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Article

Non-Targeted Metabolomic Analysis of Methanolic Extracts of Wild-Simulated and Field-Grown American Ginseng

by
Hongqiang Lin
,
Hailin Zhu
,
Jing Tan
,
Han Wang
,
Qinghai Dong
,
Fulin Wu
,
Yunhe Liu
,
Pingya Li
* and
Jinping Liu
*
Research Center of Natural Drug, School of Pharmaceutical Sciences, Jilin University, Changchun 130021, China
*
Authors to whom correspondence should be addressed.
Molecules 2019, 24(6), 1053; https://doi.org/10.3390/molecules24061053
Submission received: 10 February 2019 / Revised: 8 March 2019 / Accepted: 14 March 2019 / Published: 18 March 2019
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Abstract

:
Aiming at revealing the structural diversity of secondary metabolites and the different patterns in wild-simulated American ginseng (WsAG) and field-grown American ginseng (FgAG), a comprehensive and unique phytochemical profile study was carried out. In the screening analysis, a total of 121 shared compounds were characterized in FgAG and WsAG, respectively. The results showed that both of these two kinds of American ginseng were rich in natural components, and were similar in terms of the kinds of compound they contained. Furthermore, in non-targeted metabolomic analysis, when taking the contents of the constituents into account, it was found that there indeed existed quite a difference between FgAG and WsAG, and 22 robust known biomarkers enabling the differentiation were discovered. For WsAG, there were 12 potential biomarkers including two ocotillol-type saponins, two steroids, six damarane-type saponins, one oleanane-type saponins and one other compound. On the other hand, for FgAG, there were 10 potential biomarkers including two organic acids, six damarane-type saponins, one oleanane-type saponin, and one ursane. In a word, this study illustrated the similarities and differences between FgAG and WsAG, and provides a basis for explaining the effect of different growth environments on secondary metabolites.

1. Introduction

American ginseng (Panax quinquefolius L.) is grouped into four categories: wild, wild-simulated, woods-grown, and field-grown [1,2]. The herb growing in its native habitat is called wild American ginseng. Wild-simulated American ginseng (WsAG) refers to a method of growing ginseng in a hardwood forest environment under natural conditions without any other human intervention [2,3,4]. As such, WsAG roots are indeed indistinguishable from the wild roots due to the similar characteristics. When the seeds are planted in hardwood forests, and are grown in prepared rows or beds, or with removed ground vegetation or fertilizer and pesticides being available [5,6,7], it is called as wood-grown ginseng. This variety of American ginseng requires 6 to 9 years to mature before harvesting [8]. Different from wild-simulated category, the quality of wood-grown ginseng is between that of the wild and field-grown categories. That means, wood-grown American ginseng cannot be considered a substitute of the wild one. Field-grown American ginseng (FgAG), also called cultivated American ginseng, is intensely cultivated under artificial shade structures using fertilizers and pesticides [4,9]. Generally speaking, FgAG is harvested after 3–4 years, while WsAG is collected at least after 10–20 years or longer [10].
Modern pharmacological studies have shown that American ginseng has immunomodulatory [11], anti-tumor [12], anti-fatigue [13,14], anti-diabetic [15,16,17], anti-oxidant effects [18] and the functions of improving impaired memory and learning functions [14,19], etc. Furthermore, it is the traditional belief that roots from the wild are more medicinally efficacious, more potent and more valuable than those from cultivated sources, and wild roots thus command much higher prices on the Chinese medicine market [20,21,22]. But, since the late 18th century, natural wild American ginseng resources suffered a sharp decline due to predatory exploitation in North America under the influence of economic interests, and are nearing extinction now [23]. Meanwhile WsAG, with high quality and four to ten times the retail value of field-grown roots, is similar to the wild one [4]. Actually, planting wild-simulated ginseng is encouraged with the aim of reducing harvest pressure on wild populations [24]. Wild and wild-simulated roots could share the same export and trade regulations due to the similar morphology phenotype and market value [8,25]. Recently, because the so-called wild-simulated American ginseng could capitalize on the premium paid for wild-appearing roots, and the species appeared well suited to the practice of forest farming, American ginseng has been recommended as an agroforestry crop candidate [26]. With the continuous expansion of the folk and clinical applications of American ginseng, it is necessary to conduct an in-depth study on the chemical constituents of American ginseng aiming to clarify the material basis of efficacy. So far, there are a few comparative analysis on FgAG and wild American ginseng [27,28]. These results showed that ginsenosides are different between them [26], especially, the ratios of Rg1/Rd, Rg1/Rb1 and (Rg1 + Re)/Rd are characteristic markers for differentiating these two groups [28]. However, a comparative study on the chemical composition between FgAG and WsAG does not exist.
Untargeted metabolomics, being able to profile diverse classes of metabolites, has been successfully applied to compare and identify the overall small-molecule components of different groups of samples [29]. Ultra-high performance liquid chromatography (UPLC) combined with quadrupole time-of-flight tandem mass spectrometry (QTOF-MS) and multivariate statistical analyses are often applied to profile the different groups. For multivariate statistical analyses, principal component analysis (PCA) and orthogonal partial least squares discriminant analysis (OPLS-DA) are the most common statistical methods. Meanwhile, UPLC-QTOF-MS combined with the automated data processing software UNIFI was often applied recently in the characterization of chemical components of herbal medicines [30,31,32,33,34,35]. When the coeluting constituents possessed different m/z values, HR-MS can provide a specific and accurate mass. While, UNIFI, a highly comprehensive, high throughput, efficient and simple platform, offers a method for integrating data acquisition, data mining, library searching and reporting generation.
Aiming to find out the similarities and differences between FgAG and WsAG, and to provide a reference for quality control and material basis of efficacy, the screening and the comparative analysis of chemical constituents in FgAG and WsAG is conducted for the first time in this paper. The shared constituents would be evaluated with the UPLC-QTOF-MS method combined with UNIFI. The characteristic components were to be found using the untargeted metabolomics method. The results will also be helpful in explaining the different pharmacological activities and controlling the quality of FgAG and WsAG.

2. Results

2.1. Identification of Components from FgAG and WsAG Based on the UNIFI Platform

As a result of our screening analysis, a total of 121 compounds were identified or tentatively characterized in both positive and negative mode from FgAG and WsAG (Table 1), the base peak intensity (BPI) chromatograms are shown in Figure 1, and their chemical structures are shown in Figure 2.
In FgAG and WsAG, these compounds were all shared constituents, including 47 protopanaxdiol-type saponins, 23 protopanaxtriol-type saponins, 15 oleanane- type saponins, 10 ocotillol-type saponins, one ursane, one flavonoid, one lignin, 12 organic acids and organic acid esters, three steroids, and eight other compounds.

2.2. Biomarker Discovery for FgAG and WsAG

The QC injections were clustered tightly in PCA indicating a satisfactory stability of the system. The PCA 2D plots of the samples from FgAG and WsAG groups were classified into two clusters according to their common spectral characteristics (Figure 3), with the FgAG samples of different years clustered into one group, while the WsAG samples were clustered into another group. The FgAG and WsAG samples were clearly separated, indicating that these two herb species could be easily differentiated.
After OPLS-DA plots (Figure 4A and Figure 5A) in both negative and positive modes were generated, the maximum separation between MsAG and FgAG groups was available. In the sufficient permutation test, the lines of grouping samples were significantly located underneath the random sampling lines (Figure 4B and Figure 5B), which indicated a fine validity for the following characteristic metabolites biomarkers identification [42]. S-plots were then created to explore the potential chemical markers that contributed to the differences. Based on p values (p < 0.05) and VIP values (VIP > 3) [30,61] from univariate statistical analysis, 22 robust known biomarkers enabling the differentiation between FgAG and WsAG, were marked and listed (Figure 4C and Figure 5C and Table 2). Additionally, a heatmap was generated from these biomarkers in order to systematically evaluate the biomarkers (Figure 6), which visually showed the intensities of potential biomarkers between two species.

3. Discussion

In the screening analysis, 121 compounds were characterized in FgAG and WsAG, respectively. The results showed that both of these kinds of American ginseng were rich in natural components. These 121 compounds were all shared constituents in FgAG and WsAG, which means that they were similar in terms of the kinds of compound they contained. It has been reported that there are high ginsenoside contents in American ginseng. In this study, ginsenosides were also the main chemical components. Besides the most common dammarane-type and oleanane-type saponins, the ocotillol-type saponins are also occupying a notable proportion. The ocotillol-type is the characteristic type of saponin enabling American ginseng to be differentiated from Asian ginseng. So far, the studies on the mechanism of biosynthesis were focused on dammarane-type and oleanane-type ginsenosides. For example, dammaranediol was obtained by DS (dammarenediol synthase), and then modified by CYP450 to obtain dammarane-type saponins. Another example, oleanane-type ginsenosides were obtained by modifing β-amyrin with CYP450 and UGT (UDP-glycosyltransferase). Actually, there were little literature about the mechanism of ocotillol-type ginsenoside biosynthesis. The phytochemicals in WsAG and FgAG might provide a material basis for mechanistic studies. In short, this comprehensive and unique phytochemical profile study revealed the structural diversity of secondary metabolites and the similar patterns in FgAG and WsAG.
Furthermore, in non-targeted metabolomic analysis, when taking the contents of the constituents into account, it was found that there indeed existed quite a few differences between FgAG and WsAG, and 22 robust known biomarkers enabling the differentiation were discovered. This study illustrated the differences between FgAG and WsAG, and provided a basis for explaining the effect of different growth environments on secondary metabolites. For WsAG, there are 12 potential biomarkers, including two ocotillol-type saponins (12, 47), two steroids (22, 117), six damarane-type saponins (21, 35, 37, 42, 44, 112), one oleanane-type saponin (102) and one other compound (6). The contents of these 12 components in WsAG were much greater than in FgAG. On the other hand, for FgAG, there are 10 potential biomarkers including two organic acids (105, 115), six damarane-type saponins (13, 14, 31, 46, 81, 91, 99), one oleanane-type saponin (46), and one ursane (70), which contents in FgAG were much greater than in WsAG. It has been reported that wild American ginseng has better biological activity than the FgAG. As is known, biological activity is caused by the high contents of phytochemicals. Correlation studies between potential markers and biological activities could be performed in the future.
Even so, there are still several unresolved issues. For example, as shown in BPI chromatograms, though 121 compounds were identified, there are still some unidentified components. Further research should be carried on based on the formula of these unknown compounds.

4. Materials and Methods

4.1. Materials and Reagents

Twenty eight batches of commercially available FgAGs and WsAGs root products were collected or purchased from different cultivation areas in China and American, including 20 batches of FgAGs and eight batches of WsAGs. A detailed sample list is provided in Table 2.
For FgAGs, six roots of each sample were selected for analysis, while for WsAGs, 2–3 roots of each sample were analyzed. All the herbs were authenticated by the authors and the corresponding voucher specimens have been deposited in the Research Center of Natural Drug, School of Pharmaceutical Sciences, Jilin University, China.
A total of 25 saponins were isolated in our laboratory and identified by spectroscopic data. Among of these saponins, ginsenoside Ro [69], 15 ginsenosides [70,71] (Rb1, Rb2, Rb3, Rc, Rd, Re, 20(S)-Rg3, 20(R)-Rg3, 20(S)-Rh2, Rg1, 20(R)-Rg2, 20(S)-Rh1, 20(R)-Rh1, pseudo-ginsenoside F11, pseudo-ginsenoside RT5) and another six saponins [71] (quinquenoside L8, L9, L11, F3, 24(S)-pseudo- ginsenoside F11, gypenoside XVII) were isolated and identified by our group.
Oleanolic acid-28-O-β-d-glucopyranoside, ginsenoside Rs1, -Rs2 and methyl gallate-3-O-β-d-glucoside were also isolated in our laboratory and identified by NMR spectroscopy. Adenosine, α-maltose, l-tryptophan, notoginsenoside R1, kaempferol, l-phenylalanine, sucrose, palmitoleic acid, quinic acid and α-linolenic acid were purchased from Beijing Zhongke Quality Inspection Biotechnology Co., Ltd. (Beijing, China).
Acetonitrile and methanol suitable for UPLC-MS were purchased from Fisher Chemical Company (Geel, Belgium). Formic acid was purchased from Sigma-Aldrich Company (St. Louis, MO, USA). Deionized water was purified using a Millipore water purification system (Millipore, Billerica, MA, USA). All other chemicals were of analytical grade.

4.2. Sample Preparation and Extraction

All samples were respectively air-dried, grinded and sieved (Chinese National Standard Sieve No. 3, R40/3 series) to get a homogeneous powder. Then each fine powder was accurately weighed (0.2 g) and soaked with 10 mL of methanol overnight. On the second day, each powder was extracted in an ultrasonic bath (power of 250 W, frequency of 40 kHz) for half an hour. After cooling to room temperature, the lost weight was replenished with methanol. After filtering through a syringe filter (0.22 μm), the extracts were injected directly into the UPLC system. In addition, to ensure the stability and suitability consistency of MS analysis, a quality control (QC) sample was prepared by pooling the same volume (50 μL) from every sample and five QC injections were performed randomly through the whole worklist. The volumes injected for samples and QC were all 5 μL for each run.

4.3. UPLC-QTOF-MS

UPLC-QTOF-MSE analysis was performed on a Waters Xevo G2-XS QTOF mass spectrometer (Waters Co., Milford, MA, USA) equipped with a UPLC system through an electrospray ionization (ESI) interface. Chromatographic separation was performed on an ACQUITY UPLC BEH C18 (100 mm × 2.1 mm, 1.7 μm) from Waters Corporation (Milford, MA, USA). The mobile phases were composed of eluent A (0.1% formic acid in water, v/v) and eluent B (0.1% formic acid in acetonitrile, v/v) with flow rate of 0.4 mL/min. The elution conditions applied were: 0→2 min, 10% B; 2→26 min, 10~100% B; 26→29 min, 100% B; 29→29.1 min, 100~10% B; 29.1→32 min, 10% B. The temperature of the autosampler and the UPLC column manager were set at 15 °C and 30 °C respectively. Mixtures of 90/10 and 10/90 water/acetonitrile were used as the weak wash solvent and the strong wash solvent respectively. The mass spectrum was acquired from 100 to 1500 Da in MSE mode. The positive mode conditions were: capillary voltage, 2.6 kV; cone voltage, 40 V; source temperature, 150 °C; desolvation temperature, 400 °C; cone gas flow, 50 L/h; desolvation gas flow, 800 L/h. Negative mode conditions were identical to the positive mode conditions except for capillary voltage (2.2 kV). In MSE mode, data acquisition was performed via the mass spectrometer by rapidly switching from a low-collision energy (CE) scan to a high-CE scan during a single LC run. The low energy function was set to 6 V, while ramp collision energy of high energy function was set to 20~40 V. Leucine enkephalin (m/z 556.2771 in positive mode and 554.2615 in negative mode) was used as external reference of Lock Spray™ infused at a constant flow of 10 μL/min. During acquisition, data were collected in continumn mode for the screening analysis, and in centroid mode for the metabolomics analysis.

4.4. Chemical Information Database for the Components of FgAG and WsAG

Besides the in-house Traditional Medicine Library in the UNIFI software, a systematic investigation of chemical components was conducted [34]. A self-built database of compounds that were isolated from FgAG and WsAG was established by searching online databases or internet search engines such as PubMed, Full-Text Database (CNKI), ChemSpider, Web of Science and Medline. Chemical information including the component name, molecular formula and structure of the components from the herbs were obtained from the database [56].

4.5. The Screening Analysis by the UNIFI Platform

To quickly identify the chemical compounds, the MS raw data, compressed with Waters Compression and Archival Tool v1.10, was automatically screened and identified by using the streamlined workflow of UNIFI 1.7.0 software (Waters, Manchester, UK) [30]. The parameters were as follows: the minimum peak area of 200 was set for 2D peak detection; the peak intensity of low energy over 1000 counts and the peak intensity of high energy over 200 counts were selected for 3D peak detection. Mass error up to ±5 ppm for identified compounds, retention time in the range of ±0.1 min was allowed to match the reference substance. The matching compounds would be generated predicted fragments from structure. The negative adducts containing +COOH and -H and positive adducts containing +H and +Na were selected in the analysis. Leucine-enkephalin was selected as the reference compound, and [M − H]− 554.2620 was used for negative ion and [M + H]+ 556.2766 was used for positive ion [72].

4.6. The Metabolomics Analysis

The raw data were processed by MarkerLynx XS V4.1 software (Waters, Milford, CT, USA) for alignment, deconvolution, data reduction, etc. [73]. A MarkerLynx processing method was firstly created, and the main parameters were as follows: retention time range 0–26 min, mass range 100–1500 Da, mass tolerance 0.10, minimum intensity 5%, mass window 0.10, retention time window 0.20, marker intensity threshold 2000 counts and noise elimination level 6. After processing the data, the results could be showed in the Extended Statistics (XS) Viewer. m/z-RT pairs with corresponding intensities for all the detected peaks from each data file were listed. The same value of RT and m/z in different batched of samples were regarded as the same component. Then, multivariate statistical analysis was performed. Firstly, principal component analysis (PCA) was used to show the pattern recognition and maximum variation aiming to obtain the overview and classification. Secondly, orthogonal projections to latent structures discriminant analysis (OPLS-DA) in both positive and negative modes was performed in order to get the maximum separation between MsAG and FgAG group and to explore the potential chemical markers that contributed to the differences. Then, S-plots was created to provide visualization of the OPLS-DA predictive component loading to facilitate model interpretation. Meawhile, variable importance for the projection (VIP) was helpful to screen the different components, and the metabolites with VIP value (>3.0) were considered as potential markers [29]. In addition, the permutation test was performed to provide reference distributions of the R2/Q2-values that could indicate the statistical significance [30,31,32,33]. Simca 15.0 software (Umetrics, Malmö, Sweden) was used to show the analysis results [56,74].

5. Conclusions

In a comprehensive and unique phytochemical profile study, a total of 121 chemical compounds with different structural types were identified from WsAG and FgAG. The structural patterns included protopanaxdiol-type saponins, protopanaxtriol-type saponins, ocotillol-type saponins, oleanane-type saponins and other glyosides, organic acid and organic acid esters, steroids, etc. The results showed that WsAG and FgAG were rich in natural components. Furthermore, these 121 compounds were all shared constituents in them, meaning that they were similar in the kinds of compounds they contain. In metabolomic analysis, it was found that there indeed existed several differences in the contents of the constituents between FgAG and WsAG, and 22 robust known biomarkers enabling the differentiation were discovered. In a word, the results will fill the data gap in the study on the chemical constituents of WsAG and provide a reference for quantitative determinations in its quality control.

Author Contributions

The individual contributions of authors are specified as following: Data curation, Investigation, Writing-original draft, H.L.; Methodology, Software, H.Z.; Formal analysis, Writing-original draft, J.T.; Formal analysis, Writing editing, H.W.; Conceptualization, Methodology, Q.D.; Investigation, F.W.; Data curation, Y.L.; Funding acquisition, P.L.; Supervision, J.L.

Funding

This research is supported by the Bethune Plan Research Project of Jilin University [Grant No. 2018B22] and the Graduate Innovation Fund of Jilin University [Grant No. 101832018C08, and the Ph.D. Interdisciplinary Research Project Funding of Jilin University [Grant No. 10183201847].

Conflicts of Interest

The authors declare that they have no conflicts of interest concerning this article.

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Sample Availability: Samples of the compounds are not available from the authors.
Molecules 24 01053 g001 550
Figure 1. The representative base peak intensity (BPI) chromatograms of FgAG and WsAG in negative and positive modes.
Figure 1. The representative base peak intensity (BPI) chromatograms of FgAG and WsAG in negative and positive modes.
Molecules 24 01053 g001
Molecules 24 01053 g002a 550Molecules 24 01053 g002b 550
Figure 2. Chemical structures of compounds identified in FgAG and WsAG.
Figure 2. Chemical structures of compounds identified in FgAG and WsAG.
Molecules 24 01053 g002aMolecules 24 01053 g002b
Molecules 24 01053 g003 550
Figure 3. The PCA of FgAG and WsAG in positive mode and negative mode.
Figure 3. The PCA of FgAG and WsAG in positive mode and negative mode.
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Molecules 24 01053 g004 550
Figure 4. The OPLS-DA (A); permutation tests (B) and S-plot (C) in negative mode.
Figure 4. The OPLS-DA (A); permutation tests (B) and S-plot (C) in negative mode.
Molecules 24 01053 g004
Molecules 24 01053 g005 550
Figure 5. The OPLS-DA (A); permutation tests (B) and S-plot (C) in positive mode.
Figure 5. The OPLS-DA (A); permutation tests (B) and S-plot (C) in positive mode.
Molecules 24 01053 g005
Molecules 24 01053 g006 550
Figure 6. The heatmap visualizing the intensities of potential biomarkers.
Figure 6. The heatmap visualizing the intensities of potential biomarkers.
Molecules 24 01053 g006
Table
Table 1. Compounds identified from FgAG and WsAG by UPLC-QTOF-MSE.
Table 1. Compounds identified from FgAG and WsAG by UPLC-QTOF-MSE.
No.tR (min)FormulaCalculated Mass (Da)TheoreticalMass (Da)Mass Error (ppm)MSE FragmentationIdentificationSourcesRef.
10.57C7H12O6192.0636192.06341.0191.0563[M − H]−, 173.0454[M − H-H2O]−, 127.0407[M − H-H2O-HCOOH]−, 109.0452[M − H-2H2O-HCOOH]−, 91.0352[M − H-3H2O-HCOOH]−Quinic acidWsAG, FgAGs
20.64C12H22O11342.1162342.11650.8341.1092[M − H]−, 179.0562[M − H-Glu]−α-MaltoseWsAG, FgAGs
30.77C10H13N5O4267.0959267.0968−3.3268.1031[M+H]+, 237.0874[M + H-CH2OH]+, 226.0898[M + H-CN2H2]+, 136.0612[M + H-Rib]+, 130.0495[M + H-CH2OH-C4N4H3]+AdenosineWsAG, FgAGs
40.93C12H22O11342.1168342.11621.7341.1095[M − H]−, 287.1097[M − H-3H2O]−, 179.0563[M − H-Glu]−SucroseWsAG, FgAGs
50.95C9H11NO2165.0777165.0782−3.0166.0850[M + H]+, 150.0589[M + H-NH2]+, 132.0486[M + H-H2O-NH2]+, 120.0807[M + H-HCOOH]+, 91.0559[M + H-CH-NH2-HCOOH]+L-PhenylalanineWsAG, FgAGs
6 *1.02C14H18O10346.0903346.09001.0345.0830[M − H]−, 327.0598[M − H-H2O]−, 309.0728[M − H-2H2O]−, 165.0195[M − H-Glu]−, 150.0115[M − H-Glu-CH3]−Methyl gallate 3-O-β-d-glucosideWsAG > FgAG
VIP: 14.18
p < 0.001		s
71.51C11H12N2O2204.0899204.0899−0.1203.0826[M − H]−, 141.0660[M − H-HCOOH-NH2]−, 129.0506[M − H-C3H6O2]−L-TryptophaneWsAG, FgAGs
84.71C17H20O9368.1106368.1107−0.4367.1033[M − H]−, 191.0754[M − H-C10H9O3]−, 193.0466[M − H-GluA]−, 177.0758[M − H-GluA-CH3]−, 127.0350[M − H-GluA-H2O-OCH3]−3-O-trans-Feruloylquinic AcidWsAG, FgAG[36]
94.92C48H82O19962.5440962.5450−1.01007.5432[M + HCOO]−, 763.2898[M − H-2H2O-Glu]−, 815.4784[M − H-Rha]−, 781.3155[M − H-Glu]−, 635.2307[M − H-Glu-Rha-H2O]−, 437.1863[M − H-2Glu-Rha-3H2O]−Majoroside F6WsAG, FgAG[37]
105.18C36H58O8618.4130618.4132−0.3619.4203[M + H]+, 439.3712[M + H-Glu]+, 422.3451[M + H-Glu-OH]+, 383.2823[M + H-Glu-C4H8]+, 297.2336[M + H-Glu-C9H16O]+Oleanolic acid -28-O-β-d-glucopyranosideWsAG, FgAGs
115.32C48H82O20978.5399978.5397−0.31023.5379[M + HCOO]−, 997.5331[M − H]−,815.4972[M − H-Glu]−, 797.4718[M − H-Glu-H2O]−, 653.3389[M − H-2Glu]−, 491.2724[M − H-3Glu]−Yesanchinoside BWsAG, FgAG[38]
12 *5.54C47H80O19948.5305948.52941.2993.5270[M + HCOO]−, 815.4921[M − H-Ara]−, 653.3392[M − H-2Glu-Ara]−, 473.3030[M − H-2Glu-Ara]−, 455.3922[M − H-2Glu-Ara-H2O]−, 391.2582[M − H-2Glu-Ara-C6H12O]−Yesanchinoside CWsAG > FgAG
VIP: 6.18
p < 0.001		[38]
13 #5.78C48H82O19962.5443962.5450−1.01007.5436[M + HCOO]−, 961.5388[M − H]−, 799.4784[M − H-Glu]−, 637.2307[M − H-2Glu]−, 475.5863[M − H-3Glu]−Notoginsenoside NWsAG < FgAG
VIP: 11.83
p < 0.001		[39]
14 #5.94C42H74O15818.5031818.50280.4863.5006[M + HCOO]−, 667.4323[M − H-Rha]−, 533.2329[M − H-C6H13O2-C11H19O]−, 506.3845[M − H-Glu-Rha]−, 477.2169[M − H-C20H36O4]−Quinquenoside L9WsAG < FgAG
VIP: 7.20
p = 0.0002		s
155.94C42H72O14800.4915800.4922−0.9801.4988[M + H]+, 621.4983[M + H-Glu-H2O]+, 459.3659[M + H-2Glu]+, 423.3450[M + H-2Glu-3H2O]+Majoroside F2WsAG, FgAG[40]
166.25C26H34O11522.2097522.2101−0.7567.2079[M + HCOO]−, 521.2204[M − H]−, 458.2935[M − H-H2O-C2H5O]−, 341.1396[M − H-Glu-H2O]−, 178.0559[M − H-C20H23O5]−UrolignosideWsAG, FgAG[41]
176.48C54H92O231108.60341108.60290.41153.6016[M + HCOO]−, 961.5452[M − H-Rha]−, 799.4902[M − H-Glu-Rha]−, 637.2950[M − H-2Glu-Rha]−, 475.2681[M − H-3Glu-Rha]−Yesanchinoside EWsAG, FgAG[42]
186.77C47H80O18932.5348932.53450.3977.5318[M + HCOO]−, 931.5271[M − H]−, 799.4697[M − H-Ara]−, 769.4734[M − H-Glu]−, 637.3146[M − H-Glu-Ara]−Quinquenoside F6WsAG, FgAG[37]
196.88C48H82O19962.5450962.5450−0.11007.5432[M + HCOO]−, 859.4881[M − H-C5H10O2]−, 799.4204[M − H-Glu]−, 696.4328[M − H-Glu-C5H9O]−, 637.3158[M − H-2Glu]−, 601.2316[M − H-2Glu-2H2O]−Quinquenoside L2WsAG, FgAG[43]
207.01C42H72O14800.4914800.4922−1.0845.4896[M + HCOO]−, 799.4836[M − H]−, 653.4319[M − H-Rha]−, 491.2475[M − H-Glu-Rha]−(24S)-Pseudoginsenoside F11WsAG, FgAGs
21 *7.05C47H80O18932.5349932.53450.4977.5346[M + HCOO]−, 840.4930[M − H-2H2O-C4H7]−, 799.4859[M − H-Xyl]−, 769.4735[M − H-Glu]−, 637.4321[M − H-Glu-Xyl]−Notoginsenoside R1WsAG > FgAG
VIP: 24.59
p < 0.001		s
22 *7.10C28H48O400.3723400.37054.3423.3620[M+Na]+, 382.2862[M + H-CH3]+, 339.2934[M + H-H2O-C3H7]+, 255. 2948[M + H-H2O-C9H19]+Methylcholesta-7-en-3β-olWsAG > FgAG
VIP: 4.69
p < 0.001		[44]
237.12C48H82O19962.5435962.5450−1.51007.54171[M + HCOO]−, 961.5329[M − H]−, 799.3722[M − H-Glu]−, 637.4321[M − H-2Glu]−, 475.3722[M − H-3Glu]−, 391.4833[M − H-3Glu-C6H12]−Notoginsenoside R6WsAG, FgAG[42]
247.25C47H80O18932.5335932.5345−1.0977.5317[M + HCOO]−, 931.5282[M − H]−, 799.4701[M − H-Xyl]−, 673.3294[M − H-Xyl-Glu]−, 475.2148[M − H-Xyl-2Glu]−Notoginsenoside ST5WsAG, FgAG[45]
257.29C54H90O241122.58181122.58220.41167.5812[M + HCOO]−, 1121.5747[M − H]−, 959.5120[M − H-Glu]−, 797.4669[M − H-2Glu]−, 473.4334[M − H-4Glu]−Quinquenoside IVWsAG, FgAG[42]
267.40C42H72O14800.4918800.4922−0.5845.4900[M + HCOO]−, 784.4683[M − H-CH3]−, 637.4340[M − H-Glu]−, 471.3787[M − H-2Glu]−Ginsenoside Rg1WsAG, FgAGs
277.47C48H82O18946.5491946.5501−1.0991.5473[M + HCOO]−, 945.5413[M − H]−, 783.5142[M − H-Glu]−, 637.4125[M − H-Glu-Rha]−, 475.5147[M − H-2Glu-Rha]−Ginsenoside ReWsAG, FgAGs
287.47C28H48O400.3715400.37052.4423.3617[M+Na]+, 401.3540[M + H]+, 383.2861[M + H-H2O]+, 325.2982[M + H-H2O-CH3-C3H7]+, 284.1420[M + H-H2O-C7H15]+, 175.1221[M + H-H2O-C15H28]+CampesterolWsAG, FgAGa
297.69C45H74O17886.4926886.4925−0.1885.4853[M − H]−, 799.4748[M − H-Mal]−, 637.4303[M − H-Mal-Glu]−, 475.3751[M − H-Mal-2Glu]− Malonyl-ginsenoside Rg1WsAG, FgAG[46]
307.85C42H72O14800.4929800.49220.8845.4911[M + HCOO]−, 799.4837[M − H]−, 653.3687[M − H-Rha]−, 491.2354[M − H-Rha-Glu]−Quinquenoside L11WsAG, FgAGs
31 #7.84C51H84O211032.55051032.55322.61031.5414[M − H]−, 945.5212[M − H-Mal]−, 783.4173[M − H-Mal-Glu]−, 637.4385[M − H-Mal-Rha-Glu-Ac]−, 475.3932[M − H-Mal-2Glu-Rha]−Malonyl-ginsenoside ReWsAG < FgAG
VIP: 5.65
p = 0.0060		[39]
327.94C47H80O19948.5282948.5294−1.2947.5209[M − H]−, 815.4786[M − H-Xyl]−, 653.2758[M − H-Glu-Xyl]−, 491.1787[M − H-2Glu-Xyl]−Vinaginsenoside R6WsAG, FgAG[39]
338.15C47H80O17916.5409916.53961.4961.5377[M + HCOO]−, 915.5306[M − H]−, 783.4819[M − H-Ara]−, 753.4732[M − H-Glu]−, 621.4290[M − H-Ara-Glu]−, 459.4687[M − H-2Glu-Ara]−Quinquenoside L14WsAG, FgAG[47]
348.23C44H74O15842.4996842.5028−3.6887.4978[M + HCOO]−, 841.4939[M − H]−, 799.4833[M − H-Ac]−, 695.4459[M − H-Glu]−, 653.4321[M − H-Ac-Rha]−, 684.3932[M − H-CH3-C8H14O2]−, 491.4219[M − H-Rha-Glu-Ac]−Vinaginsenoside R1WsAG, FgAG[48]
35 *8.26C54H94O241126.61621126.61352.41171.6110[M + HCOO]−, 1125.6094[M − H]−, 975.5349 [M − H-Xyl-H2O]−, 963.5502[M − H-Glu]−, 801.3547[M − H-2Glu]−, 831.3214[M − H-Glu-Xyl]−, 507.3214[M − H-3Glu-Xyl]−Quinquenoside F3WsAG > FgAG
VIP: 3.35
p < 0.001		s
368.57C44H74O15842.5028842.5012−1.7887.4995[M + HCOO]−, 841.4939[M − H]−, 637.4321[M − H-Glu-Ac]−, 475.3030[M − H-2Glu-Ac]−, 391.4158[M − H-2Glu-Ac-C6H11]−Acetyl-Ginsenoside Rg1WsAG, FgAG[39]
37 *8.59C41H70O13770.4808770.4816−1.0815.4798[M + HCOO]−, 769.4722[M − H]−, 637.4321[M − H-Ara]−, 475.2678[M − H-Ara-Glu]−, 391.1748[M − H-Ara-Glu-C6H11]−Notoginsenoside R2WsAG > FgAG
VIP: 4.83
p < 0.001		[42]
388.63C48H82O19962.5423962.5450−2.71007.5405[M + HCOO]−, 961.5371[M − H]−, 815.4317[M − H-Rha]−, 799.4622[M − H-Glu]−, 653.4385[M − H-Glu-Rha]−, 617.4316[M − H-Glu-Rha-H2O]−, 491.2912[M − H-2Glu-Rha]−Majoroside F5WsAG, FgAG[37]
398.64C30H48O2440.3646440.3654−1.9441.3719[M + H]+, 423.3606[M + H-H2O]+, 339.2908[M + H-HCOOH-C4H8]+, 248.2948[M + H-C14H24]+, 203.1849[M + H-HCOOH-C14H24]+Deoxyoleanolic acidWsAG, FgAG[46]
408.78C48H80O18944.5338944.5345−0.6989.5320[M + HCOO]−, 943.5250[M − H]−, 781.4541[M − H-Glu]−, 619.4143[M − H-2Glu]−, 457.5876[M − H-3Glu]−Quinquenoside L1WsAG, FgAG[49]
418.83C53H88O231092.57181092.57160.21137.5696[M + HCOO]−, 1091.5641[M − H]−, 959.5571[M − H-Xyl]−, 929.4601[M − H-Glu]−, 797.4852[M − H-Glu-Xyl]−Yesanchinoside GWsAG, FgAG[50]
42 *8.89C47H78O17914.5225914.5239−1.5959.5225[M + HCOO]−, 913.5147[M − H]−, 733.2547[M − H-H2O-Glu]−, 619.4527[M − H-Glu-Xyl]−, 457.3254[M − H-2Glu-Xyl]−Quinquenoside L8WsAG > FgAG
VIP: 3.97
p = 0.0004		s
438.97C48H82O19962.5438962.5450−1.21007.5420[M + HCOO]−, 946.5212[M − H-CH3]−, 781.4533[M − H-Glu-H2O]−, 637.4321[M − H-2Glu]−, 475.3932[M − H-3Glu]−Majoroside F1WsAG, FgAG[40]
44 *9.14C42H70O13782.4325782.48161.2781.4747[M − H]−, 619.4181[M − H-Glu]−, 457.4798[M − H-2Glu]−, 376.4797[M − H-2Glu-C6H9]−Quinquenoside F1WsAG > FgAG
VIP: 4.10
p = 0.0004		[51]
459.27C15H10O6286.0480286.04770.8285.0407[M − H]−, 227.0521[M − H-C2H2O2]−, 151.0037[M − H-C8H6O2]−, 106.0148[M − H-C9H7O4]−, 112.0351[M − H-C9H5O5]−KaempferolWsAG, FgAGs
46 #9.32C53H86O241118.55141118.55090.51117.5436[M − H]−, 1040.5481[M − H-CH3OH]−, 955.3219[M − H-Glu]−, 793.2905[M − H-2Glu]−, 453.1095[M − H-3Glu-GluA]−Ginsenoside ROAWsAG < FgAG
VIP: 12.60
p < 0.001		[52]
47 *9.54C41H70O14786.4775786.47661.1831.4775[M + HCOO]−, 767.4297[M − H-H2O]−, 653.4318[M − H-Xyl]−, 491.2015[M − H-Glu-Xyl]−Majonoside R2WsAG > FgAG
VIP: 25.80
p < 0.001		[39]
489.61C48H80O19960.5285960.5294−0.91005.5267[M + HCOO]−, 941.5316[M − H-H2O]−, 797.4287[M − H-Glu]−, 635.3221[M − H-2Glu]−, 473.2684[M − H-3Glu]−Notoginsenoside GWsAG, FgAG[42]
499.68C42H72O14800.4922800.49220.0845.4904[M + HCOO]−, 799.4844[M − H]−, 783.2451[M − H-Rha]−, 621.3547[M − H-Glu-Rha]−Pseudo-ginsenoside F11WsAG, FgAGs
509.73C36H62O10654.4340654.4343−0.4699.4322[M + HCOO]−, 653.4262[M − H]−, 635.4312[M − H-H2O]−, 491.3254[M − H-Glu]−Pseudo-ginsenoside RT5WsAG, FgAGs
519.78C36H62O10654.4337654.4343−0.9655.4410[M + H]+, 599.4418[M − H-3H2O]+, 493.3437[M − H-Glu]+, 457.2651[M − H-Glu-2H2O]+Pseudo-ginsenoside RT4WsAG, FgAG[39]
529.82C59H100O271240.64581240.64520.51239.6380[M − H]−, 1107.6376[M − H-Xyl]−, 954.6930[M − H-Xyl-Glu]−, 783.4833[M − H-Xyl-2Glu]−, 621.4431[M − H-Xyl-3Glu]−, 459.4943[M − H-Xyl-4Glu]−Ginsenoside Ra3WsAG, FgAG[53]
539.96C41H70O13770.4810770.4816−0.8815.4804[M + HCOO]−, 751.4804[M − H-H2O]−, 637.4904[M − H-Ara]−, 475.3804[M − H-Glu-Ara]−Ginsenoside F5 WsAG, FgAG[39]
549.98C58H98O261210.63501210.63460.31209.6272[M − H]−, 1077.5814[M − H-Xyl]−, 945.4706[M − H-Xyl-Ara]−, 783.4803[M − H-Xyl-Ara-Glu]−, 459.4799[M − H-Xyl-Ara-3Glu]−Ginsenoside Ra2WsAG, FgAG[53]
5510.02C41H66O11734.4590734.4605−2.1735.4663[M + H]+, 589.3646[M + H-Rha]+, 457.3705[M + H-Rha-Ara]+, 441.5712[M + H-Rha-Ara-HCOOH]+Eleutheroside KWsAG, FgAG[54]
5610.04C48H80O18944.5320944.5345−2.6989.5302[M + HCOO]−, 943.5263[M − H]−, 781.4839[M − H-Glu]−, 619.4206[M − H-2Glu]−, 457.5701[M − H-3Glu]−Quinquenoside L6WsAG, FgAG-
5710.07C30H48O2440.3638440.3654−3.6441.3717[M + H]+, 394.3508[M + H-H2O-CHO]+, 328.3504[M + H-CHO-C6H12]+, 219.1792[M + H-C15H26O]+, 205.1619[M + H-H2O-C15H22O]+3β-Hydroxyolean-12-en-28-alWsAG, FgAGa
5810.14C59H100O271240.64521240.64620.81285.6444[M + HCOO]−, 1107.5976[M − H-Xyl]−, 945.4900[M − H-Xyl-Glu]−, 783.4835[M − H-Xyl-2Glu]−, 459.4929[M − H-Xyl-4Glu]−Notoginsenoside FaWsAG, FgAG[53]
5910.24C54H92O231108.60391108.60290.81153.6021[M + HCOO]−, 1107.5961[M − H]−, 943.5414[M − H-Glu]−, 763.4784[M − H-2Glu]−, 615.4417[M − H-3Glu]−Ginsenoside Rb1WsAG, FgAGs
6010.24C30H48O424.3692424.3705−3.1425.3765[M + H]+, 409.3102[M + H-H2O]+, 371.3759[M + H-CH3-C3H5]+, 189.1614[M + H-C16H26O]+, 205.1775[M + H-C15H26O]+Olean-18-en-3-oneWsAG, FgAG[55]
6110.31C57H94O261194.60541194.60331.71193.5981[M − H]−, 1077.5402[M − H-mal]−, 945.5097[M − H-mal-Glu]−, 783.4906[M − H-mal-2Glu]−, 621.4906[M − H-mal-3Glu]−Malonyl-ginsenoside Rb1WsAG, FgAG[53]
6210.33C42H72O13784.4975784.49730.3829.4957[M + HCOO]−, 768.4744[M − H-CH3]−, 635.4330[M − H-Rha]−, 471.3782[M − H-Glu-Rha]−20(R)-Ginsenoside Rg2WsAG, FgAGs
6310.35C36H62O9638.4391638.4394−0.4683.4373[M + HCOO]−, 637.4313[M − H]−, 475.2658[M − H-Glu]−, 457.2235[M − H-Glu-H2O]−20(S)-Ginsenoside Rh1WsAG, FgAGs
6410.36C41H70O13770.4817770.48160.0815.4799[M + HCOO]−, 678.4450[M − H-2H2O-C4H7]−, 637.4321[M − H-Ara]−, 590.2706[M − H-C4H7-C9H16]−, 475.2622[M − H-Glu-Ara]−Ginsenoside F3WsAG, FgAG[39]
6510.39C53H90O221078.59311078.59240.61123.5913[M + HCOO]−, 943.5423[M − H-Araf]−, 854.4890[M − H-H2O-Araf-C4H7]−, 763.4850[M − H-Glu-Araf]−Ginsenoside RcWsAG, FgAGs
6610.42C36H60O8620.4276620.4288−1.9621.4349[M + H]+, 603.4238[M + H-H2O]+, 441.3714[M + H-Glu]+, 423.3612[M + H-Glu-H2O]+, 350.2971[M + H-Glu-2H2O-C4H7]+, 341.1160[M + H-Glu-C6H12O]+Ginsenoside Rh4WsAG, FgAG[56]
6710.46C58H98O261210.63531210.63460.61209.6275[M − H]−, 1077.5914[M − H-Xyl]−, 945.4807[M − H-Xyl-Ara]−, 783.4687[M − H-Xyl-Ara-Glu]−, 459.4329[M − H-Xyl-Ara-3Glu]−Ginsenoside Ra1WsAG, FgAG[53]
6810.58C56H92O251164.59321164.59280.31163.5859[M − H]−, 1119.5976[M − H-CO2]−, 1077.6021[M − H-Mal]−, 1031.5694[M − H-Araf]−, 945.4900[M − H-Araf-Mal]−, 783.4835[M − H-Glu-Araf-Mal]−Malonyl-ginsenoside RcWsAG, FgAG[53]
6910.62C48H76O19956.4976956.4981−0.5955.4903[M − H]−, 783.4214[M − H-GluA]−, 631.4157[M − H-2Glu]−, 459.4174[M − H-2Glu-GluA]−Ginsenoside RoWsAG, FgAGs
70 #10.69C30H46O2438.3486438.3498−2.7439.3563[M + H]+, 424.3600[M + H-CH3]+, 411.1114[M + H-CO]+, 233.1676[M + H-C15H24]+, 205.1928[M + H-C15H22O2]+, 190.1778[M + H-C16H23O2]+3,11-dioxo-β-amyreneWsAG < FgAG
VIP: 6.49
p < 0.001		[57]
7110.70C53H84O231088.54021088.5403−0.11087.5326[M − H]−, 955.5235[M − H-Ara]−, 925.4610[M − H-Glu]−, 793.2350[M − H-Ara-Glu]−, 455.4611[M − H-Ara-2Glu-GluA]−Stipuleanoside R2WsAG, FgAG[39]
7210.78C53H90O221078.59241078.59240.01123.5906[M + HCOO]−, 913.5403[M − H-Glu]−, 779.4886[M − H-Glu-Ara]−, 615.4431[M − H-2Glu-Ara]−Ginsenoside Rb2WsAG, FgAGs
7310.79C53H90O221078.59241078.59240.01123.5320[M + HCOO]−, 913.4581[M − H-Glu]−, 779.3696[M − H-Glu-Xyl]−, 615.4912[M − H-2Glu-Xyl]−, 451.3672[M − H-3Glu-Xyl]−Ginsenoside Rb3WsAG, FgAGs
7410.89C55H92O231120.60091120.6029−1.81165.5991[M + HCOO]−, 1077.3151[M − H-Xyl]−, 945.5076[M − H-Ara-Xyl]−, 783.3942[M − H-Ara-Xyl-Glu]−, 621.4742[M − H-Ara-Xyl-2Glu]−Notoginsenoside FcWsAG, FgAG[53]
7510.94C56H92O251164.59371164.59280.81163.5864[M − H]−, 1077.5570[M − H-Mal]−, 945.5302[M − H-Ara-Mal]−, 783.4540[M − H-Glu-Ara-Mal]−, 621.4570[M − H-2Glu-Ara-Mal]−Malonyl-ginsenoside Rb2WsAG, FgAG[53]
7611.01C56H94O241150.61381150.61350.31195.6120[M + HCOO]−, 1149.6060[M − H]−, 1107.4997[M − H-Ac]−, 987.4976[M − H-Glu]−, 945.6047[M − H-Glu-Ac]−, 783.4864[M − H-2Glu-Ac]−Quinquenoside R1WsAG, FgAG[53]
7711.02C47H74O18926.4864926.4875−1.2925.4791[M − H]−, 793.4272[M − H-Ara]−, 612.3784[M − H-GluA-Ara]−, 540.3784[M − H-Glu-C14H21O]−, 455.2841[M − H-Glu-Ara-GluA]−Chikusetsu saponin IVWsAG, FgAG[39]
7811.14C56H92O251164.49671164.49580.81163.4925[M − H]−, 1077.5760[M − H-Mal]−, 945.5503[M − H-Mal-Xyl]−, 783.4735[M − H-Mal-Xyl-Glu]−, 621.4269[M − H-Mal-Xyl-2Glu]−Malonyl-ginsenoside Rb3WsAG, FgAG[53]
7911.16C36H62O9638.4395638.43940.2683.4366[M + HCOO]−, 637.4317[M − H]−, 475.2574[M − H-Glu]−, 457.2147[M − H-Glu-H2O]−20(R)-ginsenoside Rh1WsAG, FgAGs
8011.18C43H72O15828.4864828.4871−0.8873.4846[M + HCOO]−, 784.4798[M − H-COCH3]−, 695.2912[M − H-Xyl]−, 491.4938[M − H-Xyl-Glu-Ac]−, 455.2535[M − H-Xyl-Glu-Ac-2H2O]−Vinaginsenoside R2WsAG, FgAG[39]
81 #11.20C48H82O17930.5546930.5552−0.7929.5474[M − H]−, 767.4642[M − H-Glu]−, 605.4365[M − H-2Glu]−, 443.1196[M − H-3Glu]−Vinaginsenosides R3WsAG < FgAG
VIP: 7.60
p < 0.001		[58,59]
8211.34C42H66O14794.4447794.4453−0.8793.4368[M − H]−, 631.3279[M − H-Glu]−, 613.4222[M − H-Glu-H2O]−, 569.2927[M − H-Glu-HCOOH]−, 455.1562[M − H-Glu-GluA]−Chikusetsu saponin IIWsAG, FgAG[39]
8311.36C48H82O18946.5508946.55010.7991.5490[M + HCOO]−, 945.5430[M − H]−, 783.5147[M − H-Glu]−, 459.3241[M − H-3Glu]−Ginsenoside RdWsAG, FgAGs
8411.39C55H92O231120.60291120.60491.71119.5941[M − H]−, 1077.5699[M − H-Ac]−, 943.4874[M − H-Ac-Ara]−, 779.1224[M − H-Ac-Ara-Glu]−, 451.2649[M − H-Ac-Ara-3Glu]−Ginsenoside Rs1WsAG, FgAGs
8511.52C51H84O211032.55031032.5505−0.21031.5425[M − H]−, 987.5520[M − H-CO2]−, 945.5192[M − H-mal]−, 783.3540[M − H-mal-Glu]−, 621.2570[M − H-mal-2Glu]−, 459.3458[M − H-mal-3Glu]−Malonyl-ginsenoside RdWsAG, FgAG[53]
8611.70C55H92O231120.60391120.60290.81165.6021[M + HCOO]−, 1119.5961[M − H]−, 987.3684[M − H-Ara]−, 914.4587[M − H-Glu-Ac]−, 458.5471[M − H-3Glu-Ara-Ac]−Ginsenoside Rs2WsAG, FgAGs
8711.88C48H82O18946.5501946.5500−0.1991.5482[M + HCOO]−, 783.4871[M − H-Glu]−, 603.4416[M − H-2Glu]−Gypenoside XVIIWsAG, FgAGs
8812.20C19H36O5344.2565344.25630.6343.2486[M − H]−, 329.0232[M − H-CH3]−, 311.2112[M − H-H2O-CH3]−, 294.1609[M − H-H2O-OCH3]−, 255.1494[M − H-OCH3-C4H9]−, 242.1610[M − H-OCH3-C5H11]−, 228.2523[M − H-OCH3-C6H12]−Methyl-9,10,11-trihydroxy-12- octadecenoateWsAG, FgAG[60]
8912.27C47H80O17916.5398916.53960.2961.5380[M + HCOO]−, 866.4901[M − H-H2O-CH2OH]−, 783.4749[M − H-Ara]−, 753.4664[M − H-Glu]−, 621.4616[M − H-Glu-Ara]−, 459.4008[M − H-2Glu-Ara]−Notoginsenoside FeWsAG, FgAG[39]
9012.38C50H84O19988.5594988.5607−1.31033.5576[M + HCOO]−, 987.5539[M − H]−, 945.5428[M − H-COCH3]−, 809.4326[M − H-2H2O-C8H14O2]−, 797.4813[M − H-Glu-C2H4]−Quinquenoside IIIWsAG, FgAG[61]
91 #12.48C47H80O17916.5385916.5396−1.1961.5385[M + HCOO]−, 900.5146[M − H-CH3]−, 783.49.6[M − H-Ara]−, 630.4290[M − H-Glu-2H2O-C5H9]−, 621.3500[M − H-Glu-Ara]−, 459.2328[M − H-2Glu-Ara]−Chikusetsu saponin IIIWsAG < FgAG
VIP: 12.78
p < 0.001		[39]
9212.57C30H46O2766.4855766.4867−1.6767.4928[M + H]+, 749.3674[M + H-H2O]+, 621.2398[M + H-Rha]+, 459.2280[M + H-Glu-Rha]+, 207.1780[M + H-Glu-Rha-C16H26O]+(20E)-Ginsenoside F4WsAG, FgAG[62]
9312.68C47H80O17916.5399916.53960.3961.5381[M + HCOO]−, 814.4616[M − H-H2O-C6H11]−, 783.4923[M − H-Xyl]−, 621.4390[M − H-Glu-Xyl]−Gypenoside IXWsAG, FgAG[53]
9413.14C42H70O14798.4748798.4765−2.1797.4676[M − H]−, 651.4246[M − H-Rha]−, 489.4158[M − H-Glu-Rha]−Ginsenoside Rg8WsAG, FgAG[63]
9513.18C52H86O191014.57561014.5763−0.61059.5738[M + HCOO]−, 1013.5685[M − H]−, 945.5933[M − H-C4H5O]−, 851.4510[M − H-Glu]−, 833.4903[M − H-Glu-H2O]−, 620.2875[M − H-2Glu-C4H5O]−, 458.2663[M − H-3Glu-C4H5O]−Quinquenoside IWsAG, FgAG[61]
9613.31C48H82O17930.5548930.5552−0.4929.5470[M − H]−, 783.4642[M − H-Rha]−, 767.4695[M − H-Glu]−, 621.4365[M − H-Glu-Rha]−, 459.3956[M − H-2Glu-Rha]−Gypenoside XWsAG, FgAG-
9713.43C42H70O12766.4861766.4867−0.8765.4783[M + HCOO]−, 610.2361[M − H-CH2OH-C8H13-CH3]−, 603.2375[M − H-Glu]−, 441.1811[M − H-2Glu]−, 340.2323[M − H-C30H49O]−Ginsenoside Rk1WsAG, FgAG[39]
9813.50C47H74O18926.4862926.4875−1.4925.4789[M − H]−, 793.4879[M − H-Ara]−, 731.4457 [M − H-Ara-HCOOH]−, 727.4338[M − H-Glu-H2O]−, 659.4254[M − H-Glu-C3H4-HCOOH]−, 569.4945 [M − H-Ara-Glu-HCOOH]−, 455. 4979 [M − H-Ara- Glu-GluA]−Chikusetsu saponin IbWsAG, FgAG[39]
99 #13.52C42H72O13784.4974784.4973−0.1783.4896[M − H]−, 737.4755[M − H-CH2OH-CH3]−, 660.4330[M − H-3H2O-C5H9]−, 621.4361[M − H-Glu]−, 459.3782[M − H-2Glu]−Ginsenoside F2WsAG < FgAG
VIP: 17.01
p < 0.001		[39]
10013.57C18H30O4310.2141310.2144−1.0309.2068[M − H]−, 291.1960[M − H-H2O]−, 185.1181[M − H-COOH-C6H9]−, 171.1024[M − H-CH2COOH-C6H9]−13S-hydroperoxy-9Z,11E,15Z- octadecatrienoic acid WsAG, FgAG[64]
10113.62C36H60O7604.4334604.4339−0.8605.4407[M + H]+, 586.4285[M + H-H2O]+, 443.3860[M + H-Glu]+, 405.3657[M + H-Glu-H2O]+, 333.0939[M + H-2H2O-C16H26O]+, 296.1006[M + H-Glu-H2O-C8H13]+Isoginsenoside Rh3WsAG, FgAG[65]
102 *13.93C42H66O14794.4449794.4453−0.5793.4387[M − H]−, 613.3751[M − H-Glu]−, 569.3830[M − H-Glu-H2O-CO2]−Chikusetsusaponin Iva WsAG > FgAG
VIP:16.17
p < 0.001		[53]
10314.51C42H72O13784.4967784.4973−0.7829.4951[M + HCOO]−, 783.4892[M − H]−, 621.4442[M − H-Glu]−, 459.3684[M − H-2Glu]−20(R)-Ginsenoside Rg3WsAG, FgAGs
10414.64C17H30O2266.2246266.2246−0.1311.2228[M + HCOO]−, 168.1023[M − H-C7H13]−, 154.1074[M − H-C8H15]−, 137.2250[M − H-C7H13-OCH3]−, 115.0352[M − H-C4H7-C6H9O]−, 96.0352[M − H-C11H21O]−5-Hexenoic acid, 10-undecenyl esterWsAG, FgAGa
105 #14.74C18H28O2276.2081276.2089−2.9277.2156[M + H]+, 150.1312[M + H-C7H11O2]+, 137.0951[M + H-H2O-C9H14]+, 110.1017[M + H-C10H15O2]+Palmitoleic acidWsAG < FgAG
VIP: 8.57
p < 0.001		s
10614.75C42H72O13784.4940784.4973−4.1829.4951[M + HCOO]−, 783.4865[M − H]−, 621.4942[M − H-Glu]−, 459.4578[M − H-2Glu]−, 441.5214[M − H-2Glu-H2O]−20(S)-Ginsenoside Rg3WsAG, FgAGs
10714.90C41H70O12754.4874754.48670.8799.4856[M + HCOO]−, 621.3141[M − H-Xyl]−, 459.3887[M − H-Glu-Xyl]−, 351.2556[M − H-Xyl-H2O-C16H28O2]−, 275.1442[M − H-Glu-Xyl-2C6H11]−Gypenoside XIIIWsAG, FgAG[66]
10814.98C41H64O13764.4345764.4347−0.3763.4272[M − H]−, 613.3766[M − H-Xyl]−, 569.3856[M − H-Xyl-HCOOH]−Pseudo-ginsenoside Rp1WsAG, FgAG[39]
10915.05C17H30O2266.2244266.2246−0.7311.2226[M + HCOO]−, 222.1128[M − H-C3H7]−, 139.0826[M − H-C9H19]−, 127.1127[M − H-C8H11O2]−(2E,4E)-HydropreneWsAG, FgAGa
11015.75C43H68O14808.4610808.46090.1807.4532[M − H]−, 609.3820[M − H-Glu-H2O]−, 455.3519[M − H-Glu-Glu acid methyl ester]−, 319.1792[M − H-Glu acid methyl ester-C21H32]−Chikusetsusaponin IVa methyl esterWsAG, FgAG[39]
11115.98C18H30O3294.2194294.2195−0.3293.2122[M − H]−, 275.2013[M − H-H2O]−, 171.1024[M − H-C9H15]−, 121.1020[M − H-C9H15O3]−(E,E)-9-Oxooctadeca-10,12-dienoic acidWsAG, FgAG[34]
112 *16.90C36H62O8622.4431622.4445−2.1667.4442[M + HCOO]−, 621.4360[M − H]−, 459.2656[M − H-Glu]−, 441.4772[M − H-Glu-H2O]−Ginsenoside Rh2WsAG > FgAG
VIP: 4.68
p = 0.0032		s
11317.34C18H32O3296.2347296.23511.4295.2274[M − H]−, 278.2172[M − H-H2O]−, 233.2273[M − H-HCOOH-O]−, 184.1182[M − H-C8H15]−, 171.1023[M − H-C9H16]−, 148.1125[M − H-C8H15O2]−, 125.1174[M − H-H2O-C10H17O]−9-Hydroxyoctadeca-10,12-dienoic acidWsAG, FgAG[67]
11417.37C42H70O12766.4860766.4867−0.9811.4933[M + HCOO]−, 747.4834[M − H-H2O]−, 603.4833[M − H-Glu]−, 585.4309[M − H-Glu]−, 459.0768[M − H-Glu-Rha]−, 421.4457[M − H-Glu-Rha]−Ginsenoside Rg5WsAG, FgAG[53]
115 #17.45C18H30O2278.2245278.2246−0.1279.2321[M + H]+, 218.1936[M + H-HCOOH-CH3]+, 184.1479[M + H-C7H11]+α-Linolenic AcidWsAG < FgAG
VIP: 5.24
p < 0.001		s
11618.24C32H50O4498.3722498.37092.4521.3614[M+Na]+, 484.3365[M + H-CH3]+, 439.3322[M + H-C2H3O2]+, 303.3080[M-C12H20O2]+, 263.2783[M-C15H24O2]+, 248.2610[M + H-C16H26O2]+, 203.0991[M + H-C2H3O2-C15H22O2]+3-O-Acetyloleanolic acidWsAG, FgAGa
117 *18.50C19H24O2284.1773284.1776−1.1285.1843[M + H]+, 259.2243[M + H-C2H2]+, 243.1701[M + H-C2H2O]+, 159.1308[M + H-C8H13O]+, 122.1168[M + H-C11H11O]+Androsta-1,4-diene-3,17-dioneWsAG > FgAG
VIP: 6.16
p < 0.001		a
11819.97C16H28O3268.2039268.20380.4291.1950[M+Na]+, 223.1536[M + H-HCOOH]+, 123.0441[M + H-H2O-C7H13O2]+, 95.0141[M + H-C4H9O-C5H9O2]13-Hydroxy-9,11-hexadecanedioic acidWsAG, FgAG[34]
11920.15C17H24O2260.1766260.1776−3.8261.1839[M + H]+, 243.1708[M + H-H2O]+, 221.1479[M + H-CH3-C2H3]+, 159.0791[M + H-H2O-C6H13]+PanaxydolWsAG, FgAG[68]
12020.49C17H26O3280.3138280.31303.3303.3030[M+Na]+, 252.2401[M + H-C2H5]+, 149.1310[M + H-C10H21]+,140.1322[M + H-C10H21]+, 97.1025[M + H-C13H27]+1-EicoseneWsAG, FgAGa
12122.88C19H38O4330.2766330.2770−1.2353.2658[M+Na]+, 313.2725[M + H-H2O]+, 280.2603[M + H-2H2O-CH3]+, 239.2352[M + H-C3H7O3]+, 99.0871[M + H-C4H7O4-C8H17]+MonopalmitinWsAG, FgAG[30]
* Characteristic component in WsAG. # Characteristic component in FgAG. s Identified with a standard, a Compared with spectral data obtained from Wiley Subscription Services, Inc. (New York, NY, USA).
Table
Table 2. Details of FgAG and WsAG samples.
Table 2. Details of FgAG and WsAG samples.
Species and the Morphological FeaturesSourceGrowth YearCollection TimeBatch No.
FgAGs
Main roots 9~15 cm (length) × 1.5~3.0 cm (diameter); 2~3 branch roots with diameters of 2~3.5 cm; fibrous roots with diameters of 0.1~0.2 cm; 3~4 stem scars in rhizomes; no adventitious roots.		Ji’an City, Jilin Province, China3, 42017.09–2017.10FgAG1, 11
Fusong County, Jilin Province, China3, 42017.09–2017.10FgAG2, 12
Tonghua City, Jilin Province, China3, 42017.09–2017.10FgAG3,13
Jingyu Country, Jilin Province, China3, 42017.09–2017.10FgAG4, 14
Antu Country, Jilin Province, China3, 42017.09–2017.10FgAG5, 15
Hunchun City, Jilin Province, China3, 42017.09–2017.10FgAG6, 16
Helong City, Jilin Province, China3, 42017.09–2017.10FgAG7, 17
Huadian City, Jilin Province, China3, 42017.09–2017.10FgAG8, 18
Huairou District, Beijing Province, China3, 42017.10–2017.11FgAG9, 19
Wendeng Area, Shandong Province, China3, 42017.10–2017.11FgAG10, 20
WsAGs
Main roots 5.0~6.0 cm (length) × 1.5~2.0 cm (diameter); 2~3 branch roots with diameters of 0.5~0.9 cm; fibrous roots with diameters of 0.1~0.2 cm; 15~25 stem scars in rhizomes; adventitious roots with diameters of 0.5~0.8 cm		Lawton Coumtry, Michigan State, American>152017.09–2017.11WsAG1, 3, 6
Schoharie County, Catskill region, American>152017.09–2017.10WsAG2, 4, 8
Monongalia County, West Virginia, American>152017.10–2017.11WsAG5, 7

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Lin, H.; Zhu, H.; Tan, J.; Wang, H.; Dong, Q.; Wu, F.; Liu, Y.; Li, P.; Liu, J. Non-Targeted Metabolomic Analysis of Methanolic Extracts of Wild-Simulated and Field-Grown American Ginseng. Molecules 2019, 24, 1053. https://doi.org/10.3390/molecules24061053

AMA Style

Lin H, Zhu H, Tan J, Wang H, Dong Q, Wu F, Liu Y, Li P, Liu J. Non-Targeted Metabolomic Analysis of Methanolic Extracts of Wild-Simulated and Field-Grown American Ginseng. Molecules. 2019; 24(6):1053. https://doi.org/10.3390/molecules24061053

Chicago/Turabian Style

Lin, Hongqiang, Hailin Zhu, Jing Tan, Han Wang, Qinghai Dong, Fulin Wu, Yunhe Liu, Pingya Li, and Jinping Liu. 2019. "Non-Targeted Metabolomic Analysis of Methanolic Extracts of Wild-Simulated and Field-Grown American Ginseng" Molecules 24, no. 6: 1053. https://doi.org/10.3390/molecules24061053

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