Zero-Background Surface-Enhanced Raman Scattering Detection of Cymoxanil Based on the Change of the Cyano Group after Ultraviolet Irradiation.

A zero-background method based on surface-enhanced Raman scattering (SERS) was developed for the rapid determination of cymoxanil residue in food. Because of the influence of complex matrices, conventional Raman spectroscopy has multiple peaks that overlap with those of target molecules, which makes qualitative and quantitative detection difficult. However, the cyano group (C≡N) of cymoxanil after ultraviolet irradiation has a special characteristic peak in the Raman-silent region (1800-2800 cm-1), which eliminates the possible background interference. The intensity of the characteristic peak at 2130 cm-1 exhibited a good linear relationship (R2 = 0.9907) with the concentration of cymoxanil in the range of 1.0-50.0 mg/L, whose limit of detection was 0.5 mg/L. The novel method was also applied to the detection of cymoxanil residue in real samples such as cucumber and grape, and the results were in good agreement with those from high-performance liquid chromatography analysis. This revealed that the SERS method has great potential in the detection of cymoxanil in fruits and vegetables. Moreover, ultraperformance liquid chromatography-quadrupole-time-of-flight-mass spectrometry (UPLC-QTOF/MS) was adopted to identify the photoproducts of cymoxanil. The photolysis mechanism was explored by SERS and the UPLC-QTOF/MS technique, which provided basic information on photodegradation of cymoxanil.