Electrochemical switching of conformation of random polyampholyte brushes grafted onto polypyrrole

We demonstrate the possibilities for subtle control over redox-driven surface switching that could be obtained by altering the balance between hydrophobic, ionic, and dipolar components of polymer brushes that are grafted onto electrochemically active conducting polymers (ECP). We extend our previous work on the conformation switching of polyzwitterionic brushes grafted onto ECP to the case of ABC random polyampholyte brushes: here, a statistical near-neutral copolymer of methyl methacrylate (MMA), methacryloxyethyltrimethylammonium chloride (METAC), and 3-sulfopropyl methacrylate potassium salt (SPMA). The statistical polyampholyte differs from the polyzwitterion in that it is not strictly neutral and the charges do not have a defined spatial relationship to one another. The consequence is a significant change in the switching behavior that is also dependent on the salt concentration in the electrolyte. The results can be understood by reference to the theory of polyampholyte conformation in solution given by Higgs and Joanny modified to apply to a surface-bound brush. Three states of the polyampholyte brush are deduced from electrochemical impedance spectroscopy (EIS): collapsed, partially collapsed, and expanded. At low salt concentration, the behavior was the opposite of that of the polyzwitterion: the brush switched between partially collapsed with the ECP reduced and expanded with the ECP oxidized. With increase of salt concentration, the switch changed, to collapsed with the ECP oxidized and partially collapsed with ECP reduced. At still higher salt concentration, the switch changed back again, to partially collapsed with the ECP reduced and expanded with the ECP oxidized. Measurements of surface wetting under electrochemical control supported the interpretation. The behavior can be contrasted with that of zwitterionic brushes, which show a switch between collapsed with ECP oxidized and expanded with ECP reduced, independent of salt concentration over the same range (10(-3)-2 M NaCl) as that studied here, and that of zwitterionic-hydrophobic block copolymers where the switch is suppressed at low salt concentration. The results illustrate the significant range of behavior that can be engineered into these electrochemically switchable systems.