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The phase behavior of polyelectrolyte complexes and coacervates (PECs) at low salt concentrations has been well characterized, but their behavior at concentrations well above the binodal is not well understood. Here, we investigate the phase behavior of stoichiometric poly(styrene sulfonate)/poly(diallyldimethylammonium) mixtures at high salt and high polymer concentrations. Samples were prepared by direct mixing of PSS/PDADMA PECs, water, and salt (KBr). Phase separation was observed at salt concentrations approximately 1 M above the binodal. Characterization by thermogravimetric analysis, FTIR, and NMR revealed that both phases contained significant amounts of polymer, and that the polymer-rich phase was enriched in PSS, while the polymer-poor phase was enriched in PDADMA. These results suggest that high salt concentrations drive salting out of the more hydrophobic polyelectrolyte (PSS), consistent with behavior observed in weak polyelectrolyte systems. Interestingly, at the highest salt and polymer concentrations studied, the polymer-rich phase contained both PSS and PDADMA, suggesting that high salt concentrations can drive salting out of partially-neutralized complexes as well. Characterization of the behavior of PECs in the high concentration limit appears to be a fruitful avenue for deepening fundamental understanding of the molecular-scale factors driving phase separation in these systems.
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This content will become publicly available on September 24, 2026
Salt-responsive behaviors of PVBTACl, NaPSS, and their complex by molecular dynamics simulations and experiments
Polyelectrolytes, macromolecules with ionizable groups, play a critical role in applications ranging from energy storage and drug delivery to adhesives, owing to their strong interactions with ionic solutes and water. Despite their widespread utility, an atomistic understanding of how polyelectrolytes interact with ions remains incomplete, limiting the ability to precisely control their conformation and functional properties. To bridge this knowledge gap, we conducted molecular dynamics simulations of two representative polyelectrolytes, poly(vinylbenzyl trimethylammonium chloride) (PVBTACl) and sodium polystyrene sulfonate (NaPSS), across varying salt concentrations. We observed distinct salt-responsive behaviors: as the salt (NaCl) concentration increases from 0 to 2 M, the radius of gyration (Rg) of NaPSS decreases, indicating polymer compaction, while PVBTACl remains relatively unaffected. When the salt concentration is further increased to 6 M, PVBTACl undergoes significant collapse, whereas NaPSS remains in a compact state with minimal further conformational change. The difference in the salt-responsive behavior results from the local counterion structures, where the counterions of PVBTACl are less ordered than those of NaPSS. We further examined the PVBTACl/NaPSS complex to assess deviations from the behavior of isolated polymers, revealing enhanced association in contrast to the conventionally observed dissociation at the high salt concentration. Experimental transmittance measurements of equimolar PVBTACl/NaPSS mixtures across increasing salt concentrations confirmed stable complexation behavior under high-salt conditions, supporting the simulation-based observations of persistent association between PVBTACl and NaPSS. This study offers a mechanistic understanding of salt-induced conformational changes, providing design principles for tuning polyelectrolyte properties in functional materials.
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- Award ID(s):
- 2328188
- PAR ID:
- 10645826
- Publisher / Repository:
- Royal Society of Chemistry
- Date Published:
- Journal Name:
- Soft Matter
- Volume:
- 21
- Issue:
- 37
- ISSN:
- 1744-683X
- Page Range / eLocation ID:
- 7333 to 7343
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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