Topology and Molecular Architecture of Polyelectrolytes Determine Their pH-Responsiveness When Assembled on Surfaces

Polymer composition and topology of surface-grafted polyacids determine the amplitude of their pH-induced swelling transition. The intrinsic steric constraints characterizing cyclic poly(2-carboxypropyl-2-oxazoline) (c-PCPOXA) and poly(2-carboxyethyl-2-oxazoline) (c-PCEOXA) forming brushes on Au surfaces induce an enhancement in repulsive interactions between charged polymer segments upon deprotonation, leading to an amplified expansion and a significant increment in swelling with respect to their linear analogues of similar molar mass. On the other hand, it is the composition of polyacid grafts that governs their hydration in both undissociated and ionized forms, determining the degree of swelling during their pH-induced transition.