Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

Memory of macromolecular helicity assisted by interaction with achiral small molecules

Nature volume 399, pages 449–451 (1999)Cite this article

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.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

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.

Similar content being viewed by others

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 

Download references

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.

Author information

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

Authors
  1. Eiji Yashima
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Katsuhiro Maeda
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yoshio Okamoto
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Eiji Yashima.

Rights and permissions

Reprints and permissions

About this article

Cite this article

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

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1038/20900

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing