Abstract Surface Enhanced Raman Spectroscopy (SERS) is a highly specific, sensitive, and portable technique with great potential for on-site pesticide detection and monitoring. Endosulfan, an organochlorine pesticide known for its high toxicity, slow degradation, and bioaccumulation, has poor affinity for metallic SERS substrates. This study presents a label-free SERS detection method for endosulfan, using aggregating agents like potassium chloride (KCl), potassium hydroxide (KOH), potassium bromide (KBr), and sodium hydroxide (NaOH) to modify the behavior of Ag colloidal nanoparticles (NPs) and enhance the SERS signal of endosulfan molecules trapped within formed hot-spots. We analyzed the UV–Vis spectra, the hydrodynamic diameter, and zeta-potential of Ag NPs with the addition of these agents and endosulfan. Successful detection of both α- and ß- endosulfan isomers at μM concentrations in both ethanol and methanol was achieved with KOH-treated Ag NPs. The method was also applied to detect endosulfan in real water samples, along with simultaneous detection of λ-cyhalothrin, showcasing its capability to identify multiple analytes. The selectivity and specificity were confirmed using a mixture of endosulfan and thiabendazole, highlighting the crucial role of selecting the appropriate aggregating agent for each analyte. Overall, the findings emphasize the potential of aggregating agents to mediate the SERS enhancement of endosulfan, facilitating simple and rapid protocols for environmental pollutant detection, while shedding light on the intricate interplay between NP behavior, surface chemistry, and analyte interaction.
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