Mussel-Inspired Fabrication of SERS Swabs for Highly Sensitive and Conformal Rapid Detection of Thiram Bactericides

摘要

As an important sort of dithiocarbamate bactericide, thiram has been widely used for fruits, vegetables and mature crops to control various fungal diseases; however, the thiram residues in the environment pose a serious threat to human health. In this work, silver nanoparticles (AgNPs) were grown in-situ on cotton swab (CS) surfaces, based on the mussel-inspired polydopamine (PDA) molecule and designed as highly sensitive surface-enhanced Raman scattering (SERS) swabs for the conformal rapid detection of bactericide residues. With this strategy, the obtained CS@PDA@AgNPs swabs demonstrated highly sensitive and reproducible Raman signals toward Nile blue A (NBA) probe molecules, and the detection limit was as low as 1.0 × 10⁻¹⁰ M. More critically, these CS@PDA@AgNPs swabs could be served as flexible SERS substrates for the conformal rapid detection of thiram bactericides from various fruit surfaces through a simple swabbing approach. The results showed that the detection limit of thiram residues from pear, grape and peach surfaces was approximately down to the level of 0.12 ng/cm², 0.24 ng/cm² and 0.15 ng/cm² respectively, demonstrating a high sensitivity and excellent reliability toward dithiocarbamate bactericides. Not only could these SERS swabs significantly promote the collection efficiency of thiram residues from irregular shaped matrices, but they could also greatly enhance the analytical sensitivity and reliability, and would have great potential for the on-site detection of residual bactericides in the environment and in bioscience fields.