としての利点についても述べた。

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  • 高スピンπ共役高分子の設計と磁性 招待

    金子隆司, 青木俊樹, 寺口昌宏

    Electrochemistry   75 ( 10 )   834 - 838   2007年10月

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    記述言語:日本語   掲載種別:記事・総説・解説・論説等(学術雑誌)   出版者・発行元:電気化学会  

    分子構造を精密設計・合成できるπ共役高分子ポリラジカルには、強磁性体のみならず新しい電磁機能が期待されている。本稿では、π共役分子を使ってお互いの電子スピンを強磁性的に整列させることを目指した最近のポリラジカル合成および磁気物性の進展について解説した。

    DOI: 10.5796/electrochemistry.75.834

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  • デンドリマー分子を用いた分離膜

    金子隆司, 青木俊樹

    オレオサイエンス   6 ( 9 )   443 - 450   2006年9月

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    記述言語:日本語   掲載種別:記事・総説・解説・論説等(学術雑誌)   出版者・発行元:日本油化学会  

    本総説では、デンドリマー分子を用いた分離膜に焦点をあて、その化学構造と透過性との関連について、デンドリマー構造を側鎖に有する高分子の合成と得られた自己支持性のポリデンドロン膜の酸素選択透過性、デンドリマー分子またはハイパーブランチポリマーで架橋した高分子膜のガス選択透過性、支持膜との複合デンドリマー膜の3つの分類から解説した。

    DOI: 10.5650/oleoscience.6.443

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  • 主鎖のらせんのみに起因する不斉を持つポリフェニルアセチレンの合成-アキラル フェニルアセチレンのらせん選択重合とキラル置換ポリフェニルアセチレンの脱置換基-

    青木俊樹, 寺口昌宏, 金子隆司

    高分子加工   54 ( 12 )   542 - 550   2005年12月

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    記述言語:日本語   掲載種別:記事・総説・解説・論説等(学術雑誌)   出版者・発行元:高分子刊行会  

    著者らが見出した主鎖のみに起因する不斉を持つ置換ポリアセチレン誘導体の合成法2つを解説した。ひとつはらせん選択重合、もうひとつは膜状態での脱キラル置換基による方法である。それぞれの合成法に適するモノマー構造などを考察した。

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  • 不斉誘起重合によるキラルヘリカルポリ置換アセチレンの合成

    青木俊樹, 金子隆司, 寺口昌宏

    高分子加工   51 ( 4 )   168 - 176   2002年4月

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    記述言語:日本語   掲載種別:記事・総説・解説・論説等(学術雑誌)   出版者・発行元:高分子刊行会  

    著者らによる光学活性基置換アセチレンのらせん不斉誘起重合の発見と展開を述べた。また、キラル触媒系によるアキラル置換アセチレンのらせん選択重合および置換アセチレン高分子の分離膜素材としての利点についても述べた。

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  • 光学分割膜-分子設計と分離機構-

    青木俊樹, 金子隆司, 寺口昌宏

    化学工業   52 ( 9 )   683 - 691   2001年9月

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    記述言語:日本語   掲載種別:記事・総説・解説・論説等(学術雑誌)   出版者・発行元:化学工業社  

    光学分割膜の分子設計について報告例を分類して紹介し、それぞれの現状と問題点を考察した。特に、著者らによる置換ポリアセチレンを用いた分子設計について詳しく紹介した。

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  • アセチレンを使った精密共役ポリマーの機能美

    金子隆司

    高分子   50 ( 3 )   153 - 153   2001年3月

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    記述言語:日本語   掲載種別:記事・総説・解説・論説等(学術雑誌)   出版者・発行元:高分子学会  

    近年、一次元的な結合構造だけでなく、「モレキュラーアーキテクチャー」という言葉に代表されるように、二次元あるいは三次元的な分子構造に基づく機能発現が注目を集めている。アセチレンは剛直な直線状の構造を持つπ共役分子であることから、構成ユニットとしての期待が大きい。本稿では、種々のアセチレン誘導体から得られる、デンドリマー、線状ポリマー、キラルポリマーなどの磁気機能や分離機能について解説した。

    DOI: 10.1295/kobunshi.50.153

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  • 高分子ポリラジカルの合成と磁性

    金子隆司, 青木俊樹, 及川栄蔵

    高分子加工   48 ( 3 )   113 - 117   1999年3月

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    記述言語:日本語   掲載種別:記事・総説・解説・論説等(学術雑誌)   出版者・発行元:高分子刊行会  

    高分子ポリラジカルは、前駆体の重合を経た高分子反応によるラジカル生成あるいはラジカルモノマーの重合により合成された、高分子一分子鎖に複数の不対電子を有する高分子として位置づけられる。近年、この高分子ラジカルを用いた有機磁性材料への関心が高まっている。本稿では、磁性発現を目指した最近のポリラジカル合成および磁気物性の進展について解説した。

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  • 光学分割固体膜素材用合成高分子の設計

    青木俊樹, 金子隆司, 及川栄蔵

    膜   22 ( 3 )   126 - 134   1997年3月

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    記述言語:日本語   掲載種別:記事・総説・解説・論説等(学術雑誌)   出版者・発行元:日本膜学会  

    光学分割膜としての光学活性基を持つ新規な高分子を合成し、濃度浸透、逆浸透、パーベーパレーション、エバポミエーションの4つの方法により種々のラセミ体の光学異性体選択透過性を研究した。透過性と選択性は大まかに相反関係にあるが、他のプロセスと組み合わせることで充分利用可能になると期待できた。

    DOI: 10.5360/membrane.22.126

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  • 磁性を持った有機高分子−共役ポリラジカルでのスピン整列−

    金子隆司

    化学と工業   49 ( 2 )   139 - 142   1996年2月

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    記述言語:日本語   掲載種別:記事・総説・解説・論説等(その他)   出版者・発行元:日本化学会  

    2,6-ジ-t-ブチルフェノキシルあるいはt-ブチルニトロキシドを置換したポリ(フェニルアセチレン)やポリ(1,4-および1,2-フェニレンビニレン)での磁性的相互作用について、π共役分子構造との相関についてまとめた。

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  • 光学分割膜の高分子設計

    青木俊樹, 篠原健一, 金子隆司, 及川栄蔵

    有機合成化学協会誌   54 ( 6 )   525 - 536   1996年

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    記述言語:日本語   掲載種別:記事・総説・解説・論説等(その他)   出版者・発行元:有機合成化学協会  

    光学活性基を有する新規な高分子膜を用い、様々なラセミ体の光学分割を4種類の透過方法で検討した。硬い主鎖を持つキラル高分子は高い選択性を示したが、透過性は低かった。主鎖のより柔らかい高分子を用いると透過性が向上した。また、表面に光学活性層を持つ高分子膜は優れた光学異性体選択透過性を示した。枝に光学活性基を持つグラフトコポリマーは製膜性が優れるため高透過性の光学分割膜として期待できる。

    DOI: 10.5059/yukigoseikyokaishi.54.525

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▶ 全件表示

講演・口頭発表等

  • ガルビノキシル残基を有するポリ(1,3-フェニレンエチニレン)の片 巻優 先らせんフォルダマー形成における置換基効果

    二宮浩彰, 金子隆司, 大石智之, 垣花百合子, 寺口昌宏, 青木俊樹

    第60回高分子学会年次大会  2011年5月  高分子学会

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    記述言語:日本語   会議種別:ポスター発表  

    開催地:大阪(グランキューブ大阪)  

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  • 側鎖にニトロ基とニトロニルニトロキシド残基を有するポリ(1,3-フェニレンエチニレン)型キラルポリラジカルの合成とらせんフォルダマー形成

    廣野一也, 加藤清亮, 大石智之, 垣花百合子, 寺口昌宏, 青木俊樹, 金子隆司

    日本化学会第91回春季年会  2011年3月  日本化学会

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    記述言語:日本語   会議種別:口頭発表(一般)  

    開催地:横浜  

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  • フェノキシ置換ポリ(1,8-ナフチレンエチニレン-9,10-アントリレンエチニレン)およびそのダイマーモデルの合成

    塚本圭太, 大石智之, 垣花百合子, 寺口昌宏, 青木俊樹, 金子隆司

    日本化学会第91回春季年会  2011年3月  日本化学会

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    記述言語:日本語   会議種別:口頭発表(一般)  

    開催地:横浜  

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  • 側鎖にガルビノキシルとフェノキシルを有するポリ(1,3-フェニレンエチニレン)型ポリラジカルフォルダマーの合成とその磁気的性質

    岩村恭平, 大石智之, 垣花百合子, 寺口昌宏, 青木俊樹, 金子隆司

    第59回高分子学会北陸支部研究発表会  2010年11月  高分子学会北陸支部

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    記述言語:日本語   会議種別:口頭発表(一般)  

    開催地:富山県富山市  

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  • フェノール残基を導入した2,6-置換ポリ(9,10-アントリレンエチニレン)の合成とその電子状態

    今野良平, 大石智之, 垣花百合子, 寺口昌宏, 青木俊樹, 金子隆司

    第59回高分子学会北陸支部研究発表会  2010年11月  高分子学会北陸支部

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    記述言語:日本語   会議種別:口頭発表(一般)  

    開催地:富山県富山市  

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  • Sequential Poly(aryleneethynylene)-Based Polyradicals: Synthesis and Magnetic Property 国際会議

    Takashi Kaneko, Kiyoaki Kato, Toshihiro Saito, Masahiro Teraguchi, Toshiki Aoki

    Interanational Conference on Science and Technology of Synthetic Metals 2010  2010年7月 

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    記述言語:英語   会議種別:ポスター発表  

    開催地:Kyoto International Conference Center, Kyoto, Japan  

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  • Helix-Sense-Selective Polymerization of (3,5-Bis(hydroxymethyl)-4-phenyl)phenylacetylenes 国際会議

    Manami Osawa, Masahiro Teraguchi, Toshiki Aoki, Takashi Kaneko

    Interanational Conference on Science and Technology of Synthetic Metals 2010  2010年7月 

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    記述言語:英語   会議種別:ポスター発表  

    開催地:Kyoto International Conference Center, Kyoto, Japan  

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  • Synthesis of Poly(1,3-phenyleneethynylene)s with Pendant Galvinoxyl, Chiral and Hydrophilic Moieties, and Their Forming Ability of Helical Foldamer 国際会議

    Hiroaki Ninomiya, Masahiro Teraguchi, Toshiki Aoki, Takashi Kaneko

    Interanational Conference on Science and Technology of Synthetic Metals 2010  2010年7月 

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    記述言語:英語   会議種別:ポスター発表  

    開催地:Kyoto International Conference Center, Kyoto, Japan  

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  • Synthesis of Optically Active Poly(Binaphthyl-6,6-diylethynylene-9,10-anthryleneethynylene) Bearing Phenoxyls at 2,7-Positions of Anthracene 国際会議

    Masahiro Tsuchida, Masahiro Teraguchi, Toshiki Aoki, Takashi Kaneko

    Interanational Conference on Science and Technology of Synthetic Metals 2010  2010年7月 

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    記述言語:英語   会議種別:ポスター発表  

    開催地:Kyoto International Conference Center, Kyoto, Japan  

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  • 4位にフェニル基を有する3,5-ビス(ヒドロキシメチル)フェニルアセチレンのらせん選択重合と光学不活性な重合体からの片巻優先らせん誘起

    大澤愛実, 浪越 毅, エディ マルワンタ, 寺口昌宏, 青木俊樹, 金子隆司

    第59回高分子学会年次大会  2010年5月  高分子学会

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    記述言語:日本語   会議種別:ポスター発表  

    開催地:横浜  

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  • 側鎖にニトロニルニトロキシドを有するポリ(1,3-フェニレンエチニレン)型キラルポリラジカルのらせんフォルダマー構造制御と磁気的性質

    加藤清亮, 浪越毅, エディ マルワンタ, 寺口昌宏, 青木俊樹, 金子隆司

    第58回高分子討論会  2009年9月  高分子学会

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    記述言語:日本語   会議種別:口頭発表(一般)  

    開催地:熊本(熊本大学)  

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  • オリゴ(9,10-アントリレンエチニレン)構造を介したフェノキシラジカル類の磁気的相互作用

    高村政克, 浪越毅, エディ マルワンタ, 寺口昌宏, 青木俊樹, 金子隆司

    第58回高分子討論会  2009年9月  高分子学会

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    記述言語:日本語   会議種別:ポスター発表  

    開催地:熊本(熊本大学)  

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  • アントラセンの2,7位にフェノール残基を有する光学活性なポリ(ビナフチル-6,6'-ジイルエチニレン-9,10-アントリレンエチニレン)の合成

    土田昌弘, 浪越毅, エディ マルワンタ, 寺口昌宏, 青木俊樹, 金子隆司

    2009年支部合同新潟地方大会(第58回高分子学会北陸支部研究発表講演会)  2009年8月  日本化学会関東支部、高分子学会北陸支部

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    記述言語:日本語   会議種別:口頭発表(一般)  

    開催地:新潟(新潟大学五十嵐キャンパス)  

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  • 4位にフェニル基を有する3,5-ビス(ヒドロキシメチル)フェニルアセチレンのらせん選択重合

    大澤愛実, 浪越毅, エディ マルワンタ, 寺口昌宏, 青木俊樹, 金子隆司

    2009年支部合同新潟地方大会(第58回高分子学会北陸支部研究発表講演会)  2009年8月  日本化学会関東支部、高分子学会北陸支部

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    記述言語:日本語   会議種別:口頭発表(一般)  

    開催地:新潟(新潟大学五十嵐キャンパス)  

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  • 2位にヒドロキシエトキシ基、5位にガルビノキシル残基を有するポリ(1,3-フェニレンエチニレン)の合成とらせんフォルダマー形成能

    二宮浩彰, 浪越毅, エディ マルワンタ, 寺口昌宏, 青木俊樹, 金子隆司

    2009年支部合同新潟地方大会(第58回高分子学会北陸支部研究発表講演会)  2009年8月  日本化学会関東支部、高分子学会北陸支部

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    記述言語:日本語   会議種別:口頭発表(一般)  

    開催地:新潟(新潟大学五十嵐キャンパス)  

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  • ガルビノキシル置換オリゴ(9,10-アントリレンエチニレン)の合成及び電子構造と磁気的性質

    高村政克, 浪越 毅, エディ マルワンタ, 寺口昌宏, 青木俊樹, 金子隆司

    第58回高分子学会年次大会  2009年5月  高分子学会

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    記述言語:日本語   会議種別:ポスター発表  

    開催地:神戸  

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  • 側鎖にニトロニルニトロキシドを有するポリ(1,3-フェニレンエチニレン)型キラルポリラジカルの合成とらせんフォルダマー構造制御

    加藤清亮, 浪越 毅, エディ マルワンタ, 寺口昌宏, 青木俊樹, 金子隆司

    第57回高分子学会北陸支部研究発表講演会  2008年11月  高分子学会北陸支部

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    記述言語:日本語   会議種別:口頭発表(一般)  

    開催地:福井県福井市  

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  • 安定ラジカル部位を有するアントリレンエチニレンユニットと柔軟なオリゴメチレンユニットからなるモノマーの合成と重合

    落合健祐, 浪越 毅, エディ マルワンタ, 寺口昌宏, 青木俊樹, 金子隆司

    第57回高分子学会北陸支部研究発表講演会  2008年11月  高分子学会北陸支部

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    記述言語:日本語   会議種別:口頭発表(一般)  

    開催地:福井県福井市  

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  • Synthesis of Optically Active p-Conjugated Polymers Bearing Stable Radicals and Their Chiroptical and Magnetic Properties 国際会議

    Takashi Kaneko, Hiromasa Abe, Hiroo Katagiri, Atsuko Kawami, Tsuyoshi Namikoshi, Edy Marwanta, Masahiro Teraguchi, Toshiki Aoki

    18th Iketani Conference: Interanational Conference of Super-Hierarchical Structures and Innivative Functions of Next-Generation Conjugated Polymers  2008年10月 

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    記述言語:英語   会議種別:ポスター発表  

    開催地:Awaji Yumebutai International Conference Center, Hyogo, Japan  

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  • ガルビノキシルを有するポリ(1,3-フェニレンエチニレン)の片巻優先らせんフォルダマー形成能及び磁気的性質

    阿部 寛正, 浪越 毅, マルワンタ エディ, 寺口 昌宏, 青木 俊樹, 金子 隆司

    第57回高分子討論会  2008年9月  高分子学会

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    記述言語:日本語   会議種別:ポスター発表  

    開催地:大阪  

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  • TEMPO を有するポリ(フェニルアセチレン)の光学活性らせん形成能と磁気的性質

    川見 敦子, 金子 隆司, 浪越 毅, マルワンタ エディ, 寺口 昌宏, 青木 俊樹

    第57回高分子討論会  2008年9月  高分子学会

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    記述言語:日本語   会議種別:ポスター発表  

    開催地:大阪  

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  • ガルビノキシル残基を有するポリ{3,5-ビス(ヒドロキシメチル)-4-ベンジルオキシフェニルアセチレン}の光学活性らせん主鎖構造と磁気特性

    片桐 寛夫, 浪越 毅, エディ マルワンタ, 寺口 昌宏, 青木 俊樹, 金子 隆司

    第57回高分子討論会  2008年9月  高分子学会

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    記述言語:日本語   会議種別:口頭発表(一般)  

    開催地:大阪  

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  • Synthesis of Optically Active Helical Poly(phenylacetylene)-based Polyradicals and Magnetic Interaction Depending on Their Helicity 国際会議

    Takashi Kaneko, Yasuhiro Umeda, Hiroo Katagiri, Atsuko Kawami, Tsuyoshi Namikoshi, Edy Marwanta, Masahiro Teraguchi, Toshiki Aoki

    The 11th Int. Conf. Molecule-Based Magnets  2008年9月 

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    記述言語:英語   会議種別:ポスター発表  

    開催地:Florence, Italy  

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  • らせん選択重合により得られたガルビノキシル残基を有するポリ[3,5-ビス(ヒドロキシメチル)-4-ベンジルオキシフェニルアセチレン]の光学活性と磁気特性

    片桐寛夫, 浪越 毅, エディ マルワンタ, 寺口昌宏, 青木俊樹, 金子隆司

    第57回高分子学会年次大会  2008年5月  高分子学会

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    記述言語:日本語   会議種別:ポスター発表  

    開催地:横浜  

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  • 主鎖に光学活性なビナフチル構造を含むガルビノキシル置換ポリ(1,3-フェニレンエチニレン)の合成とそのフォルダマー形成能及び磁気特性

    阿部寛正, 浪越 毅, エディ マルワンタ, 寺口昌宏, 青木俊樹, 金子隆司

    第57回高分子学会年次大会  2008年5月  高分子学会

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    記述言語:日本語   会議種別:ポスター発表  

    開催地:横浜  

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  • TEMPOを有するポリ(フェニルアセチレン)の光学活性らせん誘起と磁気的性質

    川見敦子, 浪越 毅, エディ マルワンタ, 寺口昌宏, 青木俊樹, 金子隆司

    日本化学会第88回春季年会  2008年3月  日本化学会

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    記述言語:日本語   会議種別:口頭発表(一般)  

    開催地:東京豊島区  

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  • 側鎖にレゾルシノール誘導体を有するアセチレンモノマーの重合とその光学活性らせん誘起

    梁 暁芸, 浪越 毅, エディ マルワンタ, 寺口昌宏, 青木俊樹, 金子隆司

    日本化学会第88回春季年会  2008年3月  日本化学会

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    記述言語:日本語   会議種別:口頭発表(一般)  

    開催地:東京豊島区  

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  • TEMPO を有するフェニルアセチレン誘導体の重合とらせん構造制御

    川見 敦子, 寺口 昌宏, 青木 俊樹, 金子 隆司

    第56回高分子討論会  2007年9月  高分子学会

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    記述言語:日本語   会議種別:ポスター発表  

    開催地:名古屋  

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  • 安定ラジカル骨格を有するアントリルアセチレン誘導体の重合

    佐藤 誠之, 寺口 昌宏, 青木 俊樹, 金子 隆司

    第56回高分子討論会  2007年9月  高分子学会

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    記述言語:日本語   会議種別:ポスター発表  

    開催地:名古屋  

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  • (4-エチニルフェニル)ガルビノキシルの共重合におけるらせん方向制御とそのポリラジカルの光・磁気特性

    梅田 泰裕, 寺口 昌宏, 青木 俊樹, 金子 隆司

    第56回高分子討論会  2007年9月  高分子学会

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    記述言語:日本語   会議種別:口頭発表(一般)  

    開催地:名古屋  

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  • Helix-sense-selective Polymerization of 3,5-Bis(hydroxymethyl)-4-benzyloxyphenylacetylene Bearing Galvinoxyl, and Chiroptical and Magnetic Properties 国際会議

    Hiroo Katagiri, Takashi Kaneko, Takeshi Namikoshi, Edy Marwanta, Masahiro Teraguchi, Toshiki Aoki

    The 4th International Symposium on Advanced Materials in Asia-Pacific Rim  2007年7月 

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    記述言語:英語   会議種別:ポスター発表  

    開催地:Niigata, Japan  

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  • Synthesis of Poly(binaphthyl-6,6'-diylethynylene-1,3-phenyleneethynylene)-based Chiral Polyradical Bearing Galvinoxyl, and Its Chiroptical and Magnetic Properties 国際会議

    Hiromasa Abe, Takashi Kaneko, Takeshi Namikoshi, Edy Marwanta, Masahiro Teraguchi, Toshiki Aoki

    The 4th International Symposium on Advanced Materials in Asia-Pacific Rim  2007年7月 

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    記述言語:英語   会議種別:ポスター発表  

    開催地:Niigata, Japan  

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  • Synthesis of Oligo(anthryleneethynylene)-based Foldamers Containing Stable Radicals 国際会議

    Kensuke Ochiai, Takashi Kaneko, Takeshi Namikoshi, Edy Marwanta, Masahiro Teraguchi, Toshiki Aoki

    The 4th International Symposium on Advanced Materials in Asia-Pacific Rim  2007年7月 

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    記述言語:英語   会議種別:ポスター発表  

    開催地:Niigata, Japan  

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  • Synthesis of TEMPO-pendant Poly(phenylacetylene)s, and Their Chiroptical and Magnetic Properties 国際会議

    Atsuko Kawami, Takashi Kaneko, Takeshi Namikoshi, Edy Marwanta, Masahiro Teraguchi, Toshiki Aoki

    The 4th International Symposium on Advanced Materials in Asia-Pacific Rim  2007年7月 

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    記述言語:英語   会議種別:ポスター発表  

    開催地:Niigata, Japan  

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  • Magnetic Properties of TEMPO Radicals Included in a Supramolecular Anthracene Derivative 国際会議

    Masayuki Sato, Takashi Kaneko, Takeshi Namikoshi, Edy Marwanta, Masahiro Teraguchi, Toshiki Aoki

    The 4th International Symposium on Advanced Materials in Asia-Pacific Rim  2007年7月 

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    記述言語:英語   会議種別:ポスター発表  

    開催地:Niigata, Japan  

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  • The Control of the Helix Sense in the Copolymerization of (4-Ethynylphenyl)galvinoxyl by the Composition of Comonomer 国際会議

    Yasuhiro Umeda, Takashi Kaneko, Takeshi Namikoshi, Edy Marwanta, Masahiro Teraguchi, Toshiki Aoki

    The 4th International Symposium on Advanced Materials in Asia-Pacific Rim  2007年7月 

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    記述言語:英語   会議種別:ポスター発表  

    開催地:Niigata, Japan  

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  • Synthesis of Optically Active Poly(aryleneethynylene)s Bearing Stable Radicals and Their Chiroptical and Magnetic Properties 国際会議

    Takashi Kaneko, Hiromasa Abe, Shouta Yoshimoto, Shingo Hadano, Masahiro Teraguchi, Toshiki Aoki

    The 7th Int. Conf. on Optical Probes of -Conjugated Polymers and Functional Self-Assemblies  2007年6月 

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    記述言語:英語   会議種別:ポスター発表  

    開催地:Turku, Finland  

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  • Helix-sense-selective Polymerization of 3,5-bis(hydroxymethyl)-4-benzyloxyphenylacetylene Bearing Galvinoxyl, and Optical Activity 国際会議

    Hiroo Katagiri, Takashi Kaneko, Shingo Hadano, Masahiro Teraguchi, Toshiki Aoki

    The 7th Int. Conf. on Optical Probes of -Conjugated Polymers and Functional Self-Assemblies  2007年6月 

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    記述言語:英語   会議種別:ポスター発表  

    開催地:Turku, Finland  

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  • The Control of the Helix Sense for Poly(phenylacetylene)s Bearing Galvinoxyl Residues by the Composition of Co-monomer 国際会議

    Yasuhiro Umeda, Takashi Kaneko, Shingo Hadano, Masahiro Teraguchi, Toshiki Aoki

    The 7th Int. Conf. on Optical Probes of -Conjugated Polymers and Functional Self-Assemblies  2007年6月 

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    記述言語:英語   会議種別:ポスター発表  

    開催地:Turku, Finland  

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  • ガルビノキシル残基を有するポリ(フェニルアセチレン)のらせん方向制御とそのポリラジカルの光・磁気特性

    梅田 泰裕, 金子 隆司, 寺口 昌宏, 波多野 慎悟, 青木 俊樹

    第56回高分子学会年次大会  2007年5月  高分子学会

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    記述言語:日本語   会議種別:口頭発表(一般)  

    開催地:京都(国立京都国際会館)  

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  • ガルビノキシル残基を有する3,5-ビス(ヒドロキシメチル)-4-ベンジルオキシフェニルアセチレンのらせん選択重合とそのキラルポリラジカルの光学活性・磁気特性

    片桐寛夫, 金子隆司, 波多野慎悟, 寺口昌宏, 青木俊樹

    日本化学会第87回春季年会  2007年3月  日本化学会

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    記述言語:日本語   会議種別:口頭発表(一般)  

    開催地:吹田  

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  • 側鎖にガルビノキシルを有するポリ(ビナフチル-6,6'-ジイルエチニレン-1,3-フェニレンエチニレン)型キラルポリラジカルの合成と光学活性・磁気特性

    阿部寛正, 金子隆司, 波多野慎悟, 寺口昌宏, 青木俊樹

    日本化学会第87回春季年会  2007年3月  日本化学会

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    記述言語:日本語   会議種別:口頭発表(一般)  

    開催地:吹田  

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  • 側鎖にガルビノキシルを有するポリ(フェニルアセチレン)型キラルポリラジカルの合成と光学活性・磁気特性

    梅田泰裕, 金子隆司, 波多野慎悟, 寺口昌宏, 青木俊樹

    日本化学会第87回春季年会  2007年3月  日本化学会

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    記述言語:日本語   会議種別:口頭発表(一般)  

    開催地:吹田  

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  • Synthesis of optically active helical polyacetylenes bearing stable radicals via helix-sense-selective polymerization 国際会議

    Takashi Kaneko, Yasuhiro Umeda, Shingo Hadano, Masahiro Teraguchi, Toshiki Aoki

    International Symposiumon Fusion Tech 2006-2007  2007年1月 

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    記述言語:英語   会議種別:口頭発表(一般)  

    開催地:Niigata, Japan  

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  • ガルビノキシルを有するポリ(1,3-フェニレンエチニレン)型キラルポリラジカルの合成とその磁性及び磁気光学効果

    吉本翔太, 金子隆司, 寺口昌宏, 波多野慎悟, 青木俊樹

    第55回高分子討論会  2006年9月  高分子学会

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    記述言語:日本語   会議種別:口頭発表(一般)  

    開催地:富山(富山大学)  

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  • Synthesis of Optically Active Helical Polymers Bearing Stable Radicals and Their Chiroptical and Magnetic Properties 国際会議

    Takashi Kaneko, Yasuhiro Umeda, Shota Yoshimoto, Shingo Hadano, Masahiro Teraguchi, Toshiki Aoki

    The 10th Int. Conf. Molecule-Based Magnets  2006年8月 

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    記述言語:英語   会議種別:ポスター発表  

    開催地:Victoria, Canada  

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  • Synthesis of optically active helical polymers bearing stable radicals via helix-sense-selective polymerization of phenylacetylenes 国際会議

    Takashi Kaneko, Yasuhiro Umeda, Shingo Hadano, Masahiro Teraguchi, Toshiki Aoki

    The 10th World Multi-Conference on Systemics, Cybernetics and Informatics (WMSCI2006)  2006年7月 

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    記述言語:英語   会議種別:口頭発表(招待・特別)  

    開催地:Orland, Florida, USA  

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  • Helix-sense-selective polymerization of phenylacetylenes bearing galvinoxyl residues 国際会議

    Takashi Kaneko, Yasuhiro Umeda, Shingo Hadano, Masahiro Teraguchi, Toshiki Aoki

    3rd IUPAC-sponsored International Symposium on Macro- and Supramolecular Architectures and Materials (MAM-06)  2006年5月 

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    記述言語:英語   会議種別:口頭発表(一般)  

    開催地:Waseda, Japan  

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  • 2,7位にフェノール残基を有するオリゴ(アントリレンエチニレン)の酸化及びその電子状態と磁気特性

    田中毅, 金子 隆司, 八木政行, 寺口 昌宏, 青木 俊樹

    第55回高分子学会年次大会  2006年5月  高分子学会

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    記述言語:日本語   会議種別:ポスター発表  

    開催地:名古屋  

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  • ガルビノキシル基を有するポリ(1,3-フェニレンエチニレン)型キラルポリラジカルの合成とその光・磁気特性

    吉本翔太, 金子 隆司, 寺口 昌宏, 青木 俊樹

    第55回高分子学会年次大会  2006年5月  高分子学会

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    記述言語:日本語   会議種別:ポスター発表  

    開催地:名古屋  

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  • Helix-sense-selective polymerization of achiral and bulky phenylacetylenes 国際会議

    Takashi Kaneko, Yasuhiro Umeda, Shingo Hadano, Masahiro Teraguchi, Toshiki Aoki

    The 3rd International Symposium on Advanced Materials in Asia-Pacific Rim  2006年5月 

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    記述言語:英語   会議種別:口頭発表(一般)  

    開催地:Ulsan, Korea  

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  • Helix-sense-selective polymerization of phenylacetylene derivatives 国際会議

    Takashi Kaneko

    The 2006 symposium of the Polymer Society of Korea  2006年4月 

     詳細を見る

    記述言語:英語   会議種別:口頭発表(招待・特別)  

    開催地:Goyang, Korea  

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  • アントラセン超分子に包接された安定ラジカルの磁気特性

    佐藤誠之, 金子隆司, 青木俊樹, 寺口昌宏

    日本化学会第86回春季年会  2006年3月  日本化学会

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    記述言語:日本語   会議種別:口頭発表(一般)  

    開催地:船橋  

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  • 塩基量により分子量制御されたオリゴ(アントリレンエチニレン)誘導体の合成と単離した各オリゴマーの電子特性

    田中毅, 金子隆司, 青木俊樹, 寺口昌宏

    日本化学会第86回春季年会  2006年3月  日本化学会

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    記述言語:日本語   会議種別:口頭発表(一般)  

    開催地:船橋  

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受賞

  • 平成12年度 高分子学会 高分子研究奨励賞

    2001年5月   高分子学会  

    金子隆司

     詳細を見る

    受賞区分:国内学会・会議・シンポジウム等の賞  受賞国:日本国

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共同研究・競争的資金等の研究

  • モノマー配列でプログラミングされたらせんキラルポリラジカル高次構造と磁気光学機能

    2016年4月 - 2020年3月

    科学研究費補助金 

      詳細を見る

    資金種別:競争的資金

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  • モノマー配列でプログラミングされたらせんキラルポリラジカル磁気秩序と磁気光学機能

    2012年4月 - 2016年3月

    科学研究費補助金 

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    資金種別:競争的資金

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  • 高効率の太陽電池デバイスを目指した共役高分子材料の基礎研究

    2011年4月 - 2012年3月

    民間財団等  内田エネルギー科学振興財団試験研究費助成 

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    資金種別:競争的資金

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  • キラルポリラジカルのナノ構造制御による磁気秩序の構築と磁気光学機能

    2008年4月 - 2012年3月

    科学研究費補助金 

      詳細を見る

    資金種別:競争的資金

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  • 化学磁気メモリー素子のためのらせん主鎖ポリラジカルの開発

    2008年4月 - 2009年3月

    その他省庁等  科学技術振興機構(JST)重点地域研究開発推進事業「シーズ発掘試験」 

      詳細を見る

    資金種別:競争的資金

    researchmap

  • キラル共役ポリラジカルの合成と磁気光学機能

    2007年4月 - 2009年3月

    科学研究費補助金 

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    資金種別:競争的資金

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  • 共役ポリラジカル超分子をホスト分子とした有機ラジカル包接と化学磁気メモリー

    2006年4月 - 2008年3月

    科学研究費補助金 

      詳細を見る

    資金種別:競争的資金

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  • 共役高分子磁性体におけるナノスケールスピン整列とキラルポリラジカルへの展開

    2005年4月 - 2008年3月

    科学研究費補助金 

      詳細を見る

    資金種別:競争的資金

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  • 共役ポリラジカル磁性体の合成とそのマグネトクロミズム

    2004年4月 - 2006年3月

    科学研究費補助金 

      詳細を見る

    資金種別:競争的資金

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  • デンドリマー置換フェニルアセチレンの重合とナノ構造制御による分離膜材料への応用

    2004年4月 - 2005年3月

    民間財団等  向科学技術振興財団研究助成 

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    資金種別:競争的資金

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  • キラルポリラジカルの合成と光磁気機能

    2002年4月 - 2004年3月

    科学研究費補助金 

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    資金種別:競争的資金

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  • 精密な分岐構造を持つデンドリマーを側鎖に有するフェニルアセチレンの重合とその高分子膜の分離機能

    2001年4月 - 2003年3月

    民間財団等  旭硝子財団自然科学系研究助成(奨励研究助成) 

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    資金種別:競争的資金

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  • 光機能を複合した強磁性共役ポリラジカルの合成

    2000年4月 - 2002年3月

    科学研究費補助金 

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    資金種別:競争的資金

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  • 立体構造の制限されたデンドリマー高分子の合成とナノ構造制御による分離膜材料への応用

    1999年4月 - 2000年3月

    民間財団等  矢崎科学技術振興財団奨励研究助成 

      詳細を見る

    資金種別:競争的資金

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  • エネルギー資源を分離精製する精密高分子膜の設計に関する基礎的合成研究

    1998年4月 - 1999年3月

    民間財団等  内田エネルギー科学振興財団試験研究費助成 

      詳細を見る

    資金種別:競争的資金

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  • 環境保全のための精密高分子膜の設計に関する基礎的合成研究

    1998年4月 - 1999年3月

    民間財団等  佐々木環境技術振興財団試験研究費助成 

      詳細を見る

    資金種別:競争的資金

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  • シリル基を含有するフェニルアセチレンデンドリマーの合成と重合および酸素選択透過膜素材としての性能

    1998年4月 - 1999年3月

    民間財団等  山口育英奨学会学術研究助成 

      詳細を見る

    資金種別:競争的資金

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  • ラダー骨格に複数の安定ラジカルを持つ共役ポリマーの合成と擬二次元的強磁性相互作用

    1997年4月 - 1999年3月

    科学研究費補助金 

      詳細を見る

    資金種別:競争的資金

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  • デンドリティックマクロマーの重合とその高分子膜の高次構造空間による分子認識・分離

    1996年4月 - 1999年3月

    科学研究費補助金 

    及川 栄蔵

      詳細を見る

    資金種別:競争的資金

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▶ 全件表示

 

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