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Memory of macromolecular helicity assisted by interaction with achiral small molecules

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Abstract

The helicity of biological macromolecules such as DNA and proteins is largely governed by the homochirality of their components (D-sugars and L-amino acids). In polymer and supramolecular chemistry, control of helicity is an attractive goal because of possible applications in materials science, chemical sensing and enantioselective catalysis1,2,3,4,5,6,7,8,9,10,11,12,13. We reported recently that macromolecular helicity can be induced in a polymer by an optically active amine14. Here we show that this helicity can be ‘memorized’ when the amine is replaced by various achiral amines. Although the maintenance of helicity in the polymer is not perfect, it can ‘repair’ itself over time. Small structural changes in the achiral amines influence the efficiency of helicity retention markedly.

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Figure 1: Schematic illustration of induced one-handed helicity in poly-1, and the memory of macromolecular helicity.
Figure 2: Changes of the CD spectra of poly-1 with amines.
Figure 3: The memory of the macromolecular helicity of poly-1 with various amines.

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References

  1. Lehn, J. M. Supramolecular Chemistry(VCH, Weinheim, (1995).

    Book  Google Scholar 

  2. Constable, E. C. Oligopyridines as helicating ligands. Tetrahedron 46, 10013–10059 (1992).

    Article  Google Scholar 

  3. Amabilino, D. B. & Stoddart, J. F. Interlocked and intertwined structures and superstructures. Chem. Rev. 95, 2725–2828 (1995).

    Article  CAS  Google Scholar 

  4. Piguet, C., Bernardinelli, G. & Hopfgartner, G. Helicates as versatile supramolecular complexes. Chem. Rev. 97, 2005–2062 (1997).

    Article  CAS  Google Scholar 

  5. Okamoto, Y. & Nakano, T. Asymmetric polymerization. Chem. Rev. 94, 349–372 (1994).

    Article  CAS  Google Scholar 

  6. Nolte, R. J. M. Helical poly(isocyanides). Chem. Soc. Rev. 23, 11–19 (1994).

    Article  CAS  Google Scholar 

  7. Green, M. M.et al. Ahelical polymer with a cooperative response to chiral information. Science 268, 1860–1866 (1995).

    Article  ADS  CAS  Google Scholar 

  8. Rowan, A. E. & Nolte, R. J. M. Helical molecular programing. Angew. Chem. Int. Edn. 37, 703–706 (1998).

    Article  Google Scholar 

  9. Schlitzer, D. S. & Novak, B. M. Trapped kinetic states, chiral amplification and molecular chaperoning in synthetic polymers: chiral induction in polyguanidines through ion pair interactions. J. Am. Chem. Soc. 120, 2196–2197 (1998).

    Article  CAS  Google Scholar 

  10. Ruokolainen, J.et al. Switching supramolecular polymeric materials with multiple length scales. Science 280, 557–560 (1998).

    Article  ADS  CAS  Google Scholar 

  11. Tsukruk, V. V. Assembly of supramolecular polymers in ultrathin films. Prog. Polym. Sci. 22, 247–311 (1997).

    Article  CAS  Google Scholar 

  12. Pu, L. The study of chiral conjugated polymers. Acta Polym. 48, 116–141 (1997).

    Article  CAS  Google Scholar 

  13. Okamoto, Y. & Yashima, E. Polysaccharide derivatives for chromatographic separation of enantiomers. Angew. Chem. Int. Edn. 37, 1020–1043 (1998).

    Article  Google Scholar 

  14. Yashima, E., Matsushima, T. & Okamoto, Y. Chirality assignment of amines and amino alcohols based on circular dichroism induced by helix formation of a stereoregular poly(4-carboxyphenylacetylene) through acid-base complexation. J. Am. Chem. Soc. 119, 6345–6359 (1997).

    Article  CAS  Google Scholar 

  15. Lindsey, J. S. Self-assembly in synthetic routes to molecular devices. Biological principles and chemical perspectives: a review. New J. Chem. 15, 153–180 (1991).

    CAS  Google Scholar 

  16. Harada, N. & Nakanishi, K. Circular Dichroic Spectroscopy—Exciton Coupling in Organic Stereochemistry(University Science Books, Mill Valley, CA, (1983).

    Google Scholar 

  17. Manabe, K., Okamura, K., Date, T. & Koga, K. Effects of ion-pair structure on relative basicity in chloroform: acid-base equilibria controlled by steric repulsion, π-stacking interactions, and hydrogen bonding within an ion pair. J. Am. Chem. Soc. 115, 5324–5325 (1993).

    Article  CAS  Google Scholar 

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Acknowledgements

We thank Y. Maeda for his preliminary experimental support. We thank T. Sato, K.Akiyoshi and T. Aida for discussions. This work was supported in part by Grant-in-Aid for Scientific Research from the Ministry of Education, Science, Sports, and Culture, Japan.

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Authors and Affiliations

  1. Form and Function, Precursory Research for Embryonic Science and Technology, Japan Science and Technology Corporation, Chikusa-ku, 464-8603, Nagoya, Japan

    Eiji Yashima

  2. Department of Molecular Design and Engineering, Chikusa-ku, 464-8603, Nagoya, Japan

    Eiji Yashima & Katsuhiro Maeda

  3. Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, 464-8603, Nagoya, Japan

    Yoshio Okamoto

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  1. Eiji Yashima
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  2. Katsuhiro Maeda
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  3. Yoshio Okamoto
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Correspondence to Eiji Yashima.

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Yashima, E., Maeda, K. & Okamoto, Y. Memory of macromolecular helicity assisted by interaction with achiral small molecules. Nature 399, 449–451 (1999). https://doi.org/10.1038/20900

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