Electrochemical Quartz Crystal Impedance Study of Redox Hydrogel Mediators for Amperometric Enzyme Electrodes

Quartz crystal impedance around the resonant frequency at 10 MHz of a composite quartz crystal resonator has been studied simultaneously with cyclic voltammetry. A modified quartz crystal with a redox hydrogel (poly(allylamine)-ferrocene cross-linked with glucose oxidase) and immersed in liquid electrolyte was used. Impedance parameters (R(f) and X(L)((f))) of the surface redox gel film were obtained by fitting the resonator transfer function |V(o)/V(i)| vs ω to a BVD equivalent circuit and analyzed with the multiple nonpiezoelectric layer model of Martin. Two limiting hydrogel layers of the same composition were studied while oxidizing and reducing the ferrocene/ferricenium moieties attached to the swollen polymer backbone: thin and thick redox hydrogel films. For the thin films, the Sauerbrey approximation was valid. The mass/thickness and film viscosity changes that resulted from the anion and water exchange were evaluated while redox switching the polymer on the assumption of negligible storage modulus G' and a density of 1. For thick gel layers, on the other hand, the penetration depth of the acoustic wave was far less than the film thickness, and a liquid-like behavior was apparent. Film storage modulus and film loss modulus were simultaneously evaluated with the cyclic voltammetry.