Headspace Solid-Phase Micro-Extraction Gas Chromatography/Mass Spectrometry (HS-SPME-GC/MS)-Based Untargeted Metabolomics Analysis for Comparing the Volatile Components from 12 Panax Herbal Medicines

Abstract

Quality control of ginseng currently is mainly based on ginsenoside analysis, but rarely focuses on the volatile organic components. In the current work, an untargeted metabolomics approach, by headspace solid-phase micro-extraction gas chromatography/mass spectrometry (HS-SPME-GC/MS), was elaborated and further employed to holistically compare the compositional difference of the volatile components simultaneously from 12 Panax herbal medicines, which included P. ginseng (PG), P. quinquefolius (PQ), P. notoginseng (PN), red ginseng (PGR), P. ginseng leaf (PGL), P. quinquefolius leaf (PQL), P. notoginseng leaf (PNL), P. ginseng flower (PGF), P. quinquefolius flower (PQF), P. notoginseng flower (PNF), P. japonicus (PJ), and P. japonicus var. major (PJvm). Chromatographic separation was performed on an HP-5MS elastic quartz capillary column using helium as the carrier gas, enabling good resolution within 1 h. We were able to characterize totally 259 volatile compounds, including 82 terpenes (T), 46 alcohols (Alc), 29 ketones (K), 25 aldehydes (Ald), 21 esters (E), and the others. By analyzing 90 batches of ginseng samples based on the untargeted metabolomics workflows, 236 differential ions were unveiled, and accordingly 36 differential volatile components were discovered. It is the first report that simultaneously compares the compositional difference of volatile components among 12 Panax herbal medicines, and useful information is provided for the quality control of ginseng aside from the well-known ginsenosides.

Pseudotargeted Metabolomics Approach Enabling the Classification-Induced Ginsenoside Characterization and Differentiation of Ginseng and Its Compound Formulation Products

“…Metabolomics is a rapidly developing “-omics” technique to investigate the composition of intracellular small-molecule metabolites (<1000 Da) and their changes related to the physiology and pathology, which mainly relies on LC–MS, GC–MS (gas chromatography–mass spectrometry), and NMR (nuclear magnetic resonance). − Metabolomics has also received wide use in the quality control of medicinal herbs, particularly to differentiate those sharing the similar chemical compositions. , Comparatively, untargeted metabolomics comprehensively analyzes all of the measurable analytes in a sample through full-scan MS (MS 1 ) or MS E , thus being particularly suitable for the discovery of biomarkers . It can enable holistic differentiation among the easily confusing species, , different geographic origins, parts, growing ages, , and processing technologies . However, the full-scan MS approach often receives a limited linearity range, failing to embody the intrinsic content difference among different groups.…”

“…25,26 Comparatively, untargeted metabolomics comprehensively analyzes all of the measurable analytes in a sample through full-scan MS (MS 1 ) or MS E , thus being particularly suitable for the discovery of biomarkers. 27 It can enable holistic differentiation among the easily confusing species, 28,29 different geographic origins, 30 parts, 31 growing ages, 32,33 and processing technologies. 34 However, the full-scan MS approach often receives a limited linearity range, failing to embody the intrinsic content difference among different groups.…”

Enhanced Identification of Ginsenosides Simultaneously from Seven Panax Herbal Extracts by Data-Dependent Acquisition Including a Preferred Precursor Ions List Derived from an In-House Programmed Virtual Library

“…C. Y. Wu et K. M. Feng ( PJm ) . To date, the great potential of multiple classes of components, such as polysaccharides, lipids, volatile oils, and peptides, has been investigated, achieving the quality evaluation of both ginseng products and the related compound preparations. The contained saponins (dubbed ginsenosides), which have extensive pharmacological efficacy like the anti-inflammatory effect, cardiovascular protective activity, and antiviral and immunoregulatory effects, are the major bioactive ingredients in different Panax species. − Systematically identifying ginsenosides is of great significance to the quality control of ginseng to ensure the correct use and the discovery of new components beneficial to the development of functional foods.…”

“…30−32 The Panax genus has been receiving global interest because of its remarkable tonifying effects and currently serves as a vital source for diverse functional foods, cosmetics, and healthcare products, in addition to prominent preparations for medicinal use. 33,34 35 To date, the great potential of multiple classes of components, such as polysaccharides, 36 lipids, 37 volatile oils, 38 and peptides, 39 has been investigated, achieving the quality evaluation of both ginseng products and the related compound preparations. The contained saponins (dubbed ginsenosides), which have extensive pharmacological efficacy like the anti-inflammatory effect, cardiovascular protective activity, and antiviral and immunoregulatory effects, are the major bioactive ingredients in different Panax species.…”