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Scalable and uniform 1D nanoparticles by synchronous polymerization, crystallization and self-assembly

Nature Chemistry volume 9, pages 785–792 (2017)Cite this article

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Abstract

The preparation of well-defined nanoparticles based on soft matter, using solution-processing techniques on a commercially viable scale, is a major challenge of widespread importance. Self-assembly of block copolymers in solvents that selectively solvate one of the segments provides a promising route to core-corona nanoparticles (micelles) with a wide range of potential uses. Nevertheless, significant limitations to this approach also exist. For example, the solution processing of block copolymers generally follows a separate synthesis step and is normally performed at high dilution. Moreover, non-spherical micelles—which are promising for many applications—are generally difficult to access, samples are polydisperse and precise dimensional control is not possible. Here we demonstrate the formation of platelet and cylindrical micelles at concentrations up to 25% solids via a one-pot approach—starting from monomers—that combines polymerization-induced and crystallization-driven self-assembly. We also show that performing the procedure in the presence of small seed micelles allows the scalable formation of low dispersity samples of cylindrical micelles of controlled length up to three micrometres.

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Figure 1: Schematic representations of the preparation of polydisperse PIP-b-PFDMS cylindrical micelles.
Figure 2: PI-CDSA (at 10% w/w solids) of PIP-b-PFDMS at 10% v/v THF/n-hexanes with varying block ratios.
Figure 3: PI-CDSA (at 25% w/w solids) of PIP-b-PFDMS with a block ratio of 4.5:1.0 in 20% v/v THF/n-hexanes.
Figure 4: Living PI-CDSA (at 10% w/w solids) of PIP-b-PFDMS with a block ratio of approximately 5.3:1 in 10% v/v THF/n-hexanes.
Figure 5: AFM images of PIP-b-PFDMS cylindrical micelles (Ln = 560 nm, PDI = 1.04) prepared at 10% w/w solids by living PI-CDSA in 10% v/v THF/n-hexanes.

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Acknowledgements

C.E.B. thanks the Bristol Chemical Synthesis Centre for Doctoral Training, funded by the Engineering and Physical Sciences Research Council (EPSRC) for a PhD studentship. J.G. thanks the EPSRC for funding. D.W.H. thanks the EPSRC-funded Bristol Centre for Functional Nanomaterials doctoral training grant (EP/G036780/1).

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  1. Charlotte E. Boott and Jessica Gwyther: These authors contributed equally to this work

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

    Charlotte E. Boott, Jessica Gwyther, Robert L. Harniman, Dominic W. Hayward & Ian Manners

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Contributions

C.E.B. and J.G. contributed equally to this work. C.E.B. and J.G. devised the project and carried out the experiments. R.L.H performed AFM experiments. D.W.H. performed the scattering experiments. C.E.B., J.G. and I.M. wrote the manuscript with input from D.W.H. The project was supervised by I.M.

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Correspondence to Ian Manners.

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Boott, C., Gwyther, J., Harniman, R. et al. Scalable and uniform 1D nanoparticles by synchronous polymerization, crystallization and self-assembly. Nature Chem 9, 785–792 (2017). https://doi.org/10.1038/nchem.2721

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