Electrochemical oxidation mechanism of eugenol on graphene modified carbon paste electrode and its analytical application to pharmaceutical analysis

Electrochemical properties of eugenol were investigated on a graphene modified carbon paste electrode (CPE) by using voltammetric methods, which exhibited a well-defined irreversible peak at about 0.7 V vs Ag/AgCl, NaCl (3 M) in Britton-Robinson buffer at pH 2.0. Mechanism of the electrochemical reaction of eugenol was studied by performing density functional theory (DFT) computations and mass spectroscopic analysis. (CPCM:water)-wB97XD/aug-cc-PVTZ//(CPCM:water)-wB97XD/6-31G(d) level calculations predicted that the formation of product P2, possessing a para-quinoid structure, is preferred rather than the product P1, suggested in the literature, having an ortho-quinoid system. Determination of eugenol in a pharmaceutical sample was realized in the light of the electrochemical findings, and a validated voltammetric method for quantitative analysis of eugenol in a pharmaceutical formulation was proposed. The differential pulse voltammogram (DPV) peak currents were found to be linear in the concentration range of 1.0 × 10⁻⁷ to 1.7 × 10⁻⁵ M. The limit of detection (LOD) and the limit of quantification (LOQ) were obtained to be 7.0 × 10⁻⁹ and 2.3 × 10⁻⁸, respectively.