Highly Sensitive and Rapid Surface Enhanced Raman Spectroscopic (SERS) Determination of Thiram on the Epidermis of Fruits and Vegetables Using A Silver Nanoparticle-Modified Fibrous Swab

A surface enhanced Raman spectroscopy (SERS) substrate with high sensitivity for the rapid determination of pesticide residues was developed by combining silver nanoparticles (AgNPs) and a fibrous swab. The SERS substrate was prepared simply by forming a SERS-active area on the section of fibrous swab and centrifuge tube with a soak-absorb approach. Rhodamine 6 G (R6G), a common SERS probe molecule, was used for performance characterization of the prepared SERS substrate that was shown to have high sensitivity, good stability and good reproducibility. Due to its good flexibility, the prepared SERS substrate was used to wipe contaminated surfaces for residue extraction. High sensitivity for detecting trace-level pesticides was verified for thiram. The limits of detection (LODs) for thiram on apple, grape and eggplant epidermis were calculated to be as low as 0.5313, 0.5768, and 0.5495 ng·cm−2, respectively, nearly 2 orders of magnitude below the maximum residue limit (MRL) for pesticide in food issued by the National Food Safety Standard of China. In addition, there was a linear relationship between the SERS intensity and the concentration of thiram in these three samples, indicating the good potential of this substrate for quantitative SERS analysis.