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Effect of micellization on the thermoresponsive behavior of polymeric assemblies

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Blackman, Lewis D., Wright, Daniel Bayham, Robin, Mathew P., Gibson, Matthew I. and O’Reilly, Rachel K. (2015) Effect of micellization on the thermoresponsive behavior of polymeric assemblies. ACS Macro Letters, 4 (11). pp. 1210-1214. doi:10.1021/acsmacrolett.5b00551

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Official URL: http://dx.doi.org/10.1021/acsmacrolett.5b00551

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Abstract

The chain density of polymer micelles, dictated by their aggregation number (Nagg), is an often overlooked parameter that governs the macroscopic behavior of responsive assemblies. Using a combination of variable-temperature light scattering, turbidimetry, and microcalorimetry experiments, the cloud point and thermal collapse of micellar poly(N-isopropylacrylamide) (pNIPAM) corona chains at lower temperatures than the cloud point were found to be largely independent of the micelle’s Nagg. By controlling the core composition, the degree of hysteresis associated with the thermal transition was found to increase as a function of core hydrophobicity. We performed this study on well-characterized micelles with tunable Nagg values, composed of a thermoresponsive corona (pNIPAM) and a nonresponsive core block poly(n-butyl acrylate-co-N,N-dimethylacrylamide) (p(nBA-co-DMA)), which were synthesized using reversible addition–fragmentation chain transfer (RAFT) polymerization. This allowed for a distinction to be made between thermoresponsive behavior at both the molecular and macroscopic level. The study of the subtle differences between these behaviors was made possible using a combination of complementary techniques. These results highlight the critical need for consideration of the effect that self-assembly plays on the responsive behavior of polymer chains when compared with free unimers in solution.

Item Type: Journal Article
Divisions: Faculty of Science > Chemistry
Journal or Publication Title: ACS Macro Letters
Publisher: American Chemical Society
ISSN: 2161-1653
Official Date: 19 October 2015
Dates:
DateEvent
19 October 2015Published
12 October 2015Accepted
6 August 2015Submitted
Volume: 4
Number: 11
Page Range: pp. 1210-1214
DOI: 10.1021/acsmacrolett.5b00551
Status: Peer Reviewed
Publication Status: Published
Access rights to Published version: Restricted or Subscription Access

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