Multifunctional Surface Enhanced Raman Scattering Substrate Fe 3O4 @AgNPs@MIL-101 for Pretreatment and Rapid Detection of Pesticide Residues on the Surface of Fruit Peels

Abstract

A multifunctional surface-enhanced Raman scattering substrate Fe₃O₄@AgNPs@MIL-101 was prepared. Rapid SERS detection of pesticide residues was realized by direct pre-enrichment and separation on the peel surface. MIL-101 has an ortho-octahedral framework and large pore size, which endowed Fe₃O₄@AgNPs@MIL-101 with the ability to rapidly adsorb and separate positively charged targets. The introduction of tannic acid realized the in situ growth of AgNPs on the backbone, to modulate the electromagnetic enhancement. Pesticide molecules were adsorbed onto the surface of AgNPs mediated by central S atoms, accompanied by the interaction between pesticide molecules and AgNPs, the corresponding SERS signals of different pesticides were observed. Together with the introduction of magnetic coating Fe₃O₄, the molecules were enriched in the hotspot and separated to further enhance the SERS performance. Magnet instead of centrifugation was used to simultaneously perform surface extraction and sample separation for a noninvasive, rapid, immediate, and portable assay. The method was accomplished in measurement of thiram and thiabendazole on apple and tangerine epidermis, and the limits of detection (LODs) were 20 ng/cm² and 4 μg/cm², respectively. The recovery was reasonable, and it showed that the procedure is valuable for the rapid and nondestructive surface analysis of residual chemicals.