A computational and experimental study of cis–trans isomeric pesticides based on collision‐induced dissociation of high‐resolution mass spectrometry

Abstract

RationalePesticide isomers are widely available in agricultural production and may vary widely in biological activity, potency, and toxicity. Chromatographic and mass spectrometric analysis of pesticide isomers is challenging due to structural similarities.MethodsBased on liquid chromatography time‐of‐flight mass spectrometry, identification of cis–trans isomeric pesticides was achieved through retention time, characteristic fragment ions, and relative abundance ratio. Furthermore, theoretical and basic research has been conducted on the differences in characteristic fragment ions and their relative abundance ratios of cis–trans isomers. On the one hand, the cleavage pathways of six cis–trans isomers were elucidated through collision‐induced dissociation to explain different fragment ions of the isomers. On the other hand, for those with the same fragment ions but different abundance ratios, energy‐resolved mass spectrometry combined with computational chemical density functional theory in terms of kinetics, thermodynamics, and bond lengths was employed to explain the reasons for the differences in characteristic fragment ions and their abundance ratios.ResultsA high‐resolution mass spectrometry method was developed for the separation and analysis of cis–trans isomers of pesticides in traditional Chinese medicine Radix Codonopsis, and six pesticide isomers were distinguished by retention time, product ions, and relative abundance ratios. The limits of quantification of the six pesticides were up to 10 μg/kg, and the linear ranges of them were 10–200 μg/kg, with coefficients of determination (R2) > 0.99, which demonstrated the good linearity of the six pesticides. The recoveries of the pesticides at spiked concentrations of 10, 20, and 100 μg/kg reached 70–120% with relative standard deviations ≤20%.ConclusionsIt was demonstrated that the application of the method was well suited for accurate qualitative and quantitative analysis for isomers with different structures, which could avoid false‐negative results caused by ignoring other isomers effectively.