In-situ SERS detection of quinolone antibiotic residues in aquaculture water by multifunctional Fe3O4@mTiO2@Ag nanoparticles

Antibiotic residues in aquaculture environments disrupt the ecosystem balance and pose a potential hazard to human health when entering the food chain. Therefore, ultra-sensitive detection of antibiotics is necessary. In this study, a multifunctional Fe3O4@mTiO2@Ag core-shell nanoparticle (NP), synthesized using a layer-by-layer method, was demonstrated to be useful as an enhanced substrate for in-situ surface-enhanced Raman spectroscopy (SERS) detection of various quinolone antibiotics in aqueous environments. The results showed that the minimum detectable concentrations of the six investigated antibiotics were 1 x 10-9 mol/L (ciprofloxacin, danofloxacin, enoxacin, enrofloxacin, and norfloxacin) and 1 x 10-8 mol/L (difloxacin hydrochloride) under the enrichment and enhancement of Fe3O4@mTiO2@Ag NPs. Additionally, there was a good quantitative relationship between the antibiotics concentrations and SERS peak intensities within a certain detection range. The results of the spiked assay of actual aquaculture water samples showed that the recoveries of the six antibiotics ranged from 82.9% to 113.5%, with relative standard deviations ranging from 1.71% to 7.24%. In addition, Fe3O4@mTiO2@Ag NPs achieved satisfactory results in assisting the photocatalytic degradation of antibiotics in aqueous environments. This provides a multifunctional solution for low concentration detection and efficient degradation of antibiotics in aquaculture water.