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Tailored hierarchical micelle architectures using living crystallization-driven self-assembly in two dimensions

Nature Chemistry volume 6, pages 893–898 (2014)Cite this article

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Abstract

Recent advances in the self-assembly of block copolymers have enabled the precise fabrication of hierarchical nanostructures using low-cost solution-phase protocols. However, the preparation of well-defined and complex planar nanostructures in which the size is controlled in two dimensions (2D) has remained a challenge. Using a series of platelet-forming block copolymers, we have demonstrated through quantitative experiments that the living crystallization-driven self-assembly (CDSA) approach can be extended to growth in 2D. We used 2D CDSA to prepare uniform lenticular platelet micelles of controlled size and to construct precisely concentric lenticular micelles composed of spatially distinct functional regions, as well as complex structures analogous to nanoscale single- and double-headed arrows and spears. These methods represent a route to hierarchical nanostructures that can be tailored in 2D, with potential applications as diverse as liquid crystals, diagnostic technology and composite reinforcement.

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Figure 1: Uniform lenticular platelet micelles of controlled area by CDSA in 2D.
Figure 2: Growth of concentric lenticular block co-micelles in 2D.
Figure 3: Platelet growth from cylindrical initiators.
Figure 4: Growth of double-headed spear-like micelles.
Figure 5: Non-centrosymmetric single-headed spear-like micelles.

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Acknowledgements

Z.M.H. and P.A.R. are grateful to the European Union (EU) for Marie Curie Postdoctoral Fellowships. C.E.B. thanks the Bristol Chemical Synthesis Centre for Doctoral Training, funded by the Engineering and Physical Sciences Research Council, for a PhD studentship. M.E.R. thanks the EU for support. M.A.W. thanks the Natural Sciences and Engineering Research Council of Canada for financial support. I.M. thanks the EU for a European Research Council Advanced Investigator Grant. Correspondence and requests for materials should be addressed to M.A.W. (mwinnik@chem.utoronto.ca) or I.M. (ian.manners@bristol.ac.uk). We also thank the Wolfson Bioimaging Facility at the University of Bristol for the use of confocal microscopy facilities, and Prof. A.P. Davis for the use of a fluorescence spectrometer.

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Author notes

  1. Paul A. Rupar

    Present address: Present address: Department of Chemistry, University of Alabama, Tuscaloosa, Alabama 35487, USA,

  2. Zachary M. Hudson and Charlotte E. Boott: These authors contributed equally to this work

Authors and Affiliations

  1. School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, UK

    Zachary M. Hudson, Charlotte E. Boott, Matthew E. Robinson, Paul A. Rupar & Ian Manners

  2. Department of Chemistry, University of Toronto, 80 George Street, Toronto, M5S 3H6, Canada

    Mitchell A. Winnik

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Contributions

Z.M.H., P.A.R. and I.M devised the project. Z.M.H, C.E.B., M.E.R. and P.A.R. carried out the experiments. Z.M.H., C.E.B. and I.M. wrote the manuscript with input from M.A.W. The project was supervised by I.M. with input from M.A.W.

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Correspondence to Mitchell A. Winnik or Ian Manners.

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Hudson, Z., Boott, C., Robinson, M. et al. Tailored hierarchical micelle architectures using living crystallization-driven self-assembly in two dimensions. Nature Chem 6, 893–898 (2014). https://doi.org/10.1038/nchem.2038

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