A Sensitive SERS Sensor Combined with Intelligent Variable Selection Models for Detecting Chlorpyrifos Residue in Tea

Chlorpyrifos is one of the most widely used broad-spectrum insecticides in agriculture. Given its potential toxicity and residue in food (e.g., tea), establishing a rapid and reliable method for the determination of chlorpyrifos residue is crucial. In this study, a strategy combining surface-enhanced Raman spectroscopy (SERS) and intelligent variable selection models for detecting chlorpyrifos residue in tea was established. First, gold nanostars were fabricated as a SERS sensor for measuring the SERS spectra. Second, the raw SERS spectra were preprocessed to facilitate the quantitative analysis. Third, a partial least squares model and four outstanding intelligent variable selection models, Monte Carlo-based uninformative variable elimination, competitive adaptive reweighted sampling, iteratively retaining informative variables, and variable iterative space shrinkage approach, were developed for detecting chlorpyrifos residue in a comparative study. The repeatability and reproducibility tests demonstrated the excellent stability of the proposed strategy. Furthermore, the sensitivity of the proposed strategy was assessed by estimating limit of detection values of the various models. Finally, two-tailed paired t-tests confirmed that the accuracy of the proposed strategy was equivalent to that of gas chromatography-mass spectrometry. Hence, the proposed method provides a promising strategy for detecting chlorpyrifos residue in tea.