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.

  • Article
  • Published:

The effect of isotopic substitution on the chirality of a self-assembled helix

Nature Chemistry volume 3, pages 42–46 (2011)Cite this article

Subjects

Abstract

N,N′,N″-trialkylbenzene-1,3,5-tricarboxamides (BTAs) self-assemble by means of strong, threefold α-helix-type intermolecular hydrogen bonding into well-defined, helical, one-dimensional columnar aggregates. When a stereogenic centre is introduced into the alkyl side chains of these BTAs, strong Cotton effects are observed in dilute apolar solutions, indicating the preference for one helical conformation over the other. Here, we report the creation of a helical sense preference in self-assembled BTAs by introducing deuterium/hydrogen isotope chirality into the alkyl side chains. We determine the relative stabilities of the left- and right-handed helical conformations of these deuterated supramolecular polymers by performing a conformational analysis. Our findings show that the results of deuterium/hydrogen substitution in BTA-based supramolecular polymers and helical polyisocyanates are very similar, although the formation mechanisms differ. The selectively deuterated BTAs discussed here represent the first example of supramolecular chirality resulting from isotope substitution.

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
Figure 2: Self-assembly behaviour of (S)-D-BTA (1a) in solution.
Figure 3: Amplification of chirality experiments for (S)-D-BTA (1a) and (R)-D-BTA (1b) at 20 °C, c = 5 × 10−5 M, in dodecane.
Figure 4: Formation mechanism of (S)-D-BTA (1a) aggregates in solution.

Similar content being viewed by others

References

  1. Green, M. M. et al. Chiral studies across the spectrum of polymer science. Acc. Chem. Res. 34, 672–680 (2001).

    Article  CAS  Google Scholar 

  2. Green, M. M. et al. The macromolecular route to chiral amplification. Angew. Chem. Int. Ed. 38, 3138–3154 (1999).

    Article  CAS  Google Scholar 

  3. Green, M. M., Andreola, C., Munoz, B. & Reidy, M. P. Macromolecular stereochemistry: a cooperative deuterium isotope effect leading to a large optical rotation. J. Am. Chem. Soc. 110, 4063–4065 (1988).

    Article  CAS  Google Scholar 

  4. Teramoto, A. Cooperative conformational transitions in linear macromolecules undergoing chiral perturbations. Prog. Polym. Sci. 26, 667–720 (2001).

    Article  CAS  Google Scholar 

  5. Tanaka, F. Theoretical study of helix induction on a polymer chain by hydrogen-bonding chiral molecules. Macromolecules 37, 605–613 (2004).

    Article  CAS  Google Scholar 

  6. Yashima, E., Maeda, K. Iida, H. Furusho, Y. & Nagai, K. Helical polymers: synthesis, structures and functions. Chem. Rev. 109, 6102–6211 (2009).

    Article  CAS  Google Scholar 

  7. Yashima, E., Maeda, K. & Okamoto, Y. Memory of macromolecular helicity assisted by interaction with achiral small molecules. Nature 399, 449–451 (1999).

    Article  CAS  Google Scholar 

  8. Palmans, A. R. A. & Meijer, E. W. Amplification of chirality in dynamic systems. Angew. Chem. Int. Ed. 46, 8948–8968 (2007).

    Article  CAS  Google Scholar 

  9. Stals, P. J. M., Smulders, M. M. J., Martin-Rapun, R., Palmans, A. R. A. & Meijer, E. W. Asymmetrically substituted benzene-1,3,5-tricarboxamides: self-assembly and odd–even effects in the solid state and in dilute solution. Chem. Eur. J. 15, 2071–2080 (2009).

    Article  CAS  Google Scholar 

  10. Brunsveld, L. et al. Chiral amplification in columns of self-assembled N,N′,N″-tris((S)-3,7-dimethyloctyl)benzene-1,3,5-tricarboxamide in dilute solution. Chem. Lett. 292–293 (2000).

  11. Smulders, M. M. J., Schenning, A. P. H. J. & Meijer, E. W. Insight into the mechanisms of cooperative self-assembly: the ‘sergeants-and-soldiers’ principle of chiral and achiral C3-symmetrical discotic triamides. J. Am. Chem. Soc. 130, 606–611 (2008).

    Article  CAS  Google Scholar 

  12. Palmans, A. R. A., Vekemans, J. A. J. M., Havinga, E. E. & Meijer, E. W. Sergeants-and-soldiers principle in chiral columnar stacks of disc-shaped molecules with C3 symmetry. Angew. Chem. Int. Ed. 36, 2648–2651 (1997).

    Article  CAS  Google Scholar 

  13. van Gestel, J., Palmans, A. R. A., Titulaer, B., Vekemans, J. A. J. M. & Meijer, E. W. ‘Majority-Rules’ operative in chiral columnar stacks of C3-symmetrical molecules. J. Am. Chem. Soc. 127, 5490–5494 (2005).

    Article  CAS  Google Scholar 

  14. Smulders, M. M. J. et al. Tuning the extent of chiral amplification by temperature in a dynamic supramolecular polymer. J. Am. Chem. Soc. 132, 611–619 (2010).

    Article  CAS  Google Scholar 

  15. Smulders, M. M. J. et al. Probing the limits of the majority-rules principle in a dynamic supramolecular polymer. J. Am. Chem. Soc. 132, 620–626 (2010).

    Article  CAS  Google Scholar 

  16. Smulders, M. M. J. et al. C 3-symmetrical self-assembled structures investigated by vibrational circular dichroism. Chirality 20, 1016–1022 (2008).

    Article  CAS  Google Scholar 

  17. Lifson, S., Andreola, C., Peterson, N. C. & Green, M. M. Macromolecular stereochemistry: Helical Sense Preference in optically active polyisocyanates. Amplification of a conformational equilibrium deuterium isotope effect. J. Am. Chem. Soc. 111, 8850–8858 (1989).

    Article  CAS  Google Scholar 

  18. Jonkheijm, P., Van der Schoot, P. Schenning, A. P. H. J. & Meijer, E. W. Probing the solvent-assisted nucleation pathway in chemical self-assembly. Science 313, 80–83 (2006).

    Article  CAS  Google Scholar 

  19. Green, M. M. & Reidy, M. P. Macromolecular stereochemistry: the out-of-proportion influence of optically active comonomers on the conformational characteristics of polyisocyanates. The sergeants and soldiers experiment. J. Am. Chem. Soc. 111, 6452–6454 (1989).

    Article  Google Scholar 

  20. Green, M. M., Garetz, B. A., Munoz, B. & Chang, H. Majority rules in the copolymerization of mirror image isomers. J. Am. Chem. Soc. 117, 4181–4182 (1995).

    Article  CAS  Google Scholar 

  21. van Gestel, J. Amplification of chirality in helical supramolecular polymers: the majority rules principle. Macromolecules 37, 3894–3898 (2004).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  23. Gu, H. et al. Molecular-weight dependence of the optical rotation of poly((R)-2-deuterio-n-hexyl isocyanate). Macromolecules 28, 1016–1024 (1995).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors thank M. M. L. Nieuwenhuizen and T. M. Hermans for assistance with 2D- and 2H-NMR, C. Duxbury and A. Heise from DSM Research for their support during the initial experiments, P. J. M. Stals for providing compounds 2 and 3 and M. M. Green for intriguing discussions. This work was supported by the NRSC-C foundation and the Netherlands Organization for Scientific Research (Spinoza-NWO).

Author information

Authors and Affiliations

  1. Institute for Complex Molecular Systems and Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven, The Netherlands

    Seda Cantekin, Diederik W. R. Balkenende, Maarten M. J. Smulders, Anja R. A. Palmans & E. W. Meijer

Authors
  1. Seda Cantekin
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Diederik W. R. Balkenende
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Maarten M. J. Smulders
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Anja R. A. Palmans
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. E. W. Meijer
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

S.C. performed the experimental work and wrote most of the manuscript. D.W.R.B. contributed to the synthesis of the materials and M.M.J.S. to data analysis. A.R.A.P. and E.W.M. conceived and designed the concepts. All authors contributed to the conception of the experiments and discussion of the results, and commented on the manuscript.

Corresponding authors

Correspondence to Anja R. A. Palmans or E. W. Meijer.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 1830 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Cantekin, S., Balkenende, D., Smulders, M. et al. The effect of isotopic substitution on the chirality of a self-assembled helix. Nature Chem 3, 42–46 (2011). https://doi.org/10.1038/nchem.889

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nchem.889

This article is cited by

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