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Biomimetic radical polymerization via cooperative assembly of segregating templates

Nature Chemistry volume 4, pages 491–497 (2012)Cite this article

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Abstract

Segregation and templating approaches have been honed by billions of years of evolution to direct many complex biological processes. Nature uses segregation to improve biochemical control by organizing reactants into defined, well-regulated environments, and the transfer of genetic information is a primary function of templating. The ribosome, wherein messenger RNA is translated into polypeptides, combines both techniques to allow for ideal biopolymer syntheses. Herein is presented a biomimetic segregation/templating approach to synthetic radical polymerization. Polymerization of a nucleobase-containing vinyl monomer in the presence of a complementary block copolymer template of low molecular weight yields high molecular weight (Mw up to ~400,000 g mol−1), extremely low polydispersity (≤1.08) daughter polymers. Control is attained by segregation of propagating radicals in discrete micelle cores (via cooperative assembly of dynamic template polymers). Significantly reduced bimolecular termination, combined with controlled propagation along a defined number of templates, ensures unprecedented control to afford well-defined high molecular weight polymers.

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Figure 1: Dynamic exchange and cooperative assembly of templates.
Figure 2: Microscopic characterization of micellar assemblies.
Figure 3: High MW daughter polymer and template.
Figure 4: Polymerization rate and MW versus conversion.

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Acknowledgements

The authors thank the University of Warwick and the Engineering and Physical Sciences Research Council (grant reference: EP/H019146/1) for funding. The authors also acknowledge the Precision Polymer Materials Research Networking Programme of the European Science Foundation for funding. Some items of equipment used in this research were funded by Birmingham Science City, with support from Advantage West Midlands, and part funded by the European Regional Development Fund. We thank the Wellcome Trust (grant reference 055663/Z/98/Z) for the electron microscopy facility at Warwick. We thank O. Colombani, C. Chassenieux and T. Nicolai (all at Université du Maine, Le Mans, France) and A.H. Lu (University of Warwick) for assistance and advice on light-scattering experiments. We thank T. Wilks (University of Warwick) for assistance with graphic illustrations and C. Hansell (University of Warwick) for assistance with proof-reading. We would also like to thank M. Jewett (Northwestern University), P. Booth (University of Bristol) and A. Ellington (University of Texas, Austin) for insightful scientific discussions.

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Authors and Affiliations

  1. Department of Chemistry, Library Road, University of Warwick, Coventry, CV4 7AL, UK

    Ronan McHale, Joseph P. Patterson & Rachel K. O'Reilly

  2. Centre for Advanced Macromolecular Design (CAMD), School of Chemical Engineering, University of New South Wales, Sydney, NSW 2052, Australia

    Per B. Zetterlund

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  1. Ronan McHale
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Contributions

R.M. designed and performed the experiments and wrote the paper. J.P.P. performed the microscopy (TEM and AFM) and DSC, assisted with SLS and some synthesis and P.B.Z. designed the experiments. R.K.O.R. conceived and obtained funding for the project, designed the experiments, oversaw the research and finalized the manuscript. All authors discussed the results and commented on the manuscript.

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Correspondence to Rachel K. O'Reilly.

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McHale, R., Patterson, J., Zetterlund, P. et al. Biomimetic radical polymerization via cooperative assembly of segregating templates. Nature Chem 4, 491–497 (2012). https://doi.org/10.1038/nchem.1331

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