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Interpolyelectrolyte Complex Dissociation vs Polyelectrolyte Desorption from Oppositely Charged Surface upon Salt

Ivan V Portnov1,2,3, Igor I Potemkin1,2,4

  • 1Physics Department , Lomonosov Moscow State University , Moscow 119991 , Russian Federation.

The Journal of Physical Chemistry. B
|January 15, 2020
PubMed
Summary

Adding salt dissolves polyelectrolyte complexes and adsorbed layers by screening electrostatic interactions. Complexes dissociate at lower salt concentrations than adsorbed layers due to differences in electric field symmetry.

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Area of Science:

  • Physical Chemistry
  • Materials Science
  • Polymer Science

Background:

  • Polyelectrolyte complexes and adsorbed layers are sensitive to salt concentration.
  • High salt concentrations can lead to the dissolution of these structures due to electrostatic screening.

Purpose of the Study:

  • To comparatively analyze the salt-induced dissolution (dissociation and desorption) of polyelectrolyte complexes and adsorbed layers.
  • To elucidate the physical mechanisms underlying the differences in salt sensitivity between these two systems.

Main Methods:

  • Utilized conventional Brownian dynamics computer simulations to model polyelectrolyte behavior.
  • Compared simulation results with experimental data for cationic poly(4-vinylpyridine) adsorption on anionic liposomes.

Main Results:

  • Polyelectrolyte complexes formed by linear chains dissociate at lower salt concentrations compared to the desorption of equivalent chains from charged surfaces.
  • The difference in dissociation salt concentration is attributed to the distinct electric field symmetries binding the chains: decaying for complexes and constant for surface adsorption.
  • Computer simulations showed good quantitative agreement with experimental adsorption data.

Conclusions:

  • The symmetry of the electric field significantly influences the salt concentration required for the dissociation of polyelectrolyte assemblies.
  • Understanding these differences is crucial for controlling the behavior of polyelectrolytes in solution and at interfaces.