Profiling of phenolic flavorings using core-shell reversed-phase liquid chromatography with electrochemical detection at a boron-doped diamond electrode

A high-performance liquid chromatography (HPLC) method equipped with a boron-doped diamond (BDD) electrode was established for the simultaneous determination of phenol, 4-ethylphenol (4-EP), guaiacol, 4-ethylguaiacol (4-EG), 4-vinylguaiacol (4-VG), eugenol, and o-, m- and p-cresol. The separation was performed on a reversed-phase HALO C₁₈ core-shell column (3.0 × 50 mm, 2.7 µm) with a mobile phase comprising 10 mM formate, pH 3, and 15% acetonitrile (ACN) (v/v), a flow rate of 1.5 mL/min, corresponding to a total run time of 9 min. The electrochemical detection (ECD) was set at +1.5 V vs. Pd/H₂ in oxidative mode. Under optimized operating conditions, good linearity was obtained for the nine phenolics with corresponding coefficients of determination (R²) above 0.998. The limits of detection (LODs, S/N = 3) were 10 nM–1 µM, with an 80-fold increase in sensitivity for guaiacol achieved with ECD over ultraviolet (UV) detection. The sensitive and selective HPLC-ECD method was successfully applied for the identification and quantification of the nine phenolics in Islay, Irish, Scotch, and Highland whiskey samples, with significantly higher concentrations of the flavorings determined in Islay whiskey.