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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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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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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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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DOI: https://doi.org/10.1038/nchem.664
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