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Cyclic graft copolymer unimolecular micelles : effects of cyclization on particle morphology and thermoresponsive behavior
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Williams, Rebecca J., Pitto-Barry, Anaïs, Kirby, Nigel, Dove, Andrew P. and O’Reilly, Rachel K. (2016) Cyclic graft copolymer unimolecular micelles : effects of cyclization on particle morphology and thermoresponsive behavior. Macromolecules, 49 (7). pp. 2802-2813. doi:10.1021/acs.macromol.5b02710
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Official URL: http://dx.doi.org/10.1021/acs.macromol.5b02710
Abstract
The synthesis of cyclic amphiphilic graft copolymers with a hydrophobic polycarbonate backbone and hydrophilic poly(N-acryloylmorpholine) (PNAM) side arms via a combination of ring-opening polymerization (ROP), cyclization via copper-catalyzed azide–alkyne cycloaddition (CuAAC), and reversible addition–fragmentation chain transfer (RAFT) polymerization is reported. The ability of these cyclic graft copolymers to form unimolecular micelles in water is explored using a combination of light scattering, small-angle X-ray scattering (SAXS), and cryogenic transmission electron microscopy (cryoTEM) analyses, where particle size was found to increase with increasing PNAM arm length. Further analysis revealed differences in the solution conformations, loading capabilities, and morphologies of the cyclic graft copolymers in comparison to equivalent linear graft copolymer unimolecular micelle analogues. Furthermore, the cyclic and linear graft copolymers were found to exhibit significantly different cloud point temperatures. This study highlights how subtle changes in polymer architecture (linear graft copolymer versus cyclic graft copolymer) can dramatically influence a polymer’s nanostructure and its properties.
| Item Type: | Journal Article | ||||||
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| Subjects: | Q Science > QD Chemistry Q Science > QH Natural history |
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| Divisions: | Faculty of Science > Chemistry | ||||||
| Library of Congress Subject Headings (LCSH): | Ring formation (Chemistry) , Chemical reactions, Morphology, Polymerization | ||||||
| Journal or Publication Title: | Macromolecules | ||||||
| Publisher: | American Chemical Society | ||||||
| ISSN: | 0024-9297 | ||||||
| Official Date: | 17 March 2016 | ||||||
| Dates: |
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| Date of first compliant deposit: | 23 June 2016 | ||||||
| Volume: | 49 | ||||||
| Number: | 7 | ||||||
| Page Range: | pp. 2802-2813 | ||||||
| DOI: | 10.1021/acs.macromol.5b02710 | ||||||
| Status: | Peer Reviewed | ||||||
| Publication Status: | Published | ||||||
| Access rights to Published version: | Restricted or Subscription Access | ||||||
| Funder: | Royal Society (Great Britain), Engineering and Physical Sciences Research Council (EPSRC), European Research Council (ERC) |
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