QuEChERS Multiresidue Method Validation and Mass Spectrometric Assessment for the Novel Anthranilic Diamide Insecticides Chlorantraniliprole and Cyantraniliprole

Abstract

The gas-phase dissociation reactions of chlorantraniliprole (Rynaxypyr) and cyantraniliprole (Cyazypyr) have been studied in triple-quadrupole, ion trap, and orbitrap mass spectrometers equipped with electrospray and desorption electrospray ion sources, revealing the formation of odd-electron fragment ions, the structures of which were elucidated. The odd-electron fragments were unusually abundant, and their formation is proposed to occur via a tricyclic intermediate. The applicability of the QuEChERS multiresidue method for the quantitation of chlorantraniliprole and cyantraniliprole was also assessed in this study. Four matrices representative of oily, watery, acidic, and dry crop groups were tested, with a targeted limit of quantitation (LOQ) of 0.01 mg/kg. Average recoveries ranged between 87 and 107%, with relative standard deviations (RSD) of ≤ 8%. Linear calibration functions with correlation coefficients r > 0.99 were obtained. The study provides an expansion of the QuEChERS method to include anthranilic diamides and a mass spectrometric assessment for these two novel agrochemical active ingredients.

Determination of cyantraniliprole and its major metabolite residues in vegetable and soil using ultra‐performance liquid chromatography/tandem mass spectrometry

“…. The run time of cyantraniliprole and J9Z38 separation was 3.5 min, representing a major advantage of the proposed method when compared with previously reported HPLC‐MS/MS methods, with a run time of at least 16 min (Schwarz et al , ). The peak width at the base was 0.05 min for cyantraniliprole and J9Z38, and the MS detection conditions with a dwell time of 100 ms were maintained to ensure that approximately 20 data points were acquired for cyantraniliprole and J9Z38 chromatographic peaks.…”

“…Until nowm to our knowledge, studies of cyantraniliprole have focused on chemical synthesis, toxicology, mode of action and efficacy (Feng et al , ; Fettig et al , ; Lahm et al , ), in contrast, papers on analytical methods for cyantraniliprole residue seem to be rare. Indeed, only Schwarz et al have conducted studies on the gas‐phase dissociation reactions of cyantraniliprole in different mass spectrometers with electrospray, and the applicability of the analytical method for the determination of cyantraniliprole in crops using high‐performance liquid chromatography (HPLC) coupled with mass spectrometry (MS/MS; Schwarz et al , ). However, a residue analytical method for cyantraniliprole in soil and vegetables has not been reported to date, especially in regard to the analysis of the metabolites of cyantraniliprole.…”

Analysis of amicarbazone and its two metabolites in grains and soybeans by liquid chromatography with tandem mass spectrometry

“…Based on the solid phase, the optimization of mobile phase was also carried out in the pilot test. Formic acid , ammonium acetate and the mixture of formic acid and ammonium acetate , the most frequently used additives in the mobile phase, has been compared for analysis of the pesticides in the present study. Four mobile phases, including (A) methanol/water, (B) methanol/water containing 0.05% formic acid, (C) methanol/water containing 5 mmol/L ammonium acetate, (D) methanol/water containing 5 mmol/L ammonium acetate and 0.05% formic acid, were compared to obtain optimal instrument responses, better peak shapes and satisfactory separation efficiencies.…”

Development and Validation of QuEChERS Method for Estimation of Chlorantraniliprole Residue in Vegetables

“…The recoveries percentages are given in Table 1. A QuEChERS validated for chlorantraniliprole using acetonitrile, PSA, MgSO 4 , and citrate buffering salts, demonstrated acceptable chlorantraniliprole recoveries (>90%) from corn, wheat, lettuce and orange (Schwarz and others 2011). The disagreement to the results given in Table 1 may be due to the use of buffering salts and the matrices used in that study.…”