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:
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[1]
; [2]
; [2]
; [2]
; [1]
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- The Univ. of Chicago, Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
- The Univ. of Chicago, Chicago, IL (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- 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
- Free Publicly Accessible Full Text
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Accepted Manuscript (DOE)
- Publisher's Version of Record
- https://doi.org/10.1038/ncomms14131