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.

Pathway complexity in supramolecular polymerization

Nature volume 481, pages 492–496 (2012)Cite this article

Abstract

Self-assembly provides an attractive route to functional organic materials, with properties and hence performance depending sensitively on the organization of the molecular building blocks1,2,3,4,5. Molecular organization is a direct consequence of the pathways involved in the supramolecular assembly process, which is more amenable to detailed study when using one-dimensional systems. In the case of protein fibrils, formation and growth have been attributed to complex aggregation pathways6,7,8 that go beyond traditional concepts of homogeneous9,10,11 and secondary12,13,14 nucleation events. The self-assembly of synthetic supramolecular polymers has also been studied and even modulated15,16,17,18, but our quantitative understanding of the processes involved remains limited. Here we report time-resolved observations of the formation of supramolecular polymers from π-conjugated oligomers. Our kinetic experiments show the presence of a kinetically favoured metastable assembly that forms quickly but then transforms into the thermodynamically favoured form. Quantitative insight into the kinetic experiments was obtained from kinetic model calculations, which revealed two parallel and competing pathways leading to assemblies with opposite helicity. These insights prompt us to use a chiral tartaric acid as an auxiliary to change the thermodynamic preference of the assembly process19. We find that we can force aggregation completely down the kinetically favoured pathway so that, on removal of the auxiliary, we obtain only metastable assemblies.

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

Relevant articles

Open Access articles citing this article.

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Learn more

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

Figure 1: Pathway complexity in supramolecular polymerization of SOPV.
Figure 2: Experiments under kinetic control.
Figure 3: Analysis aggregation pathway competition with kinetic model.
Figure 4: Controlled formation of exclusively metastable aggregates via a two-step non-covalent synthetic methodology.

References

  1. Yamamoto, Y. et al. Photoconductive coaxial nanotubes of molecularly connected electron donor and acceptor layers. Science 314, 1761–1764 (2006)

    Article  ADS  CAS  Google Scholar 

  2. Percec, V. et al. Self-organization of supramolecular helical dendrimers into complex electronic materials. Nature 417, 384–387 (2002)

    Article  ADS  Google Scholar 

  3. Würthner, F. et al. Supramolecular p–n-heterojunctions by co-self-organization of oligo(p-phenylene vinylene) and perylene bisimide dyes. J. Am. Chem. Soc. 126, 10611–10618 (2004)

    Article  Google Scholar 

  4. Capito, R. M., Azevedo, H. S., Velichko, Y. S., Mata, A. & Stupp, S. I. Self-assembly of large and small molecules into hierarchically ordered sacs and membranes. Science 319, 1812–1816 (2008)

    Article  ADS  CAS  Google Scholar 

  5. Dankers, P. Y. W., Harmsen, M. C., Brouwer, L. A., Van Luyn, M. J. A. & Meijer, E. W. A modular and supramolecular approach to bioactive scaffolds for tissue engineering. Nature Mater. 4, 568–574 (2005)

    Article  ADS  CAS  Google Scholar 

  6. Powers, E. T. & Powers, D. L. Mechanisms of protein fibril formation: nucleated polymerization with competing off-pathway aggregation. Biophys. J. 94, 379–391 (2008)

    Article  ADS  CAS  Google Scholar 

  7. Baskakov, I. V., Legname, G., Baldwin, M. A., Prusiner, S. B. & Cohen, F. E. Pathway complexity of prion protein assembly into amyloid. J. Biol. Chem. 277, 21140–21148 (2002)

    Article  CAS  Google Scholar 

  8. Mulder, A. M. et al. Visualizing ribosome biogenesis: parallel assembly pathways for the 30S subunit. Science 330, 673–677 (2010)

    Article  ADS  CAS  Google Scholar 

  9. Ferrone, F. A. Analysis of protein aggregation kinetics. Methods Enzymol. 309, 256–274 (1999)

    Article  CAS  Google Scholar 

  10. Oosawa, F. & Kasai, M. A theory of linear and helical aggregations of macromolecules. J. Mol. Biol. 4, 10–21 (1962)

    Article  CAS  Google Scholar 

  11. Powers, E. T. & Powers, D. L. The kinetics of nucleated polymerizations at high concentrations: amyloid fibril formation near and above the “supercritical concentration”. Biophys. J. 91, 122–132 (2006)

    Article  ADS  CAS  Google Scholar 

  12. Bishop, M. F. & Ferrone, F. A. Kinetics of nucleation-controlled polymerization. Biophys. J. 46, 631–644 (1984)

    Article  ADS  CAS  Google Scholar 

  13. Xue, W.-F. Homans, S. W. & Radford, S. E. Systematic analysis of nucleation-dependent polymerization reveals new insights into the mechanism of amyloid self-assembly. Proc. Natl Acad. Sci. USA 105, 8926–8931 (2008)

    Article  ADS  CAS  Google Scholar 

  14. Knowles, T. P. J. et al. An analytical solution to the kinetics of breakable filament assembly. Science 326, 1533–1537 (2009)

    Article  ADS  CAS  Google Scholar 

  15. De. Greef, T. F. A. et al. Supramolecular polymerization. Chem. Rev. 109, 5687–5754 (2009)

    Article  CAS  Google Scholar 

  16. Cui, H. Chen, Z. Zhong, S., Wooley, K. L. & Pochan, D. J. Block copolymer assembly via kinetic control. Science 317, 647–650 (2007)

    Article  ADS  CAS  Google Scholar 

  17. Lund, R. et al. Structural observation and kinetic pathway in the formation of polymeric micelles. Phys. Rev. Lett. 102, 188301 (2009)

    Article  ADS  Google Scholar 

  18. Pasternack, R. F. et al. A nonconventional approach to supramolecular formation dynamics. the kinetics of assembly of DNA-bound porphyrins. J. Am. Chem. Soc. 120, 5873–5878 (1998)

    Article  CAS  Google Scholar 

  19. George, S. J. et al. Helicity induction and amplification in an oligo(p-phenylenevinylene) assembly through hydrogen-bonded chiral acids. Angew. Chem. Int. Edn Engl. 46, 8206–8211 (2007)

    Article  CAS  Google Scholar 

  20. Hoeben, F. J. M. Jonkheijm, P. Meijer, E. W. & Schenning, A. P. H. J. About supramolecular assemblies of π-conjugated systems. Chem. Rev. 105, 1491–1546 (2005)

    Article  CAS  Google Scholar 

  21. 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  ADS  CAS  Google Scholar 

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

    Article  ADS  CAS  Google Scholar 

  23. Pashuck, E. T. & Stupp, S. I. Direct observation of morphological transformation from twisted ribbons into helical ribbons. J. Am. Chem. Soc. 132, 8819–8821 (2010)

    Article  CAS  Google Scholar 

  24. Lohr, A. & Würthner, F. Evolution of homochiral helical dye assemblies: involvement of autocatalysis in the “majority-rules” effect. Angew. Chem. Int. Edn Engl. 47, 1232–1236 (2008)

    Article  CAS  Google Scholar 

  25. Wolffs, M. et al. The role of heterogeneous nucleation in the self-assembly of oligothiophenes. Chem. Commun. 4613–4615. (2008)

  26. Ajayaghosh, A. Varghese, R. Praveen, V. K. & Mahesh, S. Evolution of nano- to microsized spherical assemblies of a short oligo(p-phenylene-ethynylene) into superstructured organogels. Angew. Chem. Int. Edn Engl. 45, 3261–3264 (2006)

    Article  CAS  Google Scholar 

  27. Jonkheijm, P. et al. Transfer of π-conjugated columnar stacks from solution to surfaces. J. Am. Chem. Soc. 125, 15941–15949 (2003)

    Article  CAS  Google Scholar 

  28. Xue, W.-F., Homans, S. W. & Radford, S. E. Systematic analysis of nucleation-dependent polymerization reveals new insights into the mechanism of amyloid self-assembly. Proc. Natl Acad. Sci. USA 105, 8926–8931 (2008)

    Article  ADS  CAS  Google Scholar 

Download references

Acknowledgements

We thank Ž. Tomović for providing the SOPV. We are grateful to R. M. Kellogg (Syncom, Groningen, The Netherlands) for providing the tartaric acid derivate. We also thank H. W. H. van Roekel and R. de Bruijn for discussions. Artwork was provided by K. Pieterse. The research leading to these results has received funding from the European Research Council under the European Union’s Seventh Framework Programme (FP/2007-2013)/ERC grant agreement number 246829, and from the Netherlands Organization for Scientific Research.

Author information

Authors and Affiliations

  1. Institute for Complex Molecular Systems, Eindhoven University of Technology, PO Box 513, 5600 MB, Eindhoven, The Netherlands ,

    Peter A. Korevaar, Albert J. Markvoort, Maarten M. J. Smulders, Peter A. J. Hilbers, Tom F. A. De Greef & E. W. Meijer

  2. Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, PO Box 513, 5600 MB, Eindhoven, The Netherlands ,

    Peter A. Korevaar, Subi J. George, Maarten M. J. Smulders, Albert P. H. J. Schenning, Tom F. A. De Greef & E. W. Meijer

  3. Biomodeling and Bioinformatics Group, Eindhoven University of Technology, PO Box 513, 5600 MB, Eindhoven, The Netherlands ,

    Albert J. Markvoort, Peter A. J. Hilbers & Tom F. A. De Greef

Authors
  1. Peter A. Korevaar
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Subi J. George
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Albert J. Markvoort
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Maarten M. J. Smulders
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Peter A. J. Hilbers
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Albert P. H. J. Schenning
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Tom F. A. De Greef
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. E. W. Meijer
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

P.A.K. and M.M.J.S. performed the stopped-flow experiments. P.A.K., A.J.M. and T.F.A.D.G. analysed the data and developed the kinetic model. S.J.G. performed the experiments with DTA and SOPV. E.W.M., T.F.A.D.G., A.P.H.J.S. and P.A.J.H. supervised the research. P.A.K., T.F.A.D.G. and E.W.M. wrote the manuscript. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Tom F. A. De Greef or E. W. Meijer.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

The file contains Supplementary Figures 1-13 with legends, Supplementary Discussions 1-3 with Supplementary Data and additional references. (PDF 4092 kb)

PowerPoint slides

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Korevaar, P., George, S., Markvoort, A. et al. Pathway complexity in supramolecular polymerization. Nature 481, 492–496 (2012). https://doi.org/10.1038/nature10720

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature10720

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