Sensitive Detection of Fungicide Folpet by Surface-Enhanced Raman Scattering: Experimental and Theoretical Approach

In this work, Surface-Enhanced Raman Spectroscopy (SERS) was employed as an effective detection technique for folpet, characterized by its notable specificity and sensitivity. The investigation involved the use of UV–Vis, Raman, and SERS spectroscopy of folpet at different concentrations for a comprehensive study of plasmon-driven effects such as plasmon resonance, plasmon hybridization, and electric field enhancement resulting in the SERS’ intensification. Specifically, SERS detection of folpet solutions at concentrations below 100 µM is presented in detail by using Ag nanoparticles prepared with hydroxylamine reduction. The experimentation encompassed diverse conditions to optimize the detection process, with Raman spectra acquired for both folpet powder and aqueous solution of folpet at the natural pH. SERS analyses were conducted across a concentration range of 9.5 × 10−8 to 1.61 × 10−4 M, employing 532 nm excitation. The differences in the spectral profiles observed for folpet Raman powder and SERS are ascribed to N–S cleavage; these changes are attributed to plasmon catalysis induced by the used Ag nanoparticles. Transmission electron microscopy (TEM) was also important in the present analysis to better understand which mechanism of nanoparticles aggregation is more favorable for the SERS detection regarding the formation of hot spots in the suspension. Complementing the experimental data, the molecular structure and theoretical Raman spectra of the folpet molecule were calculated through density functional theory (DFT) methods. The outcomes of these calculations were crucial in the elucidation of folpet’s vibrational modes. The culmination of this research resulted in the successful detection of folpet, achieving a notable limit of detection at 4.78 × 10−8 M. This comprehensive approach amalgamates experimental and theoretical methodologies, offering significant insights into the detection capabilities and molecular characteristics of folpet via SERS analysis.