Kinetic studies of the oscillatory dynamics in the peroxidase-oxidase reaction catalyzed by four different peroxidases.

Oscillatory kinetics in the peroxidase-oxidase reaction catalyzed by structurally different peroxidases were investigated using NADH as a substrate. For horseradish peroxidase, lactoperoxidase, and soybean peroxidase the oscillatory waveforms of their dominating enzyme intermediates, ferric peroxidase and compound III, are similar. Coprinus peroxidase, on the other hand, has ferrous peroxidase and compound III as the dominating intermediates. The oscillatory waveform of its compound III differs from the waveforms of compound III of the three other peroxidases. Also, the phase plot of the signal for compound III versus the oxygen concentration for Coprinus peroxidase differs from the corresponding phase plots obtained using other peroxidases. A detailed model of the reaction mechanism is proposed, which is able to simulate these different kinds of behaviour. Substituting NADH with dihydroxyfumaric acid as a substrate, oscillations in the oxygen concentration were observed for about 1.5 h when a concentrated solution of this substrate was continuously fed to a solution containing horseradish peroxidase. This is the first demonstration of sustained oscillations with this substrate.