H2O2-Generating Peroxidase Electrodes as Reagentless Cyanide Sensors

Abstract
Inexpensive, reagentless, and simple (single-electrode) cyanide biosensors are developed using a pyrolytic graphite (PG) electrode on which horseradish peroxidase (HRP) is adsorbed. The electrode is poised at −300 mV vs Ag/AgCl for 40 s to reduce dissolved O2 to H2O2 at the PG surface. The generated H2O2 accumulates in the diffusion layer. The potential is then stepped to 0 mV, at which the accumulated H2O2 is reduced, though the O2 reduction does not proceed. Since the H2O2 reduction is catalyzed by HRP, the transient cathodic current is inhibited by cyanide. Therefore, the transient current is a function of the cyanide concentration. A HRP/PG electrode with saturated HRP coverage is reliable, and it can determine 10-5−10-3 M cyanide. On the other hand, the electrode with lower HRP coverage is less reliable, though it is so sensitive as to detect 2 × 10-7 M cyanide because the system is under kinetic control.