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Crosslinked p(MMA) particles by RAFT emulsion polymerisation: tuning size and stability

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posted on 2022-07-19, 13:21 authored by Catherine J Marsden, Colum Breen, James Tinkler, Thomas Berki, Daniel W Lester, Jonathan Martinelli, Lorenzo Tei, Stephen ButlerStephen Butler, Helen WillcockHelen Willcock

The controlled synthesis of amphiphilic di-block copolymers allows a large array of nanostructures to be created, including block copolymer particles, which have proved valuable for biomedical applications. Despite progress in targeting specific block copolymer architectures, control over the size and stability of spherical particles is less well explored. Here, we report the use of RAFT emulsion polymerisation to synthesise a library of p(MMA) particles, crosslinked with ethylene glycol dimethacrylate and stabilised by brush-like poly(ethylene glycol)-based polymers. We successfully synthesised a range of block copolymer particles, offering stability up to p(MMA)1000, with DLS reporting stable particle diameters of 33-176 nm and PDI < 0.2. DLS and AFM studies showed a general increase in particle diameter with increasing amounts of p(MMA). The use of a PEG methacrylate monomer with a methyl ether end group resulted in more well defined and stable particles than those with hydroxyl end groups. The copolymerisation of a suitably functionalized Gd(III) complex into the shell of the spherical p(MMA) particles resulted in Gd-loaded particles that were investigated in detail by 1H NMR relaxometry, demonstrating that the Gd complex was successfully incorporated into the particles. This study will inform the synthesis of core-shell particles with optimised stability and targeted sizes, and show a simple method to incorporate a molecular sensor, generating a macromolecular imaging agent.

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Loughborough University

DTP 2018-19 Loughborough University

Engineering and Physical Sciences Research Council

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History

School

  • Aeronautical, Automotive, Chemical and Materials Engineering
  • Science

Department

  • Chemistry
  • Materials

Published in

Polymer Chemistry

Volume

13

Issue

28

Pages

4124 - 4135

Publisher

Royal Society of Chemistry (RSC)

Version

  • AM (Accepted Manuscript)

Rights holder

Journal is © The Royal Society of Chemistry

Publisher statement

This is an Open Access Article. It is published by Royal Society of Chemistry under the Creative Commons Attribution 3.0 Unported Licence (CC BY). Full details of this licence are available at: https://creativecommons.org/licenses/by/3.0/

Acceptance date

2022-05-25

Publication date

2022-06-01

Copyright date

2022

ISSN

1759-9954

eISSN

1759-9962

Language

  • en

Depositor

Dr Helen Willcock. Deposit date: 9 June 2022

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