Counterion-Mediated Hydrogen Bonding Making Poly(styrenesulfonate)-Based Strong Polyelectrolytes pH-Responsive

Owing to the well-established fact that poly(styrenesulfonate) (PSS)-based strong polyelectrolytes are pH insensitive, their applications in smart materials have thus been severely limited. However, we demonstrate here that counterion-mediated hydrogen bonding (CMHB) makes the PSS brush pH-responsive. With decreasing pH, more hydrogen bonds are formed between the bound hydronium counterions and the sulfonate (−SO₃^–) groups in the PSS brush. At the microscale, the formation of more hydrogen bonds with decreasing pH leads to a more ordered structure and a larger tilt angle of the −SO₃^– groups in the PSS brush. On the other hand, a range of important physicochemical properties of the PSS brush, including hydration, stiffness, wettability, and adhesion, are responsive to pH, induced by the effect of CMHB on the PSS brush. Our work reveals a clear structure–property relationship for the pH-responsive PSS brush. This work not only provides a new understanding of the fundamental properties of the PSS brush but also greatly extends the applications of PSS-based strong polyelectrolytes.