High performance liquid chromatography–electrospray ionization-mass spectrometry with programmed ionization mode switching and time segment scanning approach for quantifying multi-components in traditional complex herbal medicines, Qiong-Yu-Gao as an exam

• Improved HPLC–ESI-MS method for quantifying multi-components with diverse chemical features in CHMs.
• Programmed ionization mode switching and time segment scanning designed to improve sensitivity.
• The method used to simultaneously quantify 38 components belonging to 5 chemical types in QYG.
• Preparation methods could obviously alter the global quality of QYG.

An improved high performance liquid chromatography–electrospray ionization-mass spectrometry (HPLC–ESI-MS) method was developed to quantitatively evaluate the holistic quality of traditional complex herbal medicines (CHMs). Qiong-Yu-Gao (QYG), a classical CHM consisting of Rehmanniae Radix, Poriae and Ginseng Radix, was used as an example. Thirty-eight major components (including six pairs of epimers/isomers) belonging to five chemical types, i.e., iridoid glycosides, phenethylacohol glycosides, furfural derivatives, ginsenosides and triterpenoid acids, were selected as marker compounds. Programmed ionization mode switching and time segment scanning were designed to improve the sensitivity of the MS detection concerning the diverse chemical features of the analytes. The reference compounds of the analytes were individually injected directly into MS to optimize the ionization cone voltage and to select monitoring ion of each analyte. Nine channels with eight time segments were determined for monitoring the thirty-eight analytes, among which six were detected in positive and thirty-two in negative ion modes respectively. Higher signal-to-noise ratios of the analytes were achieved when compared with full time scanning. In addition, the linearity, precision, accuracy and stability of the method were also validated. The established method was applied for the quantitative evaluation of QYG samples prepared with three different methods. Obvious difference in the contents of thirty-eight components, in particular the original ginsenosides, degraded ginsenosides and furfural derivatives, was found among these QYG samples. All these results demonstrated that the established HPLC–ESI-MS with programmed ionization mode switching and time segment scanning approach is very suitable for the standardization investigation of CHMs.

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