Influence of Anion Hydrophilicity on the Conformation of a Hydrophobic Weak Polyelectrolyte Brush

Timothy J. Murdoch, Joshua David Willott, Wiebe Matthijs de Vos, Andrew Nelson, Stuart W. Prescott, Erica J. Wanless, Grant B. Webber

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Abstract

The conformation of a hydrophobic, weak cationic poly(2-diisopropylamino)ethyl methacrylate (PDPA) brush was studied using neutron reflectometry as a function of aqueous solution pH, ionic strength, and anion identity. In pH 4, 10 mM potassium nitrate the brush is highly charged, resulting in an extended, dilute conformation; at pH 9 the uncharged brush collapses to a single, dense layer. The brush response to added salt at constant pH (4.5) for varying concentrations of the potassium salts of acetate, nitrate, and thiocyanate revealed ion-specific conformations of the brush. At low ionic strength (0.1 mM) the brush was collapsed, independent of salt identity, while at higher ionic strengths (up to 500 mM) the conformation was dependent on counterion identity. The brush exhibited extended conformations in the presence of kosmotropic acetate counterions, while collapsed conformations were retained in the presence of strongly chaotropic thiocyanate counterions. The brush showed a richer set of behaviors in the solutions containing the weakly chaotropic nitrate anion, being similar to acetate (swollen) at intermediate concentrations but similar to thiocyanate (collapsed) at high salt concentrations. Numerical self-consistent field (nSCF) simulations indicate that the response of the brush to pH changes is dominated by the hydrophobicity of the polymer at pH values near the pKa. Furthermore, the simulations reveal that the addition of a single Flory–Huggins interaction parameter analogous to the hydrophilicity of the counterion is sufficient to replicate the observed specific anion response of a hydrophobic weak polyelectrolyte brush.
Original languageEnglish
Pages (from-to)9605–9617
JournalMacromolecules
Volume49
Issue number24
DOIs
Publication statusPublished - 27 Dec 2016

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