We report the redox mediation of glucose oxidase (GOx) in aself-assembled structure of cationic poly(allylamine) modified by ferrocene (PAA-Fc) and anionic GOx depositedelectrostatically layer-by-layer onnegatively charged alkanethiol-modified Au surfaces. SuccessivePAA-Fc and GOx layers were depositedby alternate immersion of the thiol-modified Au in the respectivepolyelectrolyte and enzyme solutions.The uptake of thiol, redox polymer, and GOx on the surface wasmonitored by quartz crystal microbalance.Cyclic voltammetry shows nearly ideal surface waves of ferrocenein the polymer with charge independentof sweep rate; the redox surface concentration was obtained fromintegration of the ferrocene/ferriciniumvoltammetric peaks. The redox charge increases in step with thenumber of PAA-Fc layers deposited.Enzyme catalysis for the oxidation of
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D-glucosewas achieved with a multilayer PAA-Fc/GOx assembly,with each GOx layer contributing equally to the catalytic response.Only a small fraction of the activeassembled GOx molecules are "electrically wired" by the ferrocenepolymer although all of the enzymecould be oxidized by soluble ferrocenesulfonate when added tosolution.