PMID- 35614838 OWN - NLM STAT- PubMed-not-MEDLINE LR - 20220526 IS - 2161-1653 (Electronic) IS - 2161-1653 (Linking) VI - 4 IP - 11 DP - 2015 Nov 17 TI - Effect of Micellization on the Thermoresponsive Behavior of Polymeric Assemblies. PG - 1210-1214 LID - 10.1021/acsmacrolett.5b00551 [doi] AB - The chain density of polymer micelles, dictated by their aggregation number (N(agg)), 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 N(agg). 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 N(agg) 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. FAU - Blackman, Lewis D AU - Blackman LD AD - University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, U.K. FAU - Wright, Daniel B AU - Wright DB AD - University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, U.K. FAU - Robin, Mathew P AU - Robin MP AD - University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, U.K. FAU - Gibson, Matthew I AU - Gibson MI AD - University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, U.K. FAU - O'Reilly, Rachel K AU - O'Reilly RK AD - University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, U.K. LA - eng PT - Journal Article DEP - 20151019 PL - United States TA - ACS Macro Lett JT - ACS macro letters JID - 101574672 SB - IM EDAT- 2015/11/17 00:00 MHDA- 2015/11/17 00:01 CRDT- 2022/05/26 01:25 PHST- 2022/05/26 01:25 [entrez] PHST- 2015/11/17 00:00 [pubmed] PHST- 2015/11/17 00:01 [medline] AID - 10.1021/acsmacrolett.5b00551 [doi] PST - ppublish SO - ACS Macro Lett. 2015 Nov 17;4(11):1210-1214. doi: 10.1021/acsmacrolett.5b00551. Epub 2015 Oct 19.