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Monodisperse cylindrical micelles by crystallization-driven living self-assembly

Nature Chemistry volume 2, pages 566–570 (2010)Cite this article

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Abstract

Non-spherical nanostructures derived from soft matter and with uniform size—that is, monodisperse materials—are of particular utility and interest, but are very rare outside the biological domain. We report the controlled formation of highly monodisperse cylindrical block copolymer micelles (length dispersity ≤ 1.03; length range, ∼200 nm to 2 µm) by the use of very small (∼20 nm) uniform crystallite seeds that serve as initiators for the crystallization-driven living self-assembly of added block-copolymer unimers with a crystallizable, core-forming metalloblock. This process is analogous to the use of small initiator molecules in classical living polymerization reactions. The length of the nanocylinders could be precisely controlled by variation of the unimer-to-crystallite seed ratio. Samples of the highly monodisperse nanocylinders of different lengths that are accessible using this approach have been shown to exhibit distinct liquid-crystalline alignment behaviour.

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Figure 1: Realization of monodisperse cylindrical micelles through bidirectional epitaxial growth from small, uniform, stub-like crystallites as initiators for the crystallization-driven living self-assembly of PFS block copolymers with a crystallizable, core-forming block.
Figure 2: Characterization of PFS28-b-PDMS560 cylindrical micelles before and after sonication.
Figure 3: The length of monodisperse cylindrical micelles grown from small, uniform PFS stub-like PFS-b-PDMS crystallites is linearly dependent on the amount of block copolymers added.
Figure 4: Electric field response of PFS-containing cylindrical micelles as a 50 mg ml−1 colloidal solution of 731 nm cylinders in decane as studied by SAXS.

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Acknowledgements

J.B.G. is grateful to the Natural Sciences and Engineering Research Council (NSERC) of Canada for a postdoctoral fellowship. T.G. is grateful to the Deutsche Forschungsgemeinschaft for a postdoctoral fellowship. I.M. thanks the European Union for a Marie Curie Chair, a Reintegration Grant and an Advanced Investigator Grant, and also the Royal Society for a Wolfson Research Merit Award. We also thank G. Guerin for helpful discussions. M.A.W. also thanks NSERC for financial support.

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Authors and Affiliations

  1. School of Chemistry, University of Bristol, Bristol, BS8 1TS, United Kingdom

    Joe B. Gilroy, Torben Gädt, George R. Whittell, Laurent Chabanne, John M. Mitchels & Ian Manners

  2. H. H. Wills Physics Laboratory, University of Bristol, Bristol, BS8 1TL, United Kingdom

    Robert M. Richardson

  3. Department of Chemistry, University of Toronto, Toronto, M5S 3H6, Ontario, Canada

    Mitchell A. Winnik

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Contributions

J.B.G. and T.G. share first authorship, and were primarily responsible for the experimental results, which included contributions from G.R.W., L.C. and J.M.M. R.M.R. collected and analysed the SAXS data. J.B.G., T.G., R.M.R., M.A.W. and I.M. were responsible for preparing the manuscript and all authors have agreed to the content of the manuscript.

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Correspondence to Robert M. Richardson, Mitchell A. Winnik or Ian Manners.

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Gilroy, J., Gädt, T., Whittell, G. et al. Monodisperse cylindrical micelles by crystallization-driven living self-assembly. Nature Chem 2, 566–570 (2010). https://doi.org/10.1038/nchem.664

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