Reversible electrochemical switching of polymer brushes grafted onto conducting polymer films

We demonstrate the electrochemical switching of conformation of surface-bound polymer brushes, by grafting environmentally sensitive polymer brushes from an electrochemically active conducting polymer (ECP). Using atom transfer radical polymerization (ATRP), we grafted zwitterionic betaine homopolymer and block copolymer brushes of poly(3-(methacryloylamido)propyl)-N,N'-dimethyl(3-sulfopropyl)ammonium hydroxide) (PMPDSAH) and poly(methyl methacrylate)-b-PMPDSAH, from an initiator, surface-coupled to a poly(pyrrole-co-pyrrolyl butyric acid) film. The changes in ionic solution composition in the surface layer, resulting from oxidation and reduction of the ECP, trigger a switch in conformation of the surface-bound polymer brushes, demonstrated here by electrochemical impedance spectroscopy (EIS) and in a change of wettability. The switch is dependent upon temperature in a way that is analogous to the temperature-dependent solubility and aggregation of similar betaine polymers in aqueous solution but has a quite different dependence on salt concentration in solution. The switch is fully reversible and reproducible. We interpret the switching behavior in terms of a transition to a "supercollapsed" state on the surface that is controlled by ions that balance the charge state of the ECP and are adsorbed to the opposite charges of the zwitterionic graft, close to the graft-ECP interface. The behavior is significantly modified by hydrophobic interactions of the block copolymer graft. We speculate that the synergistic combination of properties embodied in these "smart" materials may find applications in electrochemical control of surface wetting and in the interaction with biomolecules and living cells.