title: Homolog-focused profiling of ginsenosides based on the integration of step-wise formate anion-to-deprotonated ion transition screening and scheduled multiple reaction monitoring.
abstract: Homolog-focused profiling is a favored option to bridge targeted metabolomics toward non-targeted metabolomics. In current study, an attempt was made for the large-scale ginsenoside-specific analysis in ginseng (G) and American ginseng (AG). When formic acid (0.1%, v/v) was introduced as the mobile phase additive, formate anion-to-deprotonated ion transitions ([M+HCOO](-)>[M-H](-)) with an optimal collision energy (-32eV) could result in satisfactory responses for ginsenosides. Therefore, a step-wise multiple reaction monitoring (MRM)-based method employing [M+HCOO](-)>[M-H](-) ion pairs was constructed to screen ginsenosides among 501-1250u (for Q1) with a step-size of 2u, and MRM also served as a survey experiment to trigger enhanced product ion scans for MS(2) spectrum acquisition on a hybrid triple quadrupole-linear ion trap mass spectrometer; then, the identification of those observed ginsenosides was achieved on the basis of the well-defined mass cracking patterns for ginsenosides; afterwards, scheduled MRM was introduced for large-scale relatively quantitative analysis of all detected ginsenosides. Finally, comparative metabolomics were performed to differentiate G, AG, and their processed products. Method validation was carried out using thirteen authentic compounds. A total of 221 ginsenosides, among which 185 ones were annotated, were observed and relatively quantitated. All crude materials were obviously classified into groups I-III. Above all, the MRM-based homolog-focused profiling of ginsenosides could be used as a reliable tool to gain an in-depth view for ginsenoside-enriched herbal products.
authors.affiliation: Modern Research Center for Traditional Chinese Medicine, Beijing University of Chinese Medicine, Beijing 100029, China.
authors.forename: Yuelin
authors.initials: Y
authors.lastname: Song
authors.affiliation: Modern Research Center for Traditional Chinese Medicine, Beijing University of Chinese Medicine, Beijing 100029, China; School of Chinese Materia Medica, Beijing University of Chinese Medicine, Beijing 100102, China; Baotou Medical College, Baotou 014060, China.
authors.forename: Na
authors.initials: N
authors.lastname: Zhang
authors.affiliation: Modern Research Center for Traditional Chinese Medicine, Beijing University of Chinese Medicine, Beijing 100029, China.
authors.forename: Shepo
authors.initials: S
authors.lastname: Shi
authors.affiliation: Modern Research Center for Traditional Chinese Medicine, Beijing University of Chinese Medicine, Beijing 100029, China.
authors.forename: Jun
authors.initials: J
authors.lastname: Li
authors.affiliation: Modern Research Center for Traditional Chinese Medicine, Beijing University of Chinese Medicine, Beijing 100029, China.
authors.forename: Yunfang
authors.initials: Y
authors.lastname: Zhao
authors.affiliation: Modern Research Center for Traditional Chinese Medicine, Beijing University of Chinese Medicine, Beijing 100029, China.
authors.forename: Qian
authors.initials: Q
authors.lastname: Zhang
authors.affiliation: State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Beijing 100191, China. Electronic address: yongjiang@bjmu.edu.cn.
authors.forename: Yong
authors.initials: Y
authors.lastname: Jiang
authors.affiliation: Modern Research Center for Traditional Chinese Medicine, Beijing University of Chinese Medicine, Beijing 100029, China. Electronic address: pengfeitu@163.com.
authors.forename: Pengfei
authors.initials: P
authors.lastname: Tu
mesh_terms: D000838:Anions / Q000737:chemistry; D002623:Chemistry Techniques, Analytical / Q000295:instrumentation / Q000379:methods*; D005561:Formates / Q000737:chemistry; D036145:Ginsenosides / Q000032:analysis*; D055432:Metabolomics / Q000379:methods*; D028321:Plant Preparations / Q000737:chemistry; D015203:Reproducibility of Results
chemical_list: D000838:Anions; D005561:Formates; D036145:Ginsenosides; D028321:Plant Preparations; C030544:formic acid
keywords: Formate anion-to-deprotonated ion pairing; Ginsenoside; Homolog-focused profiling; Scheduled multiple reaction monitoring; Step-wise multiple reaction monitoring