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Complementary light scattering and synchrotron small-angle X-ray scattering studies of the micelle-to-unimer transition of polysulfobetaines

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Doncom, Kay E. B., Pitto-Barry, Anaïs, Willcock, Helen, Lu, Annhelen, McKenzie, Beulah E., Kirby, Nigel and O'Reilly, Rachel K. (2015) Complementary light scattering and synchrotron small-angle X-ray scattering studies of the micelle-to-unimer transition of polysulfobetaines. Soft Matter, Volume 11 (Number 18). pp. 3666-3676. doi:10.1039/c5sm00602c ISSN 1744-683X.

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Official URL: http://dx.doi.org/10.1039/C5SM00602C

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Abstract

AB and ABA di- and triblock copolymers where A is the hydrophilic poly(oligoethylene glycol methacrylate) (POEGMA) block and B is a thermo-responsive sulfobetaine block [2-(methacryloyloxy) ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide (PDMAPS) were synthesised by aqueous RAFT polymerisation with narrow dispersity (ĐM ≤ 1.22), as judged by aqueous SEC analysis. The di- and triblock copolymers self-assembled in salt-free water to form micelles with a PDMAPS core and the self-assembly of these polymers was explored by SLS and TEM analysis. The micelles were shown, by DLS analysis, to undergo a micelle-to-unimer transition at a critical temperature, which was dependent upon the length of the POEGMA block. Increasing the length of the third, POEGMA, block decreased the temperature at which the micelle-to-unimer transition occurred as a result of the increased hydrophilicity of the polymer. The dissociation of the micelles was further studied by SLS and synchrotron SAXS. SAXS analysis revealed that the micelle dissociation began at temperatures below that indicated by DLS analysis and that both micelles and unimers coexist. This highlights the importance of using multiple complementary techniques in the analysis of self-assembled structures. In addition the micelle-to-unimer morphology transition was employed to encapsulate and release a hydrophobic dye, Nile Red, as shown by fluorescence spectroscopy.

Item Type: Journal Article
Subjects: Q Science > QD Chemistry
Divisions: Faculty of Science, Engineering and Medicine > Science > Chemistry
Library of Congress Subject Headings (LCSH): Soft condensed matter, Polymers, Small-angle x-ray scattering, Synchrotrons, Micelles
Journal or Publication Title: Soft Matter
Publisher: Royal Society of Chemistry
ISSN: 1744-683X
Official Date: 19 March 2015
Dates:
DateEvent
19 March 2015Published
19 March 2015Accepted
12 March 2015Submitted
Volume: Volume 11
Number: Number 18
Page Range: pp. 3666-3676
DOI: 10.1039/c5sm00602c
Status: Peer Reviewed
Publication Status: Published
Access rights to Published version: Open Access (Creative Commons)
Date of first compliant deposit: 29 December 2015
Date of first compliant Open Access: 29 December 2015
Funder: Engineering and Physical Sciences Research Council (EPSRC), University of Warwick

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