Influence of Ionic Strength and Specific Ion Effects on Polyelectrolyte Multilayer Films with pH-Responsive Behavior

Layer-by-layer assembled multilayer films have shown great potential for different applications owing to their responsive behavior. Herein, we systematically investigated the effects of composition, salt concentration, and ion specificity on the pH responsiveness of covalently crosslinked chitosan and alginate dialdehyde multilayer films. The changes in film swelling were measured using ellipsometry from low (0.01 mM) to high (3 M) salt (NaCl or NaSCN) concentrations at pH 3, 6, and 9. The swelling responses to increasing ionic strength matched the swelling responses observed for polyzwitterionic and weak monocomponent polyelectrolyte films and depended on the multilayer composition, pH, and ion specificity. Finally, we used the ellipsometric data to demonstrate that the pH responsiveness of such multilayer films, as measured using a quartz crystal microbalance with dissipation monitoring, strongly depends on the ionic condition under which the responses were measured. We thus show that erroneous conclusions about the pH responsiveness of polyelectrolyte multilayer films can be easily obtained if the ionic environment of the application does not closely resemble the ionic condition under which the pH responsiveness is tested.