Laser-scribed Graphene Electrodes Functionalized with Nafion/Fe₃O₄ Nanohybrids for the Ultrasensitive Detection of...

The analysis of pharmaceutical active ingredients plays an important role in quality control and clinical trials because they have a significant physiological effect on the human body even at low concentrations. Herein, a flexible three-electrode system using laser-scribed graphene (LSG) technology, which consists of Nafion/Fe₃O₄ nanohybrids immobilized on LSG as the working electrode and LSG counter and reference electrodes on a single polyimide film, is presented. A Nafion/Fe₃O₄/LSG electrode is constructed by drop coating a solution of Nafion/Fe₃O₄, which is electrostatically self-assembled between positively charged Fe₃O₄ and negatively charged Nafion on the LSG electrode and is used for the first time to determine a neurotoxicity drug (clioquinol; CQL) in biological samples. Owing to their porous 3D structure, an enriched surface area at the active edges and polar groups (OH, COOH, and -SO₃H) in Nafion/Fe₃O₄/LSG electrodes resulted in excellent wettability to facilitate electrolyte diffusion, which gave ∼twofold enhancement in electrocatalytic activity over LSG electrodes. The experimental parameters affecting the analytical performance were investigated. The quantification of clioquinol on the Nafion/Fe₃O₄/LSG electrode surface was examined using differential pulse voltammetry and chronoamperometry techniques. The fabricated sensor displays preferable sensitivity (17.4 μA μM^-1 cm^-2), a wide linear range (1 nM to 100 μM), a very low detection limit (0.73 nM), and acceptable selectivity toward quantitative analysis of CQL. Furthermore, the reliability of the sensor was checked by CQL detection in spiked human blood serum and urine samples, and satisfactory recoveries were obtained.