Molecular Design of Conductor Surfaces

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Mass and rheological changes of Nafion films deposited on a gold-coated quartz crystal resonator during their loading with Os(bpy)_3^<2+> and its ejection during electrochemical oxidation in sodium acetate buffers were analyzed on the basis of measurements of the electromechanical impedance of the Nafion film-coated resonator. Loading of the Nafion to saturation with Os(bpy)_3^<2+> caused increases in the mass and the rigidity of the film. Electrostatic cross-linking by the doubly-charged Os(bpy)_3^<2+> may be responsible for the rigidity increase. During the first anodic oxidation of the saturated coating, the film mass decreased as Os(bpy)_3 complex was ejected from the coating. After one or two voltammetric cycles a steady state was achieved in which the ionic current at the coating/solution interface was caused by the cyclic ejection and injection of Na^+ ion.Electrochemical behavior of ion complex films consisting of poly (butyleneviologen) and an anionic amphiphile was studied in NaClO_4 aqueous solutions using quartz crystal resonator. The behavior as well as a visible spectrum of the reduced film changed largely at a NaClO_4 concentration range between 0.05 and 0.1 M,indicating that the film structure changed.Electrochemical behavior of polypyrrole films in D_2O media was different from that in H_2O media. Upon oxidation, the films were swollen, and the degree of swelling was larger in D_2O media. This difference may be ascribable to different interaction between polypyrrole and the solvents.