Literature DB >> 35696210

Simultaneously qualitative and quantitative analysis of the representative components in Kadsura heteroclita stem by UHPLC-Q-Orbitrap HRMS.

Qian-Qian Liu1, Bin Li2, Kang Sun1, Cai-Hong Li1, Nuzhat Shehla2, Yu-Pei Yang2, Liang Cao2, Wei Wang2, Rong-Xia Liu1.   

Abstract

Kadsura heteroclita (Roxb) Craib stem (KHS) is a medicinal plant used for the treatment of rheumatism arthritis diseases in Tujia ethnomedicine. Thus far, the complex chemical compositions in KHS are not clear, and the levels of the major compounds in KHS are not well understood. In this study, a novel UHPLC-Q-Orbitrap HRMS method was established for the simultaneous quali-quantitative analysis of KHS. A total of 204 compounds were identified, including triterpenoids, lignans, sesquiterpenes, fatty acids, phenolic acids, and flavonoids, more than 100 of which were first discovered in KHS. Using the same method, 12 representative bioactive components were successfully quantified. The method was fully validated by linearity, LOD, LOQ, precision, stability, recovery, and matrix effects, and it was applied to quantify the 12 representative compounds in 4 batches of KHS. As this method enables retrospective data analysis and has no upper limit to the number of analytes in a single run, it can be applied to quantify more active components of KHS in the future.

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Year:  2021        PMID： 35696210      PMCID： PMC9261825          DOI： 10.38212/2224-6614.3348

Source DB:  PubMed          Journal:  J Food Drug Anal            Impact factor:   6.157


1. Introduction

Kadsura heteroclita (Roxb) Craib stem (KHS) belongs to the genus Kadsura of the schizandraceae family, a special folk medicine called Xuetong in Tujia ethnomedicine [1]. According to traditional Chinese medicine theories, KHS possesses the effects of expelling wind-evil, regulating Qi to alleviate pain, reinforcing vital energy and promoting blood circulation to relieve blood stasis, and eliminating wetness-evil [2]. The cold-humid natural environment, make Tujia people vulnerable to cold and dampness, which results in rheumatic arthralgia, articulation pain and other diseases. For the treatment of rheumatism arthralgia, Tujia people have accumulated rich experience in medicine. KHS has long been used for the prevention and treatment of wind-dampness, epigastric pain, bone pain, blood deficiency, numb hands and feet, irregular menstruation and rheumatoid arthritis in the Wuling Mountain area of China [3]. As an important local herb medicine, KHS presents strong pharmacological activity in the treatment of rheumatoid arthritis [4, 5]. These features triggered our research enthusiasm to explore the bioactive components in KHS. At present, phytochemical isolation and HPLC analysis revealed that KHS contains diverse bioactive components, including triterpenoids, lignans, sesquiterpenes, fatty acid, volatile oil, and flavonoids [6-14]. Triterpenoids and lignans are the principal active components for the treatment of rheumatoid arthritis in KHS [4], and they also display multiple pharmacological activities. Currently, there are few researches on the determination of the components in KHS [15]. This is a barrier to the identification of the diversity and synergism of the chemical constituents of KHS, which has limited the understanding of its inherent qualities. Hence, there is an urgent need to conduct a study on the comprehensive quali-quantitative analysis of the bioactive constituents in KHS. Today, ultra-high-performance liquid chromatography, coupled with hybrid quadrupole-Orbitrap HRMS (UHPLC-Q-Orbitrap HRMS) has been successfully used for rapid characterization of plant constituents with exact MS and MS2 information [16, 17]. Orbitrap HRMS can generate full scan data over a wide range of masses while enabling qualitative and quantitative analysis of the components [18-21]. It has been successfully applied to the simultaneous qualitative and quantitative analysis of targeted compounds in areas such as food safety, pesticide and veterinary drug residues, and illegal addition of herbs [22-24]. But the composition of traditional Chinese medicine is complex: besides target components, the untargeted components are also worth exploring. Therefore, it is necessary to establish a new analytical method to identify both targeted and untargeted components and quantify the active ingredients in traditional Chinese medicine. In this study, a novel quali-quantitative analytical method by UHPLC-Q-Orbitrap HRMS was developed for rapid and systematic identification and quantification of the components in KHS. The method can fulfill the simultaneous quali-quantitative analysis of KHS in a single run. In addition, our method can be used as an extended application to quantify more potential active components of KHS in the future based on the exact MS data.

2. Materials and methods

2.1. Chemicals and reagents

Schisanlactone E (SE), heteroclitalactone F (HF), heteroclitalactone B (HB), schisanlactone B (SB), heteroclitalactone M (HM), heteroclitalactone D (HD), heteroclitalactone E (HE), schisandronic acid (SDA), 6-hydroxyhinokinin-6-O-β-D-glucopyranoside (6-H-6-glc), d-Epigalbacin (d-E), schizandriside (SZD) and kadsurarin (KDA) were separated and identified from the stem of K. heteroclita in our previous researches [6-9]. The purities of reference standards were over 95%. The structures of the 12 reference standards are shown in Fig. 1.
Fig. 1

Chemical structures of 12 reference standards in KHS.

Acetonitrile, methanol, dimethyl sulfoxide (DMSO), and formic acid of HPLC grade were purchased from Merck (Darmstadt, Germany). Deionized water was produced with a Milli-Q system (Merck Millipore, USA). Four batches of Xuetong were collected in Shimen, Hunan, China in four different seasons during 2018–2019, and identified by Prof Wei Wang from Hunan University of Chinese Medicine.

2.2. Preparation of standards solutions and samples

The stock solutions of 12 reference standards (10.0 mg/mL) were prepared in DMSO and further diluted to 1.0 mg/mL with methanol. All stock solutions were stored at −20 °C until use. The working solution was freshly prepared by serial dilutions of mixed stock solution with 50% methanol to yield 1.0–2000.0 ng/mL for SZD, 6-H-6-glc, HM, HE, HD, SB, SE, HB, and HF; 1.0–200.0 ng/mL for KDA; 50.0–100,000.0 ng/mL for d-E; and 50.0–25,000.0 ng/mL for SDA. 0.5 g dried KHS powder was accurately weighed and placed into round-bottomed flask. And it was ultrasonically extracted with 15 mL of methanol for 15 min at room temperature. The solution was allowed to cool naturally and weighed again, and the lost weight was made up with methanol and shaken. The solution was centrifuged at 13,000 rpm for 10 min. The supernatant was used for the identification of KHS and quantification of HM, KDA, SB, HB, and HF, and the supernatant was diluted at 1:50 (v/v) with 50% methanol for the quantification analysis of the rest of the compounds. All samples were filtered (0.22 μm) before analyses.

2.3. Chromatographic and mass spectrometric conditions

UHPLC analysis was operated on a Waters Acquity H-Class UHPLC system (Waters, Milford, MA, USA). Sample separations were performed on an ACQUITY UPLC HSS T3 column (2.1 × 100 mm, 1.8 μm) and maintained at 40 °C. The mobile phase consisted of 0.1% formic acid aqueous solution (A) and acetonitrile/methanol (4:1, v/v) (B). The gradient elution conditions were: 0–6 min: 20–50% B; 6–14 min: 50–90% B; 14–18 min: 90% B. The column was re-equilibrated for 1 min at 20% B prior to the next injection. Flow rate was 0.4 mL/min. The temperature of the autosampler was maintained at 4 °C, and the injection volume was 5 μL. HRMS detection was conducted on a Q Exactive Orbitrap MS system (Thermo Scientific, Waltham, MA, USA) equipped with a heated electrospray ionization (HESI) source in both positive and negative ion modes. Spray voltages were +3.8 and −2.8 kV for positive and negative ion modes, respectively. Sheath gas flow rate, auxiliary gas flow rate, and sweep gas flow rate were set to 40, 10, and 0 arbitrary units, respectively. Capillary temperature and auxiliary gas heater temperature were maintained at 325 and 350 °C, respectively. The scan mode was full MS/dd-MS2 (Top 5) with resolutions of 70,000 and 17,500 FWHM. Full MS scan was acquired in the m/z range of 100–1500 Da. The stepped normalized collision energies (NCE) were set to 20, 40, and 60 eV. Data acquisition was performed in positive and negative ion mode separately. Data acquisition and processing were executed with Xcalibur 4.1 and Compound Discover 3.0 (Thermo Scientific) software, respectively. The data of full MS and dd-MS2 was used for qualitative analysis, and the peak areas of full MS were utilized for quantitative analysis.

2.4. Compound identification and validation

Compounds were verified with reference standards or tentatively identified by searching in various databases such as in-house genus Kadsura database, MassBank, mzCloud and ChemSpider. The method developed for the quantification of 12 active compounds in KHS was validated by linearity, LOD, LOQ, precision, stability, recovery, and matrix effects. They were described in detail in section 3.3 and 3.5, respectively.

3. Results and discussion

3.1. Optimization of the method

For Q-Orbitrap HRMS conditions, both positive and negative ion modes were used for qualitative analysis to obtain more components. The positive ion mode was used to quantify analytes with more compounds and higher response than negative ion mode. And the selection of 12 target compounds for quantification was based on the active ingredients for the treatment of rheumatoid arthritis in KHS, especially triterpenoids and lignans [4], and they also display multiple pharmacological activities [6, 25–31]. Cycloartane triterpenoids are the most abundant triterpenoids in KHS, so eight cycloartane triterpenoids (SE, HF, HB, SB, HM, HD, HE, and SDA) were chosen for the quantification study. Lignans in KHS mainly include four skeleton-types: dibenzocyclooctadienes, tetrahydrofurans, dibenzylbutyrolactones, and arylteralins, with KDA, d-E, 6-H-6-glc, and SZD as the respective representative compounds. The external standard method was used for quantification. For UHPLC conditions, the type of column and the compositions of mobile phase were optimized to improve the sensitivity and resolution of the analytes. The ACQUITY UPLC HSS T3 column was selected based on the better peak shapes and improved analyte responses (Fig. S1). The best response and separation for most analytes were obtained when 0.1% formic acid aqueous solution (A) and acetonitrile/methanol (4:1, v/v) (B) were utilized as the mobile phases. For the sample preparation conditions, the extraction solvent (methanol, 95% ethanol, and acetonitrile), solid-liquid ratio (1:10, 1:30, 1:50), and ultrasound extraction time (5, 15, 30 min) were examined according to the literatures [32-34] (Table S1–3). The extraction efficiency was assessed by comparing the total peak areas of each category components, respectively, and the most efficient extraction was considered as the one which extracted the highest amount of these components [35]. According to the peak shape and the extraction efficiency, the final sample preparation conditions were that 0.5 g KHS powder was ultrasonically extracted with 15 mL of methanol for 15 min at room temperature.

3.2. Advantages of our established analytical method

In recent years, there have been many qualitative and quantitative studies of traditional Chinese medicines. Most of them need to build different analytical methods for the identification and quantification researches, respectively [36, 37]. In our study, a simple and fast UHPLC-Q-Orbitrap HRMS method was developed for the simultaneous qualiquantitative analysis of KHS in a single run. In this study, the exact MS and MS2 data were used for identification, and the peak areas of extracted ions were utilized to quantify the representative compounds in KHS, making results more accurate and reliable. This method simultaneously identified 204 targeted and untargeted components in a wide mass range and quantified 12 active components over a wide linear range. There was no need to enter precursor ions or ion transitions of the analytes in advance, nor did it need to optimize collision energy values, compared with the MRM mode of triple-quadrupole MS. But it can be comparable to triple-quadrupole MS quantitative performance [38]. In addition, the method can enable retrospective data analysis, and it has no upper limit to the number of analytes in a single run. The exact MS data of new active compound can be entered into Xcalibur to obtain the peak areas for quantitative analysis. So, our method can be used as an extended application to quantify more potential active components of KHS in the future.

3.3. A systematical quali-quantitative strategy for the components in KHS

A three-step analytical strategy (Fig. 2) was established to systematically identify and quantify the chemical components in KHS. Step 1, data acquisition: samples were analyzed by UHPLC-Q-Orbitrap HRMS with the full MS/dd-MS2 scan mode. The exact MS data of reported compounds in KHS was imported in the “Inclusion list” (Table S4–S5) to acquire the MS2 information of the targeted components. The function “If idle-pick others” in dd-MS2 setting was enabled to simultaneously obtain the MS2 information of the untargeted components. Step 2, compound identification: targeted compounds were verified with reference standards or tentatively identified by in-house genus Kadsura database. For untargeted compounds, firstly, the molecular formula provided by Xcalibur was used to search in online databases such as MassBank (https://massbank.eu/MassBank/), mzCloud (https://www.mzcloud.org/) and ChemSpider (http://www.chemspider.com/). Then, the measured MS2 spectrum was compared with the known MS2 spectrum in databases or literature. Finally, the untargeted compounds were tentatively identified by comparing the measured spectrum with the known spectrum. The fragmentation pathways of triterpenoids and lignans in KHS could be proposed according to the neutral loss (NL) and diagnostic ions (DPIs), which would be applied to find untargeted compounds with similar structures. Moreover, the calculated log P (Clog P) obtained by ChemDraw 14.0 was utilized to estimate the retention time of the isomers, with larger Clog P indicating a longer retention time Clog P. Step 3, compound quantification: for each analyte, the exact masses of different adduct ions were imported into Xcalibur 4.1 to evaluate which generated the highest abundance in full MS scan spectrum. The [M+Na]+ adducts were selected for the quantification of SZD, 6-H-6-glc, KDA, HB, and HF. And the [M+H]+ adducts were utilized for the rest analytes. The method was successfully applied to quantify 12 representative compounds in four batches of KHS samples.
Fig. 2

A proposed integrated strategy for identification of the components in KHS.

3.4. Characterization of components in KHS

We conducted two experiments to screen the compounds in KHS. A total of 204 compounds were successfully identified based on this strategy, including triterpenoids, lignans, sesquiterpenes, fatty acids, phenolic acids, and flavonoids, more than 100 of which were firstly discovered in KHS. Triterpenoids and lignans were the dominant compounds. Information of the identified compounds is summarized in Table S6. Total ion chromatograms in positive and negative ion modes of KHS extracts and blank solvent have been displayed in Fig. S2–S3, which suggested that there was no obvious interference for the detection of components in KHS.

3.4.1. Identification of triterpenoids

Triterpenoids were the most abundant in KHS. According to the fragmentation rules of the reference standards, it was found that the MS2 spectrometry of triterpenoids in positive ion mode has the following characteristics: (1) the continuous NL of H2O and CO2 occurred in the high-mass fraction; (2) there were few fragment ions in the middle-mass fraction; (3) the fragment ions in the low mass fraction were densely clustered. Based on these typical features, triterpenoids can be quickly identified. Taking HD, SB, SE, and SDA as examples, the fragmentation pathways of triterpenoids were clarified.

3.4.1.1. 3,4-secocycloartane triterpenoids

This group of triterpenoids is abundant in genus Kadsura. Compound 114 displaying [M+H]+ ion at m/z 523.0348, was verified as HD based on the reference standard. As shown in Fig. 3, the fragment ion at m/z 463.2831 derived from [M+H]+ ion via the loss of an acetyl group, which further continuously lost H2O to form m/z 445.2729 and 427.2618. The fragment ion at m/z 417.2793 derived from m/z 463.2831 via the loss of a carboxyl group (−46.0038 Da). The precursor ion at m/z 463.2831 generated DPI at m/z 323.1996 by breaking the bond between C-17 and C-20. This further successively formed m/z 305.1894 and 263.1426 by NL H2O and breaking the bond between C-4 and C-5. The fragment ion at m/z 379.2617 derived from m/z 463.2831 via breaking the bond between C-23 and C-24 followed by opening the six membered α,β-unsaturated lactone ring. The fragment ion at m/z 463.2831 underwent a C-ring cleavage reaction, producing m/z 231.1381, which further generated m/z 213.1271 and 185.1319 via the loss of H2O and carboxyl group, respectively. The latter sequentially lost a series of minor ions to yield the fragment ions at m/z 157.1011, 145.1010, 131.0855, 119.0853 and 105.0697. Compound 87 was “FIShed” by DPI at m/z 323.1996, displaying [M+H]+ ion at m/z 463.2836, and it had similar fragmentation pathways with HD. Compound 87 had one less acetyl group than HD, so it was tentatively identified as lancilactone B.
Fig. 3

The exact MS2 spectrum and proposed fragmentation pathways of heteroclitalactone D (HD) in positive ion mode.

Compound 149 displayed [M+H]+ ion at m/z 467.3153, verified as SB in accordance with the reference standard. The [M+H]+ ion generated DPI at m/z 327.2315 via breaking the bond between C-17 and C-20, which further lost H2O to produce m/z 309.2204. Compound 80 was “FIShed” by DPI at m/z 327.2315 and displayed [M+H]+ ion at m/z 483.3092, suggesting that it has one more hydroxyl group than SB. The [M+H]+ ion lost OH and H to produce double bond, which further underwent the same fragmentation pathways as SB. Compound 80 was tentatively identified as kadsulactone A. Compound 177 possessed the typical MS2 features of triterpenoids, displaying a [M+H]+ ion at m/z 469.0036, which generated DPI at m/z 329.2477 by breaking the bond between C-17 and C-20. It underwent a C-ring cleavage reaction, producing DPIs at m/z 219.1378 and 249.1843. Compound 177 was verified as SE by comparison with the reference standard. The detailed fragmentation pathways of SE have been reported in our previous research [20].

3.4.1.2. Intact cycloartane triterpenoids

Compound 204, showing [M+H]+ ion at m/z 455.3515, was verified as SDA in accordance with the reference standard. As shown in Fig. S4, the [M+H]+ ion continuously lost H2O to form m/z 437.3405 and 419.3296, respectively. The fragment ion at m/z 409.3465 derived from [M+H]+ ion via the loss of a carboxyl group, which further generated m/z 95.0854. The fragment ion at m/z 329.2464 derived from [M+H]+ ion by the cleavage of A and B rings. The [M+H]+ ion underwent a C-ring cleavage reaction, producing m/z 217.1592 and 235.1689. The former sequentially lost a series of minor ions to yield the fragment ions at m/z 201.1636, 187.1476, 173.1320, 161.1322, 147.1127, 133.1010, and 119.0854, and the latter lost a carboxyl group to generate the fragment ion at m/z 189.1633, which further cracked to yield m/z 121.1010 and 107.0854. Compounds 39, 42, 46, 61, 94, 101 and 156 shared exactly the same precursor and almost the same fragments. Their MS2 spectrums were in line with the typical characteristics of terpenoids: the fragment ions in the low mass fraction were densely clustered; there were few fragment ions in the middle-mass fraction; the NL of H2O occurred in the high-mass fraction; the typical fragment ions at m/z 95, 119, 133 were observed. And the above characteristic spectrums haven’t been observed in blank solvent. So, they were tentatively identified as cycloartenone isomers.

3.4.2. Identification of lignans

Lignans from KHS were mainly divided into four different skeletons, including dibenzocyclooctadienes, tetrahydrofurans, dibenzylbutyrolactones, and arylteralins. Taking KDA, d-E, 6-H-6-glc, and SZD as the respective representative compounds, the fragmentation pathways of four different skeletons of lignans were introduced.

3.4.2.1. Dibenzocyclooctadiene lignans

Compound 103 was verified as KDA in accordance with the reference standard. As shown in Fig. 4, the [M+Na]+ ion at 595.2134 lost the acetyl group at C-7 to yield the fragment ion at m/z 535.1922. The fragment ion at m/z 435.1395 was produced bym/z 535.1922 via the loss of substituent atC-7′,which further lost Na+ to form m/z 413.1584. The fragment ion at m/z 435.1395 broke the bondbetweenC-7′ andC-8′ to yield m/z 371.1485. This further led to the loss of the methoxy group (−31.0184Da) at C-5′ or methyl group (−15.0210Da) at C-8 to for mm/z 340.1301 or 356.1275, respectively. The fragment ion at m/z 329.1023 was produced by m/z 535.1922 via breaking the bond between C-2 and C-2′, and losing methyl group at C-8. The fragment ion at m/z 495.1599 derived from[M+Na]+ ion via the loss of substituent at C-7′.
Fig. 4

The exact MS2 spectrum and proposed fragmentation pathways of kadsurarin (KDA) in positive ion mode.

3.4.2.2. Tetrahydrofuran lignans

Compound 129 was verified as d-E on the basis of the reference standard. As shown in Fig. S5, the [M+H]+ ion at m/z 341.1375 produced m/z 323.1281 via the loss of H2O (−18.0094 Da). The fragment ion at m/z 219.1014 derived from the [M+H]+ ion by breaking the bond between C-1 and C-7, which further generated m/z 201.0907 via the loss of H2O (−18.0107 Da). The fragment ion at m/z 219.1014 underwent the furan ring cleavage to yield m/z 179.0699. This further resulted in the loss of OH (−15.9948 Da) to yield m/z 163.0751 or C2H4 (−28.0310 Da) to generate m/z 151.0389. The latter produced m/z 149.0232 through dehydrogenation (−2.0157 Da) or formed DPI at m/z 135.0439 via the loss of the hydroxyl group. The fragment ion at m/z 149.0232 sequentially lost minor ions to yield m/z 123.0440, 107.0490 and 93.0333. Compound 100 was “FIShed” by DPI at m/z 135.0439 of d-E, displaying [M+H]+ ion at m/z 345.1695. The predicted MS2 fragments of kadsurindutin E was consistent with the MS2 spectrum of compound 100. Therefore, compound 100 was tentatively identified as kadsurindutin E. Similarly, compound 48 was tentatively identified as coumarinlignan.

3.4.2.3. Dibenzylbutyrolactone lignans

Compound 33 displaying [M+Na]+ ion at m/z 555.1468, was verified as 6-H-6-glc according to the reference standard. As shown in Fig. S6, the [M+Na]+ ion generated the fragment ion at m/z 392.0859 via losing a glucose (−163.0607 Da). The fragment ion at m/z 257.0423 was derived from m/z 392.0859 via breaking the bond between C-7 and C-8, which further produced m/z 107.0102 by breaking the bond between C-7′ and C-8′. The fragment ion at m/ z 173.0207 was derived from [M+Na]+ ion via losing a glucose and breaking the bond between C-7′ and C-8′. Moreover, 6-H-6-glc is formed by the combination of the hydroxyl group of 6-hydroxyhinokinin with glucose. The MS and MS2 data of compound 54 (235, 151, and 135) are consistent with those reported for 6-hydroxyhinokinin in the literature [9]; thus, it was tentatively identified as 6-hydroxyhinokinin.

3.4.2.4. Aryltetralin lignans

Compound 12 was verified as SZD according to the reference standard. In the MS spectrum, the response of [M+Na]+ peak was higher than that of [M+H]+ peak, but its MS2 fragments were scarce, which made explaining the fragmentation pathways difficult. Therefore, the MS2 data of the [M+H]+ peak was used for the description of the fragmentation pathways (Fig. S7). The [M+H]+ ion at m/z 493.0990 lost C5H9O4 (−133.9515 Da) to yield m/z 359.1475, which further generated m/z 341.1376 through the loss of H2O. The fragment ion at m/z 341.1376 successively lost CH2O (−30.0104 Da), CH4O (−32.0264 Da), and OH (−15.9953 Da) to yield m/z 311.1272, 279.1008, and 263.1055, respectively. The fragment ion at m/z 219.1017 was derived from m/z 341.1376 via breaking the bond between C-1 and C-7. This further formed m/z 201.0916 through the loss of H2O (−18.0101 Da), and m/z 201.0916 could be further broken to generate m/z 137.0592. Among the identified 204 compounds in KHS, only 12 of them were confirmed by reference standards. We will continue to separate and purify more reference standards to further verify our results in future studies.

3.5. Method validation for quantification of active compounds in KHS

The method developed for the quantification of compounds in KHS was validated by linearity, LOD, LOQ, precision, stability, recovery, and matrix effects. Calibration curves were established by plotting the peak areas of reference standards (y-axis) against their concentration (x-axis), using squares linear regression with a weighting factor (1/x2). All the calibration curves showed good linearity, with the coefficient of determination (r2) higher than 0.992. The limit of detection (LOD) and the limit of quantification (LOQ) of each analyte were calculated at signal-to-signal (S/N) of 3 and 10 as criteria, respectively. The results are shown in Table 1.
Table 1

Quantitative ion, calibration curve, linear range, LOD and LOQ of 12 analytes.

CompoundsQuantitative ion (m/z)Calibration curveLinear range (ng/mL)r2LOD (ng/mL)LOQ (ng/mL)
Schizandriside515.1888y = 35502x−173731.0–2000.00.99630.20.5
6-hydroxyhinokinin-6-O-β-D-glucopyranoside555.1473y = 141801x−88091.0–2000.00.99870.20.5
Heteroclitalactone M541.3160y = 32851x−35321.0–2000.00.99570.20.5
Heteroclitalactone E537.2847y = 146324x−913501.0–2000.00.99780.20.5
Kadsurarin595.2150y = 286026x−131281.0–200.00.99480.51.0
Heteroclitalactone D523.3054y = 156394x−192231.0–2000.00.99960.20.5
d-Epigalbacin341.1384y = 6225x−11328150.0–100000.00.99285.025.0
Schisanlactone B467.3156y = 394976x+2872121.0–2000.00.99690.20.5
Schisanlactone E469.3312y = 410969x+25737401.0–2000.00.99700.51.0
Heteroclitalactone B563.3343y = 1134850x+910171.0–2000.00.99660.10.5
Heteroclitalactone F505.3288y = 569468x−1449121.0–2000.00.99440.10.5
Schisandronic acid455.3520y = 5506x+38250450.0–25000.00.995325.050.0
Method precision was assessed by intra-day and inter-day precision. The intra-day precision was determined at the same concentration level with six replicates in one day. For inter-day precision, the above-mentioned experiment was repeated during three consecutive days. It indicated that this method had good intra-day and inter-day precisions with the RSDs within 1.5–4.7% and 0.2–4.9%, respectively. The stability of the analytes was tested by analyzing the same sample, which was stored at 4 °C, within 24 h. The result showed that the sample was stable within 24 h with the RSDs ranging from 1.1 to 4.7%. The results are shown in Table 2.
Table 2

Precision, stability, recovery and matrix effects of 12 analytes.

Precision (n = 6)StabilityRecovery (n = 6)Matrix effects (n = 6)
Intra-day (RSD, %)Inter-day (RSD, %)(n = 6) (RSD, %)Original amount (μg)Spiked amount (μg)Mean detected amount (μg)Mean (%)RSD (%)Mean (%)RSD (%)
Schizandriside4.7%3.0%3.6%135.5135.5273.3101.8%4.7%98.010.0
6-hydroxyhinokinin-6-O-β-D-glucopyranoside2.2%0.2%1.8%40.540.580.799.2%4.6%101.95.3
Heteroclitalactone M4.9%2.8%3.6%7.87.815.6100.2%4.2%100.65.2
Heteroclitalactone E1.5%2.1%3.8%27.827.857.7107.9%3.9%102.64.7
Kadsurarin2.0%1.4%3.0%0.140.140.30110.1%2.5%93.515.1
Heteroclitalactone D1.8%2.0%3.1%135.8135.8257.289.5%4.6%103.82.9
d-Epigalbacin3.4%2.7%4.5%214.5214.5459.3114.1%4.7%102.38.6
Schisanlactone B1.5%1.8%3.6%5.25.210.7107.0%4.3%105.97.1
Schisanlactone E3.8%4.0%1.1%1197.61197.62327.694.4%4.5%102.15.9
Heteroclitalactone B2.3%4.9%4.7%0.630.631.30106.7%2.3%97.36.1
Heteroclitalactone F3.5%4.5%3.5%3.83.86.880.9%4.7%107.01.4
Schisandronic acid2.9%2.8%4.3%564.0564.01191.0111.2%5.0%110.63.0
Recovery was used to evaluate the accuracy of the method. Recovery was assessed by adding 100% of the original concentration of each target compound into known amounts of a real sample. Then, the resultant samples were extracted and analyzed using the proposed method, and six experiments were repeated [35,39,40]. The recovery was calculated by the following formula: recovery (%) = (detected amount - original amount)/spiked amount × 100%. The recoveries of analytes varied from 89.5 to 114.1% with RSDs ranging from 2.3 to 5.0%, indicating that the method was accurate. The results are displayed in Table 2. The matrix effect was evaluated by comparing the peak area response of the post-extracted spiked sample with the corresponding standard containing equivalent concentrations of the analytes in blank solvents. The matrix effect was measured as follows: [(peak area of post-extracted spiked sample) − (peak area of endogenous sample)]/ (peak area of spiked standard solution) × 100% [41,42]. The matrix effect of analytes varied from 93.5 to 110.6% with RSDs ranging from 1.4 to 15.1%, indicating that the method was hardly interfered by matrix effects. The results are displayed in Table 2.

3.6. Quantification of components in KHS

The newly established and validated UHPLC-Q-Orbitrap HRMS method was applied to simultaneously quantify 12 representative compounds in four batches of KHS collected in Shimen, Hunan, China in four different seasons during 2018–2019. The extracted ion chromatogram of 12 mixed reference standards are displayed in Fig. S8, and the results of quantification are shown in Table 3.
Table 3

Contents of 12 compounds in four batches of KHS (μg/g of dry sample).

CompoundsBatch 1Batch 2Batch 3Batch 4
Schizandriside884.7756.7145.81121.4
6-hydroxyhinokinin-6-O-β-D-glucopyranoside476.2421.048.5513.5
Heteroclitalactone M8.27.210.318.7
Heteroclitalactone E123.7106.832.675.3
Kadsurarin1.132.10.10.3
Heteroclitalactone D50.241.5144.754.7
d-Epigalbacin115.5111.4346.5176.0
Schisanlactone B21.418.95.07.4
Schisanlactone E2011.21424.71220.51817.4
Heteroclitalactone B0.40.30.80.1
Heteroclitalactone F2.51.65.20.8
Schisandronic acid904.5485.2439.9240.3
Total4599.53407.32399.94025.8
The results revealed that the contents of these 12 bioactive compounds in KHS were significantly different. SE was the most abundant compound in KHS (1220.5–2011.2 μg/g), exhibiting anti-tumor activity [6] and inhibitory effect on the formation of P388 cells in leukemia [25]. In our previous study, SE exhibited a satisfactory oral bioavailability in rats (79.3%) [20]. HF, HB, SB, HM, HD, and HE, as the analogs of SE, displayed cytotoxic activity against cancer cell lines [6], with the levels of 0.8–5.2 μg/g, 0.1–0.8 μg/g, 5.0–21.4 μg/g, 7.2–18.7 μg/g, 41.5–144.7 μg/g, and 32.6–123.7 μg/g, respectively. SDA belongs to intact cycloartane triterpenoids that exhibit cytotoxic activity against leukemia and HeLa cells [26], at 240.3–904.5 μg/g in KHS. SZD, an aryltetralin lignan glycoside, displayed anti-tumor and antioxidant activities [27, 28, 30], present at a concentration of 145.8–1121.4 μg/g in KHS. d-E displayed anti-proliferative activity [31], and its content was in the range of 111.4–346.5 μg/g in our study. The content of KDA in four batches ranged from 0.1 to 32.1 μg/g, which affects HIV-1 reverse transcriptase [29].

4. Conclusion

A novel quali-quantitative method established here was able to simultaneously identify and quantify the compounds in KHS. This method proved to be simple, fast, sensitive, and efficient. As a result, 204 components were characterized, including triterpenoids, lignans, sesquiterpenes, fatty acids, phenolic acids, and flavonoids. Simultaneously, 12 representative triterpenoids and lignans were quantified successfully in KHS. This simple, fast, and sensitive method could also be used to quantify more potentially active components of KHS in the future.
Table S1.

Peak areas of 12 analytes in three different extraction solvents.

CompoundsMeOH95%EtOHACN
Schizandriside2.67E+082.34E+081.63E+08
6-hydroxyhinokinin-6-O-β-D-glucopyranoside1.97E+092.28E+091.12E+09
Heteroclitalactone M2.70E+072.70E+072.62E+07
Heteroclitalactone E9.60E+089.46E+089.60E+08
Kadsurarin1.45E+071.51E+071.56E+07
Heteroclitalactone D6.44E+086.17E+086.66E+08
d-Epigalbacin6.49E+076.05E+076.16E+07
Schisanlactone B5.21E+085.10E+085.29E+08
Schisanlactone E1.33E+101.31E+101.35E+10
Heteroclitalactone B1.88E+071.83E+071.86E+07
Heteroclitalactone F9.11E+078.32E+078.75E+07
Schisandronic acid1.07E+091.02E+091.04E+09
Total1.892E+101.891E+101.818E+10
Table S2.

Peak areas of 12 analytes in different solid-liquid ratios.

Compounds1:101:301:50
Schizandriside1.13E+083.47E+084.27E+08
6-hydroxyhinokinin-6-O-β-D-glucopyranoside9.49E+082.25E+091.93E+09
Heteroclitalactone M1.61E+072.68E+071.59E+07
Heteroclitalactone E5.90E+081.02E+096.87E+08
Kadsurarin8.23E+061.39E+071.02E+07
Heteroclitalactone D3.64E+086.29E+084.15E+08
d-Epigalbacin3.84E+077.16E+074.01E+07
Schisanlactone B3.19E+085.84E+083.68E+08
Schisanlactone E6.39E+091.42E+101.49E+10
Heteroclitalactone B1.27E+071.96E+079.38E+06
Heteroclitalactone F4.24E+078.47E+075.99E+07
Schisandronic acid5.29E+081.12E+098.46E+08
Total9.37E+092.04E+101.97E+10
Table S3.

Peak areas of 12 analytes in different ultrasound extraction time.

Compounds5min15min30min
Schizandriside3.14E+083.07E+082.99E+08
6-hydroxyhinokinin-6-O-β-D-glucopyranoside2.12E+092.13E+091.94E+09
Heteroclitalactone M2.41E+072.43E+072.49E+07
Heteroclitalactone E9.29E+089.15E+088.70E+08
Kadsurarin1.37E+071.36E+071.31E+07
Heteroclitalactone D5.98E+086.15E+085.81E+08
d-Epigalbacin5.38E+076.09E+075.63E+07
Schisanlactone B5.11E+085.11E+084.90E+08
Schisanlactone E1.31E+101.36E+101.33E+10
Heteroclitalactone B1.69E+071.85E+071.74E+07
Heteroclitalactone F8.03E+078.59E+078.43E+07
Schisandronic acid1.02E+091.04E+091.05E+09
Total1.883E+101.933E+101.870E+10
Table S4.

The inclusion list in positive ion mode.

Mass [m/z]Formula [M]Formula typeSpeciesCS [z]Polarity
645.2694C37H40O10Chemical formula[M+H]+1Positive
639.2225C37H34O10Chemical formula[M+H]+1Positive
633.2694C36H40O10Chemical formula[M+H]+1Positive
643.2174C36H34O11Chemical formula[M+H]+1Positive
641.2017C36H32O11Chemical formula[M+H]+1Positive
577.4463C35H60O6Chemical formula[M+H]+1Positive
657.2906C35H44O12Chemical formula[M+H]+1Positive
657.2906C35H44O12Chemical formula[M+H]+1Positive
637.2643C35H40O11Chemical formula[M+H]+1Positive
635.2487C35H38O11Chemical formula[M+H]+1Positive
619.2538C35H38O10Chemical formula[M+H]+1Positive
557.3837C34H52O6Chemical formula[M+H]+1Positive
555.368C34H50O6Chemical formula[M+H]+1Positive
595.2902C34H42O9Chemical formula[M+H]+1Positive
623.2487C34H38O11Chemical formula[M+H]+1Positive
621.233C34H36O11Chemical formula[M+H]+1Positive
619.2174C34H34O11Chemical formula[M+H]+1Positive
617.2017C34H32O11Chemical formula[M+H]+1Positive
541.3524C33H48O6Chemical formula[M+H]+1Positive
563.3343C33H48O6Chemical formula[M+Na]+1Positive
599.2851C33H42O10Chemical formula[M+H]+1Positive
597.2694C33H40O10Chemical formula[M+H]+1Positive
627.2436C33H38O12Chemical formula[M+H]+1Positive
611.2487C33H38O11Chemical formula[M+H]+1Positive
607.2174C33H34O11Chemical formula[M+H]+1Positive
605.2017C33H32O11Chemical formula[M+H]+1Positive
515.3731C32H50O5Chemical formula[M+H]+1Positive
499.3782C32H50O4Chemical formula[M+H]+1Positive
529.3524C32H48O6Chemical formula[M+H]+1Positive
513.3575C32H48O5Chemical formula[M+H]+1Positive
535.3394C32H48O5Chemical formula[M+Na]+1Positive
497.3625C32H48O4Chemical formula[M+H]+1Positive
519.3445C32H48O4Chemical formula[M+Na]+1Positive
559.3265C32H46O8Chemical formula[M+H]+1Positive
581.3085C32H46O8Chemical formula[M+Na]+1Positive
543.3316C32H46O7Chemical formula[M+H]+1Positive
565.3136C32H46O7Chemical formula[M+Na]+1Positive
527.3367C32H46O6Chemical formula[M+H]+1Positive
549.3187C32H46O6Chemical formula[M+Na]+1Positive
511.3418C32H46O5Chemical formula[M+H]+1Positive
495.3469C32H46O4Chemical formula[M+H]+1Positive
573.3058C32H44O9Chemical formula[M+H]+1Positive
557.3109C32H44O8Chemical formula[M+H]+1Positive
541.316C32H44O7Chemical formula[M+H]+1Positive
571.2902C32H42O9Chemical formula[M+H]+1Positive
555.2952C32H42O8Chemical formula[M+H]+1Positive
577.2772C32H42O8Chemical formula[M+Na]+1Positive
539.3003C32H42O7Chemical formula[M+H]+1Positive
561.2823C32H42O7Chemical formula[M+Na]+1Positive
523.3054C32H42O6Chemical formula[M+H]+1Positive
553.2796C32H40O8Chemical formula[M+H]+1Positive
575.2615C32H40O8Chemical formula[M+Na]+1Positive
537.2847C32H40O7Chemical formula[M+H]+1Positive
559.2666C32H40O7Chemical formula[M+Na]+1Positive
521.2898C32H40O6Chemical formula[M+H]+1Positive
543.2717C32H40O6Chemical formula[M+Na]+1Positive
601.2643C32H40O11Chemical formula[M+H]+1Positive
585.2694C32H40O10Chemical formula[M+H]+1Positive
551.2639C32H38O8Chemical formula[M+H]+1Positive
573.2459C32H38O8Chemical formula[M+Na]+1Positive
599.2487C32H38O11Chemical formula[M+H]+1Positive
583.2538C32H38O10Chemical formula[M+H]+1Positive
597.233C32H36O11Chemical formula[M+H]+1Positive
581.2381C32H36O10Chemical formula[M+H]+1Positive
547.2326C32H34O8Chemical formula[M+H]+1Positive
595.2174C32H34O11Chemical formula[M+H]+1Positive
617.1993C32H34O11Chemical formula[M+Na]+1Positive
579.2225C32H34O10Chemical formula[M+H]+1Positive
471.3833C31H50O3Chemical formula[M+H]+1Positive
439.3934C31H50OChemical formula[M+H]+1Positive
501.3575C31H48O5Chemical formula[M+H]+1Positive
523.3394C31H48O5Chemical formula[M+Na]+1Positive
485.3625C31H48O4Chemical formula[M+H]+1Positive
507.3445C31H48O4Chemical formula[M+Na]+1Positive
515.3367C31H46O6Chemical formula[M+H]+1Positive
545.3109C31H44O8Chemical formula[M+H]+1Positive
497.3262C31H44O5Chemical formula[M+H]+1Positive
577.3007C31H44O10Chemical formula[M+H]+1Positive
599.2827C31H44O10Chemical formula[M+Na]+1Positive
509.2898C31H40O6Chemical formula[M+H]+1Positive
531.2717C31H40O6Chemical formula[M+Na]+1Positive
523.269C31H38O7Chemical formula[M+H]+1Positive
587.2487C31H38O11Chemical formula[M+H]+1Positive
609.2306C31H38O11Chemical formula[M+Na]+1Positive
571.2538C31H38O10Chemical formula[M+H]+1Positive
537.2483C31H36O8Chemical formula[M+H]+1Positive
535.2326C31H34O8Chemical formula[M+H]+1Positive
583.2174C31H34O11Chemical formula[M+H]+1Positive
567.2225C31H34O10Chemical formula[M+H]+1Positive
581.2017C31H32O11Chemical formula[M+H]+1Positive
603.1837C31H32O11Chemical formula[M+Na]+1Positive
565.2068C31H32O10Chemical formula[M+H]+1Positive
611.1759C31H30O13Chemical formula[M+H]+1Positive
579.1861C31H30O11Chemical formula[M+H]+1Positive
601.168C31H30O11Chemical formula[M+Na]+1Positive
563.1912C31H30O10Chemical formula[M+H]+1Positive
453.4666C30H60O2Chemical formula[M+H]+1Positive
445.404C30H52O2Chemical formula[M+H]+1Positive
475.3782C30H50O4Chemical formula[M+H]+1Positive
497.3601C30H50O4Chemical formula[M+Na]+1Positive
427.3934C30H50OChemical formula[M+H]+1Positive
489.3575C30H48O5Chemical formula[M+H]+1Positive
473.3625C30H48O4Chemical formula[M+H]+1Positive
495.3445C30H48O4Chemical formula[M+Na]+1Positive
457.3676C30H48O3Chemical formula[M+H]+1Positive
479.3496C30H48O3Chemical formula[M+Na]+1Positive
441.3727C30H48O2Chemical formula[M+H]+1Positive
463.3547C30H48O2Chemical formula[M+Na]+1Positive
425.3778C30H48OChemical formula[M+H]+1Positive
447.3597C30H48OChemical formula[M+Na]+1Positive
487.3418C30H46O5Chemical formula[M+H]+1Positive
471.3469C30H46O4Chemical formula[M+H]+1Positive
493.3288C30H46O4Chemical formula[M+Na]+1Positive
455.352C30H46O3Chemical formula[M+H]+1Positive
477.3339C30H46O3Chemical formula[M+Na]+1Positive
439.3571C30H46O2Chemical formula[M+H]+1Positive
461.339C30H46O2Chemical formula[M+Na]+1Positive
549.3058C30H44O9Chemical formula[M+H]+1Positive
517.316C30H44O7Chemical formula[M+H]+1Positive
539.2979C30H44O7Chemical formula[M+Na]+1Positive
501.3211C30H44O6Chemical formula[M+H]+1Positive
523.303C30H44O6Chemical formula[M+Na]+1Positive
485.3262C30H44O5Chemical formula[M+H]+1Positive
507.3081C30H44O5Chemical formula[M+Na]+1Positive
469.3312C30H44O4Chemical formula[M+H]+1Positive
491.3132C30H44O4Chemical formula[M+Na]+1Positive
453.3363C30H44O3Chemical formula[M+H]+1Positive
475.3183C30H44O3Chemical formula[M+Na]+1Positive
531.2952C30H42O8Chemical formula[M+H]+1Positive
553.2772C30H42O8Chemical formula[M+Na]+1Positive
515.3003C30H42O7Chemical formula[M+H]+1Positive
499.3054C30H42O6Chemical formula[M+H]+1Positive
505.2925C30H42O5Chemical formula[M+Na]+1Positive
467.3156C30H42O4Chemical formula[M+H]+1Positive
489.2975C30H42O4Chemical formula[M+Na]+1Positive
529.2796C30H40O8Chemical formula[M+H]+1Positive
513.2847C30H40O7Chemical formula[M+H]+1Positive
497.2898C30H40O6Chemical formula[M+H]+1Positive
481.2949C30H40O5Chemical formula[M+H]+1Positive
465.2999C30H40O4Chemical formula[M+H]+1Positive
494.2901C30H39NO5Chemical formula[M+H]+1Positive
511.269C30H38O7Chemical formula[M+H]+1Positive
533.251C30H38O7Chemical formula[M+Na]+1Positive
495.2741C30H38O6Chemical formula[M+H]+1Positive
517.2561C30H38O6Chemical formula[M+Na]+1Positive
479.2792C30H38O5Chemical formula[M+H]+1Positive
575.2487C30H38O11Chemical formula[M+H]+1Positive
559.2538C30H38O10Chemical formula[M+H]+1Positive
509.2534C30H36O7Chemical formula[M+H]+1Positive
493.2585C30H36O6Chemical formula[M+H]+1Positive
589.228C30H36O12Chemical formula[M+H]+1Positive
573.233C30H36O11Chemical formula[M+H]+1Positive
557.2381C30H36O10Chemical formula[M+H]+1Positive
507.2377C30H34O7Chemical formula[M+H]+1Positive
491.2428C30H34O6Chemical formula[M+H]+1Positive
571.2174C30H34O11Chemical formula[M+H]+1Positive
537.2119C30H32O9Chemical formula[M+H]+1Positive
521.217C30H32O8Chemical formula[M+H]+1Positive
415.3934C29H50OChemical formula[M+H]+1Positive
443.352C29H46O3Chemical formula[M+H]+1Positive
457.3312C29H44O4Chemical formula[M+H]+1Positive
535.2902C29H42O9Chemical formula[M+H]+1Positive
503.3003C29H42O7Chemical formula[M+H]+1Positive
533.2745C29H40O9Chemical formula[M+H]+1Positive
517.2796C29H40O8Chemical formula[M+H]+1Positive
501.2847C29H40O7Chemical formula[M+H]+1Positive
485.2898C29H40O6Chemical formula[M+H]+1Positive
531.2589C29H38O9Chemical formula[M+H]+1Positive
545.2381C29H36O10Chemical formula[M+H]+1Positive
559.2174C29H34O11Chemical formula[M+H]+1Positive
589.1916C29H32O13Chemical formula[M+H]+1Positive
557.2017C29H32O11Chemical formula[M+H]+1Positive
541.2068C29H32O10Chemical formula[M+H]+1Positive
523.1963C29H30O9Chemical formula[M+H]+1Positive
507.2013C29H30O8Chemical formula[M+H]+1Positive
539.1912C29H30O10Chemical formula[M+H]+1Positive
521.1806C29H28O9Chemical formula[M+H]+1Positive
505.1857C29H28O8Chemical formula[M+H]+1Positive
537.1755C29H28O10Chemical formula[M+H]+1Positive
457.2949C28H40O5Chemical formula[M+H]+1Positive
501.2483C28H36O8Chemical formula[M+H]+1Positive
549.233C28H36O11Chemical formula[M+H]+1Positive
571.215C28H36O11Chemical formula[M+Na]+1Positive
533.2381C28H36O10Chemical formula[M+H]+1Positive
515.2276C28H34O9Chemical formula[M+H]+1Positive
537.2095C28H34O9Chemical formula[M+Na]+1Positive
499.2326C28H34O8Chemical formula[M+H]+1Positive
531.2225C28H34O10Chemical formula[M+H]+1Positive
553.2044C28H34O10Chemical formula[M+Na]+1Positive
511.1963C28H30O9Chemical formula[M+H]+1Positive
489.1544C28H24O8Chemical formula[M+H]+1Positive
429.2999C27H40O4Chemical formula[M+H]+1Positive
487.2326C27H34O8Chemical formula[M+H]+1Positive
509.2146C27H34O8Chemical formula[M+Na]+1Positive
501.2119C27H32O9Chemical formula[M+H]+1Positive
485.217C27H32O8Chemical formula[M+H]+1Positive
469.2221C27H32O7Chemical formula[M+H]+1Positive
533.2017C27H32O11Chemical formula[M+H]+1Positive
517.2068C27H32O10Chemical formula[M+H]+1Positive
499.1963C27H30O9Chemical formula[M+H]+1Positive
483.2013C27H30O8Chemical formula[M+H]+1Positive
505.1833C27H30O8Chemical formula[M+Na]+1Positive
515.1912C27H30O10Chemical formula[M+H]+1Positive
537.1731C27H30O10Chemical formula[M+Na]+1Positive
497.1806C27H28O9Chemical formula[M+H]+1Positive
541.228C26H36O12Chemical formula[M+H]+1Positive
473.217C26H32O8Chemical formula[M+H]+1Positive
521.2017C26H32O11Chemical formula[M+H]+1Positive
471.2013C26H30O8Chemical formula[M+H]+1Positive
533.1654C26H28O12Chemical formula[M+H]+1Positive
555.1473C26H28O12Chemical formula[M+Na]+1Positive
477.2119C25H32O9Chemical formula[M+H]+1Positive
429.2272C25H32O6Chemical formula[M+H]+1Positive
493.2068C25H32O10Chemical formula[M+H]+1Positive
475.1963C25H30O9Chemical formula[M+H]+1Positive
497.1782C25H30O9Chemical formula[M+Na]+1Positive
459.2013C25H30O8Chemical formula[M+H]+1Positive
481.1833C25H30O8Chemical formula[M+Na]+1Positive
473.1806C25H28O9Chemical formula[M+H]+1Positive
457.1857C25H28O8Chemical formula[M+H]+1Positive
433.2221C24H32O7Chemical formula[M+H]+1Positive
455.204C24H32O7Chemical formula[M+Na]+1Positive
417.2272C24H32O6Chemical formula[M+H]+1Positive
439.2091C24H32O6Chemical formula[M+Na]+1Positive
447.2013C24H30O8Chemical formula[M+H]+1Positive
431.2064C24H30O7Chemical formula[M+H]+1Positive
453.1884C24H30O7Chemical formula[M+Na]+1Positive
415.2115C24H30O6Chemical formula[M+H]+1Positive
461.1806C24H28O9Chemical formula[M+H]+1Positive
445.1857C24H28O8Chemical formula[M+H]+1Positive
467.1676C24H28O8Chemical formula[M+Na]+1Positive
477.1755C24H28O10Chemical formula[M+H]+1Positive
443.17C24H26O8Chemical formula[M+H]+1Positive
465.152C24H26O8Chemical formula[M+Na]+1Positive
359.2581C23H34O3Chemical formula[M+H]+1Positive
419.2064C23H30O7Chemical formula[M+H]+1Positive
403.2115C23H30O6Chemical formula[M+H]+1Positive
425.1935C23H30O6Chemical formula[M+Na]+1Positive
441.1884C23H30O7Chemical formula[M+H]+1Positive
433.1857C23H28O8Chemical formula[M+H]+1Positive
417.1908C23H28O7Chemical formula[M+H]+1Positive
439.1727C23H28O7Chemical formula[M+Na]+1Positive
401.1959C23H28O6Chemical formula[M+H]+1Positive
423.1778C23H28O6Chemical formula[M+Na]+1Positive
415.1751C23H26O7Chemical formula[M+H]+1Positive
437.1571C23H26O7Chemical formula[M+Na]+1Positive
345.2424C22H32O3Chemical formula[M+H]+1Positive
367.2244C22H32O3Chemical formula[M+Na]+1Positive
407.2064C22H30O7Chemical formula[M+H]+1Positive
429.1884C22H30O7Chemical formula[M+Na]+1Positive
389.1959C22H28O6Chemical formula[M+H]+1Positive
373.201C22H28O5Chemical formula[M+H]+1Positive
395.1829C22H28O5Chemical formula[M+Na]+1Positive
403.1751C22H26O7Chemical formula[M+H]+1Positive
425.1571C22H26O7Chemical formula[M+Na]+1Positive
387.1802C22H26O6Chemical formula[M+H]+1Positive
409.1622C22H26O6Chemical formula[M+Na]+1Positive
417.1544C22H24O8Chemical formula[M+H]+1Positive
439.1363C22H24O8Chemical formula[M+Na]+1Positive
401.1595C22H24O7Chemical formula[M+H]+1Positive
423.1414C22H24O7Chemical formula[M+Na]+1Positive
385.1646C22H24O6Chemical formula[M+H]+1Positive
407.1465C22H24O6Chemical formula[M+Na]+1Positive
431.1337C22H22O9Chemical formula[M+H]+1Positive
415.1387C22H22O8Chemical formula[M+H]+1Positive
399.1438C22H22O7Chemical formula[M+H]+1Positive
493.0977C22H20O13Chemical f
Table S5.

The inclusion list in negative ion mode.

Mass [m/z]Formula [M]Formula typeSpeciesCS [z]Polarity
643.2549C37H40O10Chemical formula[M−H]−1Negative
637.2079C37H34O10Chemical formula[M−H]−1Negative
631.2549C36H40O10Chemical formula[M−H]−1Negative
641.2028C36H34O11Chemical formula[M−H]−1Negative
639.1872C36H32O11Chemical formula[M−H]−1Negative
575.4317C35H60O6Chemical formula[M−H]−1Negative
655.276C35H44O12Chemical formula[M−H]−1Negative
655.276C35H44O12Chemical formula[M−H]−1Negative
635.2498C35H40O11Chemical formula[M−H]−1Negative
633.2341C35H38O11Chemical formula[M−H]−1Negative
617.2392C35H38O10Chemical formula[M−H]−1Negative
555.3691C34H52O6Chemical formula[M−H]−1Negative
553.3535C34H50O6Chemical formula[M−H]−1Negative
593.2756C34H42O9Chemical formula[M−H]−1Negative
621.2341C34H38O11Chemical formula[M−H]−1Negative
617.2028C34H34O11Chemical formula[M−H]−1Negative
615.1872C34H32O11Chemical formula[M−H]−1Negative
539.3378C33H48O6Chemical formula[M−H]−1Negative
597.2705C33H42O10Chemical formula[M−H]−1Negative
595.2549C33H40O10Chemical formula[M−H]−1Negative
625.2291C33H38O12Chemical formula[M−H]−1Negative
609.2341C33H38O11Chemical formula[M−H]−1Negative
603.1872C33H32O11Chemical formula[M−H]−1Negative
513.3586C32H50O5Chemical formula[M−H]−1Negative
497.3636C32H50O4Chemical formula[M−H]−1Negative
527.3378C32H48O6Chemical formula[M−H]−1Negative
511.3429C32H48O5Chemical formula[M−H]−1Negative
495.348C32H48O4Chemical formula[M−H]−1Negative
557.312C32H46O8Chemical formula[M−H]−1Negative
541.3171C32H46O7Chemical formula[M−H]−1Negative
525.3222C32H46O6Chemical formula[M−H]−1Negative
509.3273C32H46O5Chemical formula[M−H]−1Negative
493.3323C32H46O4Chemical formula[M−H]−1Negative
571.2913C32H44O9Chemical formula[M−H]−1Negative
555.2963C32H44O8Chemical formula[M−H]−1Negative
539.3014C32H44O7Chemical formula[M−H]−1Negative
569.2756C32H42O9Chemical formula[M−H]−1Negative
553.2807C32H42O8Chemical formula[M−H]−1Negative
537.2858C32H42O7Chemical formula[M−H]−1Negative
521.2909C32H42O6Chemical formula[M−H]−1Negative
551.265C32H40O8Chemical formula[M−H]−1Negative
535.2701C32H40O7Chemical formula[M−H]−1Negative
519.2752C32H40O6Chemical formula[M−H]−1Negative
599.2498C32H40O11Chemical formula[M−H]−1Negative
583.2549C32H40O10Chemical formula[M−H]−1Negative
549.2494C32H38O8Chemical formula[M−H]−1Negative
597.2341C32H38O11Chemical formula[M−H]−1Negative
581.2392C32H38O10Chemical formula[M−H]−1Negative
595.2185C32H36O11Chemical formula[M−H]−1Negative
579.2236C32H36O10Chemical formula[M−H]−1Negative
545.2181C32H34O8Chemical formula[M−H]−1Negative
593.2028C32H34O11Chemical formula[M−H]−1Negative
577.2079C32H34O10Chemical formula[M−H]−1Negative
469.3687C31H50O3Chemical formula[M−H]−1Negative
437.3789C31H50OChemical formula[M−H]−1Negative
499.3429C31H48O5Chemical formula[M−H]−1Negative
483.348C31H48O4Chemical formula[M−H]−1Negative
513.3222C31H46O6Chemical formula[M−H]−1Negative
543.2963C31H44O8Chemical formula[M−H]−1Negative
495.3116C31H44O5Chemical formula[M−H]−1Negative
575.2862C31H44O10Chemical formula[M−H]−1Negative
507.2752C31H40O6Chemical formula[M−H]−1Negative
521.2545C31H38O7Chemical formula[M−H]−1Negative
585.2341C31H38O11Chemical formula[M−H]−1Negative
569.2392C31H38O10Chemical formula[M−H]−1Negative
535.2337C31H36O8Chemical formula[M−H]−1Negative
581.2028C31H34O11Chemical formula[M−H]−1Negative
565.2079C31H34O10Chemical formula[M−H]−1Negative
579.1872C31H32O11Chemical formula[M−H]−1Negative
563.1923C31H32O10Chemical formula[M−H]−1Negative
609.1614C31H30O13Chemical formula[M−H]−1Negative
577.1715C31H30O11Chemical formula[M−H]−1Negative
561.1766C31H30O10Chemical formula[M−H]−1Negative
451.4521C30H60O2Chemical formula[M−H]−1Negative
473.3636C30H50O4Chemical formula[M−H]−1Negative
425.3789C30H50OChemical formula[M−H]−1Negative
487.3429C30H48O5Chemical formula[M−H]−1Negative
471.348C30H48O4Chemical formula[M−H]−1Negative
455.3531C30H48O3Chemical formula[M−H]−1Negative
439.3582C30H48O2Chemical formula[M−H]−1Negative
423.3632C30H48OChemical formula[M−H]−1Negative
485.3273C30H46O5Chemical formula[M−H]−1Negative
469.3323C30H46O4Chemical formula[M−H]−1Negative
453.3374C30H46O3Chemical formula[M−H]−1Negative
437.3425C30H46O2Chemical formula[M−H]−1Negative
547.2913C30H44O9Chemical formula[M−H]−1Negative
515.3014C30H44O7Chemical formula[M−H]−1Negative
499.3065C30H44O6Chemical formula[M−H]−1Negative
483.3116C30H44O5Chemical formula[M−H]−1Negative
467.3167C30H44O4Chemical formula[M−H]−1Negative
451.3218C30H44O3Chemical formula[M−H]−1Negative
529.2807C30H42O8Chemical formula[M−H]−1Negative
513.2858C30H42O7Chemical formula[M−H]−1Negative
497.2909C30H42O6Chemical formula[M−H]−1Negative
481.296C30H42O5Chemical formula[M−H]−1Negative
465.301C30H42O4Chemical formula[M−H]−1Negative
527.265C30H40O8Chemical formula[M−H]−1Negative
511.2701C30H40O7Chemical formula[M−H]−1Negative
495.2752C30H40O6Chemical formula[M−H]−1Negative
479.2803C30H40O5Chemical formula[M−H]−1Negative
463.2854C30H40O4Chemical formula[M−H]−1Negative
492.2756C30H39NO5Chemical formula[M−H]−1Negative
509.2545C30H38O7Chemical formula[M−H]−1Negative
493.2596C30H38O6Chemical formula[M−H]−1Negative
477.2647C30H38O5Chemical formula[M−H]−1Negative
573.2341C30H38O11Chemical formula[M−H]−1Negative
557.2392C30H38O10Chemical formula[M−H]−1Negative
507.2388C30H36O7Chemical formula[M−H]−1Negative
491.2439C30H36O6Chemical formula[M−H]−1Negative
587.2134C30H36O12Chemical formula[M−H]−1Negative
571.2185C30H36O11Chemical formula[M−H]−1Negative
555.2236C30H36O10Chemical formula[M−H]−1Negative
505.2232C30H34O7Chemical formula[M−H]−1Negative
489.2283C30H34O6Chemical formula[M−H]−1Negative
569.2028C30H34O11Chemical formula[M−H]−1Negative
535.1974C30H32O9Chemical formula[M−H]−1Negative
519.2024C30H32O8Chemical formula[M−H]−1Negative
413.3789C29H50OChemical formula[M−H]−1Negative
441.3374C29H46O3Chemical formula[M−H]−1Negative
455.3167C29H44O4Chemical formula[M−H]−1Negative
533.2756C29H42O9Chemical formula[M−H]−1Negative
501.2858C29H42O7Chemical formula[M−H]−1Negative
531.26C29H40O9Chemical formula[M−H]−1Negative
515.265C29H40O8Chemical formula[M−H]−1Negative
499.2701C29H40O7Chemical formula[M−H]−1Negative
483.2752C29H40O6Chemical formula[M−H]−1Negative
529.2443C29H38O9Chemical formula[M−H]−1Negative
543.2236C29H36O10Chemical formula[M−H]−1Negative
557.2028C29H34O11Chemical formula[M−H]−1Negative
587.177C29H32O13Chemical formula[M−H]−1Negative
555.1872C29H32O11Chemical formula[M−H]−1Negative
539.1923C29H32O10Chemical formula[M−H]−1Negative
521.1817C29H30O9Chemical formula[M−H]−1Negative
505.1868C29H30O8Chemical formula[M−H]−1Negative
537.1766C29H30O10Chemical formula[M−H]−1Negative
519.1661C29H28O9Chemical formula[M−H]−1Negative
503.1711C29H28O8Chemical formula[M−H]−1Negative
535.161C29H28O10Chemical formula[M−H]−1Negative
455.2803C28H40O5Chemical formula[M−H]−1Negative
499.2337C28H36O8Chemical formula[M−H]−1Negative
547.2185C28H36O11Chemical formula[M−H]−1Negative
531.2236C28H36O10Chemical formula[M−H]−1Negative
513.213C28H34O9Chemical formula[M−H]−1Negative
497.2181C28H34O8Chemical formula[M−H]−1Negative
529.2079C28H34O10Chemical formula[M−H]−1Negative
509.1817C28H30O9Chemical formula[M−H]−1Negative
487.1398C28H24O8Chemical formula[M−H]−1Negative
427.2854C27H40O4Chemical formula[M−H]−1Negative
485.2181C27H34O8Chemical formula[M−H]−1Negative
499.1974C27H32O9Chemical formula[M−H]−1Negative
483.2024C27H32O8Chemical formula[M−H]−1Negative
467.2075C27H32O7Chemical formula[M−H]−1Negative
531.1872C27H32O11Chemical formula[M−H]−1Negative
515.1923C27H32O10Chemical formula[M−H]−1Negative
497.1817C27H30O9Chemical formula[M−H]−1Negative
481.1868C27H30O8Chemical formula[M−H]−1Negative
513.1766C27H30O10Chemical formula[M−H]−1Negative
495.1661C27H28O9Chemical formula[M−H]−1Negative
539.2134C26H36O12Chemical formula[M−H]−1Negative
471.2024C26H32O8Chemical formula[M−H]−1Negative
519.1872C26H32O11Chemical formula[M−H]−1Negative
469.1868C26H30O8Chemical formula[M−H]−1Negative
531.1508C26H28O12Chemical formula[M−H]−1Negative
475.1974C25H32O9Chemical formula[M−H]−1Negative
427.2126C25H32O6Chemical formula[M−H]−1Negative
491.1923C25H32O10Chemical formula[M−H]−1Negative
473.1817C25H30O9Chemical formula[M−H]−1Negative
457.1868C25H30O8Chemical formula[M−H]−1Negative
471.1661C25H28O9Chemical formula[M−H]−1Negative
455.1711C25H28O8Chemical formula[M−H]−1Negative
431.2075C24H32O7Chemical formula[M−H]−1Negative
415.2126C24H32O6Chemical formula[M−H]−1Negative
445.1868C24H30O8Chemical formula[M−H]−1Negative
429.1919C24H30O7Chemical formula[M−H]−1Negative
413.197C24H30O6Chemical formula[M−H]−1Negative
459.1661C24H28O9Chemical formula[M−H]−1Negative
443.1711C24H28O8Chemical formula[M−H]−1Negative
475.161C24H28O10Chemical formula[M−H]−1Negative
441.1555C24H26O8Chemical formula[M−H]−1Negative
357.2435C23H34O3Chemical formula[M−H]−1Negative
417.1919C23H30O7Chemical formula[M−H]−1Negative
401.197C23H30O6Chemical formula[M−H]−1Negative
431.1711C23H28O8Chemical formula[M−H]−1Negative
415.1762C23H28O7Chemical formula[M−H]−1Negative
399.1813C23H28O6Chemical formula[M−H]−1Negative
413.1606C23H26O7Chemical formula[M−H]−1Negative
343.2279C22H32O3Chemical formula[M−H]−1Negative
405.1919C22H30O7Chemical formula[M−H]−1Negative
387.1813C22H28O6Chemical formula[M−H]−1Negative
371.1864C22H28O5Chemical formula[M−H]−1Negative
401.1606C22H26O7Chemical formula[M−H]−1Negative
385.1657C22H26O6Chemical formula[M−H]−1Negative
415.1398C22H24O8Chemical formula[M−H]−1Negative
399.1449C22H24O7Chemical formula[M−H]−1Negative
383.15C22H24O6Chemical formula[M−H]−1Negative
429.1191C22H22O9Chemical formula[M−H]−1Negative
413.1242C22H22O8Chemical formula[M−H]−1Negative
397.1293C22H22O7Chemical formula[M−H]−1Negative
491.0831C22H20O13Chemical formula[M−H]−1Negative
357.1708C21H26O5Chemical formula[M−H]−1Negative
401.1242C21H22O8Chemical formula[M−H]−1Negative
337.2384C20H34O4Chemical formula[M−H]−1Negative
329.1758C20H26O4Chemical formula[M−H]−1Negative
343.1551C20H24O5Chemical formula[M−H]−1Negative
327.1602C20H24O4Chemical formula[M−H]−1Negative
357.1344C20H22O6Chemical formula[M−H]−1Negative
339.1238C20H20O5Chemical formula[M−H]−1Negative
369.098C20H18O7Chemical formula[M−H]−1Negative
367.0823C20H16O7Chemical formula[M−H]−1Negative
217.1962C16H26Chemical formula[M−H]−1Negative
239.2017C15H28O2Chemical formula[M−H]−1Negative
237.186C15H26O2Chemical formula[M−H]−1Negative
221.1911C15H26OChemical formula[M−H]−1Negative
251.1653C15H24O3Chemical formula[M−H]−1Negative
219.1754C15H24OChemical formula[M−H]−1Negative
203.1805C15H24Chemical formula[M−H]−1Negative
265.1445C15H22O4Chemical formula[M−H]−1Negative
249.1496C15H22O3Chemical formula[M−H]−1Negative
233.1547C15H22O2Chemical formula[M−H]−1Negative
289.0718C15H14O6Chemical formula[M−H]−1Negative
303.051C15H12O7Chemical formula[M−H]−1Negative
301.0354C15H10O7Chemical formula[M−H]−1Negative
285.0405C15H10O6Chemical formula[M−H]−1Negative
Table S6.

Characterization of the components in KHS by UHPLC-Q-Orbitrap HRMS.

NO.tR (min)FormulaIon modeMeasured Mass (m/z)Error (ppm)MS/MS Fragments (m/z)Compound IdentificationIdentification references
10.58C12H22O11−341.1086−0.9341.1086(6), 179.0555(5), 119.0340(10), 101.0231(14), 89.0232(51), 71.0126(54), 59.0127(100)TrehaloseMassBank
20.58C6H12O6−179.0553−4.5179.0562(2), 161.0453(1), 113.0233(6), 101.0230(6), 89.0233(22), 71.0127(58), 59.0127(100)GlucoseMassBank
30.63C8H8O4−167.0342−4.8167.0342(16), 152.0105(100), 124.0141(32), 108.0205(76), 96.9588(17)5-Methoxysalicylic Acid isomerMassBank
40.63C15H14O6+291.08630.0291.0820(6), 165.0547(13), 139.0388(100), 123.0439(68)Catechin isomermzCloud
50.64C15H12O7+305.06570.3305.1592(67), 151.0388(100), 139.0389(67), 127.0389(48), 123.1164(30), 102.0912(51)Taxifolin isomermzCloud
60.84C8H8O4−167.0343−4.2167.0341(15), 152.0105(100), 123.0440(11), 108.0205(82)5-Methoxysalicylic Acid isomerMassBank
71.02C7H6O4−153.0186−4.6153.0184(14), 110.0318(5), 109.0283(100), 108.0204(10)Gentisic acidMassBank
81.12C15H14O6+291.0859−1.4291.0866(7), 165.0544(13), 139.0388(100), 123.0439(65)Catechin isomermzCloud
92.26C9H10O3−165.0550−4.2165.0545(9), 164.8946(11), 121.0284(18), 96.9588(20), 78.9577(6), 59.0127(100)3-Ethoxybenzoic acidmzCloud
102.26C10H18O5−217.1077−1.8217.1075(15), 155.1069(22), 143.0703(100), 125.0597(31), 97.0647(17), 73.0823(47)Diethylene glycol diglycidyl ether isomerChemSpider
112.41C8H14O4−173.0812−4.0173.0810(26), 128.8769(31), 111.0804(100), 83.0491(24), 61.9871(14)Suberic acidMassBank
122.57C25H32O10+493.2044−4.9341.1361(98), 311.1272(54), 279.1018(48), 219.1008(100), 137.0599(42)SchizandrisideStandard
132.58C26H34O12−537.1975−0.4511.0048(6), 491.1945(27), 359.1492(68), 344.1263(43), 341.1385(12), 313.1090(17), 299.0915(11), 295.0998(15), 241.0500(18), 173.0597(24), 159.0444(27), 129.9748(21), 109.0283(66)Diosbulbinoside F isomerChemSpider
142.94C22H24O6+385.1642−1.0385.0903(18), 311.1260(20), 207.1014(40), 189.0908(48), 180.0063(10), 175.0755(33), 161.0594(100), 137.0599(14)Schizandrin C isomerin-house database
153.31C15H24O+221.19000.0221.1897(83), 203.1792(95), 161.1323(22), 147.1166(100), 133.1010(20), 123.1166(21), 121.1010(43), 119.0854(51), 109.1011(29), 107.0854(40), 105.0697(61), 95.0854(31), 81.0697(27)(−)-Caryophyllene oxide isomermzCloud
163.33C20H24O5+345.1692−1.4253.8806(10), 236.9070(13), 226.8927(17), 201.0659(24), 177.0903(59), 163.0752(40), 137.0599(62), 90.9766(100)Kadsurindutin E isomerin-house database
173.38C10H10O3+179.07030.0179.0704(30), 178.1587(100), 161.0596(26), 147.0439(49), 133.0646(11), 119.0491(31), 91.0541(17)4-methyoxycinnamic acid isomerMassBank
183.56C9H16O4−187.0969−3.7187.0969(32), 125.0960(100), 97.0647(20)Azelaic acidMassBank
193.59C15H12O6−287.05610.0287.0568(10), 259.0605(18), 243.0322(32), 195.0111(13), 179.1673(10), 177.0547(15), 151.0027(14), 125.0233(100)MaesopsinmzCloud
203.70C20H24O5+345.1694−0.9304.8900(12), 236.9052(25), 226.8929(23), 177.0905(100), 163.0754(45), 137.0596(58), 90.9765(98)Kadsurindutin E isomerin-house database
213.72C25H32O10+515.1882−1.2515.1882 (100)Schizandriside isomerin-house database
223.73C26H34O12−537.1973−0.8419.5065(7), 326.1162(37), 311.0923(60), 283.0968(30), 129.9747(37), 112.9844(19), 89.0232(22), 61.9871(100)Diosbulbinoside F isomerChemSpider
233.86C15H26O2+239.2005−0.4239.1999(46), 221.1894(56), 203.1796(100), 174.9639(57), 147.1169(58), 133.1012(36), 119.0854(45), 109.1012(41), 107.0853(49), 95.0853(71), 81.0699(62)Oplodiol isomerDPI
243.96C30H48O2+441.3723−0.9441.3719(100), 423.3612(21), 405.3519(8), 221.1901(9), 203.1790(21), 161.1322(14), 147.1167(21), 133.1010(24), 121.1010(27), 95.0854(50)Kadsuracoccinic acid B isomerin-house database
254.02C15H20O4−263.1286−1.1263.1288(59), 219.1385(61), 204.1146(100), 203.1069(78), 189.0901(25), 185.0963(17), 161.0963(16), 136.0519(32)Abscisic acid isomerMassBank
264.38C30H48O2+441.3720−1.6441.3721(100), 423.3619(22), 405.3514(8), 221.1891(8), 203.1792(21), 161.1322(13), 147.1167(18), 133.1010(20), 121.1010(22), 95.0854(45)Kadsuracoccinic acid B isomerin-house database
274.58C15H20O4−263.1287−0.8263.1291(37), 219.1387(96), 204.1148(63), 203.1063(50), 201.1277(74), 180.6831(67), 139.0750(33)Abscisic acid isomerMassBank
284.78C10H18O4−201.1127−2.5201.1125(58), 183.1014(41), 139.1118(100), 116.9272(45)Sebacic acidMassBank
294.79C20H18O7+371.1123−0.5371.1100(1), 233.0807(5), 215.0699(11), 157.0646(5), 151.0389(100), 129.0696(5)6-hydroxyhinokinin isomerDPI
304.94C30H48O2+441.3723−0.9441.3719(100), 423.3608(25), 405.3512(10), 221.1898(9), 203.1789(20), 161.1323(14), 147.1167(25), 133.1010(25), 121.1010(30), 95.0854(46)Kadsuracoccinic acid B isomerin-house database
314.95C15H20O4+267.1590−0.4267.1577(27), 231.1376(100), 203.1425(20), 191.1064(31), 175.1118(20), 90.9764(42)Verrucarol isomerMassBank
325.28C26H28O12+555.1465−1.4555.1458(100), 434.8627(5), 318.5458(6), 157.1312(5), 135.0438(15)6-hydroxyhinokinin-6-O-β-Dglucopyranoside isomerDPI
335.50C26H28O12+555.1468−0.9555.1466(100), 392.0859(12), 257.0423(7), 173.0207(45), 107.0102(18)6-hydroxyhinokinin-6-O-β-DglucopyranosideStandard
345.51C27H40O14−577.1558−0.9369.0974(48), 325.1077(32), 297.1125(12), 189.0548(11), 182.0213(10), 175.0757(18), 161.0597(17), 136.0152(19), 121.0284(100), 108.0252(35), 83.0126(88)Vitexin-2″-O-rhamnoside isomerMassBank
355.52C20H18O7+371.1120−1.3371.1100(2), 233.0811(3), 215.0701(10), 157.0647(5), 151.0389(100), 129.0697(5)6-Hydroxyhinokinin isomerDPI
365.66C28H36O11+549.2326−0.7489.2114(89), 471.2004(34), 453.1906(20), 435.1799(20), 417.1688(5), 137.0596(100), 123.0802(11), 109.0647(25)Xuetongdilactone E isomerin-house database
376.26C10H10O3+179.0702−0.6179.0705(24), 178.1587(100), 161.0595(46), 133.0647(31), 105.0698(15)4-methyoxycinnamic acid isomerMassBank
386.31C20H20O5+341.1382−0.6341.1365(11), 323.1272(41), 201.0911(17), 149.0600111), 135.0439 (100)d-Epigalbacin isomerDPI
396.38C30H48O+425.3774−0.9425.3766(99), 407.3680(20), 217.1944(29), 203.1795(31), 161.1327(22), 147.1168(31), 135.1166(42), 133.1009(43), 123.1165(55), 119.0854(50), 109.1010(100), 95.0854(93)Cycloartenone isomerin-house database
406.42C15H20O4−263.1287−0.8263.1284(27), 219.1382(100), 165.7939(7), 136.0591(8), 73.0282(17)Abscisic acid isomerMassBank
416.44C30H48O2+441.3721−1.4441.3717(100), 423.3622(28), 405.3532(10), 221.1890(5), 203.1796(20), 161.1323(11), 147.1167(17), 133.1007(18), 121.1013(21), 95.0854(40)Kadsuracoccinic acid B isomerin-house database
426.67C30H48O+425.3772−1.4425.3789(100), 343.1303(26), 179.0788(28), 147.1165(42), 135.1168(34), 133.1006(22), 123.1164(24), 119.0862(23), 109.1012(97), 95.0856(43)Cycloartenone isomerin-house database
436.74C30H48O2+441.3723−0.9441.3723(100), 423.3629(21), 405.3539(8), 203.1790(15), 161.1322(12), 147.1170(13), 133.1009(25), 121.1012(17), 95.0854(39)Kadsuracoccinic acid B isomerin-house database
446.89C30H48O2+441.3723−0.9441.3722(100), 423.3622(26), 405.3511(11), 221.1895(9), 203.1793(19), 161.1322(13), 147.1167(16), 133.1012(22), 121.1011(25), 95.0854(37)Kadsuracoccinic acid B isomerin-house database
457.03C15H24O+221.1898−0.9221.1897(49), 203.1792(100), 161.1322(11), 147.1167(35), 133.1010(15), 121.1011(15), 119.0854(18), 109.1011(18), 107.0854(39), 105.0698(21), 95.0854(44), 81.0698(22)(−)-Caryophyllene oxide isomermzCloud
467.06C30H48O+425.3771−1.6425.3763(100), 407.3664(25), 217.1949(27), 175.1481(12), 161.1323(25), 147.1167(34), 135.1167(35), 133.1010(30), 123.1167(37), 119.0854(37), 109.1011(86), 95.0854(86)Cycloartenone isomerin-house database
477.14C30H46O2+439.3565−1.4439.3567(39), 393.3513(5), 249.1845(20), 205.1947(27), 203.1792(100), 191.1790(72), 189.1634(41), 147.1167(28), 133.1011(40), 119.0855(41), 95.0854(56)Heilaohu acid A isomerin-house database
487.34C20H16O7+369.0967−0.5369.0966(8), 351.0857(100), 321.0754(29), 293.0803(19), 235.0750(19), 203.0335(94), 175.0386(39), 161.0594(40), 135.0438(64), 131.0490(58)CoumarinlignanDPI
497.63C15H24O+221.19000.0221.1899(66), 203.1792(100), 161.1324(17), 147.1167(91), 133.1012(23), 121.1011(23), 119.0854(39), 109.1011(36), 107.0854(36), 105.0698(40), 95.0854(38), 81.0697(22)(−)-Caryophyllene oxide isomermzCloud
507.67C22H24O6+385.1642−1.0367.1532(34), 233.1170(46), 218.0938(64), 203.0703(26), 181.0856(33), 166.0625(14), 135.0439(100)Schizandrin Cin-house database
517.74C20H20O5+341.1383−0.3341.1373(29), 323.1283(9), 161.0598(20), 149.0600(11), 135.0439(100)d-Epigalbacin isomerDPI
527.78C20H16O7+369.0966−0.8351.0865(10), 231.0651(35), 203.0334(15), 187.0751(72), 175.0390(13), 161.0594(13), 157.0647(62), 135.0439(49), 131.0489(22), 129.0697(100)Coumarinlignan isomerDPI
537.88C15H24O+221.19000.0221.1897(88), 203.1792(100), 161.1322(21), 147.1167(54), 133.1010(25), 123.1166(32), 121.1012(22), 119.0854(37), 109.1011(88), 107.0854(37), 105.0698(45), 95.0854(40), 81.0698(59)(−)-Caryophyllene oxide isomermzCloud
547.91C20H18O7+371.1123−0.5371.1109(2), 233.0807(4), 215.0700(9), 157.0648(5), 151.0389(100), 129.0697(5)6-hydroxyhinokininReference [9]
557.95C15H28O2+263.1979−1.1263.1985(100), 205.1959(17), 197.9750(17), 101.9496(15)Cryptomeridiolin-house database
567.99C15H24+205.1950−0.5205.1949(16), 149.1325(14), 135.1167(50), 123.1167(100), 121.1011(4), 109.1012(14), 107.0855(13)Isocaryophyllene isomerChemSpider
577.99C10H14+135.1167−0.7135.1168(66), 107.0855(100), 93.0699(99), 91.0542(28),79.0542(39)Cymol isomerChemSpider
588.00C32H44O7+563.2974−0.9563.2975(100), 521.2543(5), 503.2778(46), 459.2842(11), 181.1255(9)Heteroclitalactone M isomerDPI
598.23C10H16+137.13250.0137.1323(27), 95.0854(80), 81.0698(100)Sabinene isomerMassBank
608.28C30H38O6+495.2733−1.6477.2634(78), 459.2529(39), 323.1999(50), 263.1424(19), 155.0699(28), 109.0648(100), 95.0854(15)Kadheterilactone A isomerin-house database
618.28C30H48O+425.3771−1.6425.3774(93), 407.3668(32), 217.1950(22), 189.1640(27), 161.1323(24), 147.1165(31), 135.1167(35), 133.1010(26), 123.1167(44), 119.0852(39), 109.1011(100), 95.0854(85)Cycloartenone isomerin-house database
628.48C15H26O2+239.2004−0.8239.1996(67), 221.1901(93), 203.1795(80), 179.6898(49), 133.1012(65), 121.1013(48), 116.9716(100), 107.0856(71), 95.0855(49), 81.0697(73)Oplodiol isomerDPI
638.57C15H24+205.19510.0205.1954(16), 149.1325(14), 135.1167(51), 123.1167(100), 121.1010(8), 109.1011(15), 107.0854(19)Isocaryophyllene isomerChemSpider
648.57C15H24O+221.19000.0221.1897(93), 203.1792(100), 161.1323(28), 147.1167(48), 133.1010(22), 121.1010(21), 119.0855(27), 109.1012(32), 107.0854(51), 105.0698(33), 95.0854(47), 81.0698(27)(−)-Caryophyllene oxide isomermzCloud
658.59C22H32O3+345.2423−0.3345.2420(70), 327.2314(100), 309.2208(27), 203.1429(41), 185.1322(40), 159.1166(39), 133.1010(32),119.0854(41), 111.0803(44), 93.0698(43)Micranoic acid BDPI
668.60C22H34O4−361.2383−0.3361.2381(100), 303.1971(10), 135.0807(7), 57.0334(35)7(S),17(S)-Dihydroxy-8(E),10(Z),13(Z),15(E),19(Z)-docosapentaenoic acid isomermzCloud
678.63C24H32O7+433.2217−0.9415.2109(100), 384.1926(81), 373.1638(14), 369.1692(34), 346.1405(29), 338.1508(26), 331.1168(18), 315.1226(15)Schizandrin isomerin-house database
688.72C15H24+205.1950−0.5205.1954(20), 149.1323(26), 135.1166(60), 123.1166(100), 121.1011(24), 109.1011(24), 107.0853(28), 81.0698(39)Isocaryophyllene isomerChemSpider
699.04C35H44O12+679.2715−1.5679.2726(100), 579.2152(13), 519.1968(44), 475.2062(23)Xuetongdilactone D/Wuweizidilactone Bin-house database
709.20C30H38O6+495.2735−1.2495.2728(93), 477.2625(100), 459.2519(60), 441.2426(49), 323.2002(57), 159.1167(64), 143.0854(61)Kadheterilactone Ain-house database
719.21C32H42O8+555.2946−1.1495.2702(32), 477.2621(95), 459.2524(93), 441.2430(34), 325.2159(67), 323.2011(41), 305.1887(36), 241.1946(66), 221.0944(24), 183.1167(33), 181.1009(40), 171.1167(45), 169.1013(53), 157.1011(61), 143.0857(63), 131.0855(53), 109.0285(100), 105.0699(80)Longipedlactone M isomerin-house database
729.24C35H44O12+679.2717−1.2679.2727(100), 579.2173(11), 519.1973(19), 475.2080(5)Xuetongdilactone D/Wuweizidilactone Bin-house database
739.31C30H38O7+511.2687−0.6511.2719(100), 427.2479(54), 367.2277(37), 323.2020(31), 155.0851(30), 143.0854(37), 105.0700(34)Kadlongilactone Fin-house database
749.31C32H42O9+571.2894−1.4511.2676(100), 427.2473(58), 369.2267(34), 324.2089(24), 323.2002(25), 281.1531(19), 263.1424(18), 235.1480(20), 221.1330(16), 197.0963(28), 183.1173(22), 157.1014(33), 143.0857(36), 105.0700(34)Longipedlactone Pin-house database
759.43C15H24O2+237.1848−0.4237.1847(53), 219.1742(58), 201.1638(52), 161.1323(100), 159.1168(47), 133.1010(32), 121.1011(47), 119.0855(81), 109.1012(56), 105.0698(54), 95.0854(54)10α-hydroxyamorphan-4-en-3-oneReference [43]
769.56C32H40O7+537.2844−0.6537.4486(100), 537.2829(7), 519.2731(5), 477.2634(36), 323.1999(19), 261.1272(11), 249.1268(11), 225.0899(10), 155.0703(11), 109.0648(32)Heteroclitalactone E isomerDPI
779.56C32H44O7+563.2977−0.4563.2972(100), 503.2758(48), 459.2781(13), 178.7752(4), 144.0420(4)Heteroclitalactone M isomerDPI
789.70C30H44O7+517.3151−1.7499.3066(5), 439.2839(100), 421.2724(15), 119.0858(9), 95.0854(12)Kadcoccilactone Cin-house database
799.86C30H42O4+467.3152−0.9467.3135(62), 449.3027(41), 431.2929(36), 407.2546(42), 385.1780(68), 247.1691(38), 233.1528(34), 159.1167(40), 145.1009(42), 133.1009(75), 119.0854(61), 107.0854(48), 95.0855(100)Schisanlactone B isomerDPI
809.95C30H42O5+483.3099−1.2483.3092(59), 465.2993(100), 447.2880(53), 429.2783(28), 325.2177(28), 307.2068(20), 247.1682(16), 159.1166(59), 133.1012(45), 119.0855(64), 107.0855(64), 95.0855(89)Kadsulactone ADPI
8110.02C30H44O7+539.29993.7479.2784(12), 461.2686(25), 325.2162(35), 241.1945(35), 155.0702(40), 109.0647(100)Kadcoccilactone Ain-house database, ClogP
8210.02C32H42O7+539.2999−0.7479.2794(12), 461.2686(25), 443.2573(9), 425.2474(6), 325.2162(35), 307.2058(9), 241.1945(35), 199.1479(11), 195.1171(11), 171.1168(14), 157.1011(21), 143.0855(13), 137.0598(15), 109.0647(100)Heteroclitalactone L isomerin-house database
8310.12C32H40O7+537.2843−0.7477.2632(100), 303.1735(5), 261.1189(18), 249.1269(6), 225.0909(5), 109.0648(27)Heteroclitalactone E isomerDPI
8410.18C32H44O7+563.2973−1.1563.2970(100), 503.2759(75), 459.2853(8)Heteroclitalactone M isomerDPI
8510.20C30H38O7+511.2686−0.8511.2697(100), 427.2454(28), 367.2263(45), 169.1006(70), 157.1009(35), 145.1013(45), 105.0697(45)kadcoccilactone Nin-house database
8610.20C30H40O5+481.2944−1.0481.2979(34), 463.2833(100), 445.2734(36), 307.2053(29), 159.1169(28), 133.1012(25), 119.0855(28)Longipedlactone B isomerin-house database
8710.22C30H38O4+463.2836−1.5463.2840(100), 445.2737(39), 427.2631(36), 323.2002(23), 305.1894(14), 277.1580(20), 269.1532(28), 221.1322(45), 183.1170(10), 157.1009(18), 119.0858(11), 95.0854(29)Lancilactone Bin-house database
8810.29C32H44O7+563.2972−1.2Heteroclitalactone MStandard
8910.32C23H28O6+401.1954−1.2401.1954(100), 370.1784(44), 355.1532(19), 337.1424(30), 323.1281(21), 318.1093(25)Kadsuranin isomerin-house database
9010.33C20H20O5+341.1381−0.9341.1379(13), 201.0908(47), 167.0701(100), 153.0546(56), 149.0232(20), 135.0438(25)d-Epigalbacin isomerDPI
9110.40C22H24O6+385.1627−4.9385.1615(59), 352.1631(83), 297.1850(32), 241.1232(27), 179.4693(23), 159.0414(100), 133.0643(77), 105.0698(20)Schizandrin C isomerin-house database
9210.44C32H40O7+537.2842−0.9537.4486(100), 477.2623(31), 459.2520(34), 323.2006(12), 263.1433(11), 207.1127(12), 193.1014(11), 155.0854(15), 143.0854(19), 119.0855(16)Heteroclitalactone E isomerDPI
9310.49C30H42O5+483.3101−0.8465.2993(100), 447.2885(13), 429.2767(7), 325.2158(18), 307.2044(4), 247.1682(16), 159.1170(9), 133.1009(11), 119.0855(18), 107.0854(18), 95.0854(23)Kadsuphilactone Bin-house database
9410.57C30H48O+425.3773−1.2425.2679(100), 407.2575(23), 285.1847(33), 183.1167(13), 171.11670(26), 157.1011(23), 145.1011(15) 133.1010(11), 119.085(21), 109.1011(8), 95.0854(21)Cycloartenone isomerin-house database
9510.64C30H36O11+595.2140−1.7554.2394(48), 431.2054(100), 356.1627(58)Kadsurarin iosmerin-house database
9610.72C30H38O5+479.2789−0.6479.2784(47), 461.2669(37), 443.2583(20), 325.2151(36), 241.1946(44), 143.0850(27), 109.0647(100)Longipedlactone Ain-house database
9710.72C30H44O7+539.29993.7479.2786(36), 461.2682(48), 325.2157(50), 241.1947(55), 157.1010(31), 109.0647(100)Angustific acid Bin-house database, ClogP
9810.72C32H42O7+539.2999−0.7479.2786(36), 461.2682(48), 443.2572(21), 425.2440(6), 325.2157(50), 307.2041(12), 241.1947(55), 229.1220(19), 197.1320(18), 171.1165(20), 157.1010(31), 143.0854(29), 137.0597(16), 109.0647(100)Heteroclitalactone L isomerin-house database
9910.75C32H40O7+537.2842−0.9537.4481(19), 477.2630(100), 303.1736(5), 267.1375(11), 261.1270(19), 249.1273(7), 233.0959(9), 225.0908(5), 207.0802(10), 109.0647(19)Heteroclitalactone EStandard
10010.78C20H24O5+345.1695−0.6345.1676(13), 223.1328(17), 205.1221(19), 191.1064(16), 175.1115(28), 153.0545(51), 135.0439(100)Kadsurindutin EDPI, Clog P
10110.82C30H48O+425.3771−1.6425.3775(100), 407.3680(25), 343.1305(64), 217.1944(27), 189.1639(34), 147.1166(34), 135.1167(33), 133.1013(38), 123.1167(49), 119.0857(47), 109.1012(96), 95.0854(83)Cycloartenone isomerin-house database
10210.89C30H44O5+485.3254−1.6467.3148(30), 431.2980(14), 327.2306(20), 221.1532(21), 173.1330(26), 159.1173(33), 145.1011(34), 133.1011(34), 119.0855(37), 105.0698(100), 95.0855(83)Kadcotrione Cin-house database, ClogP
10310.91C30H36O11+595.2137−2.2535.1956(51), 371.1488(53), 105.0697(100)KadsurarinStandard
10411.09C30H42O5+483.3096−1.9483.3077(74), 465.3026(100), 447.2913(33), 429.2750(27), 211.1479(25), 159.1170(43), 145.1012(44), 133.1015(34), 119.0856(36), 107.0855(42), 95.0854(83)Kadsuphilactone B isomerin-house database
10511.14C16H30O4−285.2069−0.7285.2070(40), 267.1960(43), 223.2062(100), 115.9196(8)Hexadecanedioic acidmzCloud
10611.30C30H40O6+497.2894−0.8479.2782(30), 461.2670(20), 383.2577(27), 365.2481(22), 341.2467(24), 243.1743(20), 201.1634(51), 159.1167(47), 145.1011(54), 119.0855(54), 107.0854(76), 95.0854(100)Longipedlactone Cin-house database, ClogP
10711.36C32H46O8+581.3077−1.4581.3066(100), 521.2863(66), 477.2963(27), 375.2271(12), 105.0698(10)Xuetongdilactone A isomerin-house database
10811.46C30H44O4+469.3311−0.2469.3289(31), 451.3191(29), 433.3083(27), 423.3232(13), 249.1855(12), 235.2696(12), 173.1324(23), 159.1167(59), 145.1011(64), 133.1010(100), 119.0854(73), 95.0854(89)Schisanlactone E isomerDPI
10911.46C30H44O5+485.3256−1.2485.3241(17), 467.3164(19), 449.3043(37), 431.2949(17), 309.2210(7), 215.1428(13), 173.1322(27), 159.1167(44), 145.1012(36), 133.1012(36), 119.0855(56), 105.0698(62), 95.0855(100)Kadcoccitone Cin-house database, ClogP
11011.47C32H46O8+581.3077−1.4581.3073(100), 521.2861(62), 503.2753(35), 477.2980(7), 459.2855(23)Xuetongdilactone Ain-house database
11111.56C30H40O6+497.2894−0.8479.2789(25), 461.2679(13), 383.2584(20), 365.2494(14), 341.2451(15), 259.1681(14), 201.1630(20), 163.1480(52), 145.1012(41), 119.0854(43), 107.0854(86), 95.0854(100)Longipedlactone C isomerin-house database, ClogP
11211.59C16H30O2+255.2316−1.2237.2206(43), 219.2104(58), 214.2528(54), 149.1324(30), 135.1170(35), 121.1011(34), 107.0853(46), 97.1011(58), 83.0854(90), 69.0699(100), 57.0702(99)Palmitoleic acidmzCloud
11311.63C30H38O4+463.2838−1.1463.2833(92), 445.2730(100), 427.2626(25), 417.2801(20), 323.2001(40), 277.1588(11), 263.1430(20), 221.1315(18), 213.1270(2), 157.1011(33), 145.1010(32), 119.0855(35), 95.0854(59)Lancilactone B isomerin-house database
11411.63C32H42O6+523.3048−1.1463.2824(47), 445.2731(100), 427.2646(23), 417.2766(26), 323.2017(18), 305.1895(27), 277.1570(13), 213.1271(25), 201.1274(17), 183.0808(28), 175.0750(23), 157.1016(23), 145.1013(34), 131.0853(27), 119.0853(30), 95.0855(45)Heteroclitalactone DStandard
11511.66C15H24+205.1949−1.0205.1948(66), 149.1324(50), 135.1166(30), 123.1166(22), 121.1010(100), 109.1011(35), 107.0854(35), 81.0698(50)Isocaryophyllene isomerChemSpider
11611.73C30H42O4+467.3153−0.6467.3169(100), 449.3052(71), 421.3082(12), 327.2317(56), 309.2206(23), 247.1690(14), 159.1166(57), 145.1011(47), 133.1011(36), 119.0855(55), 107.0855(41), 95.0854(63)Schisanlactone B isomerDPI
11711.79C15H24+205.1950−0.5205.1948(100), 149.1325(67), 135.1167(62), 123.1166(29), 121.1011(77), 109.1012(72), 107.0854(62), 81.0698(27)Isocaryophyllene isomerChemSpider
11811.95C32H40O6+521.2891−1.3461.2695(62), 443.2576(100), 425.2468(28), 415.2617(11), 377.2476(21), 245.1331(13), 221.1321(15), 213.1275(17), 207.1171(13), 193.1010(15), 184.0728(56), 169.1009(16), 157.1016(30), 143.0855(35), 131.0855(26), 105.0607(34)Heteroclitalactone Gin-house database
11912.03C30H40O4+465.2996−0.6465.2994(40), 447.2887(100), 429.2887(36), 159.1169(27), 143.0857(28), 119.1013(36), 95.0851(44)Angustific acid Ain-house database
12012.03C30H40O5+481.2941−1.7481.2981(25), 463.2833(100), 445.2728(51), 427.2654(16), 133.1006(21), 119.0854(28)longipedlactone B isomerin-house database
12112.04C30H38O4+463.2837−1.3463.2833(92), 445.2730(100), 427.2626(25), 417.2801(20), 323.2001(40), 277.1588(11), 263.1430(20), 221.1315(18), 213.1270(2), 157.1011(33), 145.1010(32), 119.0855(35), 95.0854(59)Lancilactone B isomerin-house database
12212.09C14H28O3−243.1963−1.2243.1977(15), 225.1891(11), 181.8507(12), 179.7054(16), 146.9602(87), 118.9652(36), 116.9271(33), 59.0127(100)(R)-3-Hydroxy myristic acid isomermzCloud
12312.12C30H46O5+487.3412−1.2487.3464(20), 469.3325(41), 451.3224(52), 433.3086(38), 423.3255(14), 415.1154(9), 359.2771(55), 329.2471(65), 311.2364(36), 249.1838(16), 209.1159(58), 173.1326(31), 159.1166(38), 145.1010(36), 133.1010(60), 121.1011(74), 119.0854(63), 95.0854(100)Kadcoccilactone R isomerin-house database
12412.13C32H44O7+563.2972−1.2563.2968(34), 503.2764(75), 459.2859(9), 105.0700(6)Heteroclitalactone M isomerDPI
12512.17C32H46O8+581.3076−1.5581.3080(100), 537.3158(16), 521.2866(15), 503.2760(13), 477.2972(28), 445.2342(39), 105.0698(14)Xuetongdilactone A isomerin-house database
12612.22C18H30O3+295.2265−1.0277.2158(59), 179.1427(100), 135.1166(35), 121.1010(27), 107.0854(31), 93.0698(51), 81.0698(46), 71.0855(49)9-Oxo-10(E),12(E)-octadecadienoic acid isomermzCloud
12712.23C15H24+205.1949−1.0205.1949(21), 149.1324(25), 135.1167(8), 123.1166(5), 121.1011(100), 109.1011(11), 107.0854(14), 81.0698(38)Isocaryophyllene isomerChemSpider
12812.40C18H30O3+295.2265−1.0277.2157(100), 151.1116(36), 107.0853(20), 93.0698(31), 81.0698(39)9-Oxo-10(E),12(E)-octadecadienoic acidmzCloud
12912.50C20H20O5+341.1378−1.8341.1377(12), 323.1273(3), 219.1013(23), 201.0905(9), 163.0752(52), 151.0389(26), 149.0232(16), 135.0439(100)d-EpigalbacinStandard
13012.50C10H10O2+163.0752−1.2163.0751(100), 135.0439(30), 133.0646(41), 105.0698(70), 79.0541(9)4-Methylcinnamic acid isomerMassBank
13112.50C13H12O2+201.0908−1.0201.0907(100), 186.0672(29), 171.0801(36), 143.0854(78), 128.0619(14)3-Phenoxybenzylalcohol isomerMassBank
13212.50C20H18O4+323.1277−0.3323.1270(26), 201.0906(27), 149.0596(100), 135.0438(57), 119.0490(17), 91.0541(17){4-[(2E)-3-(4-Isopropylphenyl)-2-propenoyl] phenoxy} acetateChemSpider
13312.52C33H44O7−551.2987−4.9487.2821(6), 385.2740(15), 116.9277(6), 97.0283(100), 69.0333(20)Octahydromorellin isomerChemSpider
13412.57C18H30O3+295.2265−1.0277.2159(100), 151.1117(21), 107.0854(22), 93.0699(30), 81.0698(37)9-Oxo-10(E),12(E)-octadecadienoic acid isomermzCloud
13512.58C27H40O4+429.2996−0.7429.3031(33), 411.2873(52), 393.2780(41), 147.1165(47), 133.1012(48), 121.1012(44), 119.0855(51), 107.0854(71), 95.0855(100)Kadnanolactone EDPI
13612.58C30H42O3+451.3203−0.9451.3221(100), 433.3098(78), 415.2974(15), 231.1741(26), 201.1273(19), 159.1168(33), 133.1011(38), 119.0854(50), 95.0854(62)Dysolenticin B isomerChemSpider
13712.58C30H46O5+487.3417−0.2445.9855(34), 145.1013(39), 133.1012(45), 121.1012(65), 107.0855(80), 95.0854(100)Kadcoccilactone R isomerin-house database
13812.58C30H44O4+469.3308−0.9469.3312(20), 451.3187(52), 433.3094(39), 311.2375(11), 217.1585(18), 173.1322(13), 159.1173(19), 145.1013(39), 133.1010(37), 119.0853(44), 95.0854(100)Schisanlactone E isomerDPI
13912.61C30H44O5+485.3258−0.8485.3255(14), 467.3150(100), 449.3054(38), 431.2980(14), 327.2306(20), 221.1532(21), 173.1330(26), 159.1173(33), 145.1011(34), 133.1011(34), 119.0855(37), 105.0698(100), 95.0855(83)Kadcotrione A isomerin-house database, ClogP
14012.73C14H28O3−243.1963−1.2243.1963(47), 197.1903(100), 146.9600(17)(R)-3-Hydroxy myristic acidmzCloud
14112.78C30H42O4+467.3151−1.1467.3169(100), 449.3039(48), 421.3115(7), 327.2310(23), 309.2213(10), 247.1691(10), 157.1010(38), 145.1011(36), 133.1010(30), 119.0855(40), 107.0854(28), 95.0854(50)Schisanlactone B isomerDPI
14212.82C24H32O6+417.2266−1.4417.2266(100), 347.1489(19), 316.1302(58), 301.1068(34), 285.1115(21), 242.0930(14)Deoxyschizandrin isomerin-house database
14312.85C15H24+205.1949−1.0205.1947(16), 149.1323(20), 135.1167(8), 123.1167(5), 121.1011(100), 109.1011(9), 107.0854(14), 81.0698(40)Isocaryophyllene isomerChemSpider
14412.85C10H14+135.1167−0.7135.1166(100), 107.0853(175), 93.0698(74), 91.0540(14),79.0541(34)Cymol isomerMassBank
14512.99C30H44O5+485.3249−2.7467.3163(14), 449.3040(30), 431.2943(22), 329.2473(34), 311.2370(9), 235.1696(14), 173.1325(16), 159.1170(36), 145.1012(32), 133.1010(39), 119.0853(64), 105.0696(57), 95.0854(100)Kadcotrione Ain-house database, ClogP
14613.08C30H42O5+483.3101−0.8483.3121(40), 465.3000(27), 447.2888(17), 429.2783(28), 357.1467(23), 247.1690(5), 159.1166(28), 133.1011(32), 119.0854(50), 107.0853(52), 95.0854(100)Kadsuphilactone B isomerin-house database
14713.26C23H28O6+401.1954−1.2401.1952(100), 370.1761(8), 331.1169(20), 300.0988(61), 285.0755(26), 239.2367(18), 227.0695(17)Kadsuranin isomerin-house database
14813.27C30H40O3+449.3045−1.1449.3044(100), 431.2941(91), 229.1585(52), 215.1430(47), 159.1167(50), 145.1011(57), 133.1010(48), 119.0854(59), 95.0854(72)24-Cholanal, 3,12-dioxo-24-phenyl-isomerPubChem
14913.27C30H42O4+467.3153−0.6467.3150(21), 449.3043(79), 421.3083(14), 327.2315(8), 309.2210(9), 247.1697(9), 229.1431(43), 215.1429(35), 159.1166(44), 145.1010(54), 133.1010(54), 119.0855(60), 107.0854(61), 95.0855(100)Schisanlactone BStandard
15013.40C23H28O6+401.1955−1.0401.1953(100), 370.1776(6), 331.1170(18), 300.0988(51), 285.0753(21), 227.0701(19)Kadsuranin isomerin-house database
15113.42C33H44O7−551.2987−4.9551.2996(38), 505.2885(19), 483.3109(87), 179.8263(10), 116.9275(24)Octahydromorellin isomerChemSpider
15213.48C30H40O4+465.2996−0.6465.3001(100), 447.2890(54), 429.2890(25), 159.1163(27), 145.1212(28), 119.0854(55), 95.0854(53)Schisanlactone A isomerin-house database
15313.72C30H44O5+485.3257−1.0485.3232(11), 467.3153(11), 449.3039(7), 431.2926(8), 223.1496(21), 173.1320(16), 159.1165(20), 145.1011(21), 133.1009(24), 119.0855(34), 105.0698(39), 83.0490(100)Kadnanolactone Bin-house database, ClogP
15413.77C30H42O4+467.3152−0.9467.3140(54), 449.3043(51), 421.3105(11), 327.2320(29), 309.2188(15), 247.1687(26), 229.1595(13), 215.1435(18), 159.1167(40), 145.1010(53), 133.1012(44), 119.0855(62), 107.0854(47), 95.0855(100)Schisanlactone B isomerDPI
15513.78C33H44O7−551.2987−4.9483.3103(100), 439.3203(56), 187.7213(18), 180.1498(29), 115.9193(33)Octahydromorellin isomerChemSpider
15613.96C30H48O+425.3773−1.2407.3636(58), 385.1791(53), 343.1298(58), 239.1495(45), 147.1169(32), 135.1167(63), 121.1012(67), 123.1168(37), 119.0854(31), 109.1011(56), 95.0855(100)Cycloartenone isomerin-house database
15713.97C29H52O9+544.36273.9467.3159(45), 449.3039(45), 431.2936(40), 327.2314(30), 247.1692(40), 173.1323(29), 159.1161(46), 145.1010(43), 133.1010(37), 119.0855(52), 109.1011(100),95.0854(73)2-octoxy-3-[2-(oxolan-2-ylmethoxy) ethyl] undecane-1,2,3-tricarboxylic acid isomermethoxyethoxy) methyl]-L-erythro-hex-2-enonate isomerin-house database
15814.02C30H38O2+431.2940−1.2431.2931(100), 291.2101(13), 145.1011(10), 95.0854(12)3-(3,4-Dihydro-2H-chromen-2-yl) pregna-3,5-dien-20-one isomerChemSpider
15914.02C30H40O3+449.3044−1.3449.3048(100), 431.2944(26), 229.1587(18), 215.1429(20), 159.1168(23), 145.1013(18), 133.1010(20), 119.0857(28), 95.0855(30)24-Cholanal, 3,12-dioxo-24-phenyl-isomerPubChem
16014.02C30H42O4+467.3152−0.9467.3156(100), 449.3052(94), 421.3089(12), 327.2313(29), 309.2188(15), 247.1693(24), 229.1592(73), 215.1426(21), 159.1163(62), 145.1015(64), 133.1012(56), 119.0854(62), 107.0853(67), 95.0854(90)Schisanlactone B isomerDPI
16114.02C32H46O6+527.3365−0.4467.3141(37), 451.3459(24), 449.3018(35), 431.2934(28), 327.2319(38), 309.2213(17), 247.1682(22), 229.1588(15), 215.1433(11), 201.1274(19), 185.1321(21), 171.1167(33), 159.1165(48), 157.1008(42), 145.1011(41), 133.1010(44), 119.0854(61), 95.0855(100)Heteroclitalactone A/Polysperlactone Bin-house database
16214.07C30H44O3+453.3361−0.4453.3387(42), 435.3258(100), 417.3141(7), 413.3768(27), 371.1626(68), 295.2463(24), 159.1168(62), 133.1008(43), 119.0856(53), 95.0855(56)Kadcoccine acid Gin-house database, ClogP
16314.07C32H48O5+535.3391−0.6535.3392(5), 535.3401(89), 475.3181(100), 177.0545(12), 145.0284(5), 105.0700(7)Heteroclic acid isomerin-house database
16414.08C30H44O4+469.33150.6469.4248(100), 451.3221(4), 433.3069(3), 135.1167(8), 121.1010(12), 119.0857(5), 95.0855(25)Schisanlactone E isomerDPI
16514.31C30H46O4+471.3465−0.8471.3458(22), 453.3352(21), 435.3252(20), 417.3147(7), 247.1693(14), 235.1689(21), 175.1478(14), 161.1322(35), 159.1168(17), 145.1011(20), 135.1167(28), 121.1011(72), 109.1011(47), 95.0854(100)Kadpolysperin Min-house database, ClogP
16614.45C30H46O5+487.3413−1.0487.3601(99), 469.4253(100), 451.4112(8), 423.3229(6), 163.1480(11), 149.1325(14), 135.1165(21), 121.1012(33), 119.0857(10), 109.1011(35)Kadcoccilactone R isomerin-house database
16714.51C30H42O4−465.3005−1.1465.3014(3), 325.1844(3), 183.0114(5), 116.9275(100), 99.9246(8)Schisanlactone B isomerDPI
16814.54C30H46O4+471.3466−0.6471.3445(40), 453.3349(36), 435.3261(21), 417.3148(7), 247.1692(6), 235.1682(14), 175.1480(13), 161.1322(51), 159.1168(24), 145.1012(22), 135.1167(38), 121.1012(59), 109.1011(47), 95.0854(100)Nigranoic acid isomerin-house database, ClogP
16914.54C30H48O5+489.3569−1.2489.2964(100), 471.3485(16), 453.3357(24), 435.3245(15), 425.3400(18), 401.3039(22), 235.1685(14), 189.1635(13), 161.1323(38), 159.1167(15), 147.1166(33), 133.1010(31), 121.1010(39), 95.0854(81)Kadnanosic acid Ain-house database
17014.60C30H42O3+451.3203−0.9451.3197(100), 433.3095(46), 201.1275(6), 159.1167(29), 133.1011(23), 119.0855(33), 95.0854(39)Dysolenticin B isomerChemSpider
17114.60C30H46O5+487.3415−0.6487.3596(36), 469.3315(8), 451.3206(25), 433.3094(28), 329.2476(7), 311.2345(6), 249.1847(13), 215.1434(10), 173.1324(19), 159.1167(28), 145.1010(29), 133.1010(38), 121.1010(50), 119.0855(53), 95.0854(100)Kadcoccilactone R isomerin-house database
17214.76C30H46O4+471.3465−0.8471.3459(78), 453.3348(31), 435.3241(23), 417.3140(7), 247.1684(15), 235.1689(22), 173.1321(23), 161.1324(30), 159.1168(34), 145.1010(39), 135.1166(29), 121.1011(61), 109.1011(57), 95.0854(100)Nigranoic acid isomerin-house database, ClogP
17314.80C30H38O2+431.2938−1.6431.2937(100), 291.2092(13), 197.1320(19), 145.1012(14), 95.0854(13)3-(3,4-Dihydro-2H-chromen-2-yl) pregna-3,5-dien-20-one isomerChemSpider
17414.80C30H40O3+449.3043−1.6449.3041(100), 431.2935(63), 229.1584(46), 215.1427(80), 159.1166(31), 145.1010(48), 133.1010(48), 119.0854(46), 95.0854(71)24-Cholanal, 3,12-dioxo-24-phenyl-isomerPubChem
17514.80C30H42O4+467.3153−0.6467.3149(100), 449.3044(65), 421.3105(9), 327.2313(36), 309.2215(22), 247.1693(17), 229.1583(7), 159.1168(52), 145.1011(44), 133.1010(40), 119.0855(57), 107.0854(54), 95.0855(91)Schisanlactone B isomerDPI
17614.82C30H42O3+451.3198−2.0451.3193(100), 433.3092(73), 415.2971(11), 231.1744(20), 201.1273(19), 159.1170(25), 133.1010(41), 119.0855(46), 95.0854(64)Dysolenticin B isomerChemSpider
17714.82C30H44O4+469.3306−1.3469.3310(21), 451.3219(50), 433.3095(35), 423.3276(9), 415.2991(10), 329.2477(12), 311.2370(7), 249.1843(25), 235.1696(12), 219.1378(13), 173.1324(23), 159.1167(35), 145.1009(33), 133.1010(40), 119.0855(60), 95.0855(100)Schisanlactone EStandard
17814.82C22H32O2+329.2469−1.8329.2470(100), 173.1321(14), 159.1166(15), 145.1010(15), 133.1011(18), 121.1011(21), 119.0854(22), 107.0854(28), 95.0854(35)Docosahexaenoic acidMassBank
17914.83C31H46O4+483.3460−1.9483.3465(20), 465.3355(10), 451.3201(54), 433.3102(41), 247.1693(11), 215.1427(16), 201.1634(13), 173.1322(33), 159.1166(39), 145.1011(42), 133.1010(56), 121.1011(49), 95.0854(100)Heteroclitalactone F isomerDPI
18014.83C31H48O5+501.3564−2.2469.3290(39), 451.3199(65), 433.3094(46), 423.3237(13), 415.2982(7), 329.2474(19), 261.1847(17), 249.1848(17), 235.1688(13), 219.1381(10), 173.1316(25), 159.1164(29), 145.1012(47), 133.1008(48), 119.0855(62), 95.0854(100)Kadnanolactone D isomerDPI
18114.90C20H38O2+311.2943−0.6293.2838(34), 184.8882(24), 149.1326(26), 135.1167(32), 116.9720(41), 107.0855(35), 97.1010(48), 83.0854(63), 71.0855(82), 57.0701(100)EthyloleatemzCloud
18214.96C23H32O2−339.2327−0.9339.2323(8), 163.1119(100)2,2′-Methylenebis (4-methyl-6-tert-butylphenol)ChemSpider
18314.97C20H40O3−327.2903−0.6327.2902(100), 281.0057(7), 185.0061(50), 183.0112(43)L-2-Hydroxyphytanate isomerChemSpider
18415.07C30H40O4+465.2996−0.6465.2986(100), 447.2884(78), 429.2782(48), 159.1167(35), 145.1010(34), 119.0855(74), 95.0854(74)Schisanlactone A isomerin-house database
18515.07C30H44O4+469.3309−0.6469.3298(23), 451.3201(54), 433.3094(37), 423.3244(8), 329.2472(8), 311.2357(9), 249.1853(12), 235.1683(11), 219.1382(8), 173.1324(23), 159.1167(31), 145.1009(32), 133.1010(44), 119.0854(52), 95.0854(100)Schisanlactone E isomerDPI
18615.28C30H40O5+481.2930−3.9481.3708(100), 481.3067(68), 277.1775(45), 119.0852(15)Longipedlactone Bin-house database
18715.30C30H44O4+469.3311−0.2469.3177(70), 451.3199(47), 433.3090(41), 423.3250(8), 329.2466(13), 311.2370(7), 249.1843(25), 235.1691(15), 219.1386(6), 173.1323(19), 159.1170(34), 145.1011(38), 133.1009(51), 119.0854(55), 95.0854(100)Schisanlactone E isomerDPI
18815.30C32H48O5+513.3570−1.0513.3538(4), 453.3353(22), 435.3250(56), 417.3148(5), 407.3320(7), 313.2520(70), 233.1532(15), 227.1785(15), 219.1742(15), 201.1636(31), 199.1481(21), 173.1323(24), 161.1322(35), 159.1161(47), 145.1010(52), 133.1010(100), 119.0854(57), 105.0698(65)Heteroclic acid isomerin-house database
18915.37C18H32O2−279.2327−1.1279.2328(100), 179.2416(4), 90.2343(3)Linoleic acidMassBank
19015.50C33H48O6+563.3336−1.2563.3326(99), 503.3122(100), 145.1011(7), 135.0442(10), 119.0854(9), 105.0696(8)Heteroclitalactone BStandard
19115.78C22H42O4−369.3008−0.5369.2986(29), 351.2910(17), 307.3003(100), 115.9195(8)Docosanedioic acidChemSpider
19216.11C30H44O3+453.3358−1.1453.3347(23), 435.3259(42), 371.1628(13), 201.1639(31), 173.1324(23), 159.1166(31), 133.1010(39), 119.0854(40), 109.1011(100), 95.0854(85)Neokadsuranic acid Bin-house database, ClogP
19316.14C20H40O3−327.2903−0.6327.2905(9), 326.1873(65), 185.0060(100), 183.0114(97), 59.009(67)L-2-Hydroxyphytanate isomerChemSpider
19416.19C30H44O4+469.3310−0.4469.3296(35), 451.3199(14), 433.3080(16), 423.3269(6), 249.1852(7), 235.1688(29), 219.1375(9), 173.1322(26), 159.1165(29), 145.1009(31), 133.1009(42), 119.0854(64), 95.0854(100)Kadsuranic acid ADPI, Clog P
19516.20C20H24O5+345.16970.0345.1690(11), 223.1326(14), 205.1221(16), 175.1116(25), 153.0546(44), 135.0439(100)Kadsurindutin E isomerin-house database
19616.20C30H42O3+451.3203−0.9451.3198(100), 433.3096(59), 415.2992(14), 201.1271(28), 159.1167(34), 133.1011(31), 119.0854(46), 95.0854(53)Dysolenticin B isomerChemSpider
19716.27C30H46O4+471.3465−0.8471.3461(41), 453.3346(24), 435.3239(20), 247.1684(24), 235.1684(34), 173.1326(20), 161.1323(49), 159.1168(17), 145.1011(20), 135.1166(32), 121.1012(59), 109.1011(55), 95.0854(100)Nigranoic acidin-house database, ClogP
19816.27C31H48O4+485.3618−1.4453.3360(24), 435.3251(24), 425.3402(16), 407.3298(7), 249.1845(19), 228.1591(51), 201.1640(11), 189.1641(16), 173.1327(16), 161.1325(29), 159.1165(25), 147.1168(28), 133.1011(50), 121.1012(58), 119.0856(51), 95.0854(100)Kadpolysperin J isomerin-house database
19916.45C18H34O2−281.2484−0.7281.2485(100), 249.4335(3), 150.2208(3), 96.9584(3)Oleic acid isomerMassBank
20016.65C20H24O5+345.1693−1.2345.1697(7), 223.1326(14), 205.1221(18), 175.1115(26), 153.0547(41), 135.0439(100)Kadsurindutin E isomerin-house database
20116.77C31H46O4+483.3463−1.2483.3470(17), 465.3406(7), 451.3198(29), 433.3090(31), 263.2001(19), 249.1848(16), 233.1533(11), 215.1433(13), 201.1637(11), 173.1325(27), 159.1168(32), 145.1011(40), 133.1010(59), 121.1011(57), 95.0854(100)Heteroclitalactone FStandard
20217.10C30H46O2+439.3566−1.1439.3593(34), 357.1466(88), 249.1848(14), 205.1947(27), 203.1792(100), 191.1791(94), 121.1011(45), 119.0855(26), 95.0854(100)Heilaohu acid A isomerin-house database
20317.76C30H46O2+439.3566−1.1439.3572(45), 357.1466(100), 233.1896(17), 159.1170(11), 135.1168(10), 121.1010(10), 119.0852(14), 95.0853(14)Heilaohu acid A isomerin-house database
20417.97C30H46O3+455.3515−1.1455.3510(30), 437.3405(38), 419.3296(7), 409.3465(3), 329.2464(3), 235.1689(30), 217.1592(9), 201.1636(22), 189.1633(21), 187.1476(14), 173.1320(14), 161.1322(50), 147.1127(30), 133.1010(36), 121.1010(43), 119.0854(43), 107.0854(40), 95.0854(100)Schisandronic acidStandard
  36 in total

Review 1.  Coupling liquid chromatography to Orbitrap mass spectrometry.

Authors:  Alexander Makarov; Michaela Scigelova
Journal:  J Chromatogr A       Date:  2010-02-20       Impact factor: 4.759

2.  Bioactive compounds from Taiwania cryptomerioides.

Authors:  K He; L Zeng; G Shi; G X Zhao; J F Kozlowski; J L McLaughlin
Journal:  J Nat Prod       Date:  1997-01       Impact factor: 4.050

3.  Qualitative and quantitative analysis of sesquiterpene lactones in Centipeda minima by UPLC-Orbitrap-MS & UPLC-QQQ-MS.

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Journal:  Arch Pharm Res       Date:  2010-12-30       Impact factor: 4.946

8.  New triterpenoids from Kadsura heteroclita and their cytotoxic activity.

Authors:  Wei Wang; Jinzhi Liu; Jian Han; Zhengren Xu; Rongxia Liu; Peng Liu; Weixing Wang; Xiaochi Ma; Shuhong Guan; Dean Guo
Journal:  Planta Med       Date:  2006-04       Impact factor: 3.352

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Journal:  J Chromatogr A       Date:  2019-10-13       Impact factor: 4.759

10.  Rapid qualitative and quantitative analyses of eighteen phenolic compounds from Lycium ruthenicum Murray by UPLC-Q-Orbitrap MS and their antioxidant activity.

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Journal:  Food Chem       Date:  2018-06-30       Impact factor: 7.514
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