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2003 Fiscal Year Final Research Report Summary

Development of Molecular Memory System Using Hydrogen Bonding-Based Dynamic Controlled Recognition Process

Research Project

Project/Area Number 13031039
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionNagoya University

Principal Investigator

YASHIMA Eiji  Nagoya University, Graduate School of Eng., Professor, 工学研究科, 教授 (50191101)

Project Period (FY) 2001 – 2003
KeywordsPolyphenylacetylene / Helical Structure / Induced CD / Polymerization / Helicity Induction / Polyelectrolyte / Chirality Memory / Chiral Amplification
Research Abstract

The synthesis of helical polymers with controlled helix-sense has aroused considerable interest in polymer chemistry. In this study, we developed a series of helical polymers whose helicity could be induced upon complexation with small chiral molecules. We also investigated the mechanism of the helicity induction and the memory of helical chirality by means of IR, UV, and CD spectroscopies.
We found that a similar, but unusual memory of the helical chirality is also possible for poly (4-carboxyphenyl isocyanide). In this case, the macromolecular helicity induced on the polymer could be "memorized" without any achiral amines. Most of the poly(phenylacetylenes) prepared were soluble in water and exhibited ICDS with free amino acids through electrostatic interactions in water. Particularly, poly(phenylacetylene)s bearing the phosphonate residues were highly sensitive to the chirality of a variety of biomolecules including amino acids and peptides. A poly(phenylacetylene) bearing an achiral oligoglycine residue could form a one-handed helix with chiral oligopeptides such as an alanine trimer through hydrogen-bonding interaction in water. Another dynamic helical poly(phenlacetylene) with the bulky crown ether as the pendant responded to an extremely small enantiomeric imbalance in amino acids (less than 0.005% enantiomeric excess of alanine for example) and exhibits ICDs with a strong positive non-linear effect. An optically active. C_<60>-based helical poly(phenyl-acetylene) was also prepared by the copolymerization of an achiral fullerene monomer with an optically active phenylacetylene, where the achiral C_<60> pendants arrange in a helical array with a predominant screw-sense along the polymer backbone, thus exhibiting an ICD in the fullerene chromophore region. These methodologies described above are useful for constructing a novel helical polymer with the desired pendant in a one-handed helical array.

  • Research Products

    (14 results)

All Other

All Publications (14 results)

  • [Publications] H.Goto, H.Q.Zhang, E.Yashima: "Chiral Stimuli-Responsive Gels : Helicity Induction in Poly(phenylacetylene) Gels Bearing a Carboxyl Group with Chiral Amines"J.Am.Chem.Soc.. 125. 2516-2523 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] R.Nonokawa, E.Yashima: "Detection and Amplification of a Small Enantiomeric Imbalance in a-Amino Acids by a Helical Poly(phenylacetylene) with Crown Ether Pendants"J.Am.Chem.Soc.. 125. 1278-1283 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Maeda, K.Morlno, E.Yashima: "Solvent-Induced Switching of the Macromolecular Helicity of Poly((4-carboxyphenyl)acetylene) Induced by a Single Chiral Amino Alcohol"J.Polym.Sci.Part A, Polym.Chem.. 40. 3625-3631 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Kawamura, M.Ishikawa, K.Maeda, E.Yashima: "Cu(II)-assisted Helicity Induction on a Poly(phenylacetylene) Derivative Bearing an Achiral Glycine Residue with Amino Acids in Water"Chem.Lett.. 32. 1086-1087 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Ishikawa, K.Maeda, Y.Mitsutsuji, E.Yashima: "An Unprecedented Memory of Macromolecular Helicity Induced in an Achiral Polvisocvanide in Water"J.Am.Chem.Soc.. 126. 732-733 (2004)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Maeda, K.Morino, Y.Okamoto, T.Sato, E.Yashima: "Studies on the Mechanism of Helix Induction on a Stereoregular Poly((4-carboxyphenyl)acetyleiie) with Chiral Amines and on the Memory of the Macromolecular Helicity Assisted by Interaction with Achiral Amines"J.Am.Chem.Soc.. 126. 4329-4342 (2004)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Katsuhiro Maeda, Seiji Okada, Eiji Yashima, Yoshio Okamoto: "Helix Formation of Poly (phenylacetylene) Derivatives Beariing Amino Groups at the Meta Position Induced by Optically Active Carboxylic Acids"J. Polym. Sci. Part A, Polym. Chem.. 39. 3180-3189 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Katsuhiro Maeda, Hidetoshi Goto, Eiji Yashima: "Stereospecific Polymerization of Propiolic Acid with Rhodium Complexes in the Presence of Bases and Helix Induction on the Polymer in Water"Macromolecules. 34. 1160-1164 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Onouchi, K.Maeda, E.Yashima: "A Helical Polyelectrolyte Induced by Specific Interactions with Biomolecules in Water"J. Am. Chem. Soc.. 123. 7441-7442 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Ishikawa, K.Maeda, E.Yashima: "Macromolecular Chirality Induction on Optically Inactive Poly (4-carboxyphenyl isocyanide) with Chiral Amines : A Dynamic Conformational Transition of Poly (phenyl isocyanide) Derivatives"J. Am. Chem. Soc.. 124. 7448-7458 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Nishimura, K.Takatani, S.-I.Sakurai, K.Maeda, E.Yashima: "A Helical Array of Pendant Fullerenes of an Optically Active Polyphenylacetylene"Angew. Chem., Int. Ed.. 41. 3602-3604 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] R.Nonokawa, E.Yashima: "Detection and Amplification of a Small Enantiomeric Imbalance in α-Amino Acids by a Helical Poly (phenylacetylene) with Crown Ether Pendants"J. Am. Chem. Soc.. 125. 1278-1283 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Masayoshi Ishikawa, Katsuhiro Maeda, Yuuki Mitsutsuji, Eiji Yashima: "An Unprecedented Memory of Macromolecular Hilicity Induced in an Achiral Polyisocyanide in Water"J. Am. Chem. Soc.. 126. 732-733 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Katsuhiro Maeda, Kazuhide Morino, Yoshio Okamoto, Takahiro Sato, Eiji Yashima: "Studies on the Mechanism of Helix Induction on a Poly ((4-carboxyphenyl) acetylene) with Chiral Amines and on the Memory of the Macromolecular Helicity Assisted by Interaction with Achiral Amines"J. Am. Chem. Soc.. 126. 4329-4342 (2004)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2005-04-19  

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