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Complementary light scattering and synchrotron small-angle X-ray scattering studies of the micelle-to-unimer transition of polysulfobetaines
journal contribution
posted on 2016-05-06, 11:25 authored by Kay E.B. Doncom, Anais Pitto-Barry, Helen WillcockHelen Willcock, Annhelen Lu, Beulah E. McKenzie, Nigel Kirby, Rachel K. O'ReillyAB 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.
Funding
The authors would like to thanks the EPSRC and the University of Warwick Postgraduate Research Scholarship for funding. The University of Warwick Research Development Fund and the Swiss National Science Foundation are also acknowledged for financial support.
History
School
- Aeronautical, Automotive, Chemical and Materials Engineering
Department
- Materials
Published in
Soft MatterVolume
11Issue
18Pages
3666 - 3676 (11)Citation
DONCOM, K.E.B. ... et al, 2015. Complementary light scattering and synchrotron small-angle X-ray scattering studies of the micelle-to-unimer transition of polysulfobetaines. Soft Matter, 11 (18), pp. 3666 - 3676.Publisher
Royal Society of ChemistryVersion
- VoR (Version of Record)
Publisher statement
This work is made available according to the conditions of the Creative Commons Attribution 3.0 Unported (CC BY 3.0) licence. Full details of this licence are available at: http://creativecommons.org/licenses/by/3.0/Acceptance date
2015-03-19Publication date
2015Notes
This is an Open Access article published by the Royal Society of Chemistry and licensed under the terms of the Creative Commons Attribution 3.0 Licence, http://creativecommons.org/licenses/by/3.0/ISSN
1744-6848Publisher version
Language
- en