論文

査読有り
2012年1月

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

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

17
1
開始ページ
433
終了ページ
451
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.3390/molecules17010433
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.

リンク情報
DOI
https://doi.org/10.3390/molecules17010433
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000299535700029&DestApp=WOS_CPL
ID情報
  • DOI : 10.3390/molecules17010433
  • ISSN : 1420-3049
  • Web of Science ID : WOS:000299535700029

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