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Helical self-assembled polymers from cooperative stacking of hydrogen-bonded pairs

Nature volume 407, pages 167170 (14 September 2000) | Download Citation

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Abstract

The double helix of DNA epitomizes this molecule's ability to self-assemble in aqueous solutions into a complex chiral structure using hydrogen bonding and hydrophobic interactions. Non-covalently interacting molecules in organic solvents are used to design systems that similarly form controlled architectures1,2,3,4,5,6,7. Peripheral chiral centres in assemblies8,9 and chiral side chains attached to a polymer backbone10,11 have been shown to induce chirality at the supramolecular level, and highly ordered structures stable in water are also known12,13,14,15. However, it remains difficult to rationally exploit non-covalent interactions for the formation of chiral assemblies that are stable in water, where solvent molecules can compete effectively for hydrogen bonds. Here we describe a general strategy for the design of functionalized monomer units and their association in either water or alkanes into non-covalently linked polymeric structures with controlled helicity and chain length. The monomers consist of bifunctionalized ureidotriazine units connected by a spacer and carrying solubilizing chains at the periphery. This design allows for dimerization through self-complementary quadruple hydrogen bonding between the units and solvophobically induced stacking of the dimers into columnar polymeric architectures, whose structure and helicity can be adjusted by tuning the nature of the solubilizing side chains.

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References

  1. 1.

    , & Molecular self-assembly and nanochemistry—A chemical strategy for the synthesis of nanostructures. Science 254, 1312–1319 ( 1991).

  2. 2.

    , & Electron-microscopic study of supramolecular liquid-crystalline polymers formed by molecular-recognition-directed self-assembly from complementary chiral components. Proc. Natl Acad. Sci. USA 90, 163–167 (1993).

  3. 3.

    et al. Reversible polymers formed from self-complementary monomers using quadruple hydrogen-bonding. Science 278, 1601–1604 (1997).

  4. 4.

    , & Polycaps—Reversibly formed polymeric capsules. Proc. Natl Acad. Sci. USA 94, 7132–7137 (1997).

  5. 5.

    Foldamers—a manifesto. Acc. Chem. Res. 31, 172–180 (1998).

  6. 6.

    et al. Beta-peptides - synthesis by Arndt-Eistert homologation with concomitant peptide coupling - structure determination by NMR and CD spectroscopy and by X-ray crystallography - helical secondary structure of a beta-hexapeptide in solution and its stability towards pepsin. Helv. Chim. Acta 79, 913–941 ( 1996).

  7. 7.

    , , & Solvophobically driven folding of nonbiological oligomers. Science 277, 1793–1796 ( 1997).

  8. 8.

    , , & Sergeants-and-soldiers principle in chiral columnar stacks of disc-shaped molecules with C3 symmetry. Angew. Chem. Int. Edn Engl. 36, 2648–2651 ( 1997).

  9. 9.

    , , , & Complete asymmetric induction of supramolecular chirality in a hydrogen-bonded assembly. Nature 398, 498–502 (1999).

  10. 10.

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

  11. 11.

    , , & Twist sense bias induced by chiral side chains in helically folded oligomers. Angew. Chem. Int. Edn Engl. 39, 228– 230 (2000).

  12. 12.

    et al. The self-recognition and self-assembly of folic-acid salts in isotropic water solution. Helv. Chim. Acta 79, 220–234 (1996).

  13. 13.

    , , & Formation of short, stable helices in aqueous solution by β-amino acid hexamers. J. Am. Chem. Soc. 121 , 2309–2310 (1999).

  14. 14.

    & Hydrophobic effects—opinions and facts. Angew. Chem. Int. Edn Engl 32, 1545–1579 (1993).

  15. 15.

    Synthetic bilayer-membranes—molecular design, self-organization, and application. Angew. Chem. Int. Edn Engl. 31, 709–726 (1992).

  16. 16.

    , , , & Self-complementarity achieved through quadruple hydrogen-bonding. Angew. Chem. Int. Edn Engl. 37, 75–78 ( 1998).

  17. 17.

    Chromonic liquid crystal phases. Curr. Opin. Colloid Interface Sci. 3, 458–466 ( 1998).

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Acknowledgements

We thank K. Pieterse for creation of the molecular cartoons; Laboratoire León Brillouin for providing the SANS beam time; and F. Boué for assistance. This work was supported by The National Research School Combination: Catalysis and the Dutch Science Foundation (NWO); we thank DSM Research for a grant.

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  1. Laboratory of Macromolecular and Organic Chemistry and Dutch Polymer Institute, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven, The Netherlands

    • J. H. K. Ky Hirschberg
    • , Luc Brunsveld
    • , Aissa Ramzi
    • , Jef A. J. M. Vekemans
    • , Rint P. Sijbesma
    •  & E. W. Meijer

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Correspondence to E. W. Meijer.

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https://doi.org/10.1038/35025027

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