Electrochemical Characterization of Polyelect.pdf

Electrochemical Characterization of Polyelectrolyte Multilayers Deposited at Liquid-Liquid Interfaces Christopher J. Slevin, Annika Malkia, Peter Liljeroth, Martina Toiminen, and Kyo?sti Kontturi* Helsinki University of Technology, Laboratory of Physical Chemistry and Electrochemistry, P.O. Box 6100, FIN-02015 HUT, Finland Received October 11, 2002. In Final Form: November 27, 2002 The deposition of polyelectrolyte multilayers at an aqueous solution-organic gel interface by layer by layer deposition of anionic poly(sodium 4-styrenesulfonate) and cationic poly(allylamine hydrochloride) is described. With suitable electrolytes and electrodes in both phases, alternating current voltammetry is employed to measure the capacitance of the polyelectrolyte multilayer as a function of the number and type of layers deposited. The charge distribution across the interface is investigated by analyzing the capacitance measurements based on a theoretical model that describes the potential profile across the multilayer at the interface between the two electrolyte solutions. Subsequently, cyclic voltammetry is used to probe the transfer of cationic tetraethylammonium and the cationic Alzheimer drug 9-amino-1,2,3,4- tetrahydroacridine (tacrine) across the polyelectrolyte multilayer. The effective transfer rate constant is reduced by the presence of the multilayer film, and the lower rate observed for a polycation- compared with a polyanion-terminated multilayer is interpreted in terms of the theoretical model. Introduction The electrostatic adsorption of alternating layers of oppositely charged polyions on a charged substrate may be used to produce ultrathin polyelectrolyte (PE) multi- layer films with controlled properties. Such layer by layer deposition of polyanions and polycations is a relatively straightforward and simple procedure, and in principle there are few restrictions on the choice of polyionic species deposited. 1,2 The method enables the film properties such as thicknes