Qualitative and Quantitative Analysis of Chemical Components in Yinhua Pinggan Granule with High-Performance Liquid Chromatography Coupled with Q-Exactive Mass Spectrometry

Yalkun, Imranjan; Wan, Haofang; Ye, Lulu; Yu, Li; He, Yu; Li, Chang; Wan, Haitong

doi:10.3390/molecules29102300

Open AccessArticle

Qualitative and Quantitative Analysis of Chemical Components in Yinhua Pinggan Granule with High-Performance Liquid Chromatography Coupled with Q-Exactive Mass Spectrometry

Zhejiang Chinese Medical University, Hangzhou 310053, China

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Authors to whom correspondence should be addressed.

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The authors contributed equally to this work.

Molecules 2024, 29(10), 2300; https://doi.org/10.3390/molecules29102300

Submission received: 18 April 2024 / Revised: 2 May 2024 / Accepted: 10 May 2024 / Published: 14 May 2024

(This article belongs to the Section Natural Products Chemistry)

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Abstract

:

Yinhua Pinggan Granule (YPG) is an approved compounded traditional Chinese medicine (TCM) prescription for the treatment of cold, cough, viral pneumonia, and related diseases. Due to its complicated chemical composition, the material basis of YPG has not been systematically investigated. In this study, an analytical method based on high-performance liquid chromatography (HPLC) coupled with Q-Exactive mass spectrometry was established. Together with the help of a self-built compound database and Compound Discoverer software 3.1, the chemical components in YPG were tentatively identified. Subsequently, six main components in YPG were quantitatively characterized with a high-performance liquid chromatography–diode array detector (HPLC-DAD) method. As a result, 380 components were annotated, including 19 alkaloids, 8 organic acids, 36 phenolic acids, 27 other phenols, 114 flavonoids, 75 flavonoid glycoside, 72 terpenes, 11 anthraquinones, and 18 other compounds. Six main components, namely, chlorogenic acid, puerarin, 3′-methoxypuerarin, polydatin, glycyrrhizic acid, and emodin, were quantified simultaneously. The calibration curves of all six analytes showed good linearity (R² > 0.9990) within the test ranges. The precision, repeatability, stability, and recovery values were all in acceptable ranges. In addition, the total phenol content and DPPH scavenging activity of YPG were also determined. The systematic elucidation of the chemical components in YPG in this study may provide clear chemical information for the quality control and pharmacological research of YPG and related TCM compounded prescriptions.

Keywords:

Yinhua Pinggan Granule; HPLC–Q-Exactive MS; chemical components; quantitative analysis; quality control of TCM

Graphical Abstract

1. Introduction

Yinhua Pinggan Granule (YPG) is a patent compounded traditional Chinese medicine (TCM) prescription approved by the State Food and Drug Administration of China (No. Z20133007) for the treatment of cold, cough, viral pneumonia, and other related diseases. YPG was originally developed from an ancient TCM formula, Ma-huang-Tang (Ephedra Decoction), which was recorded in the TCM classic Shang Han Lun (Treatise on Febrile Diseases). YPG is composed of six herbs, namely, Lonicerae Japonicae Flos, Puerariae Lobatae Radix, Polygoni Cuspidati Rhizoma Et Radix, Ephedrae Herba, Glycyrrhizae Radix Et Rhizoma, and Armeniacae Semen Amarum, in a ratio of 4:4:4:2:2:1. In recent years, pharmacological and clinical studies of YPG have made effective progress. Previous studies have shown that YPG can inhibit the replication of influenza virus and regulate the occurrence of apoptosis caused by influenza virus infection [1]. In addition, YPG has a significant antiviral effect on H1N1 influenza virus-infected RAW264.7 cells and can protect influenza virus-infected pneumonia mice by reducing their lung injury [2]. At the same time, recent research showed that YPG and its components have significant inhibitory effects on the proliferation of the H1N1 virus [3]. Meanwhile, a randomized, double-blind, parallel, controlled clinical trial program with a total of 240 participants is in progress to test the clinical efficacy of YPG as a complementary therapy against community-acquired drug-resistant bacterial pneumonia [4].

TCM, including YPG, has shown unique advantages in the treatment of influenza virus and related diseases [5,6,7], especially during the COVID-19 pandemic [8,9,10]. However, the chemical complexity of TCM not only leads to great challenges in elucidating the pharmacological mechanisms of TCM but also hinders the deciphering of the material basis and quality control [11]. Therefore, the chemical profiling of compounded TCM prescriptions is of great importance. With its high sensitivity and high resolution, the liquid chromatography–mass spectrometry (LC-MS) technique has been widely applied in the qualitative analysis of TCM products in recent years [12,13].

Considering that most research on YPG has focused on pharmacology and clinical efficacy, the present study aimed to systematically identify and quantitatively characterize the phytochemical constituents of YPG. Based on the HPLC–Q-Exactive MS system, the global qualitative analysis of YPG was carried out, and then the main representative components were simultaneously quantified with HPLC-DAD detection technology in order to provide a theoretical basis for its future clinical application and quality control of YPG.

2. Results and Discussion

2.1. Optimization of Chromatographic Conditions

In order to systematically elucidate the chemical components of YPG, both the extraction method (Table S3 in Supporting Information) and the chromatography conditions were optimized. In particular, three different columns based on C18 packing material were tested, namely, the Welch Ultimate XB-C18 column (Welch, Shanghai, China) (150 mm × 4.0 mm, 3.0 μm), Agilent Poroshell 120 EC-C18 column (Agilent, Santa Clara, CA, USA) (150 mm × 3.0 mm, 2.7 μm), and Capcell Pak C18 MG II (Osaka Soda Co., Ltd., Osaka, Japan) (150 mm × 4.6 mm, 3 μm). Compared with the other chromatographic columns, the MG II column exhibited better separation capacity under optimal conditions. The acetonitrile–water system showed a better resolution and response in the selection of the mobile phase, and the addition of 0.1% or 0.5% formic acid could effectively improve the ionization efficiency and peak shape of some compounds. Finally, the HPLC-UV chromatogram obtained under optimized conditions is shown in Figure 1.

2.2. Qualitative Analysis of YPG by HPLC–Q-Exactive MS

Under the optimal chromatographic conditions, the mass spectrometry information of YPG was acquired in both positive and negative modes to cover more components. The base peak chromatograms (BPCs) are presented in Figure 2. Then, as described in Section 3, the data were tentatively annotated with corresponding compounds with the help of Compound Discoverer software according to the values of the accurate molecular weight and patterns of secondary fragmentation [14]. In particular, [M + H]⁺ and [M − H]⁻ were the common quasi-molecular ions in the positive and negative modes, respectively, from which the chemical formulas were preliminarily inferred, with a mass deviation ≤ 5 ppm. After compound library searching, reference comparison, and fragmentation study, a total of 380 components were tentatively identified in YPG. Among them, 45 compounds were also verified by comparison with reference compounds. The mass spectrometry information of the identified compounds is summarized in Table 1 (for additional information, see Table S1 in Supporting Information).

In general, the 380 proposed chemical components of YPG can be classified into 9 categories based on chemical structure, including 19 alkaloids, 8 organic acids, 36 phenolic acids, 27 other phenols, 114 flavonoids, 75 flavonoid glycoside,72 terpenes, 11 anthraquinones and 18 other compounds (Figure 3a). While in the term of plant source, 114 compounds are from Glycyrrhizae Radix Et Rhizoma, 93 from Lonicerae Japonicae Flos, 76 from Puerariae Lobatae Radix, 47 from Ephedrae Herba, 42 from Polygoni Cuspidati Rhizoma Et Radix, and 8 from Armeniacae Semen Amarum (Figure 3b).

2.3. Identification of Several Specific Compounds in YPG

Based on the global identification of the components in YPG, the chemical structures of some compounds were inferred from the MS² fragment ions, the proposed fragmentation pathways, and published references.

2.3.1. Phenolic Acids

Chlorogenic acid and its isomers, including neochlorogenic acid, cryptochlorogenic acid, etc., are typical phenolic acids found in YPG with high contents [15,16]. As shown in Figure 4, in the positive ion mode, the chlorogenic acid molecule is ionized to produce an [M + H]⁺ peak at m/z 355.1014. It is observed that fragmentation occurred via the neutral loss of quinic acid (C₇H₁₁O₆), resulting in the formation of a product ion at m/z 163.0388. Alternatively, the [M + H]⁺ ion may lose a neutral molecule of C₈H₁₂O₇ to generate a product ion at m/z 135.0440.

2.3.2. Flavonoids

In YPG, 114 flavonoids were identified and were the most abundant compound type. As the most basic natural product in plant medicine, flavonoids have a wide variety of biological activities and efficacies [17,18]. In this study, puerarin was taken as an example to illustrate its fragmentation pathway. As a representative compound with high content in YPG, puerarin was observed in multiple characteristic fragmentation patterns in secondary mass spectrometry (Figure 5). The [M − H]⁻ ion (m/z 415.1035) of puerarin loses a C₄H₈O₄ moiety to generate a product ion at m/z 295.0608. Further neutral loss of H₂O (18 Da) and CO (28 Da) then produced the fragment ions at m/z 277.0507 and 267.0661, respectively.

2.3.3. Alkaloids

The alkaloids in YPG are mainly ephedra alkaloids and isomers from Herba Ephedrae [19]. As a representative compound, the fragmentation pathway of methylephedrine is discussed herein. As shown in Figure 6, based on the protonated methylephedrine ion at m/z 180.1382, three characteristic fragment ions were observed at m/z 162.1275, 148.1076, and 138.0804, which can be attributed to [M + H − H₂O]⁺, [M + H − H₂O − CH₂]⁺, and [M + H − C₂H₇N]⁺, respectively.

2.3.4. Terpenoids

A total of 72 terpenoids were tentatively identified in YPG, of which triterpenoid saponins were mainly concentrated in Lonicera Japonica Thunb, Puerariae Lobatae Radix, and Glycyrrhizae Radix. Glycyrrhizic acid is the main active ingredient of Glycyrrhizae Radix, and it possesses various pharmacological effects, such as detoxification and anti-inflammatory activities [20,21,22]. As shown in Figure 7, the [M + H]⁺ ion of glycyrrhizic acid at m/z 823.4086 subsequently loses two gluconic acid moieties to form fragment ions at m/z 647.3788 and 471.3457. The latter ion can further lose one molecule of H₂O to produce a product ion at m/z 453.3356.

2.4. Quantitative Analysis, Total Phenolic Content, and DPPH Radical Scavenging Activity of YPG

In addition to the qualitative analysis of YPG, the contents of six main components in YPG, namely, chlorogenic acid, puerarin, 3′-methoxypuerarin, polydatin, glycyrrhizic acid, and emodin, were also determined with the help of the HPLC-DAD method. The method validation results in Table 2 reveal that all analytes showed good linear regression in the range of 0.01–2.00 mg/mL (R² ≥ 0.9990). The limits of detection (LODs) were 0.38–2.13 μg/mL, and the limits of quantitation (LOQs) ranged between 1.14 and 6.47 μg/mL. The repeatability RSD was 1.18–2.94%, and the intermediate precision was 2.00–3.89%, indicating that the method has good precision. The RSD of stability was less than 3.60%, indicating that the six components were stable under storage conditions. The method also showed satisfactory accuracy, with recovery values ranging from 96.79% to 103.13%, and the RSD was less than 3.15% (data shown in Table S2 in Supporting Information).

As presented in Table 3 and Figure 8, chlorogenic acid (34.15 ± 1.25 mg/g) and puerarin (28.30 ± 1.09 mg/g) were found as the most abundant compounds in YPG, followed by 3′-methoxypuerarin (9.63 ± 0.12 mg/g), polydatin (10.83 ± 0.57 mg/g), glycyrrhizic acid (3.33 ± 0.56 mg/g), and emodin (4.14 ± 0.34 mg/g). The contents of the six compounds were stable in three batches of YPG samples, which suggested that the six compounds may be used as quality markers of YPG.

Considering that the six compounds are phenols with antioxidative and radical scavenging activities, total phenolic contents and DPPH scavenging capacities were also determined. The total phenolic contents of three batches of YPG were calculated as 144.66 ± 2.21 mg/g with the Folin–Ciocalteu method (Table 3). In addition, the results of an online HPLC-based DPPH radical quenching assay revealed that all six main components were good radical scavengers with scavenging percentages ranging from 30.3% to 59.2% (Table 3 and Figure S1 in Supporting Information). Emodin exhibited a lower capacity against the DPPH radical compared with the other five compounds.

3. Materials and Methods

3.1. Reagents and Materials

YPG (Batch No. 200404) was provided by Shaanxi Dongke Pharmaceutical Co., Ltd. (Xianyang, China). Chlorogenic acid (≥95%), gallic acid (≥95%), 2,2-diphenyl-1-picrylhydrazyl (≥97%), and sodium carbonate anhydrous (≥99.8%) were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. (Shanghai, China); 3′-methoxypuerarin (≥98%) and polydatin (≥98%) were purchased from Chengdu Efa Biotechnology Co., Ltd. (Chengdu, China); puerarin (≥98%) and Folin–Ciocalteu reagent (>99.5%) were purchased from Shanghai Yien Chemical Technology Co., Ltd. (Shanghai, China); glycyrrhizic acid (≥98%) was purchased from Dalian Meilun Biotechnology Co., Ltd. (Dalian, China); emodin (≥99%) was obtained from China Institute for Food and Drug Control (Beijing, China). LC-MS-grade methanol, acetonitrile, and formic acid for HPLC analysis and LC-MS analysis were purchased from Tedia Co. (Fairfield, OH, USA). The water used was obtained from a Milli-Q water purification system (Bedford, MA, USA).

3.2. Sample Preparation

First, 100.00 mg of YPG was accurately weighed and added to 50% methanol (v/v, 1 mL). After extraction in an ultrasonic bath (300 W, 40 kHz, 50 °C) for 30 min, the extracted solution was centrifuged (13,000 rpm, 10min) and filtered through a 0.22 μm membrane. The obtained solution was kept at 4 °C until analysis.

3.3. Preparation of Standard Solutions

Six reference standards (chlorogenic acid 20.00 mg, puerarin 16.00 mg, 3′-methoxypuerarin 15.00 mg, polydatin 10.00 mg, glycyrrhizic acid 10.00 mg, emodin 5.00 mg) were accurately weighed and dissolved in 10 mL of 50% (v/v) methanol to prepare the respective stock solutions. The stock solutions were mixed and diluted with 50% methanol to prepare a series of mixed reference solutions in certain concentrations. All standard solutions were prepared in a 10 mL dark-brown volumetric flask and stored in a refrigerator at 4 °C before use.

3.4. Qualitative Analysis with HPLC–Q-Exactive MS

HPLC analysis was performed on a Thermo U3000 HPLC system (Thermo, San Jose, CA, USA). A CAPCELL PAK C18 MG II (150 mm × 4.6 mm, 3 μm; Osaka Soda, Osaka, Japan) column was used. The mobile phase consisted of 0.5% formic acid (A) and acetonitrile (B), with the elution gradient as follows: 0–10 min, 5–20% B; 10–30 min, 20–35% B; 30–32 min, 35–55% B; 32–35 min, 55–95% B; 35–42 min, 95% B, flow rate 0.4 mL/min. The column temperature was maintained at 35 °C, and the injection volume was 5 μL.

The Q-Exactive mass spectrometer (Thermo, San Jose, USA) equipped with a heated electrospray ion source (HESI) was operated in both positive and negative modes. The MS parameters were set as follows: scanning mode, Full MS/ddMS²; nebulizer voltage, 2.5 kV; sheath gas, 50 arb; aux gas, 14 arb; capillary temperature 320 °C; probe heater temperature, 300 °C; scanning range, m/z 100–1500. For different compounds, the collision energy was 30 and 40 eV. Instrument control and data acquisition were achieved using Xcalibur 2.3.1 (Thermo, San Jose, USA).

The raw data were processed with Compound Discoverer 3.1 (CD, Thermo, San Jose, USA) using a self-built compound library and workflow. The compound information was collected from public databases, including PubChem (https://pubchem.ncbi.nlm.nih.gov/), CAS SciFinder (https://scifindern.cas.org/), and CNKI (https://www.cnki.net/). Then, the original data of MS detection were matched with the self-built database in Compound Discoverer 3.1. The workflow included peak extraction, normalization, and compound annotation, and the specific parameters in the process were as follows: retention time range, 0–42 min; mass range, 100–1500 Da; positive adducts, [M + H]⁺, [2M + H]⁺; negative adducts, [M − H]⁻, [2M − H]⁻, [M − 2H]²⁻; mass tolerance, 5.0 ppm; S/N threshold, 3; minimum peak intensity, 100000.

3.5. Quantitative Analysis by HPLC-DAD

For quantitative analysis, an Agilent 1260 system equipped with a G7112C Quat Pump, a G7129A Vial sampler, and a G7117C diode array detector (DAD) was used (Agilent, Santa Clara, CA, USA). The chromatographic parameters were the same as described in Section 3.4. The chromatograms were recorded at 254 nm.

3.6. Quantitative Analysis Method Validation

In order to verify the applicability of the established method, the linearity, limits of quantitation (LOQs), limits of detection (LODs), repeatability, precision, stability, and recovery were validated. In the linear relationship experiment, the standard solution with a certain concentration gradient was used to draw the curve of the peak area (y) of the standard and the corresponding concentration (x, mg/mL). In the precision test, the standard solution was analyzed 6 times continuously, the intra-day precision was analyzed, and the intermediate precision was analyzed by different analysts at different times. The sample solution was analyzed at 0, 2, 4, 8, and 12 h in the stability test. In the repeatability test, the contents of the six target compounds in the sample solution were quantified. At the same time, the standard substance of each analyte was added to the sample according to 80%, 100%, and 120% of its content in the sample solution to prepare the sample solution for the recovery test. Three replicates were required for each spiked amount, and the recovery rate was calculated as described previously [16].

3.7. Determination of Total Phenolic Contents

3.7.1. Total Phenol Standard Curve Drawing

The total phenolic contents were measured according to a previously reported Folin–Ciocalteu reagent-based method, with gallic acid as a reference substance [23,24]. The absorbance was measured at 760 nm with an ultraviolet spectrophotometer. With absorbance as y, and total phenol mass concentration as x, the standard curve was drawn. The linear regression equation of gallic acid was y = 0.0965x + 0.0277 (R² = 0.9992), and the linear range was 0.01–0.50 mg/mL.

3.7.2. Total Phenol Content in the Sample

Different batches of YPG samples were taken, and the solution was prepared according to the above method. The determination was repeated three times, and the content of each sample was calculated according to the linear regression equation.

3.8. In Vitro Antioxidant Activity Evaluation—DPPH Radical Scavenging Activity

The DPPH free radical scavenging activities of the six components in YPG were evaluated with an HPLC-based method, as previously reported [14]. The scavenging percentages were calculated using the following equation:

Scavenging percentage (%) = (A_original − A_DPPH)/A_original × 100%

where A_original stands for the absolute HPLC peak area of each ingredient, and A_DPPH stands for the HPLC peak area of each ingredient after YPG reacted with DPPH.

4. Conclusions

In this study, a set of integrated methods, which include the qualitative HPLC–Q-Exactive MS method and the quantitative HPLC-DAD method, were established to profile the chemical properties of YPG from a macroscopic and systematic view. In the qualitative analysis part, 380 components were tentatively identified in YPG with the help of a self-built compound database and Compound Discoverer software. In the quantitative analysis part, the contents of six main components in YPG were determined with a validated method. These results may provide clear chemical information for the quality control and pharmacological research of YPG. This study may also contribute as a valuable reference for research on other complex TCM compounded prescriptions.

Supplementary Materials

The following supporting information can be downloaded at https://www.mdpi.com/article/10.3390/molecules29102300/s1: Table S1: Mass spectrometric information of chemical components of Yinhua Pinggan Granule; Table S2: Recovery of six representative components. Table S3: The contents of representative components of YPG under different extraction conditions. Figure S1. The HPLC chromatograms at 254 nm of YPG before and after the reaction with DPPH. Refs. [25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48,49,50,51,52,53,54,55,56,57,58,59,60] are cited in the Supplementary Materials.

Author Contributions

Conceptualization, C.L.; methodology, I.Y. and L.Y. (Li Yu); validation, H.W. (Haofang Wan), L.Y. (Lulu Ye) and L.Y. (Li Yu); formal analysis, H.W. (Haofang Wan); investigation, I.Y., H.W. (Haofang Wan) and L.Y. (Lulu Ye); resources, H.W. (Haitong Wan); data curation, I.Y. and C.L.; writing—original draft preparation, I.Y. and H.W. (Haofang Wan); writing—review and editing, C.L., Y.H. and H.W. (Haitong Wan); supervision, C.L., Y.H. and H.W. (Haitong Wan); project administration, C.L.; funding acquisition, C.L. and H.W. (Haitong Wan). All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the National Natural Science Foundation of China [81930111] and the Key Laboratory of TCM Encephalopathy of Zhejiang Province [2020E10012].

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The data presented in this study are available in article and Supplementary Materials. Additional data that support the findings of this study are also available on request from the corresponding author.

Conflicts of Interest

The authors declare no conflicts of interest.

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Figure 1. The HPLC chromatogram of YPG (wavelength = 254 nm). 1. Chlorogenic acid; 2. puerarin; 3. 3′-methoxypuerarin; 4. polydatin; 5. glycyrrhizic acid; 6. emodin.

Figure 2. The BPCs of YPG in positive (A) and negative (B) modes.

Figure 3. (a) The distribution of plant sources tentatively identified in YPG; (b) the types of compounds tentatively identified in YPG.

Figure 4. MS/MS spectrum of [M + H]⁺ ions and plausible fragmentation pathway of chlorogenic acid (positive ion mode).

Figure 5. MS/MS spectrum of [M − H]⁻ ions and plausible fragmentation pathway of puerarin (negative ion mode).

Figure 6. MS/MS spectrum of [M + H]⁺ ions and plausible fragmentation pathway of methylephedrine (positive ion mode).

Figure 7. MS/MS spectrum of [M + H]⁺ ions and plausible fragmentation pathway of glycyrrhizic acid (positive ion mode).

Figure 8. Quantitative analysis results of six main components in YPG.

Table 1. Mass spectrometry information of chemical components in YPG.

No.	Name	RT (min)	Formula	Ion Type	Molecular Ion (m/z)	Main Product Ion (m/z)
1	ephedrannin A	3.40	C₃₀H₂₀O₁₁	[M + H]⁺	557.1104	395.1281, 215.0650, 177.0543, 145.0284
2	glucose	3.63	C₆H₁₂O₆	[M + H]⁺	181.0705	163.0792, 144.0655, 109.0286, 81.0340
2	glucose	3.63	C₆H₁₂O₆	[M − H]⁻	179.0551	161.0445, 141.0181, 117.0181, 87.0073
3	secologanic acid	3.67	C₁₆H₂₂O₁₀	[M − H]⁻	373.1134	347.9473, 189.0156, 161.0234, 135.0440
4	D-mannitol	3.82	C₆H₁₄O₆	[M + H]⁺	183.0862	147.0650, 129.0543, 104.1073, 69.0342
5	sucrose	3.86	C₁₂H₂₂O₁₁	[M + H]⁺	343.1227	306.1183, 145.0495, 127.0390, 85.0290
5	sucrose	3.86	C₁₂H₂₂O₁₁	[M − H]⁻	341.1083	261.7968, 179.0559, 113.0230, 59.0125
6	allantoin	3.99	C₄H₆N₄O₃	[M + H]⁺	159.0512	142.0862, 114.0915, 99.0193, 70.0658
* 7	quinic acid	4.13	C₇H₁₂O₆	[M + H]⁺	193.0706	157.0492, 147.0652, 129.0546, 111.0443
8	salicylic acid	4.14	C₇H₆O₃	[M + H]⁺	139.0389	122.0714, 111.0443, 97.0287, 85.0289
9	4-aminophenol	5.72	C₆H₇NO	[M + H]⁺	110.0604	87.0046, 81.0340, 78.9949
* 10	citric acid	5.59	C₆H₈O₇	[M + H]⁺	193.0343	161.0595, 151.0388, 133.0647, 105.0702
* 10	citric acid	5.59	C₆H₈O₇	[M − H]⁻	191.0188	173.0085, 129.0180, 111.0075, 87.0071
11	guanosine	6.34	C₁₀H₁₃N₅O₅	[M + H]⁺	284.0986	258.4957, 152.0566, 135.0302, 110.0351
11	guanosine	6.34	C₁₀H₁₃N₅O₅	[M − H]⁻	282.0843	169.3754, 150.0411, 88.1632, 61.9871
12	adenosine	6.46	C₁₀H₁₃N₅O₄	[M + H]⁺	268.1037	213.3238, 169.7115, 136.0617, 85.0288
* 13	gallic acid	7.23	C₇H₆O₅	[M + H]⁺	171.0291	154.0974, 130.0863, 115.0392, 70.0658
14	coumalic acid	7.40	C₆H₄O₄	[M + H]⁺	141.0184	113.9639, 90.9481, 72.9378, 56.9430
15	tachioside	8.05	C₁₃H₁₈O₈	[M − H]⁻	301.0926	283.1918, 257.0457, 221.1909, 151.0029
16	isotachioside	8.27	C₁₃H₁₈O₈	[M − H]⁻	301.0926	284.0321, 243.0658, 178.9978, 151.0026
17	ephedroxane	8.27	C₁₁H₁₃NO₂	[M + H]⁺	192.1019	164.9844, 146.9612, 106.0654, 87.0445
18	quinaldic acid	8.27	C₁₀H₇NO₂	[M + H]⁺	174.0551	146.9612, 128.9507, 105.9351, 55.9352
* 19	hordenine	8.56	C₁₀H₁₅NO	[M + H]⁺	166.1225	151.0101, 121.0649, 103.0546, 93.0703
20	leonuriside A	8.99	C₁₄H₂₀O₉	[M − H]⁻	331.1035	285.0384, 253.0501, 169.0130, 125.0231
21	4-vinylguaiacol	9.19	C₉H₁₀O₂	[M + H]⁺	151.0755	133.0761, 123.9456, 119.0493, 91.0547
22	7α-morroniside	9.50	C₁₇H₂₆O₁₁	[M − H]⁻	405.1401	371.0939, 243.0672, 191.0199, 111.0070
23	tetramethylpyrazine	9.83	C₈H₁₂N₂	[M + H]⁺	137.1075	111.0080, 93.0704, 68.9978
24	shuangkangsu	10.49	C₂₀H₃₀O₁₄	[M − H]⁻	493.1560	447.2225, 431.0965, 269.0450, 169.0130
25	epi-gallocatechin	10.69	C₁₅H₁₄O₇	[M + H]⁺	307.0807	289.1790, 243.1704, 208.9966, 139.0389
25	epi-gallocatechin	10.69	C₁₅H₁₄O₇	[M − H]⁻	305.0665	247.5994, 219.0664, 165.0182, 125.0232
26	robinin	10.73	C₃₃H₄₀O₁₉	[M + H]⁺	741.2226	678.4389, 579.1688, 381.0964, 297.0752
27	5-(hydroxymethyl)furfural	10.85	C₆H₆O₃	[M + H]⁺	127.0393	111.9689, 110.0238, 84.9603, 55.9352
28	N-ethylbenzylamine	10.90	C₈H₁₁N	[M + H]⁺	122.0967	107.0732, 105.0336, 95.0495, 88.0237
29	vicenin-2	11.00	C₂₇H₃₀O₁₅	[M + H]⁺	595.1641	433.1127, 415.1019, 313.0700, 283.0596
29	vicenin-2	11.00	C₂₇H₃₀O₁₅	[M − H]⁻	593.1510	539.2719, 521.2607, 463.2737, 226.9863
30	4′-hydroxyacetophenone	11.09	C₈H₈O₂	[M + H]⁺	137.0599	122.0364, 116.9720, 95.0497, 55.9352
31	6-hydroxykynurenic acid	11.35	C₁₀H₇NO₄	[M + H]⁺	206.0445	178.0497, 148.1121, 117.0699, 90.0797
31	6-hydroxykynurenic acid	11.35	C₁₀H₇NO₄	[M − H]⁻	204.0293	168.1795, 160.0393, 132.0446, 110.1680
32	chlorogenic acid butyl ester	11.36	C₂₀H₂₆O₉	[M − H]⁻	409.1495	365.0681, 337.0357, 241.0023, 169.0135
33	mirificin-4′-O-glucoside	11.73	C₃₂H₃₈O₁₈	[M + H]⁺	711.2118	579.1680, 417.1183, 399.1065, 297.0753
33	mirificin-4′-O-glucoside	11.73	C₃₂H₃₈O₁₈	[M − H]⁻	709.1986	487.1239, 457.1142, 294.0533, 266.0583
34	mandelonitrile	11.82	C₈H₇NO	[M + H]⁺	134.0600	106.0654, 91.0544, 79.0548
35	kakkalide	11.83	C₂₈H₃₂O₁₅	[M + H]⁺	609.1803	447.1279, 411.1072, 327.0857, 297.0755
35	kakkalide	11.83	C₂₈H₃₂O₁₅	[M − H]⁻	607.1663	588.1254, 487.1243, 309.0403, 281.0458
36	mahuannin A	11.87	C₃₀H₂₄O₁₀	[M − H]⁻	543.1324	528.5940, 497.2623, 381.1213, 265.0987
37	2,6-dihydroxybenzoic acid	11.92	C₁₇H₂₄O₉	[M + H]⁺	373.1480	308.2842, 237.3755, 151.0375, 107.0485
38	8-epi-loganic acid	11.96	C₁₆H₂₄O₁₀	[M + H]⁺	377.1438	357.1662, 339.1559, 265.0587, 237.0277
38	8-epi-loganic acid	11.96	C₁₆H₂₄O₁₀	[M − H]⁻	375.1292	315.8566, 265.2063, 201.0163, 113.0231
39	swertiamarin	12.02	C₁₆H₂₂O₁₀	[M − H]⁻	373.1134	357.0130, 295.0618, 201.0158, 135.0433
40	8-epi-loganin	12.30	C₁₇H₂₆O₁₀	[M − H]⁻	389.1448	371.8339, 345.1187, 227.0693, 185.0593
41	5-methoxysalicylic acid	12.31	C₈H₈O₄	[M + H]⁺	169.0498	151.0391, 128.9508, 111.0444, 93.0339
42	norephedrine	12.65	C₉H₁₃NO	[M + H]⁺	152.1068	134.0964, 117.0700, 115.0545, 91.0547
43	7-epi-vogeloside	12.81	C₁₇H₂₄O₁₀	[M − H]⁻	387.1295	341.1095, 272.9591, 227.0690, 179.0566
44	loganic acid	12.88	C₁₆H₂₄O₁₀	[M − H]⁻	375.1292	287.1191, 201.0159, 189.0158, 135.0440
* 45	protocatechuic acid	12.90	C₇H₆O₄	[M + H]⁺	155.0339	137.0233, 117.0701, 107.0495, 72.9379
46	polygalin B	13.12	C₂₈H₃₂O₁₅	[M + H]⁺	609.1803	555.7846, 447.1268, 285.0752, 270.0516
46	polygalin B	13.12	C₂₈H₃₂O₁₅	[M − H]⁻	607.1663	460.8990, 325.0714, 310.0492, 282.0534
47	lonijaposide B	13.15	C₂₅H₃₂NO₁₂	[M − H]⁻	537.1833	511.3804, 375.0705, 335.0791, 201.0155
48	3′-hydroxypuerarin	13.17	C₂₁H₂₀O₁₀	[M − H]⁻	431.0975	415.0348, 311.0557, 283.0609, 255.0659
49	norpseudoephedrine	13.19	C₉H₁₃NO	[M + H]⁺	152.1068	134.0964, 117.0700, 106.0655
50	loganin	13.30	C₁₇H₂₆O₁₀	[M − H]⁻	389.1448	371.8339, 326.0798, 227.0693, 185.0593
51	secologanoside	13.43	C₁₆H₂₂O₁₁	[M + H]⁺	391.1222	239.0796, 241.0385, 163.0388, 151.0389
51	secologanoside	13.43	C₁₆H₂₂O₁₁	[M − H]⁻	389.1083	280.5215, 194.8876, 121.0647, 95.0489
52	leucodelphidin	13.74	C₁₅H₁₄O₈	[M − H]⁻	321.0607	305.2140, 265.0519, 253.0507, 186.9385
53	secologanin	13.83	C₁₇H₂₄O₁₀	[M − H]⁻	387.1295	/
54	glucoisoliquiritin	14.04	C₂₇H₃₂O₁₄	[M − H]⁻	579.1715	529.4413, 491.9212, 463.1199, 255.0662
55	glucoliquiritin apioside	14.07	C₃₂H₄₀O₁₈	[M − H]⁻	711.2134	678.4865, 549.119, 457.1141, 255.0664
* 56	chlorogenic acid	14.15	C₁₆H₁₈O₉	[M + H]⁺	355.1014	163.0388, 135.0440
* 56	chlorogenic acid	14.15	C₁₆H₁₈O₉	[M − H]⁻	353.0871	191.0553, 161.0234, 135.0440, 127.0385
* 57	neochlorogenic acid	14.22	C₁₆H₁₈O₉	[M + H]⁺	355.1014	338.1603, 289.0706, 235.0594, 163.0390
* 58	catechin	14.25	C₁₅H₁₄O₆	[M + H]⁺	291.0857	255.7885, 107.0648, 139.0389, 123.0442
* 58	catechin	14.25	C₁₅H₁₄O₆	[M − H]⁻	289.0714	245.0817, 203.0705, 151.0387.123.0439
59	ephedrine	14.36	C₁₀H₁₅NO	[M + H]⁺	166.1225	148.1119, 133.0886, 117.0700, 91.0548
* 60	cryptochlorogenic acid	14.37	C₁₆H₁₈O₉	[M + H]⁺	355.1014	337.0915, 235.0589, 205.0494, 163.0388
61	pseudoephedrine	14.43	C₁₀H₁₅NO	[M + H]⁺	166.1225	148.1119, 133.0887, 117.0701, 91.0546
62	ephedrannin D4	14.44	C₃₀H₂₄O₁₄	[M − H]⁻	607.1089	563.1151, 487.1202, 413.0903, 267.0680
63	puerarin 6″-O-xyloside	14.61	C₂₆H₂₈O₁₃	[M + H]⁺	549.1590	417.1175, 381.0964, 297.0753, 267.0648
63	puerarin 6″-O-xyloside	14.61	C₂₆H₂₈O₁₃	[M − H]⁻	547.1447	437.0846, 295.0609, 277.0504, 267.0661
64	chrysoeriol 7-O-neohesperidoside	14.65	C₂₈H₃₂O₁₅	[M + H]⁺	609.1803	447.1284, 429.1182, 327.0859, 285.0755
64	chrysoeriol 7-O-neohesperidoside	14.65	C₂₈H₃₂O₁₅	[M − H]⁻	607.1663	547.1422, 487.1246, 295.0607, 267.0660
* 65	p-hydroxybenzoic acid	14.70	C₇H₆O₃	[M + H]⁺	139.0389	121.0286, 111.0443, 93.0339
* 66	amygdalin	14.72	C₂₀H₂₇NO₁₁	[M + H]⁺	458.1647	355.1036, 213.0755, 163.0389, 107.0495
* 66	amygdalin	14.72	C₂₀H₂₇NO₁₁	[M − H]⁻	456.1505	382.6093, 323.0968, 256.1356, 161.0449
67	methyl caffeate	14.83	C₁₀H₁₀O₄	[M + H]⁺	195.0652	177.0544, 163.0388, 145.0283, 117.0336
68	3,4-dimethyl-5-phenyloxazolidine	14.94	C₁₁H₁₅NO	[M + H]⁺	178.1227	162.1274, 147.1040, 117.0700, 105.0702
69	apigenin 5-rhamnoside	15.01	C₂₁H₂₀O₉	[M + H]⁺	417.1167	381.0964, 321.0743, 297.0753, 267.0647
69	apigenin 5-rhamnoside	15.01	C₂₁H₂₀O₉	[M − H]⁻	415.1027	295.0608, 267.0661, 253.0509, 223.0762
* 70	puerarin	15.02	C₂₁H₂₀O₉	[M + H]⁺	417.1167	399.1072, 381.0956, 363.0844, 255.0646
* 70	puerarin	15.02	C₂₁H₂₀O₉	[M − H]⁻	415.1035	295.0608, 277.0507, 267.0661
71	mirificin	15.04	C₂₆H₂₈O₁₃	[M + H]⁺	549.1590	417.1168, 399.1069, 297.0754, 267.0648
71	mirificin	15.04	C₂₆H₂₈O₁₃	[M − H]⁻	547.1447	418.4808, 295.0609, 267.0660, 114.2369
72	tectorigenin 7-O-xylosylglucoside	15.07	C₂₇H₃₀O₁₅	[M + H]⁺	595.1641	379.0811, 325.0695, 216.0653, 121.0283
72	tectorigenin 7-O-xylosylglucoside	15.07	C₂₇H₃₀O₁₅	[M − H]⁻	593.1510	495.0386, 473.1082, 310.0499, 282.0529
73	methylephedrine	15.14	C₁₁H₁₇NO	[M + H]⁺	180.1382	162.1275, 148.1076, 135.0804
74	methylpseudoephedrine	15.18	C₁₁H₁₇NO	[M + H]⁺	180.1382	162.1275, 147.1042, 135.0803, 117.0700
75	7-O-ethylsweroside	15.26	C₁₈H₂₆O₁₀	[M − H]⁻	401.1451	325.7480, 269.1024, 253.0505, 178.0263
76	isoviolanthin	15.47	C₂₇H₃₀O₁₄	[M + H]⁺	579.1692	417.1190, 399.1072, 297.0753, 267.0649
76	isoviolanthin	15.47	C₂₇H₃₀O₁₄	[M − H]⁻	577.1554	531.2839, 518.0385, 283.0610, 268.0376
* 77	3′-methoxypuerarin	15.53	C₂₂H₂₂O₁₀	[M + H]⁺	447.1277	285.0751, 270.0516, 225.0542, 137.0232
* 77	3′-methoxypuerarin	15.53	C₂₂H₂₂O₁₀	[M − H]⁻	445.1134	430.0887, 367.1027, 327.1080, 215.0089
* 78	glycitin	15.54	C₂₂H₂₂O₁₀	[M + H]⁺	447.1277	429.1190, 411.1062, 327.0855, 297.0754
* 78	glycitin	15.54	C₂₂H₂₂O₁₀	[M − H]⁻	445.1135	379.8243, 325.0714, 282.0530, 254.0597
79	benzyl alcohol	15.67	C₇H₈O	[M + H]⁺	109.0653	94.0148, 91.0546, 87.0045, 81.0704
80	methyl,4-hydroxycinnamate	15.68	C₁₀H₁₀O₃	[M + H]⁺	179.0705	162.1276, 147.1041, 117.0700, 109.0651
81	γ-octalactone	15.94	C₈H₁₄O₂	[M + H]⁺	143.1068	128.9508, 116.9721, 113.9639, 84.9603
82	(6S-9R)-roseoside	15.98	C₁₉H₃₀O₈	[M + H]⁺	387.2004	369.1341, 297.0762, 267.0641, 151.0388
83	syringin	15.98	C₁₇H₂₄O₉	[M + H]⁺	373.1480	308.0842, 292.1605, 237.3755, 151.0375
84	5,7-dihydroxyisobenzofuran	15.99	C₈H₆O₄	[M + H]⁺	167.0339	148.1120, 133.0885, 117.0700, 111.0442
85	kingiside	16.01	C₁₇H₂₄O₁₁	[M − H]⁻	403.1240	371.1025, 310.7592, 243.0664, 174.8555
* 86	puerarin-7-O-glucoside	16.04	C₂₇H₃₀O₁₄	[M + H]⁺	579.1692	561.1633, 399.1074, 297.0753, 267.0647
87	sweroside	16.09	C₁₆H₂₂O₉	[M + H]⁺	359.1333	297.8041, 265.6036, 197.0808, 127.0391
* 88	caffeic acid	16.29	C₉H₈O₄	[M + H]⁺	181.0494	163.0388, 145.0284, 135.0441, 117.0337
* 88	caffeic acid	16.29	C₉H₈O₄	[M − H]⁻	179.0341	164.0098, 135.0440, 112.1822, 107.0492
89	ephedrannin D1	16.53	C₃₀H₂₄O₁₃	[M + H]⁺	593.1279	576.3641, 447.1271, 327.0849, 297.0745
90	5-p-coumaroylquinic acid	16.70	C₁₆H₁₈O₈	[M + H]⁺	339.1071	266.4322, 245.8672, 147.0439, 119.0494
90	5-p-coumaroylquinic acid	16.70	C₁₆H₁₈O₈	[M − H]⁻	337.0930	191.0553, 163.0390, 119.0470, 93.0332
91	loniceracetalide A	16.71	C₂₁H₃₂O₁₁	[M − H]⁻	459.1869	/
92	piceatannol 3′-O-glucoside	16.77	C₂₀H₂₂O₉	[M − H]⁻	405.1190	359.0753, 243.0659, 201.0549, 159.0440
93	lonijaposide D	16.82	C₂₆H₃₂NO₁₃	[M − H]⁻	565.1774	550.4224, 519.2438, 445.1137, 325.0718
94	ephedralone	16.90	C₁₁H₉NO₄	[M + H]⁺	220.0602	192.0652, 164.0699, 151.4024, 119.0490
94	ephedralone	16.90	C₁₁H₉NO₄	[M − H]⁻	218.0452	174.0550, 159.0315, 144.0077, 131.0365
95	neochlorogenic acid methyl ester	17.85	C₁₇H₂₀O₉	[M + H]⁺	369.1173	191.9904, 177.0544, 145.0283, 117.0336
95	neochlorogenic acid methyl ester	17.85	C₁₇H₂₀O₉	[M − H]⁻	367.1029	255.0194, 191.0552, 173.0447, 134.0361
96	isoschaftoside	17.86	C₂₆H₂₈O₁₄	[M + H]⁺	565.1542	479.5669, 415.1016, 313.0699, 283.0596
96	isoschaftoside	17.86	C₂₆H₂₈O₁₄	[M − H]⁻	563.1340	341.0680, 311.0559, 283.0609, 149.0235
97	2,6-dihydroxyphenylacetic acid	18.07	C₈H₈O₄	[M + H]⁺	169.0498	151.0389, 146.9612, 128.9508, 123.0441
98	schaftoside	18.35	C₂₆H₂₈O₁₄	[M + H]⁺	565.1542	520.6823, 433.1122, 313.0700, 283.0597
98	schaftoside	18.35	C₂₆H₂₈O₁₄	[M − H]⁻	563.1340	529.1846, 341.0670, 311.0558, 283.0610
* 99	vanillic acid	18.50	C₈H₈O₄	[M + H]⁺	169.0498	151.0388, 146.9612, 128.9508, 123.0442
100	flavoyadorinin B	18.51	C₂₃H₂₄O₁₁	[M + H]⁺	477.1379	327.1659, 279.0375, 204.5438, 145.0499
101	ephedrannin D2	18.54	C₃₀H₂₄O₁₃	[M − H]⁻	591.1150	547.1453, 462.7491, 285.0408, 253.0507
* 102	cinnamic acid	18.59	C₉H₈O₂	[M + H]⁺	149.0597	133.0885, 121.0648, 103.0548, 95.0497
103	hydroxyphenylacetic acid	18.65	C₈H₈O₃	[M + H]⁺	153.0546	135.1167, 112.0395, 90.9481, 72.9378
104	3-O-caffeoylshikimic acid	18.81	C₁₆H₁₆O₈	[M + H]⁺	337.0910	181.0494, 163.0388, 145.0283, 95.0495
104	3-O-caffeoylshikimic acid	18.81	C₁₆H₁₆O₈	[M − H]⁻	335.0771	269.1091, 179.0345, 161.0233, 133.0282
105	leucopelargonidin	18.82	C₁₅H₁₄O₆	[M + H]⁺	291.0857	273.0753, 207.0647, 147.0440, 139.0389
105	leucopelargonidin	18.82	C₁₅H₁₄O₆	[M − H]⁻	289.0714	245.0818, 203.0705, 151.0392, 123.0441
106	licuraside	19.43	C₂₆H₃₀O₁₃	[M − H]⁻	549.1609	502.1001, 429.1062, 255.0660, 119.0490
107	genistein 7-O-glucoside	20.25	C₂₁H₂₀O₁₀	[M + H]⁺	433.1120	271.0595, 215.0700, 137.0231
* 108	liquiritin apioside	20.29	C₂₆H₃₀O₁₃	[M − H]⁻	549.1609	482.5059, 297.0778, 255.0660, 135.0076
109	isoliquiritin apioside	20.34	C₂₆H₃₀O₁₃	[M − H]⁻	549.1609	488.6683, 429.1148, 255.0659, 135.0076
* 110	liquiritin	20.38	C₂₁H₂₂O₉	[M − H]⁻	417.1186	402.1664, 373.0210, 255.0662, 119.0490
111	secologanin dimethyl acetal	20.39	C₁₉H₃₀O₁₁	[M − H]⁻	433.1706	/
112	3-methoxyphenol	20.50	C₇H₈O₂	[M + H]⁺	125.0599	102.9706, 97.0287, 84.9602
113	piceid gallate A	20.63	C₂₇H₂₆O₁₃	[M − H]⁻	557.1293	/
* 114	polydatin	20.92	C₂₀H₂₂O₈	[M − H]⁻	389.1236	227.0707, 185.0598, 159.0808, 143.0491
115	lonicerin	21.02	C₂₇H₃₀O₁₅	[M + H]⁺	595.1641	433.1108, 313.0717, 271.0596, 215.0697
115	lonicerin	21.02	C₂₇H₃₀O₁₅	[M − H]⁻	593.1510	430.4479, 329.5679, 285.0396, 227.0705
116	isoliquiritin	21.24	C₂₁H₂₂O₉	[M − H]⁻	417.1186	255.0660, 153.0182, 135.0075, 119.0489
* 117	quercetin 3-glucoside	21.69	C₂₁H₂₀O₁₂	[M − H]⁻	463.0880	300.0272, 271.0247, 255.0296, 151.0027
118	kaempferol 7-O-glucopyranoside	21.69	C₂₁H₂₀O₁₁	[M + H]⁺	449.1072	330.0535, 287.0545, 203.4280, 153.0181
118	kaempferol 7-O-glucopyranoside	21.69	C₂₁H₂₀O₁₁	[M − H]⁻	447.0931	410.9457, 325.0732, 285.0397, 256.0383
119	neoisoliquiritin	22.95	C₂₁H₂₂O₉	[M − H]⁻	417.1186	374.0878, 255.0660, 153.0183, 135.0076
* 120	coumarin	23.54	C₉H₆O₂	[M + H]⁺	147.0442	131.9743, 119.0493, 113.9640
* 121	daidzein	23.56	C₁₅H₁₀O₄	[M − H]⁻	253.0502	224.0468, 209.0598, 197.0602, 135.0076
122	rhoifolin	23.76	C₂₇H₃₀O₁₄	[M + H]⁺	579.1692	515.2410, 429.1205, 327.0858, 297.0754
* 123	isochlorogenic acid A	23.89	C₂₅H₂₄O₁₂	[M − H]⁻	515.1185	353.0883, 335.0772, 173.0445, 135.0440
124	reynoutrin	24.65	C₂₀H₁₈O₁₁	[M − H]⁻	433.0771	/
125	avicularin	25.43	C₂₀H₁₈O₁₁	[M − H]⁻	433.0771	/
* 126	resveratroloside	25.46	C₂₀H₂₂O₈	[M + H]⁺	391.1375	229.0856, 211.0759, 135.0440, 107.0495
127	liquiritigenin 7,4′-diglucoside	25.61	C₂₇H₃₂O₁₄	[M + H]⁺	581.1848	538.0963, 431.0979, 311.0434, 287.0430
128	centauroside	25.64	C₃₄H₄₆O₁₉	[M − H]⁻	757.2545	679.1150, 525.1623, 458.1185, 254.0573
129	3,4-dicaffeoylquinic acid	25.75	C₂₅H₂₄O₁₂	[M − H]⁻	515.1185	437.3583, 353.0874, 191.0552, 135.0440
130	herniarin	26.18	C₁₀H₈O₃	[M + H]⁺	177.0546	149.0597, 145.0283, 117.0336, 89.0390
131	catechin-5-O-β-D-glucopyranoside	26.54	C₂₁H₂₄O₁₁	[M − H]⁻	451.1243	313.0739, 289.0719, 191.0340, 167.0340
132	vanillin	26.58	C₈H₈O₃	[M + H]⁺	153.0546	131.9743, 125.0597, 111.0443, 93.0338
133	4,7-dihydroxyflavone 7-D-glucoside	26.84	C₂₁H₂₀O₉	[M + H]⁺	417.1167	338.5892, 255.0647, 227.0695, 199.0747
134	methyl chlorogenate	27.00	C₁₇H₂₀O₉	[M + H]⁺	369.1173	313.0666, 285.0745, 207.0644, 161.0596
135	ketologanin	27.07	C₁₇H₂₄O₁₀	[M + H]⁺	389.1433	371.1681, 324.1584, 225.0426, 151.0388
136	naringin	27.96	C₂₇H₃₂O₁₄	[M + H]⁺	581.1848	449.1047, 431.0979, 329.0610, 311.0434
137	(E)-aldosecologanin	28.10	C₃₄H₄₆O₁₉	[M − H]⁻	757.2545	679.1150, 595.2075, 525.1623, 458.1185
138	dihydrocaffeic acid	28.25	C₉H₁₀O₄	[M + H]⁺	183.0649	165.0545, 151.0389, 123.0441, 113.9639
139	p-coumaric acid	28.25	C₉H₈O₃	[M + H]⁺	165.0544	137.0597, 133.0283, 109.0650, 79.0547
140	secoxyloganin	28.25	C₁₇H₂₄O₁₁	[M + H]⁺	405.1379	373.2119, 309.2449, 165.0545, 151.0389
141	benzoic acid	28.26	C₇H₆O₂	[M + H]⁺	123.0441	105.0450, 95.0495, 67.0549
142	1,5-dicaffeoylquinic acid	28.63	C₂₅H₂₄O₁₂	[M − H]⁻	515.1185	454.9042, 353.0873, 191.0552, 173.0446
143	vogeloside	28.65	C₁₇H₂₄O₁₀	[M + H]⁺	389.1433	233.2362, 195.0655, 151.0389, 107.0495
144	3-O-caffeoylquinic acid methyl ester	28.94	C₁₇H₂₀O₉	[M + H]⁺	369.1173	207.0649, 177.0546, 148.0514, 107.0857
145	quercitrin	30.05	C₂₁H₂₀O₁₁	[M + H]⁺	449.1072	330.0535, 287.0545, 269.0448, 153.0181
145	quercitrin	30.05	C₂₁H₂₀O₁₁	[M − H]⁻	447.0931	403.1030, 241.0501, 197.0599, 174.9555
146	4-feruloylquinic acid	30.26	C₁₇H₂₀O₉	[M + H]⁺	369.1173	239.4636, 207.0649, 177.0539, 148.0516
* 147	naringenin	31.32	C₁₅H₁₂O₅	[M − H]⁻	271.0609	230.0589, 177.0189, 151.0026, 119.0490
148	kuzubutenolide A	31.41	C₂₃H₂₄O₁₀	[M + H]⁺	461.1433	299.0909, 253.0853, 193.0497, 107.0494
149	pueroside A	31.42	C₂₉H₃₄O₁₄	[M + H]⁺	607.2010	461.1439, 376.1363, 299.0908, 107.0494
150	epicatechingallate	31.75	C₂₂H₁₈O₁₀	[M + H]⁺	443.0962	390.0869, 291.0855, 273.0755, 123.0441
151	garbanzol	31.76	C₁₅H₁₂O₅	[M + H]⁺	273.0752	242.4491, 189.0543, 153.0180, 123.0441
152	chrysoeriol 7-O-glucopyranoside	31.80	C₂₂H₂₂O₁₁	[M + H]⁺	463.1220	445.1107, 427.1008, 343.0803, 313.0704
153	sophoraside A	31.92	C₂₄H₂₆O₁₀	[M + H]⁺	475.1587	313.1061, 267.1010, 253.0853, 107.0494
153	sophoraside A	31.92	C₂₄H₂₆O₁₀	[M − H]⁻	473.1447	377.9086, 311.0924, 267.1024, 252.0786
154	vitexin	32.25	C₂₁H₂₀O₁₀	[M + H]⁺	433.1120	415.1018, 397.0909, 313.0698, 283.0597
154	vitexin	32.25	C₂₁H₂₀O₁₀	[M − H]⁻	431.0975	269.0453, 240.0423, 225.0551, 193.4129
155	5-O-coumaroylcaffeoylquinic acid	32.38	C₂₅H₂₄O₁₁	[M + H]⁺	501.1379	483.1254, 320.0835, 255.0652, 163.0388
155	5-O-coumaroylcaffeoylquinic acid	32.38	C₂₅H₂₄O₁₁	[M − H]⁻	499.1244	431.0978, 291.0275, 269.0454, 240.0423
* 156	resveratrol	32.64	C₁₄H₁₂O₃	[M + H]⁺	229.0856	211.0747, 183.0808, 135.0441, 107.0494
* 157	ferulic acid	32.90	C₁₀H₁₀O₄	[M + H]⁺	195.0652	177.0544, 163.0389, 138.0661, 107.0494
* 157	ferulic acid	32.90	C₁₀H₁₀O₄	[M − H]⁻	193.0498	165.0005, 134.0361, 126.9024, 102.9472
* 158	isoferulic acid	32.91	C₁₀H₁₀O₄	[M + H]⁺	195.0652	177.0544, 163.0388, 149.0596, 109.0287
* 158	isoferulic acid	32.91	C₁₀H₁₀O₄	[M − H]⁻	193.0498	161.0233, 149.0236, 134.0363, 121.0281
159	kudzusaponin A1	34.62	C₅₂H₈₄O₂₃	[M − H]⁻	1075.5314	1029.5265, 763.3842, 603.3890, 485.3619
160	hyperoside	35.15	C₂₁H₂₀O₁₂	[M + H]⁺	465.1023	447.1085, 303.0492, 286.0449, 257.0425
161	polygalin A	35.16	C₂₃H₂₄O₁₁	[M + H]⁺	477.1379	355.1165, 315.0853, 271.0960, 229.0856
161	polygalin A	35.16	C₂₃H₂₄O₁₁	[M − H]⁻	475.1241	267.0660, 252.0424, 201.9968, 132.0607
162	7-hydroxy-4-methoxy-5-methylcoumarin	35.24	C₁₁H₁₀O₄	[M + H]⁺	207.0650	189.0544, 161.0599, 150.0261, 123.0807
163	glycitin-6″-O-xylosyl	36.12	C₂₇H₃₀O₁₄	[M + H]⁺	579.1692	433.1124, 337.0699, 313.0699, 283.0596
164	cuspidatumin A	36.14	C₁₄H₁₂O₄	[M + H]⁺	245.0805	229.0854, 161.0122, 121.0286, 98.9757
164	cuspidatumin A	36.14	C₁₄H₁₂O₄	[M − H]⁻	243.0661	225.1119, 207.1026, 174.9554, 146.9600
165	3,5-dicaffeoylquinic acid methyl ester	36.23	C₂₆H₂₆O₁₂	[M + H]⁺	531.1486	513.1385, 369.1514, 283.0595, 163.0388
* 166	rutin	36.27	C₂₇H₃₀O₁₆	[M + H]⁺	611.1602	465.1010, 303.0493, 257.0441, 229.0495
* 167	taxifolin	36.27	C₁₅H₁₂O₇	[M + H]⁺	305.0653	287.1236, 269.1125, 227.1023, 191.0814
168	pueroside B	36.31	C₃₀H₃₆O₁₅	[M + H]⁺	637.2119	475.1591, 313.1064, 267.1011, 107.0494
169	pueroside C	36.31	C₂₄H₂₆O₁₀	[M + H]⁺	475.1587	457.3117, 313.1034, 249.1549, 107.0486
170	macranthoidin B	36.35	C₆₅H₁₀₆O₃₂	[M + H]⁺	1399.6711	1075.5695, 943.5251, 795.2725, 633.2202
170	macranthoidin B	36.35	C₆₅H₁₀₆O₃₂	[M − H]⁻	1397.6552	1073.5525, 911.5010, 749.4481, 603.3898
171	kudzusaponin SA2	36.39	C₄₇H₇₆O₁₉	[M + H]⁺	945.5027	848.4162, 763.4678, 679.2439, 421.3453
172	macranthoidin A	36.40	C₅₉H₉₆O₂₇	[M + H]⁺	1237.6183	1076.5618, 943.5206, 751.4630, 603.2128
172	macranthoidin A	36.40	C₅₉H₉₆O₂₇	[M − H]⁻	1235.6036	1189.5997, 1073.5534, 911.5006, 749.4482
173	kudzusaponin SA4	36.40	C₄₇H₇₄O₂₀	[M + H]⁺	959.4806	892.2470, 764.6243, 615.3878, 421.3457
174	saponin 1	36.43	C₅₈H₉₄O₂₆	[M + H]⁺	1207.6077	1075.5693, 913.5162, 751.4610, 603.2120
174	saponin 1	36.43	C₅₈H₉₄O₂₆	[M − H]⁻	1205.5934	881.4901, 749.4479, 603.3898, 471.3479
175	24-hydroxy-licorice-saponin A3	36.45	C₄₈H₇₂O₂₂	[M + H]⁺	1001.4559	825.4282, 763.0059, 631.3789, 469.3288
176	3,4-O-dicaffeoylquinic acid methyl ester	36.46	C₂₆H₂₆O₁₂	[M + H]⁺	531.1486	319.0808, 271.0598, 177.0545, 163.0388
176	3,4-O-dicaffeoylquinic acid methyl ester	36.46	C₂₆H₂₆O₁₂	[M − H]⁻	529.1344	443.6241, 367.1035, 191.0554, 135.1440
177	isoquercetin	36.47	C₂₁H₂₀O₁₂	[M + H]⁺	465.1023	303.0494, 257.0439, 229.0495, 153.0182
178	soyasaponin A3	36.48	C₄₈H₇₈O₁₉	[M + H]⁺	959.5183	813.4605, 439.3565, 141.0181, 85.0289
178	soyasaponin A3	36.48	C₄₈H₇₈O₁₉	[M − H]⁻	957.5065	911.5010, 749.4482, 587.3950, 471.3475
179	dipsacoside B	36.49	C₅₃H₈₆O₂₂	[M − H]⁻	1073.5519	912.0020, 749.4480, 585.3804, 471.3478
180	kudzusaponin B1	36.52	C₄₈H₇₆O₂₁	[M + H]⁺	989.4921	843.4330, 681.3870, 469.3314, 141.0181
180	kudzusaponin B1	36.52	C₄₈H₇₆O₂₁	[M − H]⁻	987.4794	926.4868, 763.7924, 661.3583, 503.3387
181	saponin 4	36.55	C₅₈H₉₄O₂₇	[M − 2H]²⁻	610.2908	/
182	licoricesaponin A3	36.57	C₄₈H₇₂O₂₁	[M + H]⁺	985.4612	809.4323, 615.3887, 453.3356, 189.1634
182	licoricesaponin A3	36.57	C₄₈H₇₂O₂₁	[M − H]⁻	983.4483	943.1790, 821.3969, 645.3637, 351.0566
183	neoliquiritin	36.58	C₂₁H₂₂O₉	[M + H]⁺	419.1326	315.0854, 257.0803, 217.0483, 124.0392
184	6″-O-malonyldaidzin	36.58	C₂₄H₂₂O₁₂	[M + H]⁺	503.1170	480.9303, 392.3837, 255.0647, 199.0751
185	(2E)-1-(2,3-dihydroxy-4-methoxyphenyl)-3-(4-hydroxyphenyl)-2-propen^--one	36.58	C₁₆H₁₄O₅	[M + H]⁺	287.0908	245.0804, 207.0649, 193.0492, 121.0285
185		36.58	C₁₆H₁₄O₅	[M − H]⁻	285.0765	270.0532, 177.0185, 150.0311, 108.0206
186	loniceroside D	36.59	C₅₃H₈₆O₂₃	[M + H]⁺	1091.5607	1033.7538, 945.5055, 783.4556, 421.3455
186	loniceroside D	36.59	C₅₃H₈₆O₂₃	[M − H]⁻	1089.5470	1071.5394, 943.4768, 882.4898, 763.4315
187	akebiasaponin D	36.60	C₄₇H₇₆O₁₈	[M + H]⁺	929.5079	767.4589, 635.4064, 437.3408, 189.1637
188	kudzusaponin A2	36.61	C₄₂H₆₈O₁₆	[M + H]⁺	829.4560	764.7684, 649.3955, 455.3521, 269.0806
188	kudzusaponin A2	36.61	C₄₂H₆₈O₁₆	[M − H]⁻	827.4425	763.3452, 677.4987, 516.0891, 333.8636
189	isorhamnetin 3-O-glucopyranoside	36.62	C₂₂H₂₂O₁₂	[M + H]⁺	479.1170	397.5868, 317.0649, 274.0458, 120.0809
* 190	astragalin	36.62	C₂₁H₂₀O₁₁	[M + H]⁺	449.1072	409.0180, 346.9581, 287.0544, 252.9790
* 190	astragalin	36.62	C₂₁H₂₀O₁₁	[M − H]⁻	447.0931	316.5085, 284.0322, 255.0294, 227.0343
191	7,4′-dihydroxyflavone	36.63	C₁₅H₁₀O₄	[M + H]⁺	255.0645	227.0696, 199.0752, 137.0234, 91.0546
191	7,4′-dihydroxyflavone	36.63	C₁₅H₁₀O₄	[M − H]⁻	253.0502	224.0470, 208.0522, 135.0076, 91.0174
192	isorhamentin 3-O-rutinoside	36.66	C₂₈H₃₂O₁₆	[M + H]⁺	625.1743	479.1161, 317.0652, 302.0414, 85.0289
192	isorhamentin 3-O-rutinoside	36.66	C₂₈H₃₂O₁₆	[M − H]⁻	623.1613	527.7530, 415.1031, 252.0425, 223.0404
* 193	4′-methoxypuerarin	36.67	C₂₂H₂₂O₉	[M + H]⁺	431.1326	395.1120, 365.1009, 311.0910, 271.0595
194	4,5-O-dicaffeoylquinic acid methyl ester	36.67	C₂₆H₂₆O₁₂	[M − H]⁻	529.1344	483.1268, 463.2749, 367.1032, 253.0501
195	quercetin 3-O-arabinoside	36.67	C₂₀H₁₈O₁₁	[M + H]⁺	435.0917	303.0501, 271.0596, 153.0180, 121.0280
196	loniceroside A	36.69	C₅₂H₈₄O₂₁	[M − H]⁻	1043.5422	1025.5223, 763.3167, 709.8038, 532.3125
* 197	rhein	36.71	C₁₅H₈O₆	[M + H]⁺	285.0392	269.0440, 257.0428, 151.0385, 121.0283
* 197	rhein	36.71	C₁₅H₈O₆	[M − H]⁻	283.0246	268.0373, 217.0500, 175.0391, 133.0284
198	3,4,5-tricaffeoylquinic acid	36.72	C₃₄H₃₀O₁₅	[M + H]⁺	679.1633	499.1226, 322.2479, 163.0387, 135.0440
198	3,4,5-tricaffeoylquinic acid	36.72	C₃₄H₃₀O₁₅	[M − H]⁻	677.1511	515.1179, 353.0875, 173.0446, 135.0440
199	choerospondin	36.74	C₂₁H₂₂O₁₀	[M + H]⁺	435.1296	303.0501, 271.0596, 231.0647, 153.0180
200	4,5-dicaffeoylquinic acid	36.75	C₂₅H₂₄O₁₂	[M + H]⁺	517.1326	499.1223, 453.8935, 269.0803, 163.0387
201	pollenitin B	36.76	C₂₂H₂₂O₁₂	[M + H]⁺	479.1170	412.8673, 317.0651, 302.0415, 274.0472
202	medicarpin3-O-glucoside	36.77	C₂₂H₂₄O₉	[M + H]⁺	433.1482	312.0939, 271.0596, 214.2812, 153.0182
203	lonfuranacid A	36.77	C₁₂H₂₀O₅	[M + H]⁺	245.1377	229.0853, 189.1119, 125.0962, 97.1015
204	questin	36.78	C₁₆H₁₂O₅	[M + H]⁺	285.0751	270.0518, 253.0490, 242.0574, 153.0179
205	Tricin 7-O-glucoside	36.78	C₂₃H₂₄O₁₂	[M + H]⁺	493.1326	331.0807, 315.0493, 287.0537, 270.0518
206	tectoridin	36.79	C₂₂H₂₂O₁₁	[M + H]⁺	463.1220	301.0700, 286.0467, 258.0517, 153.0181
* 207	liquiritigenin	36.80	C₁₅H₁₂O₄	[M + H]⁺	257.0805	239.0705, 211.0756, 147.0439, 137.0232
* 207	liquiritigenin	36.80	C₁₅H₁₂O₄	[M − H]⁻	255.0660	209.0605, 153.0183, 135.0077, 119.0490
208	subproside V	36.80	C₅₄H₈₈O₂₄	[M − H]⁻	1119.5575	1073.5519, 911.5007, 749.4478, 603.3897
209	loniceroside E	36.81	C₅₃H₈₆O₂₁	[M − H]⁻	1057.5570	1039.5623, 849.4960, 763.3219, 413.0908
210	kudzusaponin A5	36.82	C₄₈H₇₈O₂₀	[M + H]⁺	975.5131	829.4545, 764.4423, 667.4020, 455.3510
211	torachrysone	36.82	C₁₄H₁₄O₄	[M + H]⁺	247.0960	229.0856, 214.0621, 201.0907, 198.0673
211	torachrysone	36.82	C₁₄H₁₄O₄	[M − H]⁻	245.0812	230.0579, 215.0343, 202.0625, 159.0440
212	macranthoside B	36.83	C₅₃H₈₆O₂₂	[M + H]⁺	1075.5658	943.5235, 781.4703, 619.4197, 437.3409
213	glycyroside	36.83	C₂₇H₃₀O₁₃	[M + H]⁺	563.1743	431.1331, 413.1223, 311.0907, 281.0803
213	glycyroside	36.83	C₂₇H₃₀O₁₃	[M − H]⁻	561.1608	523.2799, 339.0867, 309.0767, 266.0582
214	ohyscion	36.84	C₁₆H₁₂O₅	[M + H]⁺	285.0751	270.0518, 242.0567, 189.4096, 113.0597
214	ohyscion	36.84	C₁₆H₁₂O₅	[M − H]⁻	283.0609	268.0375, 240.0419, 211.0391, 184.0518
215	afzelin	36.88	C₂₁H₂₀O₁₀	[M + H]⁺	433.1120	418.8996, 271.0596, 243.0644, 215.0699
215	afzelin	36.88	C₂₁H₂₀O₁₀	[M − H]⁻	431.0975	269.0454, 240.0424, 225.0552, 152.9942
216	kudzusaponin SA3	36.89	C₅₃H₈₆O₂₃	[M + H]⁺	1091.5607	929.5117, 767.4597, 635.4111, 437.3414
216	kudzusaponin SA3	36.89	C₅₃H₈₆O₂₃	[M − H]⁻	1089.5470	1043.5427, 881.4904, 749.4480, 603.3900
217	22β-acetoxyglycyrrhizin	36.91	C₄₄H₆₄O₁₈	[M + H]⁺	881.4143	705.3826, 511.3415, 451.3196, 107.0859
218	kudzusaponin C1	36.93	C₅₄H₈₈O₂₃	[M + H]⁺	1105.5767	959.5132, 797.498, 603.4246, 423.3591
219	questinol	36.94	C₁₆H₁₂O₆	[M + H]⁺	301.0701	286.0460, 269.0439, 167.0338, 134.0362
220	3′-methoxydaidzin	36.96	C₂₂H₂₂O₁₀	[M + H]⁺	447.1277	384.1155, 327.0859, 285.0752, 229.0857
221	loniceroside B	36.96	C₅₈H₉₄O₂₅	[M + H]⁺	1191.6127	817.3367, 763.4253, 619.4137, 437.3397
222	citreorosein	36.97	C₁₅H₁₀O₆	[M + H]⁺	287.0542	271.0596, 269.0443, 259.0960, 217.0491
222	citreorosein	36.97	C₁₅H₁₀O₆	[M − H]⁻	285.0402	268.0367, 257.0461, 196.0532, 133.0284
223	herbacetin	37.01	C₁₅H₁₀O₇	[M + H]⁺	303.0492	286.0430, 257.0442, 229.0497, 153.0181
223	herbacetin	37.01	C₁₅H₁₀O₇	[M − H]⁻	301.0351	284.0315, 273.0407, 178.9976, 151.0026
224	betulonic acid	37.02	C₃₀H₄₆O₃	[M + H]⁺	455.3507	409.3467, 388.4104, 203.1793, 189.1635
225	kudzusaponin A3	37.05	C₄₈H₇₈O₂₀	[M + H]⁺	975.5131	829.4545, 667.4020, 455.3510, 141.0181
* 226	ononin	37.08	C₂₂H₂₂O₉	[M + H]⁺	431.1326	269.0805, 254.0569, 213.0910, 107.0494
227	kaempferol 3-O-rutinoside	37.11	C₂₇H₃₀O₁₅	[M + H]⁺	595.1641	525.0455, 433.1108, 287.0544, 271.0596
228	isobavachalcone	37.11	C₂₀H₂₀O₄	[M + H]⁺	325.1429	309.0781, 285.0754, 189.0906, 95.0163
229	liqcoumarin	37.18	C₁₂H₁₀O₄	[M + H]⁺	219.0648	201.0910, 174.0674, 133.1012, 105.0702
230	isokaempferide	37.19	C₁₆H₁₂O₆	[M + H]⁺	301.0701	283.0596, 255.0636, 227.0698, 123.1169
231	uralsaponin F	37.21	C₄₄H₆₄O₁₉	[M + H]⁺	897.4094	763.6343, 679.2714, 527.3329, 334.7203
232	daidzein 4′,7-diglucoside	37.25	C₂₇H₃₀O₁₄	[M + H]⁺	579.1692	503.0054, 447.1283, 285.0753, 229.0858
233	liquoric acid	37.26	C₃₀H₄₄O₅	[M + H]⁺	485.3245	323.1276, 255.0648, 199.0751, 163.0385
234	isoorientin	37.27	C₂₁H₂₀O₁₁	[M + H]⁺	449.1072	330.0535, 287.0545, 153.0181, 135.0439
235	isorhodoptilometrin	37.31	C₁₇H₁₄O₆	[M + H]⁺	315.0856	300.0623, 272.0670, 153.0185, 95.0858
235	isorhodoptilometrin	37.31	C₁₇H₁₄O₆	[M − H]⁻	313.0715	298.0479, 270.0529, 227.0343, 183.0454
236	chrysophanol	37.34	C₁₅H₁₀O₄	[M + H]⁺	255.0645	237.0549, 227.0692, 199.0751, 187.0725
237	licoricesaponin G2	37.34	C₄₂H₆₂O₁₇	[M + H]⁺	839.4040	663.3734, 487.3410, 469.3306, 141.0181
237	licoricesaponin G2	37.34	C₄₂H₆₂O₁₇	[M − H]⁻	837.3906	763.7259, 724.4032, 351.0571, 193.0345
238	kudzusaponin SA1	37.35	C₄₂H₆₈O₁₅	[M + H]⁺	813.4611	764.7317, 439.3548, 141.0181, 95.0860
238	kudzusaponin SA1	37.35	C₄₂H₆₈O₁₅	[M − H]⁻	811.4482	765.4406, 603.3923, 432.7037, 283.0584
239	1,4-dicaffeoylquinic acid	37.38	C₂₅H₂₄O₁₂	[M + H]⁺	517.1326	460.9336, 414.0990, 269.0804, 213.0906
240	ethyl caffeate	37.38	C₁₁H₁₂O₄	[M + H]⁺	209.0806	163.0388, 145.1011, 135.0441, 117.0337
240	ethyl caffeate	37.38	C₁₁H₁₂O₄	[M − H]⁻	207.0654	179.0341, 161.0233, 135.0441, 121.0284
241	apigenin 7-glucoside	37.41	C₂₁H₂₀O₁₀	[M + H]⁺	433.1120	379.0797, 337.0701, 313.0699, 271.0596
241	apigenin 7-glucoside	37.41	C₂₁H₂₀O₁₀	[M − H]⁻	431.0975	311.0562, 269.0453, 225.0554, 152.9949
* 242	daidzin	37.42	C₂₁H₂₀O₉	[M + H]⁺	417.1167	387.2100, 297.0747, 255.0648, 199.0753
243	2,5-dimethyl-7-hydroxychromenone	37.46	C₁₁H₁₀O₃	[M + H]⁺	191.0699	151.0387, 131.0856, 107.0861, 95.0860
244	prunetin	37.46	C₁₆H₁₂O₅	[M + H]⁺	285.0751	253.0489, 242.0572, 211.0750, 151.0390
244	prunetin	37.46	C₁₆H₁₂O₅	[M − H]⁻	283.0609	268.0380, 240.0423, 197.0600, 168.0650
245	glabrolide	37.47	C₃₀H₄₄O₄	[M + H]⁺	469.3298	233.1540, 175.1479, 135.1167, 107.0858
246	pinocembrin	37.53	C₁₅H₁₂O₄	[M + H]⁺	257.0805	239.0701, 229.0850, 211.0752, 147.0440
247	polygonin B	37.54	C₂₆H₂₆O₁₃	[M + H]⁺	547.1430	299.0909, 284.0674, 239.0702, 163.0385
* 248	glycyrrhizic acid	37.56	C₄₂H₆₂O₁₆	[M + H]⁺	823.4086	647.3788, 471.3457, 453.3356
* 248	glycyrrhizic acid	37.56	C₄₂H₆₂O₁₆	[M − H]⁻	821.3959	763.8063, 469.3315, 351.0569, 193.0347
249	echinatin	37.56	C₁₆H₁₄O₄	[M + H]⁺	271.0960	254.2115, 147.0438, 137.0596, 123.0441
249	echinatin	37.56	C₁₆H₁₄O₄	[M − H]⁻	269.0816	251.0708, 225.0552, 151.0030, 119.0490
250	hesperetin	37.62	C₁₆H₁₄O₆	[M + H]⁺	303.0853	258.0517, 153.0183, 106.0866, 88.0762
250	hesperetin	37.62	C₁₆H₁₄O₆	[M − H]⁻	301.0714	273.0774, 255.0296, 230.0580, 183.0447
251	(S)-naringenin	37.62	C₁₅H₁₂O₅	[M + H]⁺	273.0752	189.0543, 153.0180, 123.0441
252	puerol B	37.64	C₁₈H₁₆O₅	[M + H]⁺	313.1063	267.1011, 253.0854, 107.0495
252	puerol B	37.64	C₁₈H₁₆O₅	[M − H]⁻	311.0922	296.0689, 267.1026, 252.0789, 161.0233
253	coumestrol	37.72	C₁₅H₈O₅	[M + H]⁺	269.0437	254.0572, 241.0492, 213.0543, 185.0595
253	coumestrol	37.72	C₁₅H₈O₅	[M − H]⁻	267.0297	251.0709, 225.0550, 181.0649, 151.0026
254	polygonin A	37.73	C₂₅H₂₄O₁₃	[M + H]⁺	533.1273	488.1885, 360.1438, 285.0753, 270.0517
254	polygonin A	37.73	C₂₅H₂₄O₁₃	[M − H]⁻	531.1141	341.9318, 253.0502, 229.0135, 191.0555
255	tricin	37.73	C₁₇H₁₄O₇	[M + H]⁺	331.0804	315.0492, 302.0406, 270.0519, 73.0291
255	tricin	37.73	C₁₇H₁₄O₇	[M − H]⁻	329.0664	271.0247, 211.1332, 171.1017
256	neobavaisoflavone	37.76	C₂₀H₁₈O₄	[M + H]⁺	323.1272	308.0663, 267.0647, 255.0648, 239.0698
257	biochanin	37.76	C₁₆H₁₂O₅	[M + H]⁺	285.0751	270.0516, 253.0491, 225.0540, 137.0233
257	biochanin	37.76	C₁₆H₁₂O₅	[M − H]⁻	283.0609	268.0377, 240.0423, 224.0474, 135.0075
258	gancaonin V	37.76	C₁₉H₂₀O₄	[M + H]⁺	313.1425	281.1162, 244.0359, 153.0181
258	gancaonin V	37.76	C₁₉H₂₀O₄	[M − H]⁻	311.1285	296.0687, 267.1025, 252.0789, 161.0232
259	6,7-dimethoxycoumarin	37.76	C₁₁H₁₀O₄	[M + H]⁺	207.0650	189.1636, 175.0388, 148.0517, 91.0547
260	puerol A	37.78	C₁₇H₁₄O₅	[M + H]⁺	299.0908	284.0674, 256.0726, 239.0698, 95.0163
260	puerol A	37.78	C₁₇H₁₄O₅	[M − H]⁻	297.0764	281.0457, 256.0376, 239.0346, 151.0025
261	biapigenin	37.78	C₃₀H₁₈O₁₀	[M + H]⁺	539.0958	522.9716, 387.0856, 286.0465, 184.0731
261	biapigenin	37.78	C₃₀H₁₈O₁₀	[M − H]⁻	537.0822	521.0623, 417.0622, 375.0506, 331.0608
262	2-methoxy-6-acetyl-7-methyljuglone	37.79	C₁₄H₁₂O₅	[M + H]⁺	261.0754	243.0648, 215.0699, 200.0466, 187.0754
262	2-methoxy-6-acetyl-7-methyljuglone	37.79	C₁₄H₁₂O₅	[M − H]⁻	259.0608	243.1414, 231.0657, 216.0422, 188.0471
263	kudzusaponin SB1	37.79	C₅₃H₈₆O₂₂	[M + H]⁺	1075.5658	943.5235, 751.4603, 437.3405, 189.1636
263	kudzusaponin SB1	37.79	C₅₃H₈₆O₂₂	[M − H]⁻	1073.5519	911.5006, 749.4489, 603.3903, 471.3480
264	diosmetin	37.81	C₁₆H₁₂O₆	[M + H]⁺	301.0701	286.0468, 258.0523, 241.0491, 88.0762
264	diosmetin	37.81	C₁₆H₁₂O₆	[M − H]⁻	299.0557	284.0325, 256.0372, 227.0344, 151.0030
265	(-)-epiafzelechin	37.82	C₁₅H₁₄O₅	[M + H]⁺	275.0906	257.0795, 217.0492, 189.0544, 107.0495
265	(-)-epiafzelechin	37.82	C₁₅H₁₄O₅	[M − H]⁻	273.0766	258.0532, 230.0579, 215.0343, 135.0076
266	licoricesaponin E2	37.85	C₄₂H₆₀O₁₆	[M + H]⁺	821.3938	764.7926, 451.3198, 173.1327, 121.1012
267	methyl glycyrrhizate	37.86	C₄₃H₆₄O₁₆	[M + H]⁺	837.4255	764.7705, 663.3716, 469.3308, 141.0181
268	licoisoflavanone	37.88	C₂₀H₁₈O₆	[M + H]⁺	355.1169	337.1062, 299.0546, 179.0337, 123.0441
268	licoisoflavanone	37.88	C₂₀H₁₈O₆	[M − H]⁻	353.1027	335.0921, 312.0276, 217.0863, 189.0913
269	3-methoxyherbacetin	37.89	C₁₆H₁₂O₇	[M + H]⁺	317.0647	302.0411, 237.0383, 153.0181, 127.0391
269	3-methoxyherbacetin	37.89	C₁₆H₁₂O₇	[M − H]⁻	315.0506	300.0272, 272.0323, 188.0482, 112.9845
270	erybacin B	37.89	C₁₉H₁₈O₅	[M + H]⁺	327.1222	271.0597, 117.0367, 95.0163, 77.0059
270	erybacin B	37.89	C₁₉H₁₈O₅	[M − H]⁻	325.1076	309.2072, 297.0051, 197.1174, 171.1016
271	soyasaponin I	37.91	C₄₈H₇₈O₁₈	[M + H]⁺	943.5241	797.4680, 764.6400, 423.3611, 85.0289
271	soyasaponin I	37.91	C₄₈H₇₈O₁₈	[M − H]⁻	941.5101	912.5775, 763.8070, 615.3933, 438.3518
272	licoricesaponin B2	37.93	C₄₂H₆₄O₁₅	[M + H]⁺	809.4296	633.3988, 439.3564, 285.2223, 107.0859
272	licoricesaponin B2	37.93	C₄₂H₆₄O₁₅	[M − H]⁻	807.4168	763.8304, 520.9705, 351.0565, 193.0345
273	ephedrannin B	37.94	C₃₀H₂₀O₁₀	[M + H]⁺	541.1106	415.0806, 389.1013, 171.0287, 153.0181
273	ephedrannin B	37.94	C₃₀H₂₀O₁₀	[M − H]⁻	539.0981	521.2609, 507.2097, 396.8802, 266.9637
274	medicarpin	37.97	C₁₆H₁₄O₄	[M + H]⁺	271.0960	253.0497, 229.0855, 197.0594, 121.0285
* 275	kaempferol	37.99	C₁₅H₁₀O₆	[M + H]⁺	287.0542	271.0556, 254.0524, 226.0577, 153.0181
* 275	kaempferol	37.99	C₁₅H₁₀O₆	[M − H]⁻	285.0402	268.0364, 257.0451, 241.0497, 211.0396
276	glyasperin D	38.04	C₂₂H₂₆O₅	[M + H]⁺	371.1844	315.1218, 303.1219, 167.0701, 123.0441
277	isoliquiritigenin	38.09	C₁₅H₁₂O₄	[M + H]⁺	257.0805	239.0698, 211.0755, 147.0440, 137.0232
277	isoliquiritigenin	38.09	C₁₅H₁₂O₄	[M − H]⁻	255.0660	153.0182, 135.0077, 119.0489, 91.0175
278	3′-hydroxydaidzein	38.10	C₁₅H₁₀O₅	[M + H]⁺	271.0594	253.0492, 243.0647, 215.0702, 153.0180
279	kaikasaponin III	38.15	C₄₈H₇₈O₁₇	[M + H]⁺	927.5280	767.4596, 635.4124, 437.3406, 203.1794
280	3,4,3′,4′-tetrahydroxychalcone	38.16	C₁₅H₁₂O₅	[M + H]⁺	273.0752	245.0811, 171.0285, 153.0181, 123.0442
281	araboglycyrrhizin	38.21	C₄₁H₆₂O₁₄	[M + H]⁺	779.4183	/
282	macranthoside A	38.22	C₄₇H₇₆O₁₇	[M + H]⁺	913.5130	781.4694, 617.4044, 423.3610, 141.0180
282	macranthoside A	38.22	C₄₇H₇₆O₁₇	[M − H]⁻	911.5004	749.4489, 603.3895, 471.3479, 423.3271
283	hydnocarpin	38.23	C₂₅H₂₀O₉	[M + H]⁺	465.1173	447.1065, 286.0468, 257.0440, 147.0438
283	hydnocarpin	38.23	C₂₅H₂₀O₉	[M − H]⁻	463.1033	447.2420, 285.0402, 255.0293, 208.9755
284	puerariafuran	38.24	C₁₆H₁₂O₅	[M + H]⁺	285.0751	270.0512, 253.0493, 242.0569, 211.0754
285	vestitol	38.29	C₁₆H₁₆O₄	[M + H]⁺	273.1118	255.1017, 227.1794, 137.0233, 121.0285
286	homobutein	38.31	C₁₆H₁₄O₅	[M + H]⁺	287.0908	269.0440, 241.0491, 185.0592, 151.0389
287	glycycoumarin	38.34	C₂₁H₂₀O₆	[M + H]⁺	369.1324	351.1228, 297.0746, 193.0494, 165.0545
288	licoricesaponin J2	38.34	C₄₂H₆₄O₁₆	[M + H]⁺	825.4243	764.8267, 455.3507, 189.1634, 141.0181
288	licoricesaponin J2	38.34	C₄₂H₆₄O₁₆	[M − H]⁻	823.4119	763.2627, 473.1696, 351.0565, 193.0342
289	licoricesaponin C2	38.35	C₄₂H₆₂O₁₅	[M + H]⁺	807.4139	764.8302, 678.4443, 631.3784, 437.3406
289	licoricesaponin C2	38.35	C₄₂H₆₂O₁₅	[M − H]⁻	805.4016	763.3167, 453.3408, 351.0559, 193.0349
290	3′-hydroxy-4′-O-methylglabridin	38.39	C₂₁H₂₂O₅	[M − H]⁻	353.1393	/
291	blumenol A	38.39	C₁₃H₂₀O₃	[M + H]⁺	225.1483	210.1245, 167.9932, 114.0913, 95.0860
292	dihydrodaidzein	38.40	C₁₅H₁₂O₄	[M + H]⁺	257.0805	239.0690, 229.0851, 211.0744, 147.0439
* 293	formononetin	38.44	C₁₆H₁₂O₄	[M + H]⁺	269.0803	254.0567, 213.0907, 118.0414, 95.0859
* 293	formononetin	38.44	C₁₆H₁₂O₄	[M − H]⁻	267.0660	252.0423, 225.0553, 195.0443, 132.0204
294	lupiwighteone	38.44	C₂₀H₁₈O₅	[M + H]⁺	339.1219	322.2484, 283.0594, 271.0597, 209.1646
* 295	quercetin	38.48	C₁₅H₁₀O₇	[M + H]⁺	303.0492	285.0393, 257.0439, 229.0493, 153.0181
* 295	quercetin	38.48	C₁₅H₁₀O₇	[M − H]⁻	301.0351	283.0246, 255.0298, 227.0342, 138.0312
296	glycyuralin E	38.52	C₂₁H₂₂O₆	[M + H]⁺	371.1480	353.1372, 339.1213, 285.0749, 167.0695
296	glycyuralin E	38.52	C₂₁H₂₂O₆	[M − H]⁻	369.1341	311.0558, 229.0865, 206.0213, 139.0390
297	estradiol	38.53	C₁₈H₂₄O₂	[M + H]⁺	273.1845	255.1007, 248.4772, 153.0180, 119.0856
298	licoflavone A	38.57	C₂₀H₁₈O₄	[M + H]⁺	323.1272	280.0719, 267.0648, 254.0570, 239.0700
299	irisolidone	38.67	C₁₇H₁₄O₆	[M + H]⁺	315.0856	297.0751, 226.0619, 199.0751, 153.0182
299	irisolidone	38.67	C₁₇H₁₄O₆	[M − H]⁻	313.0715	295.0610, 270.0479, 224.0468, 167.2795
300	1-methoxyphaseollidin	38.68	C₂₁H₂₂O₅	[M + H]⁺	355.1532	299.0548, 221.1169, 165.0546, 123.0441
300	1-methoxyphaseollidin	38.68	C₂₁H₂₂O₅	[M − H]⁻	353.1393	338.1162, 292.0359, 253.0505, 150.0311
301	cupressuflavone	38.69	C₃₀H₁₈O₁₀	[M + H]⁺	539.0958	497.0887, 403.0439, 377.0645, 335.0543
301	cupressuflavone	38.69	C₃₀H₁₈O₁₀	[M − H]⁻	537.0822	521.2611, 505.2242, 375.0520, 266.9636
302	licoarylcoumarin	38.69	C₂₁H₂₀O₆	[M + H]⁺	369.1324	313.0699, 271.0596, 243.0647, 147.0439
303	isoformononetin	38.71	C₁₆H₁₂O₄	[M + H]⁺	269.0803	251.0697, 241.0828, 237.0537, 107.0855
303	isoformononetin	38.71	C₁₆H₁₂O₄	[M − H]⁻	267.0660	252.0424, 241.0503, 197.0604, 96.9588
304	kakkasaponin I	38.72	C₄₇H₇₆O₁₆	[M − H]⁻	895.5067	877.5569, 763.6689, 678.9240, 509.4025
305	β-amyrone	38.76	C₃₀H₄₈O	[M + H]⁺	425.3767	/
306	tuberosin	38.82	C₂₀H₁₈O₅	[M − H]⁻	337.1080	309.0397, 281.0454, 254.0585, 203.1068
307	glicophenone	38.83	C₂₀H₂₂O₆	[M + H]⁺	359.1482	301.0710, 283.0596, 175.0389, 153.0545
307	glicophenone	38.83	C₂₀H₂₂O₆	[M − H]⁻	357.1341	247.0974, 232.0737, 189.0186, 109.0282
308	7,4′-dihydroxy-3′-methoxyisoflavan	38.83	C₁₆H₁₆O₄	[M + H]⁺	273.1118	245.1898, 163.0750, 137.0596, 123.0442
308	7,4′-dihydroxy-3′-methoxyisoflavan	38.83	C₁₆H₁₆O₄	[M − H]⁻	271.0973	241.0499, 225.0550, 197.0596, 181.0652
309	2′,3′-dihydro-7,7′-dihydroxy-5′-methoxy-2′,2′-dimethyl[3,6′-bi-4H-1-benzopyran]-4-one	38.89	C₂₁H₂₀O₆	[M + H]⁺	369.1324	313.0699, 285.0752, 270.0518, 243.0648
309		38.89	C₂₁H₂₀O₆	[M − H]⁻	367.1182	337.0717, 309.0403, 256.0376, 203.0708
310	3,4-didehydroglabridin	38.98	C₂₀H₁₈O₄	[M + H]⁺	323.1272	267.0648, 255.0647, 239.0698, 95.0163
310	3,4-didehydroglabridin	38.98	C₂₀H₁₈O₄	[M − H]⁻	321.1129	277.0503, 265.0505, 252.0424, 149.0598
311	glyasperin C	38.98	C₂₁H₂₄O₅	[M + H]⁺	357.1689	301.1063, 221.1165, 165.0546, 123.0441
311	glyasperin C	38.98	C₂₁H₂₄O₅	[M − H]⁻	355.1547	298.0483, 229.0865, 174.0313, 125.0232
312	neouralenol	39.01	C₂₀H₁₈O₇	[M + H]⁺	371.1119	315.0856, 268.2631, 183.0287, 165.0181
312	neouralenol	39.01	C₂₀H₁₈O₇	[M − H]⁻	369.0976	351.0870, 310.0444, 283.0975, 193.0135
313	phaseol	39.05	C₂₀H₁₆O₅	[M + H]⁺	337.1065	319.0956, 283.0596, 255.0646, 163.0388
314	eurycarpin A	39.08	C₂₀H₁₈O₅	[M + H]⁺	339.1219	322.2490, 293.0592, 163.0388, 114.0915
314	eurycarpin A	39.08	C₂₀H₁₈O₅	[M − H]⁻	337.1080	293.1182, 268.0376, 224.0470, 135.0077
315	glyurallin A	39.10	C₂₁H₂₀O₅	[M − H]⁻	351.1236	335.0564, 323.0929, 308.0317, 191.0711
316	sophoraisoflavone A	39.10	C₂₀H₁₆O₆	[M + H]⁺	353.1014	335.0906, 325.1064, 283.02599, 191.0343
317	licocoumarone	39.11	C₂₀H₂₀O₅	[M + H]⁺	341.1379	323.1265, 267.0648, 209.1646, 114.0915
317	licocoumarone	39.11	C₂₀H₂₀O₅	[M − H]⁻	339.1233	296.0677, 268.0377, 219.0656, 119.0490
318	dehydrovomifoliol	39.18	C₁₃H₁₈O₃	[M + H]⁺	223.1326	135.1167, 107.0858, 81.0704
318	dehydrovomifoliol	39.18	C₁₃H₁₈O₃	[M − H]⁻	221.1177	205.1224, 164.0829, 148.0516, 118.5610
319	fallacinol	39.20	C₁₆H₁₂O₆	[M + H]⁺	301.0701	283.0598, 269.0440, 227.0701, 199.0752
319	fallacinol	39.20	C₁₆H₁₂O₆	[M − H]⁻	299.0557	284.0317, 255.0649, 240.0422, 212.0468
320	genkwanin	39.23	C₁₆H₁₂O₅	[M + H]⁺	285.0751	270.0519, 253.0494, 225.0542, 137.0233
320	genkwanin	39.23	C₁₆H₁₂O₅	[M − H]⁻	283.0609	268.0378, 240.0423, 186.6367, 118.3947
321	kanzonol U	39.25	C₁₉H₁₆O₄	[M + H]⁺	309.1115	/
322	2,3-dehydrokievitone	39.26	C₂₀H₁₈O₆	[M + H]⁺	355.1169	337.1066, 229.0854, 179.0338, 123.0442
322	2,3-dehydrokievitone	39.26	C₂₀H₁₈O₆	[M − H]⁻	353.1027	284.0319, 243.1021, 216.0419, 201.0915
323	2,3,4-trimethyl-5-phenyloxazolidine	39.28	C₁₂H₁₇NO	[M + H]⁺	192.1382	133.1011, 119.0493, 91.0547
324	pratensein	39.29	C₁₆H₁₂O₆	[M + H]⁺	301.0701	283.0598, 269.0440, 227.0701, 199.0752
325	lupenone	39.32	C₃₀H₄₈O	[M + H]⁺	425.3767	/
326	corylifol B	39.35	C₂₀H₂₀O₅	[M + H]⁺	341.1379	267.0648, 209.1646, 114.0916
326	corylifol B	39.35	C₂₀H₂₀O₅	[M − H]⁻	339.1233	269.0453, 233.0818, 187.1117, 167.0340
327	4-O-methylglabridin	39.36	C₂₁H₂₂O₄	[M + H]⁺	339.1586	322.2483, 209.1644, 114.0916, 95.0163
328	luteone	39.43	C₂₀H₁₈O₆	[M + H]⁺	355.1169	338.3415, 299.0540, 267.0284, 239.0334
328	luteone	39.43	C₂₀H₁₈O₆	[M − H]⁻	353.1027	257.0063, 227.0702, 165.0179, 125.0232
329	glyinflanin H	39.43	C₁₉H₁₆O₄	[M + H]⁺	309.1115	291.1940, 223.0596, 113.0600, 95.0163
330	butyl octyl phthalate	39.44	C₂₀H₃₀O₄	[M − H]⁻	333.2062	293.0450, 281.0451, 252.0419, 201.0916
331	glycyrrhetic acid 3-O-glucuronide	39.45	C₃₆H₅₄O₁₀	[M + H]⁺	647.3769	453.3359, 357.2422, 285.2203, 121.1012
331	glycyrrhetic acid 3-O-glucuronide	39.45	C₃₆H₅₄O₁₀	[M − H]⁻	645.3641	580.9614, 521.2628, 469.3308, 322.6431
332	glyasperin A	39.46	C₂₅H₂₆O₆	[M − H]⁻	421.1654	403.9289, 353.1024, 312.0273, 280.0371
333	1-methoxyphaseollin	39.47	C₂₁H₂₀O₅	[M − H]⁻	351.1236	294.4448, 243.1023, 227.0710, 125.0232
334	licochalcone D	39.53	C₂₁H₂₂O₅	[M + H]⁺	355.1532	338.3410, 311.0542, 193.0494, 135.0440
335	wighteone	39.54	C₂₀H₁₈O₅	[M + H]⁺	339.1219	321.2453, 311.0548, 209.1647, 114.0916
335	wighteone	39.54	C₂₀H₁₈O₅	[M − H]⁻	337.1080	321.0765, 309.1127, 253.0500, 209.0596
336	2′-O-demethylbidwillol B	39.54	C₁₉H₁₈O₄	[M + H]⁺	311.1269	293.1166, 278.0932, 263.0694, 95.0163
337	glycyrol	39.63	C₂₁H₁₈O₆	[M + H]⁺	367.1168	337.0697, 227.0702, 167.0337, 91.0547
337	glycyrol	39.63	C₂₁H₁₈O₆	[M − H]⁻	365.1026	335.0560, 307.0247, 295.0245, 254.0220
338	3-hydroxyglabrol	39.65	C₂₅H₂₈O₅	[M − H]⁻	407.1863	387.2756, 371.2437, 150.9878, 93.0001
339	kumatakenin	39.72	C₁₇H₁₄O₆	[M + H]⁺	315.0856	255.0647, 227.0699, 153.0180, 60.0452
339	kumatakenin	39.72	C₁₇H₁₄O₆	[M − H]⁻	313.0715	295.0606, 283.0609, 267.0663, 239.0712
340	eriodictyol	39.73	C₁₅H₁₂O₆	[M + H]⁺	289.0697	271.0959, 229.0855, 163.0388, 153.0181
340	eriodictyol	39.73	C₁₅H₁₂O₆	[M − H]⁻	287.0559	272.0326, 258.0119, 216.0419, 155.1432
341	licoflavone B	39.74	C₂₅H₂₆O₄	[M + H]⁺	391.1897	358.2020, 323.1262, 267.0647, 195.0430
342	gancaonin U	39.76	C₂₄H₂₈O₄	[M − H]⁻	379.1908	/
343	dehydroglyceollin I	39.78	C₂₀H₁₆O₄	[M + H]⁺	321.1115	306.0873, 187.0752, 159.0803, 147.0439
343	dehydroglyceollin I	39.78	C₂₀H₁₆O₄	[M − H]⁻	319.0970	303.0658, 289.0504, 243.0657, 161.0233
344	tectorigenin	39.80	C₁₆H₁₂O₆	[M + H]⁺	301.0701	283.0598, 255.0646, 227.0698, 199.0748
344	tectorigenin	39.80	C₁₆H₁₂O₆	[M − H]⁻	299.0557	284.0317, 267.0301, 240.0422, 212.0468
345	derrone	39.87	C₂₀H₁₆O₅	[M + H]⁺	337.1065	309.1118, 267.0650, 225.0545, 91.0549
345	derrone	39.87	C₂₀H₁₆O₅	[M − H]⁻	335.0921	319.0606, 305.0436, 278.3866, 158.8393
346	abyssinone II	39.91	C₂₀H₂₀O₄	[M + H]⁺	325.1429	269.0804, 241.0850, 135.0440, 95.0163
346	abyssinone II	39.91	C₂₀H₂₀O₄	[M − H]⁻	323.1283	308.1031, 201.0914, 187.0761, 135.0441
347	corylin	39.96	C₂₀H₁₆O₄	[M + H]⁺	321.1115	306.0870, 279.0649, 265.0488, 137.0232
348	ephedradine A	39.98	C₂₈H₃₆N₄O₄	[M + H]⁺	493.2800	465.2870, 394.2122, 219.1489, 120.0809
349	kudzusapogenol A	40.02	C₃₀H₅₀O₅	[M − H]⁻	489.3575	/
350	kanzonol Y	40.04	C₂₅H₃₀O₅	[M − H]⁻	409.2015	391.2520, 373.2436, 235.0971, 177.0912
351	kanzonol W	40.11	C₂₀H₁₆O₅	[M + H]⁺	337.1065	321.1119, 281.0443, 253.0488, 163.0388
351	kanzonol W	40.11	C₂₀H₁₆O₅	[M − H]⁻	335.0921	320.0677, 291.1024, 199.0758, 135.0078
352	isoglycyrol	40.13	C₂₁H₁₈O₆	[M + H]⁺	367.1168	349.1074, 325.0702, 291.0630, 167.0338
352	isoglycyrol	40.13	C₂₁H₁₈O₆	[M − H]⁻	365.1026	349.0708, 309.0393, 216.0423, 192.0055
353	licoisoflavone B	40.17	C₂₀H₁₆O₆	[M + H]⁺	353.1014	311.0558, 299.0544, 153.0180, 95.0163
353	licoisoflavone B	40.17	C₂₀H₁₆O₆	[M − H]⁻	351.0869	337.0660, 283.0974, 241.0864, 199.0756
354	6,8-diprenylgenistein	40.26	C₂₅H₂₆O₅	[M + H]⁺	407.1844	339.1198, 283.0596, 237.0534, 91.0547
354	6,8-diprenylgenistein	40.26	C₂₅H₂₆O₅	[M − H]⁻	405.1704	387.2755, 371.2439, 281.0460, 150.9878
355	parvisoflavone A	40.29	C₂₀H₁₆O₆	[M + H]⁺	353.1014	335.0906, 325.1068, 191.0328, 153.0180
356	licoricidin	40.30	C₂₆H₃₂O₅	[M + H]⁺	425.2315	369.1328, 313.0703, 175.0388, 139.0389
357	kanzonol C	40.31	C₂₅H₂₈O₄	[M + H]⁺	393.2051	376.1539, 329.0271, 268.0656, 215.0684
* 358	emodin	40.43	C₁₅H₁₀O₅	[M + H]⁺	271.0594	243.0650, 229.0493, 197.0596, 173.0591
* 358	emodin	40.43	C₁₅H₁₀O₅	[M − H]⁻	269.0450	241.0503, 225.0551, 197.0597, 181.0647
359	apigenin	40.43	C₁₅H₁₀O₅	[M + H]⁺	271.0594	229.0495, 201.0543, 173.0597, 91.0548
359	apigenin	40.43	C₁₅H₁₀O₅	[M − H]⁻	269.0450	241.0501, 225.0551, 210.0314, 181.0644
360	genistein	40.44	C₁₅H₁₀O₅	[M + H]⁺	271.0594	243.0642, 229.0495, 201.0543, 371.0596
360	genistein	40.44	C₁₅H₁₀O₅	[M − H]⁻	269.0450	241.0504, 225.0550, 197.0597, 181.0647
361	lupalbigenin	40.45	C₂₅H₂₆O₅	[M + H]⁺	407.1844	373.1034, 283.0597, 213.0541, 149.0232
362	angustone A	40.51	C₂₅H₂₆O₆	[M − H]⁻	421.1654	404.9251, 352.0951, 269.0453, 201.0913
363	dehydroglyasperin D	40.59	C₂₂H₂₄O₅	[M + H]⁺	369.1688	313.0700, 295.0597, 197.0441, 179.0337
363	dehydroglyasperin D	40.59	C₂₂H₂₄O₅	[M − H]⁻	367.1545	351.9669, 322.9651, 269.0455, 240.0420
364	corymbosin	40.63	C₁₉H₁₈O₇	[M + H]⁺	359.1118	329.0648, 313.0695, 269.0804, 95.0163
365	euchrenone a5	40.64	C₂₅H₂₆O₄	[M + H]⁺	391.1897	358.2020, 267.0647, 239.0701, 149.0236
365	euchrenone a5	40.64	C₂₅H₂₆O₄	[M − H]⁻	389.1751	319.0978, 298.0473, 266.0580, 195.1691
366	paratocarpin L	40.75	C₂₅H₂₈O₅	[M − H]⁻	407.1863	/
367	diisobutyl phthalate	40.79	C₁₆H₂₂O₄	[M + H]⁺	279.1583	167.0340, 149.0232, 121.0284, 57.0706
367	diisobutyl phthalate	40.79	C₁₆H₂₂O₄	[M − H]⁻	277.1438	245.3889, 193.7951, 134.0361, 121.0283
368	glyurallin B	40.79	C₂₅H₂₆O₆	[M + H]⁺	423.1793	/
369	angustone B	40.82	C₂₅H₂₄O₆	[M + H]⁺	421.1637	365.1014, 309.0388, 281.0439, 140.0342
369	angustone B	40.82	C₂₅H₂₄O₆	[M − H]⁻	419.1497	402.9280, 375.0866, 363.0872, 308.0323
370	licoagrocarpin	40.93	C₂₁H₂₂O₄	[M + H]⁺	339.1586	/
371	palmitic acid	41.04	C₁₆H₃₂O₂	[M − H]⁻	255.2322	170.3186, 162.0524, 116.9273, 74.0233
372	2′-hydroxyisolupalbigenin	41.11	C₂₅H₂₆O₆	[M − H]⁻	421.1654	404.9261, 363.0872, 227.0711, 193.0862
373	butesuperin A	41.15	C₂₆H₂₂O₈	[M + H]⁺	463.1375	445.1275, 283.0597, 255.0647, 161.0594
* 374	luteolin	41.16	C₁₅H₁₀O₆	[M − H]⁻	285.0402	268.9432, 257.0451, 242.0536, 196.0504
375	sophoracoumestan A	41.19	C₂₀H₁₄O₅	[M + H]⁺	335.0909	320.0672, 307.0952, 292.0722, 137.0237
* 376	glycyrrhetic acid	41.41	C₃₀H₄₆O₄	[M + H]⁺	471.3456	317.2107, 269.0803, 189.1636, 121.1013
377	8-prenylphaseollinisoflavan	41.74	C₂₅H₂₈O₄	[M + H]⁺	393.2051	339.0701, 269.0807, 167.0337, 149.0232
377	8-prenylphaseollinisoflavan	41.74	C₂₅H₂₈O₄	[M − H]⁻	391.1912	289.1443, 271.1335, 187.0393, 119.0490
378	stearic acid	41.75	C₁₈H₃₆O₂	[M − H]⁻	283.2635	/
379	puerarol	41.75	C₂₅H₂₄O₅	[M + H]⁺	405.1683	319.0950, 281.0439, 209.0591, 171.0138
379	puerarol	41.75	C₂₅H₂₄O₅	[M − H]⁻	403.1546	387.2754, 371.2439, 333.0764, 150.9877
380	hederagenin	41.79	C₃₀H₄₈O₄	[M + H]⁺	473.3615	310.8371, 189.1640, 133.1015, 59.0162
380	hederagenin	41.79	C₃₀H₄₈O₄	[M − H]⁻	471.3470	429.2146, 403.1549, 319.0597, 280.0376

*: Verified with its reference standard.

Table 2. Quantitative method validation results of YPG.

Main Components	Calibration Curve	Linear Range (mg/mL)	R²	LOD (μg/mL)	LOQ (μg/mL)	Repeatability RSD (%)	Stability RSD (%)	Intermediate Precision (%, n = 12)
chlorogenic acid	y = 12,757x – 376.29	0.05–2.00	0.9991	2.13	6.47	1.18%	1.37%	2.82%
puerarin	y = 37,995x + 303.18	0.05–1.60	0.9990	1.85	5.61	1.23%	2.60%	2.00%
3′-methoxypuerarin	y = 25,755x + 64.034	0.04–1.50	0.9998	1.26	3.83	2.94%	1.09%	2.81%
polydatin	y = 9872.5x – 89.081	0.03–1.00	0.9992	1.25	3.80	2.27%	3.10%	3.45%
glycyrrhizic acid	y = 7190.5x + 101.33	0.02–1.00	0.9994	0.77	2.33	2.03%	1.30%	3.89%
emodin	y = 33,371x + 138.83	0.01–0.50	0.9992	0.38	1.14	1.26%	3.59%	3.53%

Table 3. Quantitative analysis, total phenol content, and DPPH radical scavenging results of YPG.

Main Components	Sample S1 (mg/g)	Sample S2 (mg/g)	Sample S3 (mg/g)	Content (mg/g)	Scavenging Percentage of DPPH Radical (%)
chlorogenic acid	33.16	33.72	35.56	34.15 ± 1.25	59.2
puerarin	27.30	28.15	29.46	28.30 ± 1.09	49.6
3′-methoxypuerarin	9.73	9.66	9.50	9.63 ± 0.12	58.9
polydatin	10.29	10.76	11.43	10.83 ± 0.57	58.0
glycyrrhizic acid	3.18	2.85	3.94	3.33 ± 0.56	54.6
emodin	4.15	4.48	3.80	4.14 ± 0.34	30.3
total phenol	144.11	147.89	147.99	144.66 ± 2.21	/

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Yalkun, I.; Wan, H.; Ye, L.; Yu, L.; He, Y.; Li, C.; Wan, H. Qualitative and Quantitative Analysis of Chemical Components in Yinhua Pinggan Granule with High-Performance Liquid Chromatography Coupled with Q-Exactive Mass Spectrometry. Molecules 2024, 29, 2300. https://doi.org/10.3390/molecules29102300

AMA Style

Yalkun I, Wan H, Ye L, Yu L, He Y, Li C, Wan H. Qualitative and Quantitative Analysis of Chemical Components in Yinhua Pinggan Granule with High-Performance Liquid Chromatography Coupled with Q-Exactive Mass Spectrometry. Molecules. 2024; 29(10):2300. https://doi.org/10.3390/molecules29102300

Chicago/Turabian Style

Yalkun, Imranjan, Haofang Wan, Lulu Ye, Li Yu, Yu He, Chang Li, and Haitong Wan. 2024. "Qualitative and Quantitative Analysis of Chemical Components in Yinhua Pinggan Granule with High-Performance Liquid Chromatography Coupled with Q-Exactive Mass Spectrometry" Molecules 29, no. 10: 2300. https://doi.org/10.3390/molecules29102300

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Qualitative and Quantitative Analysis of Chemical Components in Yinhua Pinggan Granule with High-Performance Liquid Chromatography Coupled with Q-Exactive Mass Spectrometry

Abstract

1. Introduction

2. Results and Discussion

2.1. Optimization of Chromatographic Conditions

2.2. Qualitative Analysis of YPG by HPLC–Q-Exactive MS

2.3. Identification of Several Specific Compounds in YPG

2.3.1. Phenolic Acids

2.3.2. Flavonoids

2.3.3. Alkaloids

2.3.4. Terpenoids

2.4. Quantitative Analysis, Total Phenolic Content, and DPPH Radical Scavenging Activity of YPG

3. Materials and Methods

3.1. Reagents and Materials

3.2. Sample Preparation

3.3. Preparation of Standard Solutions

3.4. Qualitative Analysis with HPLC–Q-Exactive MS

3.5. Quantitative Analysis by HPLC-DAD

3.6. Quantitative Analysis Method Validation

3.7. Determination of Total Phenolic Contents

3.7.1. Total Phenol Standard Curve Drawing

3.7.2. Total Phenol Content in the Sample

3.8. In Vitro Antioxidant Activity Evaluation—DPPH Radical Scavenging Activity

4. Conclusions

Supplementary Materials

Author Contributions

Funding

Institutional Review Board Statement

Informed Consent Statement

Data Availability Statement

Conflicts of Interest

References

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