Application of an ultrahigh-performance liquid chromatography coupled to quadrupole-orbitrap high-resolution mass spectrometry for the rapid screening, identification and quantification of illegal adulterated glucocorticoids in herbal medicines

- Ultra-sensitive and unambiguous detection of 14 glucocorticoids in herbal medicines.
- Q-Orbitrap HRMS in full MS/dd-MS2 mode was used for qualitation and quantitation.
- Good linearity, accuracy, precision and selectivity were observed upon HRMS analysis.
- Prednisone, prednisone acetate and cortisone acetate were detected in collected samples.

In this work, the ultrahigh-performance liquid chromatography quadrupole orbitrap high resolution mass spectrometry (UHPLC-Q-Orbitrap HRMS) was applied to the rapid screening, identification and quantification of the illegal adulterated glucocorticoids in herbal medicines. The mass spectrometer was operated in positive ion mode and Full MS/dd-MS2 (data-dependent MS2) mode, where selected ions were subjected to a dd-MS2 scan with given fragmentation energy following a Full MS scan. The application of 70 000 FWHM mass resolution and narrow mass windows (5 ppm) effectively improve the selectivity of the method, and a single injection was sufficient to perform the simultaneous screening and identification/quantification of 14 glucocorticoids in 15 min. The method validation including selectivity, sensitivity, calibration curve, accuracy, precision, recovery, matrix effect and stability were evaluated. The results of all analytes showed excellent linear relationship while all coefficient of determination (r2) were > 0.9990 over wide concentration ranges (e.g., 5-1000 ng/mL for hydrocortisone butyrate, r2 = 1.0000). The recoveries were in the range of 86.1-102.7%, while the matrix effects ranged from 95.8%-105.8%. Accuracies and precisions were performed. The intra- and inter-day accuracies ranged from 90.6% to 108.9%, while the intra- and inter-day precisions were in the range of 0.5% to 8.5%. Finally, the established method was employed to detect illegal adulterated glucocorticoids in herbal medicines. It will provide more reliable technical basis for the drug quality supervision department and ensure public health.