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Probing the causes of thermal hysteresis using tunable Nagg micelles with linear and brush-like thermoresponsive coronas
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Blackman, Lewis D., Gibson, Matthew I. and O'Reilly, Rachel K. (2016) Probing the causes of thermal hysteresis using tunable Nagg micelles with linear and brush-like thermoresponsive coronas. Polymer Chemistry, 8 . pp. 233-243. doi:10.1039/C6PY01191H ISSN 1759-9954.
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Official URL: http://dx.doi.org/10.1039/C6PY01191H
Abstract
Self-assembled thermoresponsive polymers in aqueous solution have great potential as smart, switchable materials for use in biomedical applications. In recent years, attention has turned to the reversibility of these polymers’ thermal transitions, which has led to debate over what factors influence discrepancies in the transition temperature when heating the system compared to the temperature obtained when cooling the system, known as the thermal hysteresis. Herein, we synthesize micelles with tunable aggregation numbers (Nagg) whose cores contain poly(n-butyl acrylate-co-N,N-dimethylacrylamide) (p(nBA-co-DMA)) and four different thermoresponsive corona blocks, namely poly(N-isopropylacrylamide) (pNIPAM), poly(N,N-diethylacrylamide) (pDEAm), poly(diethylene glycol monomethyl ether methacrylate) (pDEGMA) and poly(oligo(ethylene glycol) monomethyl ether methacrylate) (pOEGMA). By studying their thermoresponsive behavior, we elucidate the effects of changing numerous important characteristics both in the thermoresponsive chain chemistry and architecture, and in the structure of their self-assemblies. Our findings demonstrate large deviations in the reversibility between the self-assemblies and the corresponding thermoresponsive homopolymers; specifically we find that micelles whose corona consist of polymers with a brush-like architecture (pDEGMA and pOEGMA) exhibit irreversible phase transitions at a critical chain density. These results lead to a deeper understanding of stimuli-responsive self-assemblies and demonstrate the potential of tunable Nagg micelles for uncovering structure–property relationships in responsive polymer systems.
Item Type: | Journal Article | ||||||||||
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Subjects: | Q Science > QD Chemistry | ||||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry Faculty of Science, Engineering and Medicine > Medicine > Warwick Medical School |
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Library of Congress Subject Headings (LCSH): | Self-assembly (Chemistry), Thermoresponsive polymers, Hysteresis, Biomedical materials, Micelles | ||||||||||
Journal or Publication Title: | Polymer Chemistry | ||||||||||
Publisher: | Royal Society of Chemistry | ||||||||||
ISSN: | 1759-9954 | ||||||||||
Official Date: | 9 January 2016 | ||||||||||
Dates: |
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Volume: | 8 | ||||||||||
Page Range: | pp. 233-243 | ||||||||||
DOI: | 10.1039/C6PY01191H | ||||||||||
Status: | Peer Reviewed | ||||||||||
Publication Status: | Published | ||||||||||
Access rights to Published version: | Open Access (Creative Commons) | ||||||||||
Date of first compliant deposit: | 5 September 2016 | ||||||||||
Date of first compliant Open Access: | 23 February 2017 | ||||||||||
RIOXX Funder/Project Grant: |
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