| Summary: | Herein, a complete study of the electrochemical behavior of the most commonly used tetracycline antibiotics (TCs) on unmodified carbon screen-printed electrodes (SPEs) is presented. In addition, the oxidation pathway of TCs on SPE is elucidated, for the first time, with liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-QTOF-MS). Square wave voltammetry (SWV) was used to study the electrochemical fingerprint (EF) of the antibiotics shaping the different oxidation processes of the TCs in a pH range from 2 to 12. Their characteristic structure and subsequent EF offer the possibility of distinguishing this class of antibiotics from other types. Under the optimized parameters, calibration curves of tetracycline (TET), doxycycline (DOXY), oxytetracycline (OXY), and chlortetracycline (CHL) in a Britton Robinson buffer solution (pH 9) exhibited a linear range between 5 and 100 µM with excellent reproducibilities (RSD<sub>TET</sub> = 3.01%, RSD<sub>DOXY</sub> = 3.29%, RSD<sub>OXY</sub> = 9.78% and RSD<sub>CHL</sub> = 6.88% at 10 µM, N = 3) and limits of detection (LOD) of LOD<sub>TET</sub> = 4.15 µM, LOD<sub>DOXY</sub> = 2.14 µM, LOD<sub>OXY</sub> = 3.07 µM and LOD<sub>CHL</sub> = 4.15 µM. Furthermore, binary, tertiary, and complex mixtures of all TCs were analyzed with SWV to investigate the corresponding EF. A dual pH screening (pH 4 and pH 9), together with the use of a custom-made Matlab script for data treatment, allowed for the successful confirmation of a single presence of TCs in the unknown samples. Overall, this work presents a straightforward study of the electrochemical behavior of TCs in SPE, allowing for the future on-site identification of residues of tetracycline antibiotics in real samples.
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