Sequential cyclic-square-wave voltammetric determination of sulfanilamide and ciprofloxacin in environment water samples using a 3D-printed electrochemical device

• Published in: Electrochimica acta Vol. 481; p. 143945
• Main Authors: Di-Oliveira, Marina, Araújo, Diele A.G., Ramos, David L.O., Faria, Lucas V. de, Rocha, Raquel G., Sousa, Raquel M.F., Richter, Eduardo M., Paixão, Thiago R.L.C., Munoz, Rodrigo A.A.
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 20-03-2024
• Subjects: 3D-printing; Activation procedure; Antibiotics; Cyclic-square-wave voltammetry; Environmental analysis; Activation procedure; Environmental analysis; Antibiotics; Cyclic-square-wave voltammetry; 3D-printing
• ISSN: 0013-4686; 1873-3859
• DOI: 10.1016/j.electacta.2024.143945

Sulfanilamide (SAD) and ciprofloxacin (CIP) are widely used antibiotics, and their indiscriminate use and disposal contribute to the increase in the contamination levels of aquatic environments. Herein, we propose a 3D-printed carbon black/polylactic acid (CB/PLA) electrochemically activated electrode to determine CIP and SAD concurrently by cyclic square-wave voltammetry (C-SWV) technique. Firstly, square wave voltammetry measurements were performed exploiting the oxidation processes of CIP and SAD (Ox1CIP and Ox1SAD at around +1.3 V and +1.1 V vs. Ag|AgCl|KCl(sat.)). However, the lack of selectivity was verified in the analysis of water samples. Then, the C-SWV strategy was employed and enabled the selective determination of CIP (Ox1CIP) in the forward scan and SAD (Red1SAD) at around +0.5 V vs. Ag|AgCl|KCl(sat.)) in the reverse scan. Under selected C-SWV conditions, linear ranges from 4.96 to 40.61 µmol L−1 (r = 0.9977) for CIP (Ox1CIP) and 1.99 to 10.78 µmol L−1 (r = 0.9989) for SAD (Red1SAD) were obtained. The limits of detection for SAD and CIP were 0.2 and 0.6 µmol L−1, respectively, and sensitivity was enhanced by 25 % for CIP and 60 % for SAD, employing the C-SWV protocol. In addition, this technique improves the selectivity once the analytes can be determined in distinct potential scans. Satisfactory recovery values ranging from 85 to 112 % were obtained in the analysis of spiked water samples (no dilution step), suggesting no pronounced matrix interference effect, and indicating that the C-SWV methodology ensures good accuracy. This work demonstrates that the union of 3D-printed CB/PLA electrodes and the C-SWV technique can enhance selectivity and sensitivity in the sequential analysis of CIP and SAD, and it is a promising strategy to monitor other pharmacological species in water samples.