Qualitative and quantitative analysis of chlorpyrifos residues in tea by surface-enhanced Raman spectroscopy (SERS) combined with chemometric models

Abstract

Surface-enhanced Raman spectroscopy (SERS) combined with chemometric models were employed to develop a rapid, low-cost, and sensitive method for qualitative and quantitative analysis of chlorpyrifos residues in tea. Au@Ag nanoparticles (NPs) with high enhancement factor were synthesized and coupled with chemometric algorithms for SERS measurements. K-nearest neighbors (KNN) classification models gave the best performance model with high classification rates (90.84–100.00%) achieved. For the quantification models for predicting chlorpyrifos contents, the genetic algorithm-partial least squares (GA-PLS) models and synergy interval partial least squares-genetic algorithm (siPLS-GA) models applied to standard normal variate transformation (SNV) preprocessed training and validation data set showed better prediction performances with excellent regression quality (slope = 0.98–1.00), higher correlation coefficient of determination (r2 = 0.96–0.98), and lower root-mean-square error of prediction (RMSEP = 0.29, 0.31) than other quantification models. Paired sample t-test exhibited no statistically significant difference between the reference values determined by GC-MS and the predicted values in most quantification models. The proposed method would be a more effective and powerful tool for classification and determination of chlorpyrifos (CPS) residues in tea samples.