Flexible TiO2/ZrO2/AuCNAs Surface-Enhanced Raman Scattering Substrates for the Detection of Asomate in Apple Peel

(1) Background: Asomate, as a dithiocarbamate compound, is moderately toxic to the human body; thus, it is necessary to develop a rapid and efficient method for detection. To meet this need, this study introduced a rapid, non-destructive, and efficient method for detecting asomate residues on the surface of apples based on surface-enhanced Raman spectroscopy (SERS) combined with flexible substrates. (2) Methods: Concave Au nanorods (AuCNAs) were synthesized in advance. Then, the AuCNAs were loaded on an electrostatically spun film to generate a flexible TiO₂/ZrO₂/AuCNAs substrate for detection. (3) Results: The flexible substrate exhibited strong SERS activity, with an enhancement factor (EF) up to 9.40 × 10⁷ for 4-MBA. Meanwhile, the finite-difference time-domain (FDTD) simulation showed that the localized surface plasmon resonance (LSPR) effects related to the enhancement of the SERS signal are mainly generated from the 'hot spots' in AuCNAs. The density functional theory (DFT) simulation detailedly revealed that the SERS peaks could be generated by the interaction among asomate molecules, disassociated Au atoms, and Au facets. Moreover, the asomate in apple peel was analyzed with the limit of detection (LOD) as low as below 10 nM, allowing for the rapid detection of asomate directly on apple peels. (4) Conclusions: The flexible TiO₂/ZrO₂/AuCNAs film can be used for the in situ detection of asomate in apple peel at low concentrations. Moreover, the simulation methods, including FDTD and DFT, explained the mechanism of SERS from the flexible substrates.