Tuning the pH Response of Weak Polyelectrolyte Brushes with Specific Anion Effects

The positively charged poly(N,N'-dimethylaminoethyl methacrylate) (PDMAEMA) brushes have been employed as model weak polyelectrolyte brushes (WPBs) to demonstrate the tuning of the pH response of WPBs with specific anion effects. The charge density of PDMAEMA brushes can be modulated by specific ion-pairing interactions between counterions and the protonated dimethylamino group; as a result, the strength of the pH response of PDMAEMA brushes can be tuned by specific anion effects. A more chaotropic counterion can more strongly interact with the protonated dimethylamino group, thereby more effectively neutralizing the positively charged group associated with the grafted weak polyelectrolyte chains and more remarkably suppressing the pH response of PDMAEMA brushes. Although the pH response of PDMAEMA brushes is insensitive to the anion identity at a low salt concentration, it can be tuned by specific anion effects at relatively high salt concentrations. Our study demonstrates that the pH-responsive properties of PDMAEMA brushes including hydration, conformation, oil wettability, and adhesion can be tuned by specific anion effects. The work presented here provides a method to tune the pH response of WPBs by the anion identity.