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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) (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.

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. https://doi.org/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. https://doi.org/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. https://doi.org/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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