5-hydroxytryptophan (5-HTPP) as a precursor of a catalyst for the oxidation of NADH

Abstract

Following oxidation of 5-hydroxytryptophan (5-HTPP) at a pyrolytic graphite electrode at pH 7.5, two quasi-reversible redox couples emerge at −0.170 and +0.032 V, respectively, due to oxidation products strongly adsorbed to the electrode surface.These redox processes have been electrochemically and kinetically characterized in terms of the dependence of the formal potential (E°‘) with pH, variation of the current density with scan rate, operational stability, and electron-transfer rate constant (ks). The wave centered at +0.032 V could mediate the oxidation of NADH, exhibiting a strong and persistent electrocatalytic response. A quinone-imine structure has been proposed as the electrocatalytically active species. The kinetics of the reaction between the mediator and NADH has been characterized via rotating disk electrode voltammetry, and it has been found that the rate constant for the reaction is dependent on the solution concentration of NADH. 5-HTPP modified electrodes could be employed in the amperometric detection of NADH with a limit of detection in the nanomolar range. Moreover, 5-HTPP modified electrodes retain their electrocatalytic activity for at least one week. The potential application of these electrodes to amperometric biosensor is demonstrated.