Development of a novel wavelength selection method for the trace determination of chlorpyrifos on Au@Ag NPs substrate coupled surface-enhanced Raman spectroscopy

A novel wavelength selection method, namely interval combination population analysis-minimal redundancy maximal relevance (ICPA-mRMR), was employed for the trace level detection of chlorpyrifos (CPS) coupled surface-enhanced Raman spectroscopy (SERS). Herein, a highly sensitive SERS enhancement substrate, Au@Ag nanoparticles (NPs), was synthesized possessing strong enhancement of Raman signals for CPS quantification (enhancement factor: 2.5 × 106). Compared with other established methods such as partial least squares (PLS), synergy interval partial least squares-genetic algorithm (siPLS-GA) and competitive adaptive reweighted sampling-partial least squares (CARS-PLS), ICPA-mRMR yielded the best results with higher correlation coefficients (Rc = 0.9917, RP = 0.9895), ratios of performance to deviation (RPD = 6.8797), and lower root mean square errors (RMSEC = 0.1998, RMSEP = 0.2271). The proposed method was employed for the determination of trace level CPS in tea samples, and the recovery percentages were in the range 90%–108%. Meanwhile, this method was validated using a standard GC-MS method indicating no significant difference (P > 0.05). The proposed methodology offers a rapid, sensitive and powerful analytical platform for the detection of pesticide residues in food.