Ratiometric fluoroprobe based on Eu-MOF@Tb3+ for detecting tetracycline hydrochloride in freshwater fish and its application in rapid visual detection

Abstract

Tetracycline hydrochloride (TCH), a prevalent antibiotic in aquaculture for treating bacterial infections, poses challenges for on-site detection. This study employed the reversed-phase microemulsion method to synthesize a uniform nano metal-organic framework (MOF) material, europium-benzene-p-dicarboxylic acid (Eu-BDC), doped with Tb3+ to form a dual-emission fluorescence probe. By leveraging the combined a-photoinduced electron-transfer (a-PET) and inner filter effect (IFE) mechanisms, high-sensitivity TCH detection in Carassius auratus and Ruditapes philippinarum was achieved. The detection range for TCH is 0.380–75 μM, with a low limit of detection (LOD) at 0.115 μM. Upon TCH binding, Eu-BDC fluorescence rapidly decreased, while Tb3+ fluorescence remained constant, establishing a ratiometric fluorescence change. Investigation into the TCH quenching mechanism on Eu-BDC was conducted using time-dependent density functional theory (TD-DFT) calculations and fluorescence quenching kinetic equations, suggesting a mixed quenching mechanism. Furthermore, a novel photoelectric conversion fluorescence detection device (FL-2) was developed and evaluated in conjunction with high-performance liquid chromatography-diode-array detection (HPLC-DAD). This is the first dedicated fluorescence device for TCH detection, showcasing superior photoelectric conversion performance and stability that reduces experimental errors associated with smartphone photography methods, presenting a promising avenue for on-site rapid TCH detection.