A theoretical treatment of damped oscillations in the transient state kinetics of single‐enzyme reactions

An extension of the available kinetic theory for reactions in the transient state is presented which establishes that single‐enzyme reactions may exhibit damped oscillations under the conditions of standard kinetic experiments performed by stopped‐flow techniques. Such oscillations may occur for reasonable magnitudes of rate constants in the enzymic reaction mechanism and at physiological concentrations of enzyme and substrate. In the simplest reaction systems, the oscillations will be strongly damped and lead to progress curves resembling those of a reaction governed by standard exponential transients; statistical regression methods may then have to be applied for their detection and characterization. The observation that single‐enzyme reactions may exhibit oscillatory behaviour points to a previously unrecognized possible source of the damped oscillations observed in metabolic systems such as the pathways of glycolysis or photosynthesis.