Effect of Salt Concentration on the pH Responses of Strong and Weak Polyelectrolyte Brushes

Strong polyelectrolyte brushes (SPB) and weak polyelectrolyte brushes (WPB) have different origins with response to pH, which makes their pH-responsive properties sensitive to salt concentration in different ways. Herein, we have employed poly[2-(methacryloyloxy)ethyl trimethylammonium chloride] (PMETAC) and poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) brushes as model systems for SPB and WPB, respectively, to investigate the effect of salt concentration on the pH responses of SPB and WPB using several surface-sensitive techniques. The pH-responsive properties of the PMETAC brushes are governed by the reorganization of the interchain hydrogen bonds between the grafted chains, whereas the pH response of the PDMAEMA brushes is controlled by the charge of the grafted chains. The response of the properties of the PMETAC brushes including hydration, conformation, and surface wettability becomes weaker with increasing salt concentration induced by the competitive adsorption of counterions to the brushes between OH^- and Cl^-. The weakening of the pH response of the PMETAC brushes is more remarkable at the relatively high pH values. The pH response of the PDMAEMA brushes also exhibits a salt-concentration dependence. As the salt concentration increases, the weakening of the pH response of the PDMAEMA brushes is attributed to the decrease in osmotic pressure within the brushes at relatively low pH values.