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Title: Translating Thermal Response of Triblock Copolymer Assemblies in Dilute Solution to Macroscopic Gelation and Phase Separation

Abstract

The thermal response of semi-dilute solutions (5 w/w%) of two amphiphilic thermoresponsive poly(ethylene oxide)-b-poly(N,N-diethylacrylamide)-b-poly(N,N-dibutylacrylamide) (PEO 45-PDEAm x-PDBAm 12) triblock copolymers, which differ only in the size of the central responsive block, in water was examined in this paper. Aqueous PEO45-PDEAm41-PDBAm12 solutions, which undergo a thermally induced sphere-to-worm transition in dilute solution, were found to reversibly form soft (G'≈10 Pa) free-standing physical gels after 10 min at 55 °C. PEO 45-PDEAm 89-PDBAm 12 copolymer solutions, which undergo a thermally induced transition from spheres to large compound micelles (LCM) in dilute solution, underwent phase separation after heating at 55 °C for 10 min owing to sedimentation of LCMs. The reversibility of LCM formation was investigated as a non-specific method for removal of a water-soluble dye from aqueous solution. Finally, the composition and size of the central responsive block in these polymers dictate the microscopic and macroscopic response of the polymer solutions as well as the rates of transition between assemblies.

Authors:
 [1];  [2];  [1]; ORCiD logo [3];  [1]; ORCiD logo [1]
  1. Stony Brook Univ., NY (United States). Dept. of Chemistry
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials; Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering. Dept. of Applied Physics and Applied Mathematics
Publication Date:
Research Org.:
Stony Brook Univ., NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
Contributing Org.:
Columbia Univ., New York, NY (United States)
OSTI Identifier:
1361270
Report Number(s):
BNL-113913-2017-JA
Journal ID: ISSN 1433-7851; KC0403020
Grant/Contract Number:  
SC0012704; DMR-1105622; CBET-1335787
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 6; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; block copolymers; gels; micelles; nanostructures; self-assembly

Citation Formats

Sun, Zhe, Tian, Ye, Hom, Wendy L., Gang, Oleg, Bhatia, Surita R., and Grubbs, Robert B. Translating Thermal Response of Triblock Copolymer Assemblies in Dilute Solution to Macroscopic Gelation and Phase Separation. United States: N. p., 2016. Web. doi:10.1002/anie.201609360.
Sun, Zhe, Tian, Ye, Hom, Wendy L., Gang, Oleg, Bhatia, Surita R., & Grubbs, Robert B. Translating Thermal Response of Triblock Copolymer Assemblies in Dilute Solution to Macroscopic Gelation and Phase Separation. United States. doi:10.1002/anie.201609360.
Sun, Zhe, Tian, Ye, Hom, Wendy L., Gang, Oleg, Bhatia, Surita R., and Grubbs, Robert B. Wed . "Translating Thermal Response of Triblock Copolymer Assemblies in Dilute Solution to Macroscopic Gelation and Phase Separation". United States. doi:10.1002/anie.201609360. https://www.osti.gov/servlets/purl/1361270.
@article{osti_1361270,
title = {Translating Thermal Response of Triblock Copolymer Assemblies in Dilute Solution to Macroscopic Gelation and Phase Separation},
author = {Sun, Zhe and Tian, Ye and Hom, Wendy L. and Gang, Oleg and Bhatia, Surita R. and Grubbs, Robert B.},
abstractNote = {The thermal response of semi-dilute solutions (5 w/w%) of two amphiphilic thermoresponsive poly(ethylene oxide)-b-poly(N,N-diethylacrylamide)-b-poly(N,N-dibutylacrylamide) (PEO45-PDEAmx-PDBAm12) triblock copolymers, which differ only in the size of the central responsive block, in water was examined in this paper. Aqueous PEO45-PDEAm41-PDBAm12 solutions, which undergo a thermally induced sphere-to-worm transition in dilute solution, were found to reversibly form soft (G'≈10 Pa) free-standing physical gels after 10 min at 55 °C. PEO45-PDEAm89-PDBAm12 copolymer solutions, which undergo a thermally induced transition from spheres to large compound micelles (LCM) in dilute solution, underwent phase separation after heating at 55 °C for 10 min owing to sedimentation of LCMs. The reversibility of LCM formation was investigated as a non-specific method for removal of a water-soluble dye from aqueous solution. Finally, the composition and size of the central responsive block in these polymers dictate the microscopic and macroscopic response of the polymer solutions as well as the rates of transition between assemblies.},
doi = {10.1002/anie.201609360},
journal = {Angewandte Chemie (International Edition)},
number = 6,
volume = 56,
place = {United States},
year = {2016},
month = {12}
}

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Works referenced in this record:

New directions in thermoresponsive polymers
journal, January 2013

  • Roy, Debashish; Brooks, William L. A.; Sumerlin, Brent S.
  • Chemical Society Reviews, Vol. 42, Issue 17
  • DOI: 10.1039/c3cs35499g

Block copolymers: controlling nanostructure to generate functional materials – synthesis, characterization, and engineering
journal, January 2016

  • Epps, III, Thomas H.; O'Reilly, Rachel K.
  • Chemical Science, Vol. 7, Issue 3
  • DOI: 10.1039/C5SC03505H

Smart micro/nanoparticles in stimulus-responsive drug/gene delivery systems
journal, January 2016

  • Karimi, Mahdi; Ghasemi, Amir; Sahandi Zangabad, Parham
  • Chemical Society Reviews, Vol. 45, Issue 5
  • DOI: 10.1039/C5CS00798D

Polymersomes
journal, August 2006


Self-assembly of block copolymers
journal, January 2012

  • Mai, Yiyong; Eisenberg, Adi
  • Chemical Society Reviews, Vol. 41, Issue 18
  • DOI: 10.1039/c2cs35115c

Multiple Morphologies and Characteristics of “Crew-Cut” Micelle-like Aggregates of Polystyrene- b -poly(acrylic acid) Diblock Copolymers in Aqueous Solutions
journal, January 1996

  • Zhang, Lifeng; Eisenberg, Adi
  • Journal of the American Chemical Society, Vol. 118, Issue 13
  • DOI: 10.1021/ja953709s

Emerging applications of stimuli-responsive polymer materials
journal, January 2010

  • Stuart, Martien A. Cohen; Huck, Wilhelm T. S.; Genzer, Jan
  • Nature Materials, Vol. 9, Issue 2, p. 101-113
  • DOI: 10.1038/nmat2614

Self-Assembled Block Copolymer Aggregates: From Micelles to Vesicles and their Biological Applications
journal, February 2009

  • Blanazs, Adam; Armes, Steven P.; Ryan, Anthony J.
  • Macromolecular Rapid Communications, Vol. 30, Issue 4-5
  • DOI: 10.1002/marc.200800713

Stimuli-responsive polymer gels
journal, January 2008

  • Ahn, Suk-kyun; Kasi, Rajeswari M.; Kim, Seong-Cheol
  • Soft Matter, Vol. 4, Issue 6
  • DOI: 10.1039/b714376a