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Title: Gel phase formation in dilute triblock copolyelectrolyte complexes

Abstract

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. 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:
; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE; National Institute of Standards and Technology (NIST)
OSTI Identifier:
1345421
Resource Type:
Journal Article
Resource Relation:
Journal Name: Nature Communications; Journal Volume: 8; Journal Issue: 02, 2017
Country of Publication:
United States
Language:
ENGLISH
Subject:
36 MATERIALS SCIENCE

Citation Formats

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., 2017. 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. Thu . "Gel phase formation in dilute triblock copolyelectrolyte complexes". United States. doi:10.1038/ncomms14131.
@article{osti_1345421,
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. 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 = 02, 2017,
volume = 8,
place = {United States},
year = {Thu Feb 23 00:00:00 EST 2017},
month = {Thu Feb 23 00:00:00 EST 2017}
}