Determination of Trace Levels of Fenbendazole in Milk, Yogurt and Curd Using Surface Enhanced Raman Spectroscopy (SERS)

Abstract

A simple, rapid and sensitive surface enhanced Raman spectroscopy (SERS) method is described for the determination of fenbendazole (FBZ) residues in milk and fermented dairy products using yogurt and curd as examples. An extraction method was used to purify the samples from interfering components of the matrix. 5-Nitrothiabendazole, which has similar physicochemical properties, was used as an internal standard. The detection limits for milk were 1.8 nM, 8.8 nM for yogurt, and 13.5 nM for curd. Using partial least squares (PLS), a calibration model was built for the determination of fenbendazole from 100 to 1000 nM. The root-mean square error of calibration (RMSEC) and the root-mean square error of prediction (RMSEP) were 39.4 and 46.5 nM, respectively. The recovery rate was from 97% to 120% and the relative standard deviation was less than 5.0%. The difference between this technique from the widely used liquid chromatography–mass spectrometry (LC–MS) method is in the reduction in time for preliminary sample preparation and significantly lower costs for reagents and consumables. The article examines the influence of order when mixing reagents in a SERS experiment, which is an important tool for optimizing the sensitivity and reproducibility of the method. It was shown for the first time that when various alkaline earth metal chlorides were used for agglomeration of silver nanoparticles (AgNPs), a change in the ratio of peak intensities of the two analytes in the solution was observed. This phenomenon may be used to increase the selectivity of SERS analysis of multicomponent samples.