A new method for covalently cross-linking chitosan is developed by chemically oxidizing catechol to o-quinone which subsequently reacts with and cross-links chitosan through Michael addition and Schiff base formation. The cross-linked chitosan film shows a pH-responsive, switchlike behavior toward the negatively charged redox probe, Fe(CN)(6)(3-/4-), and withstands harsh acidic conditions. The negative Fe(CN)(6)(3-/4-) is found to be trapped and enriched in the catechol-cross-linked chitosan film under acidic conditions and released into solution by either increasing pH or applying a negative voltage. Chitosan films made with different techniques, i.e., solvent evaporation (simple deposition), electrodeposition, and covalent cross-linking, are examined using cyclic voltammetry and electrochemical impedance spectroscopy (EIS), and the results demonstrate that fabrication methods greatly affect the properties of the chitosan films.
© 2012 American Chemical Society