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Title: Gel phase formation in dilute triblock copolyelectrolyte complexes

Journal Article · · Nature Communications
DOI:https://doi.org/10.1038/ncomms14131· OSTI ID:1345009
 [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)

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.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS); Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
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)
Grant/Contract Number:
AC05-00OR22725; AC02-06CH11357
OSTI ID:
1345009
Alternate ID(s):
OSTI ID: 1421606
Journal Information:
Nature Communications, Vol. 8; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 89 works
Citation information provided by
Web of Science

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Cited By (14)

Coarse-grained modelling of self-assembling poly(ethylene glycol)/poly(lactic acid) diblock copolymers journal February 2018
Sequence and entropy-based control of complex coacervates journal November 2017
Topologically frustrated dynamics of crowded charged macromolecules in charged hydrogels journal June 2018
Solvent-non-solvent rapid-injection for preparing nanostructured materials from micelles to hydrogels journal August 2019
New frontiers for the materials genome initiative journal April 2019
Dynamics of bridge–loop transformation in a membrane with mixed monolayer/bilayer structures journal January 2018
Molecular engineering solutions for therapeutic peptide delivery journal January 2017
Structure and rheology of polyelectrolyte complex coacervates journal January 2018
Mapping the phase behavior of coacervate-driven self-assembly in diblock copolyelectrolytes journal January 2019
Tardigrade inspired polyelectrolyte complexation and functional materials journal January 2019
Effect of temperature on the structure and dynamics of triblock polyelectrolyte gels journal October 2018
Micro- to macro-phase separation transition in sequence-defined coacervates journal January 2020
Advances in medical adhesives inspired by aquatic organisms’ adhesion journal October 2017
Relaxation Behavior by Time-Salt and Time-Temperature Superpositions of Polyelectrolyte Complexes from Coacervate to Precipitate journal January 2018

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