Effect of micellization on the thermoresponsive behavior of polymeric assemblies

Research output: Contribution to journalLetterpeer-review

Standard

Effect of micellization on the thermoresponsive behavior of polymeric assemblies. / Blackman, Lewis D.; Wright, Daniel B.; Robin, Mathew P.; Gibson, Matthew I.; O'Reilly, Rachel K.

In: ACS Macro Letters, Vol. 4, No. 11, 17.11.2015, p. 1210-1214.

Research output: Contribution to journalLetterpeer-review

Harvard

APA

Vancouver

Author

Blackman, Lewis D. ; Wright, Daniel B. ; Robin, Mathew P. ; Gibson, Matthew I. ; O'Reilly, Rachel K. / Effect of micellization on the thermoresponsive behavior of polymeric assemblies. In: ACS Macro Letters. 2015 ; Vol. 4, No. 11. pp. 1210-1214.

Bibtex

@article{9e5522dc612b4b67800049d717fda3fd,
title = "Effect of micellization on the thermoresponsive behavior of polymeric assemblies",
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{\textquoteright}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.",
author = "Blackman, {Lewis D.} and Wright, {Daniel B.} and Robin, {Mathew P.} and Gibson, {Matthew I.} and O'Reilly, {Rachel K.}",
year = "2015",
month = nov,
day = "17",
doi = "10.1021/acsmacrolett.5b00551",
language = "English",
volume = "4",
pages = "1210--1214",
journal = "ACS Macro Letters",
issn = "2161-1653",
publisher = "American Chemical Society",
number = "11",

}

RIS

TY - JOUR

T1 - Effect of micellization on the thermoresponsive behavior of polymeric assemblies

AU - Blackman, Lewis D.

AU - Wright, Daniel B.

AU - Robin, Mathew P.

AU - Gibson, Matthew I.

AU - O'Reilly, Rachel K.

PY - 2015/11/17

Y1 - 2015/11/17

N2 - 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.

AB - 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.

UR - http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=ORCID&SrcApp=OrcidOrg&DestLinkType=FullRecord&DestApp=WOS_CPL&KeyUT=WOS:000365147000005&KeyUID=WOS:000365147000005

U2 - 10.1021/acsmacrolett.5b00551

DO - 10.1021/acsmacrolett.5b00551

M3 - Letter

VL - 4

SP - 1210

EP - 1214

JO - ACS Macro Letters

JF - ACS Macro Letters

SN - 2161-1653

IS - 11

ER -