A novel neutral loss/product ion scan-incorporated integral approach for the untargeted characterization and comparison of the carboxyl-free ginsenosides from Panax ginseng, Panax quinquefolius, and Panax notoginseng

Wen-Zhi Yang; Xiao-Jian Shi; Chang-Liang Yao; Yong Huang; Jin-Jun Hou; Su-Mei Han; Zi-Jin Feng; Wen-Long Wei; Wan-Ying Wu; De-An Guo

doi:10.1016/j.jpba.2019.112813

A novel neutral loss/product ion scan-incorporated integral approach for the untargeted characterization and comparison of the carboxyl-free ginsenosides from Panax ginseng, Panax quinquefolius, and Panax notoginseng

J Pharm Biomed Anal. 2020 Jan 5:177:112813. doi: 10.1016/j.jpba.2019.112813. Epub 2019 Aug 14.

Authors

Affiliations

¹ Shanghai Research Center for Modernization of Traditional Chinese Medicine, National Engineering Laboratory for TCM Standardization Technology, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Haike Road 501, Shanghai 201203, China.
² Shanghai Research Center for Modernization of Traditional Chinese Medicine, National Engineering Laboratory for TCM Standardization Technology, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Haike Road 501, Shanghai 201203, China. Electronic address: wanyingwu@simm.ac.cn.
³ Shanghai Research Center for Modernization of Traditional Chinese Medicine, National Engineering Laboratory for TCM Standardization Technology, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Haike Road 501, Shanghai 201203, China. Electronic address: daguo@simm.ac.cn.

PMID: 31472326
DOI: 10.1016/j.jpba.2019.112813

Abstract

Differentiated composition in precursor ions for different subclasses of ginsenosides in the negative electrospray-ionization mode has been reported, which lays a foundation for the sorted and untargeted identification of ginsenosides. Carboxyl-free ginsenosides simultaneously from Panax ginseng, P. quinquefolius, and P. notoginseng, were comprehensively characterized and statistically compared. A neutral loss/product ion scan (NL-PIS) incorporated untargeted profiling approach, coupled to ultra-high performance liquid chromatography, was developed on a linear ion-trap/Orbitrap mass spectrometer for characterizing carboxyl-free ginsenosides. It incorporated in-source fragmentation (ISF) full scan-MS¹, mass tag-MS², and product ion scan-MS³. Sixty batches of ginseng samples were analyzed by metabolomics workflows for the discovery of ginsenoside markers. Using formic acid (FA) as the additive, carboxyl-free ginsenosides (protopanaxadiol-type, protopanaxatriol-type, and octillol-type) gave predominant FA-adducts, while rich deprotonated molecules were observed for carboxyl-containing ginsenosides (oleanolic acid-type and malonylated) when source-induced dissociation (SID) was set at 0 V. Based on the NL transition [M+FA‒H]^- > [M-H]^- and the characteristic sapogenin product ions, a NL-PIS approach was established. It took advantage of the efficient full-information acquisition of ISF-MS¹ (SID: 50 V), the high specificity of mass tag (NL: 46.0055 Da)-induced MS² fragmentation, and the substructure fragmentation of product ion scan-MS³. We could characterize 216 carboxyl-free ginsenosides, and 21 thereof were potentially diagnostic for the species differentiation. Conclusively, sorted and untargeted characterization of the carboxyl-free ginsenosides was achieved by the established NL-PIS approach. In contrast to the conventional NL or PIS-based survey scan strategies, the high-accuracy MSⁿ data obtained can enable more reliable identification of ginsenosides.

Keywords: Carboxyl-free; Ginsenoside; LTQ-Orbitrap-MS; Mass tag; Panax; Sorted characterization.

Publication types

Comparative Study

MeSH terms

Chromatography, High Pressure Liquid / methods
Ginsenosides / analysis*
Ions / analysis
Mass Spectrometry / methods*
Panax / chemistry*
Panax / classification

Substances

Ginsenosides
Ions