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:
-
- Stony Brook Univ., NY (United States). Dept. of Chemistry
- Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
- 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. 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}
}
Web of Science
Works referenced in this record:
RAFT Synthesis and Aqueous Solution Behavior of Novel pH- and Thermo-Responsive (Co)Polymers Derived from Reactive Poly(2-vinyl-4,4-dimethylazlactone) Scaffolds
journal, September 2013
- Quek, Jing Yang; Zhu, Yicheng; Roth, Peter J.
- Macromolecules, Vol. 46, Issue 18
New directions in thermoresponsive polymers
journal, January 2013
- Roy, Debashish; Brooks, William L. A.; Sumerlin, Brent S.
- Chemical Society Reviews, Vol. 42, Issue 17
Shape-changing polymer assemblies
journal, January 2013
- Grubbs, Robert B.; Sun, Zhe
- Chemical Society Reviews, Vol. 42, Issue 17
Stimuli-responsive copolymer solution and surface assemblies for biomedical applications
journal, January 2013
- Kelley, Elizabeth G.; Albert, Julie N. L.; Sullivan, Millicent O.
- Chemical Society Reviews, Vol. 42, Issue 17
Temperature-Sensitive Nanoparticle-to-Vesicle Transition of ABC Triblock Copolymer Corona–Shell–Core Nanoparticles Synthesized by Seeded Dispersion RAFT Polymerization
journal, February 2014
- Dan, Meihan; Huo, Fei; Xiao, Xin
- Macromolecules, Vol. 47, Issue 4
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
The conundrum of gel formation by molecular nanofibers, wormlike micelles, and filamentous proteins: gelation without cross-links?
journal, January 2012
- Raghavan, Srinivasa R.; Douglas, Jack F.
- Soft Matter, Vol. 8, Issue 33
New Perspectives for the Design of Molecular Actuators: Thermally Induced Collapse of Single Macromolecules from Cylindrical Brushes to Spheres
journal, February 2004
- Li, Chengming; Gunari, Nikhil; Fischer, Karl
- Angewandte Chemie International Edition, Vol. 43, Issue 9
Design of Environmentally Responsive Fluorescent Polymer Probes for Cellular Imaging
journal, July 2015
- Yamada, Arisa; Hiruta, Yuki; Wang, Jian
- Biomacromolecules, Vol. 16, Issue 8
Thermally Induced Changes in Amphiphilicity Drive Reversible Restructuring of Assemblies of ABC Triblock Copolymers with Statistical Polyether Blocks
journal, February 2011
- Cai, Yu; Aubrecht, Katherine B.; Grubbs, Robert B.
- Journal of the American Chemical Society, Vol. 133, Issue 4
To aggregate, or not to aggregate? considerations in the design and application of polymeric thermally-responsive nanoparticles
journal, January 2013
- Gibson, Matthew I.; O'Reilly, Rachel K.
- Chem. Soc. Rev., Vol. 42, Issue 17
“Schizophrenic” Self-Assembly of Block Copolymers Synthesized via Aqueous RAFT Polymerization: From Micelles to Vesicles † † Paper number 143 in a series on Water-Soluble Polymers.
journal, February 2010
- Smith, Adam E.; Xu, Xuewei; Kirkland-York, Stacey E.
- Macromolecules, Vol. 43, Issue 3
Wormlike Micelles of a C22-Tailed Zwitterionic Betaine Surfactant: From Viscoelastic Solutions to Elastic Gels
journal, December 2007
- Kumar, Rakesh; Kalur, Gokul C.; Ziserman, Lior
- Langmuir, Vol. 23, Issue 26
Fluorescent Polymeric AND Logic Gate with Temperature and pH as Inputs
journal, March 2004
- Uchiyama, Seiichi; Kawai, Narumi; de Silva, A. Prasanna
- Journal of the American Chemical Society, Vol. 126, Issue 10
Polymersomes
journal, August 2006
- Discher, Dennis E.; Ahmed, Fariyal
- Annual Review of Biomedical Engineering, Vol. 8, Issue 1
Self-assembly of block copolymers
journal, January 2012
- Mai, Yiyong; Eisenberg, Adi
- Chemical Society Reviews, Vol. 41, Issue 18
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
Thermally induced micelle to vesicle morphology transition for a charged chain end diblock copolymer
journal, January 2010
- Moughton, Adam O.; O’Reilly, Rachel K.
- Chem. Commun., Vol. 46, Issue 7
Functional Group-Dependent Self-Assembled Nanostructures from Thermo-Responsive Triblock Copolymers
journal, April 2014
- Banerjee, Rakesh; Dhara, Dibakar
- Langmuir, Vol. 30, Issue 14
Sterilizable Gels from Thermoresponsive Block Copolymer Worms
journal, May 2012
- Blanazs, Adam; Verber, Robert; Mykhaylyk, Oleksandr O.
- Journal of the American Chemical Society, Vol. 134, Issue 23
Reversible Restructuring of Aqueous Block Copolymer Assemblies through Stimulus-Induced Changes in Amphiphilicity
journal, September 2008
- Sundararaman, Anand; Stephan, Tim; Grubbs, Robert B.
- Journal of the American Chemical Society, Vol. 130, Issue 37
Morphological transitions in aggregates of thermosensitive poly(ethylene oxide)- b -poly( N -isopropylacrylamide) block copolymers prepared via RAFT polymerization: Morphological Transitions in PEO- b -PNIPAM
journal, July 2009
- Zhao, Junpeng; Zhang, Guangzhao; Pispas, Stergios
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 47, Issue 16
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
Does PNIPAM block really retard the micelle-to-vesicle transition of its copolymer?
journal, July 2011
- Wei, Kongchang; Su, Lu; Chen, Guosong
- Polymer, Vol. 52, Issue 16
Programmable Polymer-Based Supramolecular Temperature Sensor with a Memory Function
journal, April 2014
- Sambe, Léna; de La Rosa, Victor R.; Belal, Khaled
- Angewandte Chemie, Vol. 126, Issue 20
RAFT Synthesis of a Thermally Responsive ABC Triblock Copolymer Incorporating N -Acryloxysuccinimide for Facile in Situ Formation of Shell Cross-Linked Micelles in Aqueous Media †
journal, January 2006
- Li, Yuting; Lokitz, Brad S.; McCormick, Charles L.
- Macromolecules, Vol. 39, Issue 1
Smart wormlike micelles
journal, January 2013
- Chu, Zonglin; Dreiss, Cécile A.; Feng, Yujun
- Chemical Society Reviews, Vol. 42, Issue 17
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
Study of the phase transition of poly(N,N-diethylacrylamide) in water by rheology and dynamic light scattering
journal, June 2003
- Lessard, D. G.; Ousalem, M.; Zhu, X. X.
- Journal of Polymer Science Part B: Polymer Physics, Vol. 41, Issue 14
Bis-Hydrophilic Block Terpolymers via RAFT Polymerization: Toward Dynamic Micelles with Tunable Corona Properties
journal, November 2008
- Walther, Andreas; Millard, Pierre-Eric; Goldmann, Anja S.
- Macromolecules, Vol. 41, Issue 22
Stimuli-responsive polymer gels
journal, January 2008
- Ahn, Suk-kyun; Kasi, Rajeswari M.; Kim, Seong-Cheol
- Soft Matter, Vol. 4, Issue 6
Multiple Morphologies of "Crew-Cut" Aggregates of Polystyrene-b-poly(acrylic acid) Block Copolymers
journal, June 1995
- Zhang, L.; Eisenberg, A.
- Science, Vol. 268, Issue 5218
Triply-responsive boronic acid block copolymers: solution self-assembly induced by changes in temperature, pH, or sugar concentration
journal, January 2009
- Roy, Debashish; Cambre, Jennifer N.; Sumerlin, Brent S.
- Chemical Communications, Issue 16
Ein neuer Weg zu molekularen Aktuatoren: der thermisch induzierteÜbergang einzelner Makromoleküle von zylindrischen Bürsten zu kugelförmigen Objekten
journal, February 2004
- Li, Chengming; Gunari, Nikhil; Fischer, Karl
- Angewandte Chemie, Vol. 116, Issue 9
A comparison of thermoreactive water-soluble poly-N,N-diethylacrylamide prepared by anionic and by group transfer polymerization
journal, December 1994
- Freitag, Ruth; Baltes, Thomas; Eggert, Martin
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 32, Issue 16
Testing the Vesicular Morphology to Destruction: Birth and Death of Diblock Copolymer Vesicles Prepared via Polymerization-Induced Self-Assembly
journal, January 2015
- Warren, Nicholas J.; Mykhaylyk, Oleksandr O.; Ryan, Anthony J.
- Journal of the American Chemical Society, Vol. 137, Issue 5
Programmable Polymer-Based Supramolecular Temperature Sensor with a Memory Function
journal, April 2014
- Sambe, Léna; de La Rosa, Victor R.; Belal, Khaled
- Angewandte Chemie International Edition
Works referencing / citing this record:
Light‐Switching Azo‐Copolymers Self‐Assembly in Multi‐Stationary States
journal, March 2019
- Dong, Shumin; Sun, Wen; Wang, Dongsheng
- Macromolecular Rapid Communications, Vol. 40, Issue 9
Morphology transformation of self-assembled organic nanomaterials in aqueous solution induced by stimuli-triggered chemical structure changes
journal, January 2017
- Zhang, Wenbo; Gao, Changyou
- Journal of Materials Chemistry A, Vol. 5, Issue 31
“Smart” Polymers: Physicochemical Characteristics and Applications in Bio-Separation Strategies
journal, December 2017
- Hernández-Vargas, Gustavo; Ponce-Ponce de León, César Alejandro; González-Valdez, José
- Separation & Purification Reviews, Vol. 47, Issue 3