Flow-based method for epinephrine determination using a solid reactor based on molecularly imprinted poly(FePP–MAA–EGDMA)

Abstract

A solid phase reactor based on molecularly imprinted poly(iron (III) protoporphyrin-methacrylic acid-ethylene glycol dimethacrylate) (MIP–MAA) has been synthesized by bulk method and applied as an selective material for the epinephrine determination in the presence of hydrogen peroxide. In order to prove the selective behaviour of MIP, two blank polymers named non-imprinted polymer (NIP1), non-imprinted polymer in the absence of hemin (NIP2) as well as a poly(iron (III) protoporphyrin-4-vynilpyridine-ethylene glycol dimethacrylate) (MIP–4VPy) were synthesized. The epinephrine-selective MIP–MAA reactor was used in a flow injection system, in which an epinephrine solution (120μL) at pH 8.0 percolates in the presence of hydrogen peroxide (300μmolL−1) through MIP–MAA. The oxidation of epinephrine by hydrogen peroxide is increased by using MIP–MAA, being the product formed monitored by amperometry at 0.0V vs. Ag/AgCl. The MIP–MAA showed better selective behaviour than NIP1, NIP2 and MIP–4VPy, demonstrating the effectiveness of molecular imprinting effect. Highly improved response was observed for epinephrine in detriment of similar substances (phenol, ascorbic acid, methyl-l-DOPA, p-aminophenol, catechol, l-DOPA and guaiacol). The method provided a calibration curve ranging from 10 to 500μmolL−1 and a limit of detection of 5.2μmolL−1. Kinetic data indicated a value of maximum rate Vmax (0.993μA) and apparent Michaelis–Menten constant of Kmapp(725.6μmolL−1). The feasibility of biomimetic solid reactor was attested by its successful application for epinephrine determination in pharmaceutical formulation.