The specific ion response of polyelectrolyte brushes depends on polymer and anion hydrophilicity

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Date
2016-11-29
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Publisher
Australian Institute of Nuclear Science and Engineering
Abstract
We have previously shown that the pH and ionic strength response of weak, polybasic brushes is dependent on the location of the counterion within the Hofmeister series and the relative hydrophobicity of the polymer.[1-3] Recent measurements of a hydrophobic poly(2-diisopropylamino) ethyl methacrylate (PDPA) brush on Platypus reflectometer show that a collapsed conformation independent of anion identity is formed at low ionic strength, 0.1 mM. At higher ionic strengths, up to 500 mM, extended conformations are observed in potassium acetate solutions, while potassium thiocyanate solutions collapse the brush. Numerical self consistent field (nSCF) calculations allowed previous hypotheses regarding the accumulation and hydration strength of the counterions to be tested. Addition of a single Flory-Huggins interaction parameter (χ) analogous to the anion hydrophilicity was sufficient to replicate the measured brush behaviour.
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Keywords
Polymers, Neutron reflectors, Anions, Potassium, Hydration, Numerical analysis
Citation
Murdoch, T. J., Willott, J. D., de Vos, W. M., Nelson, A., Prescott, S. W., Wanless, E. J., & Webber, J. B. (2016). The specific ion response of polyelectrolyte brushes depends on polymer and anion hydrophilicity. Paper presented at 13th AINSE-ANBUG Neutron Scattering Symposium, Sydney, NSW, Australia, 29-30 November 2016.