Use this URL to cite or link to this record in EThOS: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.629112
Title: Bromo and thio maleimides for functionalisation and fluorescent labelling of polymers and polymer nanoparticles
Author: Robin, Mathew P.
ISNI:       0000 0004 5348 2664
Awarding Body: University of Warwick
Current Institution: University of Warwick
Date of Award: 2014
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Abstract:
This thesis explores the use of bromo and thio maleimide functional groups in polymer chemistry. The reactivity of bromomaleimide groups towards thiols is exploited as a new and efficient post-polymerisation modification reaction, while the fluorescence of the dithiomaleimide (DTM) products is utilised for labelling of polymers and polymer nanoparticles. Chapter 1 gives an introduction to ways in which control over free radical polymerisation can be achieved using reversible-deactivation mechanisms. The incorporation of functionality into polymers, and the synthesis of polymer nanoparticles is also discussed, leading to a review of the different strategies for fabrication of fluorescent polymer nanoparticles. In Chapter 2 novel reversible addition-fragmentation chain transfer (RAFT) agents are developed with the aim of introducing monobromomaleimide (MBM) or dibromomaleimide (DBM) as a polymer end-group via RAFT. In Chapter 3 the fluorescent properties of the DTM group are first explored, then a novel RAFT agent/ring-opening polymerisation initiator is used for site-specific introduction of DTM fluorophores into linear polymers. Site-specific introduction of DTM groups by post-polymerisation functionalisation reaction of DBM-terminated polymers (synthesised in Chapter 2) with thiols is also developed. In Chapter 4 novel DTM and DBM-functional vinyl monomers are synthesised, and their RAFT polymerisation with non-functional comonomers is used to incorporate DTM and DBM functionality along polymer backbones. Post-polymerisation functionalisation of these DBM-functional polymers with thiols is also demonstrated. In Chapter 5 fluorescently-labelled polymer nanoparticles containing DTM fluorophores are synthesised, using the DTM-functional RAFT agent developed in Chapter 3, and DTM-functional monomers developed in Chapter 4. Nanoparticles are fabricated by block copolymer self-assembly and emulsion polymerisation. These fluorescent nanoparticles are analysed by steady-state and time-resolved fluorescence spectroscopy to assess their utility as contrast agents. Chapter 6 summarises RAFT polymerisation data from Chapters 2, 3 and 4 to assess the extent to which the DBM and DTM groups interfere in RAFT polymerisation, and the mechanism by which this may occur.
Supervisor: Not available Sponsor: Engineering and Physical Sciences Research Council
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID: uk.bl.ethos.629112  DOI: Not available
Keywords: QD Chemistry
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