Published in

American Chemical Society, Journal of Physical Chemistry B (Soft Condensed Matter and Biophysical Chemistry), 26(112), p. 7713-7720, 2008

DOI: 10.1021/jp801911a

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Ionic Effects in Collapse of Polyelectrolyte Brushes

Journal article published in 2008 by Tao Jiang, Jianzhong Wu ORCID
This paper is available in a repository.
This paper is available in a repository.

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Abstract

We investigated the effect of counterion valence on the structure and swelling behavior of polyelectrolyte brushes using a nonlocal density functional theory that accounts for the excluded-volume effects of all ionic species and intrachain and electrostatic correlations. It was shown that charge correlation in the presence of multivalent counterions results in collapse of a polyelectrolyte brush at an intermediate polyion grafting density. At high grafting density, the brush reswells in a way similar to that in a monovalent ionic solution. In the presence of multivalent counterions, the nonmonotonic swelling of a polyelectrolyte brush in response to the increase of the grafting density can be attributed to a competition of the counterion-mediated electrostatic attraction between polyions with the excluded-volume effect of all ionic species. While a polyelectrolyte brush exhibits an "osmotic brush" regime at low salt concentration and a "salted brush" regime at high salt concentration regardless of the counterion valence, we found a smoother transition as the valence of the counterions increases. As observed in recent experiments, a quasi-power-law dependence of the brush thickness on the concentration ratio can be identified when the monovalent counterions are replaced with trivalent counterions at a fixed ionic strength.