Plasmonic 3-D wrinkled polymeric shrink film-based SERS substrates for pesticide detection on real-world surfaces

The continuous and excessive use of agrochemicals for crop improvement and protection has raised widespread concern, as they exert adverse effects on human health and the local environment. Surface Enhanced Raman Spectroscopy (SERS) provides a method for the quick identification and detection of such hazardous substances in a short amount of time due to its properties of being robust, accurate, sensitive and non-destructive. Despite the fact that several SERS substrates have been developed, the bulk of them are ineffective in terms of sample collection or providing reproducible results. In this study, we showed that a 3-D wrinkled polymeric heat-shrink film coated with Au bead@Ag nanorods (silver nanorods) serves as a potential SERS substrate for trace analysis. The surface of the heat-shrink film became wrinkled after heating, and this, along with the spatial arrangement of nanoparticles, significantly enhances the Raman signal of the analytes. The fabricated SERS substrate was able to sense two model analytes 1,4-benzenedithiol (BDT) and 2-naphthalenethiol (NT) up to 10^-13 M and 10^-11 M concentrations. The fabricated substrate was also effective in sensing thiram down to 10^-13 M concentration. Additionally, the SERS substrate was applied in a real-world setting for the detection of the pesticide thiram spiked onto apple skin surfaces. To collect the thiram residues, the substrate was simply swabbed across the surface of the apple. This allowed for the detection of thiram at concentrations as low as 10^-9 M (1 ppb). The fabricated SERS substrate can thus detect analytes in an efficient, sensitive, dependable and accurate manner, allowing for the sensing of trace analytes like pesticides in a real-world environment.