Rapid determination of antiviral drugs in yellow catfish (Pelteobagrus fulvidraco) using graphene/silica nanospheres (G/KCC-1) based pipette tip solid-phase extraction with ultra-performance liquid chromatography-tandem mass spectrometry

Yellow catfish ( Pelteobagrus fulvidraco ) is commonly contaminated by protease inhibitors because of the illegal use of antiviral drugs in aquaculture, so the determination of antiviral drugs is essential in food safety supervision. In this study, a novel sorbent, graphene and silica nanospheres composite (G/KCC-1), was synthesized for pipette-tip-based solid-phase extraction (PT-SPE) and purification of ritonavir, saquinavir, and indinavir in yellow catfish, followed by ultra-performance liquid chromatography and tandem mass spectrometry (UPLC-MS/MS) analysis. The wrinkly structure of G/KCC-1 with center-radial nanowrinkles enlarged the surface area and increased the capacity of absorbing the target analyte. With the proposed G/KCC-1 based PT-SPE UPLC-MS/MS method, the pH of sample solution, aspirating/dispensing cycles for extraction and elution were optimized to be 4.0, 25, and 10 respectively, and the eluting solvent was methanol/ammonia (95:5, v/v) with 0.02 M sodium chloride. This new method was further validated to be linear (correlation coefficient R 2 , 0.9993–0.9996), sensitive (limit of detection, LOD ≤ 0.8 ng mL −1 ), accurate (89.3–114.2%), and precise (relative standard deviation, RSD ≤ 6.23%). These results indicated that the proposed method is qualified in bioanalytical method validation and meets the requirements for detecting illegally used antiviral drugs in yellow catfish. The demonstrated G/KCC-1 based PT-SPE UPLC-MS/MS method is a potential analytical method in food and drug administration.