Equilibrium Electrostatics of Responsive Polyelectrolyte Monolayers

Published

January 14, 2009

Author(s)

Rebecca A. Zangmeister, Rastislav Levicky, Kang Wang

Abstract

The physical behavior of polyelectrolytes at solid-liquid interfaces presents challenges both in measurement and in interpretation. An informative, yet often overlooked, property that characterizes the equilibrium organization of these systems is their membrane or rest potential. Here a general classification scheme is presented of the relationship between the rest potential and structural response of polyelectrolyte films to salt concentration. A numerical lattice theory, adapted from the polymer community, is used to analyze the rest potential response of polyelectrolyte brushes in which electrostatics and short range contact interactions conspire to bring about different structural states. As an experimental quantity the rest potential is a readily accessible, non-perturbing metric of the equilibrium structure of a polyelectrolyte layer. A first set of measurements is reported on monolayers of end-tethered, single-stranded DNA brushes in monovalent (NaCl) and divalent (MgCl2) counterion environments. Intriguingly, in NaCl electrolyte at least two different mechanisms appear by which the DNA layers can structurally relax in response to changing salt conditions. In MgCl2 the layers appear to collapse. The possible molecular mechanisms behind these behaviors are discussed. These studies provide insight into phenomena more generally underlying polyelectrolyte applications in the chemical, environmental, and biotechnological fields.

Citation

Journal of the American Chemical Society

Volume

131

Issue

1

Pub Type

Journals

Keywords

DNA, lattice theory, polyelectrolyte, rest potential, solid-liquid interface

Citation

Zangmeister, R. , Levicky, R. and Wang, K. (2009), Equilibrium Electrostatics of Responsive Polyelectrolyte Monolayers, Journal of the American Chemical Society (Accessed October 13, 2024)