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Title: Gel phase formation in dilute triblock copolyelectrolyte complexes

Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (<1% by mass) has been observed in scattering experiments and molecular dynamics simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chain aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Finally, our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.
Authors:
 [1] ;  [2] ;  [2] ;  [2] ;  [1] ;  [3] ;  [4] ;  [1] ;  [1]
  1. The Univ. of Chicago, Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
  2. The Univ. of Chicago, Chicago, IL (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. National Institute of Standards and Technology, Gaithersburg, MD (United States)
Publication Date:
Grant/Contract Number:
AC05-00OR22725; AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; US Dept. of Commerce, National Institute of Standards and Technology (NIST), Center for Hierarchical Materials Design (CHiMaD)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; gels and hydrogels; molecular self-assembly; self-assembly
OSTI Identifier:
1345009
Alternate Identifier(s):
OSTI ID: 1421606

Srivastava, Samanvaya, Andreev, Marat, Levi, Adam E., Goldfeld, David J., Mao, Jun, Heller, William T., Prabhu, Vivek M., de Pablo, Juan J., and Tirrell, Matthew V.. Gel phase formation in dilute triblock copolyelectrolyte complexes. United States: N. p., Web. doi:10.1038/ncomms14131.
Srivastava, Samanvaya, Andreev, Marat, Levi, Adam E., Goldfeld, David J., Mao, Jun, Heller, William T., Prabhu, Vivek M., de Pablo, Juan J., & Tirrell, Matthew V.. Gel phase formation in dilute triblock copolyelectrolyte complexes. United States. doi:10.1038/ncomms14131.
Srivastava, Samanvaya, Andreev, Marat, Levi, Adam E., Goldfeld, David J., Mao, Jun, Heller, William T., Prabhu, Vivek M., de Pablo, Juan J., and Tirrell, Matthew V.. 2017. "Gel phase formation in dilute triblock copolyelectrolyte complexes". United States. doi:10.1038/ncomms14131. https://www.osti.gov/servlets/purl/1345009.
@article{osti_1345009,
title = {Gel phase formation in dilute triblock copolyelectrolyte complexes},
author = {Srivastava, Samanvaya and Andreev, Marat and Levi, Adam E. and Goldfeld, David J. and Mao, Jun and Heller, William T. and Prabhu, Vivek M. and de Pablo, Juan J. and Tirrell, Matthew V.},
abstractNote = {Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (<1% by mass) has been observed in scattering experiments and molecular dynamics simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chain aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Finally, our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.},
doi = {10.1038/ncomms14131},
journal = {Nature Communications},
number = ,
volume = 8,
place = {United States},
year = {2017},
month = {2}
}