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.

The characterization of biological systems on a molecular level has led to sweeping developments in industries including pharmaceuticals, consumer product manufacturing, and environmental monitoring. The integrity of the sample preparation process is critical for development and discovery efforts in these fields. The art of biological sample preparation is in a perpetual state of evolution where boundaries and limitations reflect the sophistication of contemporary technology. Historical methods required laborious multistep procedures that resulted in analytical measurements with limited throughput and poor detection limits due to analyte losses. Present efforts in the scientific community are moving toward automated methods that require minimal sample volume and minimal sample cleanup. This change in the approach is due to the increasing selectivity of analytical systems that allow analyte separation and purification to be performed online with a variety of detectors. Trends of this nature are consistent with the ‘green chemistry’ efforts, where less solvent consumption provides a more environmental friendly (and cost‐effective) platform for the next stage of development in this field. This article revisits historical approaches and describes current trends in the preparation of biological samples.