Square-Wave Voltammetry Determination of Ciprofloxacin in Pharmaceutical Formulations and Milk Using a Reduced Graphene Oxide Sensor

In this paper, a simple, sensitive and precise electroanalytical method was developed using a chemically-reduced graphene-oxide (CRGO)-modified glassy carbon electrode and square wave voltammetry (SWV) for determination of ciprofloxacin in pharmaceutical formulations (tablets) and milk samples. Advantages of this sensor include a potential displacement of 100 mV and a 5-fold current increase for the electrochemical oxidation of ciprofloxacin, which resulted in a highly sensitive sensor, when compared to unmodified electrode. The improved properties of the modified electrode are likely due to the formation of a porous surface evidenced by the change in electrode kinetics (thin-layer diffusion process). The proposed sensor is free from interference of sample matrix (pharmaceutical formulations and low/high-fat milk) avoiding cumbersome processes such as previous separations, solvent extraction, or sample filtration (samples were only diluted in Britton-Robinson buffer solution). The results by SWV showed a limit of detection of 0.21 µmol L-1 (correspondent to 0.069 mg L-1), which is lower than the ones obtained using other carbon-based electrodes, relative standard deviations lower than 12%, and satisfactory recoveries in the range from 84 to 109%. The results obtained were statistically similar (95% confidence level) with those performed through high-performance liquid chromatography (HPLC).