Theoretical predictions and experimental verifications of SERS detection in colorants

Synthetic colorants added during food processing not only fail to provide nutrients, but also can be harmful to human health when used in excess. To establish a simple, convenient, rapid and low-cost surface-enhanced Raman spectroscopy (SERS) detection method for colorants, an active surface-enhanced substrate of colloidal gold nanoparticles (AuNPs) was prepared in this study. The density functional theory (DFT) method of B3LYP with 6-31G(d) was applied to determine the theoretical Raman spectra of erythrosine, basic orange 2, 21 and 22, and to attribute their characteristic spectral peaks. The SERS spectra of the four colorants were pre-processed using local least squares (LLS) and morphological weighted penalized least squares (MWPLS), and multiple linear regression (MLR) models were established to quantify the four colorants in beverages. The results showed that the prepared AuNPs with a particle size of about 50 nm were reproducible and stable, with a good enhancement of the SERS spectrum of rhodamine 6G at 10^-8 mol L^-1. The theoretical Raman frequencies were in good agreement with the experimental Raman frequencies, and the peak position differences of the main characteristic peaks of the four colorants were within 20 cm^-1. The MLR calibration models for the concentrations of the four colorants showed relative errors of prediction (REP) of 2.97-8.96%, root mean square errors of prediction (RMSEP) of 0.03-0.94, R² of 0.973-0.999, and limits of detection of 0.06 μg mL^-1. The present method could be used to quantify erythrosine, basic orange 2, 21, and 22, revealing its wide range of applications in food safety.