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Article

Systematic Screening of the Chemical Constituents of Lanqin Oral Liquid by Ultra-High-Performance Liquid Chromatography Combined with Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

by
Ting Liu
* and
Shu Lin
School of Pharmacy, Shenyang Medical College, Shenyang 110034, China
*
Author to whom correspondence should be addressed.
Molecules 2023, 28(20), 7053; https://doi.org/10.3390/molecules28207053
Submission received: 27 August 2023 / Revised: 23 September 2023 / Accepted: 9 October 2023 / Published: 12 October 2023
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Abstract

:
A rapid and sensitive method that combined ultra-high-performance liquid chromatography combined with Fourier transform ion cyclotron resonance mass spectrometry (UHPLC-FT-ICR-MS) was used to identify the chemical constituents in Lanqin oral liquid. On the basis of UHPLC-FT-ICR-MS analysis, systematic characterization of the chemical profile of Lanqin oral liquid was carried out, and a total of 441 compounds were identified or tentatively characterized including alkaloids, flavonoids, terpenoids, organic acids, phenylpropanoids, and other types. The results provide a reference for improving quality control, contribute to establishing higher quality standards, provide a scientific basis for further research on the pharmacodynamic material basis, and help illustrate the relationship between the complicated constituents and therapeutic effects of Lanqin oral liquid.

1. Introduction

Lanqin oral liquid is the classic traditional Chinese medicine antipyretic prescription. Lanqin oral liquid has the functions of clearing heat, detoxification, liyan, and detumescence effects. The recipe is composed of five valuable herbal medicines, including banlangen-Isatidis Radix, guangqin-Scutellariae Radix, zhizi-Gardeniae Fructus, pangdahai-Sterculiae Lychnophorae Semen, and huangbai-Phellodendri Chinensis Cortex, and has been widely employed in treatments as an antipyretic and anti-inflammatory preparation. Radix Scutellariae possesses anti-inflammatory and antipyretic activities [1,2]. Isatidis Radix has antibacterial, antiviral, antioxidant, anti-inflammatory, and immunomodulatory activities [3]. Gardeniae Fructus has hepatoprotective and choleretic effects and anti-inflammatory, antioxidant, neuroprotective, antidiabetic, antiapoptotic, and antitumor activities [4]. Sterculiae Lychnophorae Semen has anti-inflammatory, analgetic, antibacterial, antiviral, and immunomodulatory activities [5]. Phellodendri Chinensis Cortex has antimicrobic, antitumor, antioxidant, and anti-inflammatory activities [6].
Traditional Chinese medicine (TCM) prescriptions collectively exert therapeutic effects and display a synergistic action via the multicomponents-to-multitargets mechanism guided by the compatibility rules of TCM theory. Given the highly complicated and diverse components in these systems, it is inevitably difficult to identify compounds because these ingredients have rich structural types, wide polarity ranges, and significant differences in content; this always makes the separation and identification challenging and, accordingly, creates difficulties in quality control and the elucidation of pharmacodynamic substances, which hinders modernization. Hence, to ensure the safety and effectiveness of TCM, it is unquestionable that systematic and comprehensive chemical characterization using analytical instruments with high resolution, sensitivity, and accuracy are needed. Recently, the chemical compositions in TCM are increasingly being studied systematically through the use of high-performance liquid chromatography (UHPLC) combined with high-resolution mass spectrometry (HRMS) [7,8]. The overall separation of complex compounds can be efficiently carried out by UPLC; then, these compounds can be accurately characterized and identified by HRMS. A total of 170 and 175 compounds in Lanqin oral liquid were identified or putatively characterized in the previous literature [9,10]. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) has been widely used in the identification and characterization of chemical constituents in TCM for high mass accuracy, good sensitivity, high resolution, and rich data [11,12]. A combination of UPLC separation with an FT-ICR-MS system (UPLC-FT-ICR-MS) is suitable for screening and identifying chemical components in complex matrices in terms of the advantages of rapid analysis, high mass accuracy, high resolution, and high detection sensitivity [13,14].
In this study, a rapid, sensitive, and systematic chemical identification and characterization method with UHPLC-FT-ICR-MS was applied to identify and characterize the chemical components of Lanqin oral liquid. A total of 441 compounds including alkaloids, flavonoids, terpenoids, organic acids, phenylpropanoids, and other types were detected, and their structures were tentatively identified based on the retention time, accurate molecular weight measurement, and characteristic mass fragment information with correlative reference standards or reference data. Results of this investigation lay a foundation for the quality control of Lanqin oral liquid; provide a reference and promising experimental data support for further study of the relationship between the effective substances and their pharmacology; illustrate the relationship between the complicated constituents and the therapeutic effects; and, thus, promote the development of Lanqin oral liquid.

2. Results and Discussion

2.1. Chemical Profiling of Lanqin Oral Liquid

As shown in Figure 1, the representative base peak intensity chromatograms (BPCs) in the positive and negative modes showed the whole profiling of chemical constituents in Lanqin oral liquid. Compounds were identified based on the extracted ion chromatograms, retention time, accurate precursor mass measurements, and diagnostic fragments data. The isomers of compounds with the same molecular formula but different chemical structures were distinguished by characteristic MS/MS fragments and retention time compared with the reference standards and the literature data. In total, 441 chemical constituents, including 134 flavonoids, 88 alkaloids, 108 terpenoids, 51 organic acids, 29 phenylpropanoids, and 31 other compounds in Lanqin oral liquid were unambiguously identified when reference standards were available or tentatively characterized when reference standards were not available by analyzing their MS/MS fragmentation patterns and retention behaviors in comparison with reference standards and the literature data [7,8,9,10,14,15,16,17,18,19,20,21,22,23,24,25,26,27]. The details of the identified compounds are summarized in Table 1, Table 2, Table 3, Table 4 and Table 5.

2.1.1. Characterization and Identification of Flavonoids

Flavonoid compounds are natural compounds containing the basic skeleton C6-C3-C6. A total of 134 flavonoids were tentatively identified in Lanqin oral liquid. The chemical structures of major flavonoid compounds are shown in Figure 2.
The precursor ion [M-H]− of compound F12 was at m/z 461.07229 and was observed at 8.22 min. The molecular formula was C21H18O12, as predicted by the precursor ion. The fragment ion at m/z 285.04039 was observed, indicating the elimination of a glucuronosyl unit in its structure. The compound was identified as scutellarin [9]. Compound F31 was found at 9.72 min, and the molecular formula was C24H26O13, as established by the [M-H]− peak at m/z 521.12952. The characteristic fragments were m/z 359.07727, m/z 344.05343, and m/z 329.02992, corresponding to an excimer ion [M + H]+ successively removing a fragment ion of glucose, one and two methyl groups. It was tentatively characterized as 5,2′,6′-trihydroxy-6,7,8-trimethoxyflavone-2′-O-glucoside [7]. Compound F76 with a retention time of 13.97 min generated the precursor ion of [M + H]+ at m/z 491.11836 in the negative ion mode, and the molecular formula was predicted as C23H22O12. The characteristic fragment were m/z 315.08567, m/z 300.06218, and m/z 285.03875, corresponding to an excimer ion [M + H]+ successively removing a fragment ion of glucose, one and two methyl groups. It was tentatively characterized as 5,7-dihydroxy-6,8-dimethoxyflavone-7-O-glucuronide [7]. The extracted ion chromatogram and MS/MS mass spectrum of 5,7-dihydroxy-6,8-dimethoxyflavone-7-O-glucuronide are shown in Figure 3. The cleavage at the glycosidic linkages was the main fragmentation pattern of O-glycoside.
The precursor ions [M + H]+ of compound F26 and compound F46 were at m/z 417.11859 and m/z 417.11836 and were observed at 9.40 and 11.24 min; the molecular formula was C21H20O9, as predicted by the precursor ion. In the MS/MS spectrum, the characteristic fragment ions of compound F26 at m/z 399.10614, m/z 381.09575, m/z 363.08537, m/z 351.08537, m/z 339.08545, m/z 335.09070, m/z 327.08588, m/z 321.07497, m/z 307.09563, m/z 297.07507, m/z 279.06454, and m/z 267.06457 were detected, which corresponded to [M + H-H2O]+, [M + H-2H2O]+, [M + H-3H2O]+, [M + H-CH2O-2H2O]+, [M + H-C2H4O2-H2O]+, [M + H-3H2O-CO]+, [M + H-C3H6O3]+, [M + H-C2H4O2-2H2O]+, [M + H-3H2O-2CO]+, [M + H-C4H8O4]+, [M + H-C4H8O4-H2O]+, and [M + H-C5H10O5]+, respectively. The characteristic fragment ions of compound F46 at m/z 381.09610, m/z 363.08528, m/z 351.08569, m/z 345.07486, m/z 335.09070, m/z 333.07491, m/z 321.07497, m/z 307.09570, m/z 297.07508, m/z 293.08047, m/z 279.06454, and m/z 267.06455 were detected, which corresponded to [M + H-2H2O]+, [M + H-3H2O]+, [M + H-CH2O-2H2O]+, [M + H-4H2O]+, [M + H-3H2O-CO]+, [M + H-CH2O-3H2O]+, [M + H-C2H4O2-2H2O]+, [M + H-3H2O-2CO]+, [M + H-C4H8O4]+, [M+H-C2H4O2-2H2O-CO]+, [M + H-C4H8O4-H2O]+, and [M + H-C5H10O5]+, respectively. Compound F26 and compound F46 were tentatively characterized as chrysin 8-C-glucoside and chrysin 6-C-glucoside [15]. The ions produced by losing CH2O, C2H4O2, C3H6O3, C4H8O4, C5H10O5, and water molecules from the precursor ions were the main fragmentation patterns of C-glycoside.
Compounds F118 and F130 with a retention time of 20.12 min and 22.60 min generated the precursor ion of [M-H]− at m/z 343.08212 and m/z 343.08199 in the negative ion mode, and the molecular formula was predicted as C18H15O7. In the MS/MS experiments of compound F118, fragment ions at m/z 328.05879, m/z 313.03510, m/z 298.01173, m/z 285.04033, and m/z 270.01684 corresponded to [M-H-CH3]−, [M-H-2CH3]−, [M-H-3CH3]−, [M-H-2CH3-CO]−, and [M-H-3CH3-CO]−. In the MS/MS experiments of compound F130, fragment ions at m/z 328.05887, m/z 313.03516, m/z 298.01176, m/z 295.02482, and m/z 270.01718 corresponded to [M-H-CH3]−, [M-H-2CH3]−, [M-H-3CH3]−, [M-H-2CH3-H2O]−, and [M-H-3CH3-CO]−. Compounds F118 and F130 were tentatively characterized as rivularin and 5,2′-dihydroxy-6,7,8-trimethoxyflavone [8]. The extracted ion chromatogram and MS/MS mass spectrum of 5,2′-dihydroxy-6,7,8-trimethoxyflavone are shown in Figure 4.

2.1.2. Characterization and Identification of Alkaloids

Alkaloids are a class of basic organic compounds containing nitrogen that exist in nature. A total of 88 alkaloids were tentatively identified in Lanqin oral liquid, mainly containing tetrahydroperoberberines such as phellodendrine, aporphines such as magnoflorine, benzylisoquinoline such as N-methylhigenamine 7-glucopyranoside, protoberberines such as palmatine, and other types such as indirubin. The chemical structures of the major alkaloid compounds are shown in Figure 5.
The precursor ion of compound A28 at m/z 342.16909 was observed at 6.05 min. We speculated that the molecular formula was C20H24NO4. In the MS/MS spectrum, the characteristic fragment ion produced was at m/z 192.10132, corresponding to fragment ion [M-C9H10O2]+. The compound was tentatively characterized as phellodendrine [9,10]. The extracted ion chromatogram and MS/MS mass spectrum of phellodendrine are shown in Figure 6.
The precursor ion of compound A34 at m/z 342.16988 was observed at 6.52 min. We speculated that the molecular formula was C20H24NO4. In the MS/MS spectrum, the characteristic fragment ions produced were at m/z 297.11172, m/z 282.08828, m/z 265.08555, and m/z 237.09072, corresponding to fragment ions [M-NH(CH3)2]+, [M-NH(CH3)2-CH3]+, [M-NH(CH3)2-CH3OH]+, and [M-NH(CH3)2-CH3OH-CO]+. The compound was tentatively characterized as magnoflorine [16].
The precursor ion of compound A29 at m/z 448.19537 was observed at 6.15 min. We speculated that the molecular formula was C23H29NO8. In the MS/MS spectrum, the characteristic fragment ions at m/z 286.14311 and m/z 255.10092 were detected, which corresponded to [M + H-glucose]+ and [M + H-glucose-NH2CH3]+. The compound was tentatively characterized as N-methylhigenamine 7-glucopyranoside [10]. The extracted ion chromatogram and MS/MS mass spectrum of N-methylhigenamine 7-glucopyranoside are shown in Figure 7.
The precursor ion of compound A74 at m/z 352.15457 was observed at 11.97 min. We speculated that the molecular formula was C21H22NO4. In the MS/MS spectrum, the characteristic fragment ions at m/z 336.12260, m/z 320.12862, and m/z 308.12759 were detected, which corresponded to [M-CH4]+, [M-CH2O]+, and [M-CH4-CO]+. The compound was chemically defined as palmatine [9,10].
The precursor ion [M + H]+ of compound A86 was at m/z 263.08145 and was observed at 23.49 min. The molecular formula was C16H11N2O2, as predicted by the precursor ion. In the MS/MS spectrum, the characteristic fragment ions at m/z 245.07024, m/z 235.08585, and m/z 219.09110 corresponded to [M + H-H2O]+, [M+H-CO]+, and [M + H-CO2]+. The compound was chemically defined as indirubin. The precursor ion [M + H]+ of compound A88 was at m/z 263.08146 and was observed at 21.69 min. The MS spectra of the two compounds were highly similar to each other. The compound was chemically defined as indigo [17].

2.1.3. Characterization and Identification of Terpenoids

Terpenoid compounds are compounds and derivatives derived from methylglutaric acid, and their basic structural unit is a prenyl unit (C5 unit). A total of 108 terpenoids were tentatively identified in Lanqin oral liquid, mainly contain iridoids such as geniposidic acid, monoterpenoids such as jasminoside B, diterpenoids such as crocin I, and triterpenoids such as obacunone. The chemical structures of major terpenoid compounds are shown in Figure 8.
The precursor ion [M-H]− of compound T5 was at m/z 373.11374 and was observed at 2.34 min, indicating the formation of C16H22O10. The characteristic fragments were m/z 211.06098, m/z 193.05035, m/z 167.07122, m/z 149.06069, and m/z 123.04507, corresponding to fragment ions [M-H-Glc]−, [M-H-Glc-H2O]−, [M-H-Glc-CO2]−, [M-H-Glc-H2O-CO2]−, and [M-H-Glc-H2O-CO2-C2H2]−. The compound was tentatively characterized as geniposidic acid [9,10,18]. The precursor ion [M-H]− of compound T38 was at m/z 225.07668 and was observed at 7.36 min, indicating the formation of C11H14O5. Daughter ions at m/z 147.04498 [M-H-C2H6O3]− were observed in the MS/MS spectrum. The compound was tentatively characterized as genipin [18,19,20]. Compound T22 was found at 5.70 min, and the molecular formula was C23H34O15, as established by the [M + COOH]− peak at m/z 595.18640 and the [M-H]− peak at m/z 549.18166. Daughter ions at m/z 225.07659 [M-H-2C6H10O5]−, m/z 207.06613 [M-H-2C6H10O5-H2O]−, m/z 147.04499 [M-H-2C6H10O5-C2H6O3]−, m/z 123.04505 [M-H-2C6H10O5-H2O-C4H4O2]−, and m/z 101.02435 [M-H-2C6H10O5-C7H8O2]− were observed in the MS/MS spectrum. Compound T22 was tentatively characterized as genipin-1-O-β-D-gentiobioside [10,18,19,20]. The precursor ion [M-H]− of compound T55 was at m/z 695.21845 and was observed at 9.72 min, indicating the formation of C32H40O17. Daughter ions at m/z 469.13465 [M-H-C11H14O5]−, m/z 367.10302 [M-H-C15H20O8]−, m/z 349.09286 [M-H-C15H20O8-H2O]−, m/z 307.08244 [M-H-C11H14O5-C6H10O5]−, m/z 265.07151 [M-H-C19H26O11]−, m/z 235.06085 [M-H-C20H28O12]−, m/z 207.06596 [M-H-C21H28O13]−, m/z 163.03996 [M-H-C11H12O4-2C6H10O5]−, m/z 145.02945 [M-H-C11H12O4-2C6H10O5-H2O]−, and m/z 123.04507 [M-H-C9H6O2-2C6H10O5-H2O-C4H4O2]− were observed in the MS/MS spectrum. The compound was tentatively characterized as 6″-O-trans-p-coumaroylgenipin gentiobioside [19,20,21]. The extracted ion chromatogram and MS/MS mass spectrum of 6″-O-trans-p-coumaroylgenipin gentiobioside are shown in Figure 9.
The precursor ions [M + COOH]− and [M-H]− of compound T18 were at m/z 391.16044 and m/z 345.15548 and were observed at 4.96 min, indicating the formation of C16H26O8. The characteristic fragment ions at m/z 179.05598 [M-H-C10H14O2]−, m/z 165.09202 [M-H-C6H12O6]−, and m/z 161.04543 [M-H-C10H16O3]− were observed in the MS/MS spectrum. The compound was tentatively characterized as jasminoside B [10].
The precursor ion [M-H]− of compound T60 was at m/z 975.37046 observed at 10.34 min, indicating the formation of C44H63O24. Daughter ions at m/z 651.26536 [M-H-2glucose]− were observed in the MS/MS spectrum. The compound was tentatively characterized as crocin I [9].
The precursor ion [M + H]+ of compound T96 was at m/z 455.20596 and was observed at 24.02 min, indicating the formation of C26H30O7. Daughter ions at m/z 437.19518 [M + H-H2O]+, m/z 419.18444 [M + H-2H2O]+, m/z 409.20033 [M + H-CH2O2]+, m/z 391.1899 [M + H-CH2O2-H2O]+, 359.12727 [M + H-C3H12O3]+, 349.14242 [M + H-C4H10O3]+, 331.13297 [M + H-C4H12O4]+, and 315.13702 [M + H-C4H12O5]+ were observed in the MS/MS spectrum. The compound was tentatively characterized as obacunone [22]. The extracted ion chromatogram and MS/MS mass spectrum of obacunone are shown in Figure 10.

2.1.4. Characterization and Identification of Organic Acids

Organic acids refer to some organic compounds with acidity, most commonly containing a carboxyl group (–COOH, 44 Da). A total of 51 organic acids were tentatively identified in Lanqin oral liquid. The chemical structures of major organic acid compounds are shown in Figure 11. Compound O1 with a retention time of 0.94 min generated the precursor ion of [M-H]− at m/z 191.05582 in negative ion mode, and the molecular formula was predicted as C7H12O6. In the MS/MS spectrum, the characteristic fragment ions produced were at m/z 173.04533 and m/z 127.03983, corresponding to fragment ions [M-H-H2O]− and [M-H-H2O-H2CO2]−. It was tentatively characterized as quinic acid [8]. Compound O17 with a retention time of 6.17 min generated the precursor ion of [M-H]− at m/z 179.03487 in negative ion mode, and the molecular formula was predicted as C9H8O4. In the MS/MS spectrum, the characteristic fragment ion produced was at m/z 135.04512, corresponding to fragment ion [M-H-CO2]−. It was identified as caffeic acid [8,18]. The precursor ion [M-H]− of compound O33 was at m/z 559.14509 and was observed at 9.99 min, indicating the formation of C27H28O13. Daughter ions at m/z 379.10338 [M-H-C9H8O4]−, m/z 364.07967 [M-H-C10H11O4]−, m/z 353.08759 [M-H-C11H10O4]−, m/z 335.07676 [M-H-C11H12O5]−, m/z 223.06100 [M-H-C16H16O8]−, m/z 205.05048 [M-H-C16H18O9]−, m/z 191.05598 [M-H-C20H16O7]−, m/z 179.03487 [M-H-C18H20O9]−, m/z 173.04543 [M-H-C20H18O8]−, m/z 164.04778 [M-H-C18H19O10]−, m/z 161.02423 [M-H-C18H22O10]−, m/z 155.03476 [M-H-C20H20O9]−, m/z 149.02429 [M-H-C19H22O10]−, m/z 137.02427 [M-H-C20H22O10]−, and m/z 135.04506 [M-H-C19H20O11]− were observed in the MS/MS spectrum. Fragment ions at m/z 379.10338 and m/z 364.07967 corresponded to successive losses of caffeoyl and methyl groups. Fragment ions at m/z 353.08759 and m/z 335.07680 corresponded to successive losses of a sinapoyl group and H2O. Fragment ions at m/z 223.06100, m/z 205.05048, and m/z 164.04778 corresponded to successive losses of caffeoyl + quinic acid, H2O, and CO2, and also can be regarded as [M-H]−, [M-H-H2O]−, and [M-H-H2O-CO2]− ions of sinapinic acid. Fragment ions at m/z 191.05598, m/z 173.04543, m/z 155.03476, and m/z 137.02427 corresponded to successive losses of a caffeoyl + sinapoyl group, H2O, H2O, and CO2. Fragment ions at m/z 179.03487, m/z 161.02423, and m/z 135.04506 corresponded to losses of sinapoyl + quinic acid, H2O, and CO2, and also can be regarded as [M-H]−, [M-H-H2O]−, and [M-H-H2O-CO2]− ions of caffeic acid. The compound was tentatively characterized as 3-O-caffeoyl-4-O-sinapoylquinic acid [10]. The extracted ion chromatogram and MS/MS mass spectrum of 3-O-caffeoyl-4-O-sinapoylquinic acid are shown in Figure 12.

2.1.5. Characterization and Identification of Phenylpropanoids

Phenylpropanoid compounds are natural compounds with one or more C6-C3 as the basic skeleton. A total of 29 phenylpropanoids were tentatively identified in Lanqin oral liquid. The chemical structures of major phenylpropanoid compounds are shown in Figure 13. The precursor ion [M + H]+ of compound P1 was at m/z 341.08642 and was observed at 4.40 min. The molecular formula was predicted as C15H16O9. In the MS/MS spectrum, the characteristic fragment ion produced was at m/z 179.03357 [M + H-glucose]+. The compound was tentatively characterized as esculin [23]. The precursor ion [M + COOH]− of compound P2 was at m/z 387.12932 and was observed at 5.03 min, indicating the formation of C16H22O8. In the MS/MS spectrum, the characteristic ions at m/z 341.12388 [M-H]− and m/z 179.07122 [M-H-glucose]− were observed. The compound was tentatively characterized as coniferin [24]. The precursor ion [M-H]− of compound P10 was at m/z 523.21827 and was observed at 7.40 min. The molecular formula was predicted as C26H36O11. In the MS/MS spectrum, the characteristic fragment ion produced was at m/z 361.16525, which corresponded to [M-H-C6H10O5]−. The compound was tentatively characterized as (−)-secoisolariciresinol 4-O-β-D-glucopyranoside [8]. The extracted ion chromatogram and MS/MS mass spectrum of (−)-secoisolariciresinol 4-O-β-D-glucopyranoside are shown in Figure 14.
According to the above analysis results, chemical identification of the compounds was performed based on an integrated consideration of accurate MS data, characteristic fragment ions, and retention time using a reference substance or the reference literature. A total of 441 compounds in Lanqin oral liquid were identified in this study. In the previous literature, a total of 170 compounds were identified or putatively characterized by ultra-high-performance liquid chromatography coupled with ion mobility-quadrupole time-of-flight mass spectrometry [9], and 175 compounds were identified or putatively characterized by ultra-high-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry in Lanqin oral liquid [10], while 441 compounds were identified or tentatively characterized in Lanqin oral liquid by UHPLC-FT-ICR-MS/MS. It was found that the applied UHPLC-FT-ICR-MS/MS method with high mass accuracy, good sensitivity, and high resolution was more sensitive for detecting and identifying the chemical compounds in Lanqin oral liquid.
Compounds including flavonoids, alkaloids, terpenoids, organic acids, and phenylpropanoids were identified in Lanqin oral liquid. The content of compounds, such as baicalin, wogonoside, baicalein, wogonin, phellodendrine, magnoflorine, berberine, palmatine, indirubin, genipin-1-O-β-D-gentiobioside, geniposide, obaculactone, obacunone, and chlorogenic acid, were determined in Lanqin oral liquid [28]. Based on the combined content and pharmacological activity studies of the compounds, these chemical constituents with high content and pharmacological activity could be the pharmacodynamic substances that play an important role in vivo. Flavonoids, for example, baicalein, baicalin, wogonin, wogonoside, oroxylin A, and scutellarin, show anti-inflammatory activity [29,30], and baicalin also shows an antipyretic effect [31]. Alkaloids, for example, phellodendrine and berberine, show anti-inflammatory activity [32,33], and indigo and indirubin show antioxidant activity [34]. Terpenoids, for example, geniposidic acid, protects LPS-induced ALI through the TLR4/MyD88 signaling pathway [35], and geniposide, genipin, and crocin-I show anti-inflammatory activity [36,37,38]. Obacunone shows antioxidant and anti-inflammatory activities [39]. Organic acids, for example, caffeic acid and chlorogenic acid, show antioxidant, antibacterial, and anti-inflammatory activities [40,41]. Phenylpropanoids, for example, esculin, shows anti-inflammatory and antioxidative stress effects [42]; pinoresinol-4-O-glucoside shows antioxidant activity [43]; and lariciresinol-4-O-β-D-glucopyranoside shows anti-inflammatory and antiviral effects [44]. It can also be assumed that not only the main chemical constituents with high content but also all of these compounds identified in the Lanqin oral liquid have the probability of being bioactive constituents. Moreover, this study provides the necessary basis for further research on the functional spectrum of Lanqin oral liquid, which may explore and elucidate the therapeutic basis and the possible action mechanism of Lanqin oral liquid on the functions of clearing heat and detoxification, liyan, and detumescence effects.

3. Materials and Methods

3.1. Chemicals and Reagents

Lanqin oral liquid (lot no. 19122821) was purchased from Yangtze River Pharmaceutical Group (Jiangsu, China). Reference compounds (purity > 98%) of chlorogenic acid, caffeic acid, scutellarin, baicalin, palmatine, wogonoside, apigenin, baicalein, wogonin, indirubin, and indigo were purchased from Chengdu Must Bio-Technology Co., Ltd. (Chengdu, China). Acetonitrile and formic acid of HPLC grade were obtained from Fisher Scientific (Fair Lawn, NJ, USA). Purified water was purchased from Hangzhou Wahaha Corporation (Hangzhou, China). All other chemical reagents used in this study were of analytical grade.

3.2. Sample Preparation

1 mL of Lanqin oral liquid was accurately measured and diluted with 1 mL of water. The mixture was vortexed for 3 min, and then the solution was prepared by diluting 5-fold with ultrapure water. The mixture was vortexed for 3 min, then centrifuged at 12,000 rpm for 10 min. The supernatant was collected and filtered through a 0.22 µm filter membrane before UHPLC-FT-ICR-MS/analysis.

3.3. Liquid Chromatography

An Agilent 1260 UHPLC system (Agilent, Santa Clara, CA, USA) was used for the analysis. Chromatographic separation was performed on an ACQUITY UPLC HSS T3 column (2.1 mm × 100 mm, 1.8 µm, Waters, Wexford, Ireland) with an ACQUITY UPLC HSS T3 VanGuard Pre-Column (2.1 mm × 5 mm, 1.8 µm, Waters, Wexford, Ireland) kept at 35 °C. With a flow rate of 0.30 mL/min, the mobile phase was a gradient system consisting of water infused with 0.1% formic acid (A) and acetonitrile (B), with the gradient as follows: 0–2 min, 8–20% B; 2–20 min, 20–50% B; 20–26 min, 50–98% B; 26–33 min, an isocratic elution of B. The injection volume was set at 10 µL.

3.4. Mass Spectrometry

Mass spectrometric detection was carried out on a Solarix 7.0T FT-ICR mass spectrometer (Bruker, Bremen, Germany) coupled with an electrospray ionization (ESI) interface. The full-scan MS data acquired in both positive and negative modes scanned from 100 to 1200 Da. The capillary voltage was 4500 V, the endplate offset was 500 V, dry gas flow was 8 L/min, dry gas temperature was 200 °C, and nebulizer gas pressure was 4 bar. The collision gas and nebulizing gas were high-purity argon (Ar) and high-purity nitrogen (N2), respectively. Full-scan MS data were acquired over an m/z range of 100–1200 Da. And the collision energy were set from 10 to 40 eV for fragmentation information. Bruker Compass Hystar (version 4.1, Bruker Daltonics, Bremen, Germany) and Fourier Transform Mass Spectrometer Control (version 2.1, Bruker Daltonics, Bremen, Germany) were used for instrument control and data acquisition. Data Analysis Software (version 4.4, Bruker Daltonics, Bremen, Germany) was used for data analysis.

4. Conclusions

In our study, a rapid, sensitive, and specific analytical method using UHPLC-FT-ICR-MS/MS was successfully applied to separate and identify chemical constituents of Lanqin oral liquid. A total of 441 compounds were identified or tentatively characterized in Lanqin oral liquid, revealing that flavonoids, alkaloids, terpenoids, organic acids, and phenylpropanoids were the main components. The applied UHPLC-FT-ICR-MS method with the advantages of good separation, high sensitivity, high resolution, and high accuracy for the detection of chemical constituents in Lanqin oral liquid provided comprehensive chemical information on Lanqin oral liquid and could aid in quality control and an understanding of the pharmacodynamic material basis and thus promote the development of Lanqin oral liquid.

Author Contributions

Conceptualization, investigation, formal analysis, visualization, writing—original draft preparation, writing—review and editing, supervision, project administration, funding acquisition, T.L.; writing—review and editing, S.L. All authors have read and agreed to the published version of the manuscript.

Funding

This research was supported by the National Natural Science Foundation of China (grant number 82003935), Basic Scientific Research Project of Education Department of Liaoning Province (grant number LJKQZ20222409), Natural Science Foundation of Liaoning Province (grant number 2023-MS-326), and Startup Foundation for Doctors of Shenyang Medical College (grant number 20195077).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Data are contained within the article.

Conflicts of Interest

The authors declare no conflict of interest.

Sample Availability

Not applicable.

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Molecules 28 07053 g001
Figure 1. UHPLC-FT-ICR-MS base peak intensity chromatogram in positive (A) and negative (B) modes of Lanqin oral liquid.
Figure 1. UHPLC-FT-ICR-MS base peak intensity chromatogram in positive (A) and negative (B) modes of Lanqin oral liquid.
Molecules 28 07053 g001
Molecules 28 07053 g002
Figure 2. Structures of major flavonoid compounds identified in Lanqin oral liquid. Glu A: glucuronic acid; Glc: glucose; Rha: rhamnose.
Figure 2. Structures of major flavonoid compounds identified in Lanqin oral liquid. Glu A: glucuronic acid; Glc: glucose; Rha: rhamnose.
Molecules 28 07053 g002
Molecules 28 07053 g003
Figure 3. The extracted ion chromatogram (A) and MS/MS mass spectrum (B) of 5,7-dihydroxy-6,8-dimethoxyflavone-7-O-glucuronide in positive mode.
Figure 3. The extracted ion chromatogram (A) and MS/MS mass spectrum (B) of 5,7-dihydroxy-6,8-dimethoxyflavone-7-O-glucuronide in positive mode.
Molecules 28 07053 g003
Molecules 28 07053 g004
Figure 4. The extracted ion chromatogram (A) and MS/MS mass spectrum (B) of 5,2′-dihydroxy-6,7,8-trimethoxyflavone in negative mode.
Figure 4. The extracted ion chromatogram (A) and MS/MS mass spectrum (B) of 5,2′-dihydroxy-6,7,8-trimethoxyflavone in negative mode.
Molecules 28 07053 g004
Molecules 28 07053 g005
Figure 5. Structures of major alkaloid compounds identified in Lanqin oral liquid.
Figure 5. Structures of major alkaloid compounds identified in Lanqin oral liquid.
Molecules 28 07053 g005
Molecules 28 07053 g006
Figure 6. The extracted ion chromatogram (A) and MS/MS mass spectrum (B) of phellodendrine in positive mode.
Figure 6. The extracted ion chromatogram (A) and MS/MS mass spectrum (B) of phellodendrine in positive mode.
Molecules 28 07053 g006
Molecules 28 07053 g007
Figure 7. The extracted ion chromatogram (A) and MS/MS mass spectrum (B) of N-methylhigenamine 7-glucopyranoside in positive mode.
Figure 7. The extracted ion chromatogram (A) and MS/MS mass spectrum (B) of N-methylhigenamine 7-glucopyranoside in positive mode.
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Molecules 28 07053 g008
Figure 8. Structures of major terpenoid compounds identified in Lanqin oral liquid.
Figure 8. Structures of major terpenoid compounds identified in Lanqin oral liquid.
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Molecules 28 07053 g009
Figure 9. The extracted ion chromatogram (A) and MS/MS mass spectrum (B) of 6″-O-trans-p-coumaroylgenipin gentiobioside in negative mode.
Figure 9. The extracted ion chromatogram (A) and MS/MS mass spectrum (B) of 6″-O-trans-p-coumaroylgenipin gentiobioside in negative mode.
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Molecules 28 07053 g010
Figure 10. The extracted ion chromatogram (A) and MS/MS mass spectrum (B) of obacunone in positive mode.
Figure 10. The extracted ion chromatogram (A) and MS/MS mass spectrum (B) of obacunone in positive mode.
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Molecules 28 07053 g011
Figure 11. Structures of major organic acid compounds identified in Lanqin oral liquid.
Figure 11. Structures of major organic acid compounds identified in Lanqin oral liquid.
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Molecules 28 07053 g012
Figure 12. The extracted ion chromatogram (A) and MS/MS mass spectrum (B) of 3-O-caffeoyl-4-O-sinapoylquinic acid in negative mode.
Figure 12. The extracted ion chromatogram (A) and MS/MS mass spectrum (B) of 3-O-caffeoyl-4-O-sinapoylquinic acid in negative mode.
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Molecules 28 07053 g013
Figure 13. Structures of major phenylpropanoid compounds identified in Lanqin oral liquid.
Figure 13. Structures of major phenylpropanoid compounds identified in Lanqin oral liquid.
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Molecules 28 07053 g014
Figure 14. The extracted ion chromatogram (A) and MS/MS mass spectrum (B) of (−)-secoisolariciresinol 4-O-β-D-glucopyranoside in negative mode.
Figure 14. The extracted ion chromatogram (A) and MS/MS mass spectrum (B) of (−)-secoisolariciresinol 4-O-β-D-glucopyranoside in negative mode.
Molecules 28 07053 g014
Table 1. Flavonoids identified in Lanqin oral liquid by UHPLC-FT-ICR MS.
Table 1. Flavonoids identified in Lanqin oral liquid by UHPLC-FT-ICR MS.
No.RT (min)Identification[M-H]+[M-H]−Product Ion (m/z)
ObservedCalculatedError (ppm)FormulaObservedCalculatedError (ppm)Formula
F16.02Apigenin-6,8-di-C-glucoside----593.15122593.15119−0.04C27H29O15(−): 503, 473, 383, 353
F26.96Schaftoside565.15541565.15518−0.41C26H29O14563.14072563.14063−0.16C26H27O14(−): 545, 515, 503, 485, 473, 455, 443, 437, 425, 413, 407, 395, 383, 365, 353, 337, 335, 325, 323, 311, 297
F37.16Isoschaftoside565.15754565.15518−4.17C26H29O14563.14032563.140630.55C26H27O14(−): 545, 515, 503, 485, 473, 455, 443, 437, 425, 413, 407, 395, 383, 365, 353, 337, 335, 325, 323, 311, 297
F47.19Viscidulin III-2′-O-glucoside isomer509.13073509.12897−3.46C23H25O13507.11404507.114410.73C23H23O13(+): 347
F57.34Chrysin-6,8-di-C-glucoside579.17156579.17083−1.25C27H31O14577.15585577.156280.75C27H29O14(−): 487, 457, 409, 397, 379, 367, 349, 337, 321, 319, 309, 295, 281, 267
F67.82Rutin611.16025611.160660.67C27H31O16609.14542609.146111.13C27H29O16(+): 465, 303
F77.90Chrysin 6-C-glucoside 8-C-arabinoside549.15924549.160271.87C26H29O13547.14467547.145711.92C26H27O13(+): 531, 513, 495, 483, 477, 465, 459, 447, 441, 429, 423, 417, 411, 405, 399, 393, 387, 375, 363, 357, 351, 345, 339, 333, 321, 309, 291, 279
F87.95Isovitexin433.11379433.11292−1.99C21H21O10----(+): 415, 397, 379, 367, 361, 351, 349, 337, 323, 313, 309, 295, 283
F98.09Tetrahydroxyflavanone289.07117289.07066−1.77C15H13O6287.05575287.056111.26C15H11O6(+): 153
F108.10Isoquercitrin465.10341465.10275−1.41C21H21O12463.08779463.088200.88C21H19O12(+): 303
F118.15Kaempferol-3-O-rhamnose-7-O-glucose----593.15122593.15119−0.04C27H29O15(−): 285
F128.22Scutellarin *463.08755463.08710−0.96C21H19O12461.07229461.072550.56C21H17O12(−): 285
F138.24Hyperin465.10326465.10275−1.10C21H21O12463.08787463.088200.71C21H19O12(+): 303
F148.262′,3′,4′,5,7-pentahydroxyflavone303.04997303.04993−0.12C15H11O7301.03517301.035380.70C15H9O7(+): 153
F158.34Viscidulin III-2′-O-glucoside509.12956509.12897−1.17C23H25O13507.11389507.114411.04C23H23O13(+): 347
F168.37Luteolin-7-O-rutinoside----593.14991593.151192.17C27H29O15(−): 285
F178.43Chrysin-6-C-arabinoside-8-C-glucoside549.15943549.160271.52C26H29O13547.14480547.145711.68C26H27O13(−): 487,457, 427, 409, 397, 391, 379, 373, 367, 363, 349, 337, 333, 331, 321, 319, 309, 307, 295, 293, 281
F188.56Tetrahydroxyflavanone289.07094289.07066−0.95C15H13O6287.05535287.056112.65C15H11O6(+): 153
F198.57Quercetin 7-O-glucoside465.10325465.10275−1.07C21H21O12463.08776463.088200.94C21H19O12(−): 301, 151
F208.62Chrysin-6-C-arabinoside-8-C-glucoside isomer549.16023549.160270.07C26H29O13547.14503547.145711.25C26H27O13(−): 487,457, 427, 409, 397, 391, 379, 373, 367, 363, 349, 337, 333, 331, 321, 319, 309, 307, 295, 293, 281
F218.71Nicotiflorin595.16729595.16575−2.60C27H31O15593.15093593.151190.45C27H29O15(+): 287
F228.92Kaempferol-3-O-rhamnose-7-O-glucose isomer595.16675595.16575−1.69C27H31O15593.15039593.151191.35C27H29O15(−): 285
F239.045,6′-dihydroxy-6,7-dimethoxyflavone-2′-O-glucoside493.13457493.13405−1.06C23H25O12491.11905491.119500.91C23H23O12(−): 329
F249.16Quercitrin449.10890449.10784−2.37C21H21O11447.09288447.093290.91C21H19O11(−): 301
F259.16Oroxin B595.16702595.16575−2.14C27H31O15593.15081593.151190.65C27H29O15(−): 269
F269.40Chrysin 8-C-glucoside417.11859417.11801−1.40C21H21O9415.10314415.103460.77C21H19O9(+): 399, 381, 363, 351, 339, 335, 327, 321, 307, 297, 279, 267
F279.43Apigenin-7-O-glucoside433.11325433.11292−0.75C21H21O10431.09772431.098371.51C21H19H10(+): 271
F289.49Linarin----591.17133591.171931.02C28H31O14(−): 283
F299.55Isorhamnetin-3-O-glucoside479.11935479.11840−1.98C22H23O12477.10352477.103850.70C22H21O12(+): 317
F309.58Hesperidin----609.18261609.18249−0.19C28H33O15(−): 301
F319.725,2′,6′-dihydroxy-6,7,8-trimethoxyflavone-2′-O-glucoside523.14492523.14462−0.59C24H27O13521.12952521.130061.04C24H25O13(−): 359, 344, 329
F329.84Kaempferide 3-glucuronide477.10324477.10275−1.02C22H21O12475.08784475.088200.76C22H19O12(−): 299, 284
F339.86Astragalin449.10851449.10784−1.50C21H21O11447.09287447.093290.93C21H19O11(+): 287
F349.95Viscidulin I303.05004303.04993−0.37C15H11O7301.03513301.035380.81C15H9O7(−): 151
F3510.01Chrysoeriol-5-O-β-D-glucuronide477.10317477.10275−0.88C22H21O12475.08768475.088201.09C22H19O12(−): 299
F3610.11Scutellarein-4′-methyl ether-O-glucuronide477.10272477.102750.06C22H21O12475.08773475.088200.99C22H19O12(−): 443, 284, 173, 155
F3710.27Scutellarein287.05510287.05501−0.29C15H11O6285.04023285.040460.81C15H9O6(+): 269, 241
F3810.272′,6′,7-trihydroxy-5-methoxyflavanone303.08649303.08631−0.58C16H15O6301.07155301.071760.72C16H13O6(+): 167, 152, 123
F3910.60Syringetin347.07655347.07614−1.17C17H15O8345.06107345.061591.50C17H13O8(+): 332
F4010.93Dihydrokaempferol289.07086289.07066−0.67C15H13O6287.05588287.056110.82C15H11O6(+): 271, 153
F4110.94Trihyroxy-dimethoxy flavone-O-glucuronide507.11405507.11332−1.44C23H23O13505.09814505.098761.23C23H21O13(+): 331
F4211.05Baicalin *447.09220447.09219−0.03C21H19O11445.07677445.077631.94C21H17O11(−): 269
F4311.06Fisetin287.05504287.05501−0.09C15H11O6----(+): 269, 258, 241, 231, 223, 213
F4411.12Viscidulin III347.07619347.07614−0.14C17H15O8345.06120345.061591.14C17H13O8(+): 332, 314, 286
F4511.20Oroxin A433.11331433.11292−0.89C21H21O10431.09794431.098371.01C21H19O10(+): 271
F4611.24Chrysin 6-C-glucoside417.11836417.11801−0.85C21H21O9415.10304415.103461.01C21H19O9(+): 381, 363, 351, 345, 335, 327, 333, 321, 307, 297, 293, 279, 267
F4711.33Tetrahydroxyflavanone289.07083289.07066−0.56C15H13O6287.05592287.056110.68C15H11O6(+): 153
F4811.38Trihyroxy-dimethoxy flavone-O-glucuronide507.11429507.11332−1.91C23H23O13505.09829505.098760.94C23H21O13(+): 331
F4911.56Tetrahydroxyflavanone289.07097289.07066−1.05C15H13O6287.05586287.056110.89C15H11O6(+): 153
F5011.67Baicalin ethyl ester or isomer475.12476475.12349−2.68C23H23O11473.10838473.108941.17C23H21O11(+): 271
F5111.78Chrysoeriol-7-O-β-D-glucuronide477.10404477.10275−2.71C22H21O12475.08786475.088200.72C22H19O12(−): 299, 284
F5211.885,6-dihydroxyl flavanone-7-O-glucuronide449.10885449.10784−2.25C21H21O11447.09264447.093291.44C21H19O11(−): 271
F5311.89Trihydroxyflavanone273.07602273.07575−0.97C15H13O5271.06090271.061201.08C15H11O5(+): 153
F5412.08Oroxin A isomer----431.09797431.098370.92C21H19O10(−): 269
F5512.08Oroxylin A 7-O-β-D-glucoside447.13030447.12857−3.85C22H23O10445.11344445.114021.31C22H21O10(−): 268
F5612.16Dihydroxyl flavanone-O-glucuronide449.10921449.10784−3.06C21H21O11447.09263447.093291.46C21H19O11(−): 271
F5712.26Norwogonin-7-O-glucuronide447.09270447.09219−1.14C21H19O11445.07679445.077631.90C21H17O11(−): 269
F5812.382′-hydroxyformononetin285.07651285.07575−2.66C16H13O5283.06083283.061201.29C16H11O5(+): 270
F5912.42Fisetin isomer287.05580287.05501−2.74C15H11O6285.04020285.040460.91C15H9O6(+): 241
F6012.50Hydroxyl oroxylin-A-7-O-glucuronide477.10448477.10275−3.62C22H21O12475.08756475.088201.35C22H19O12(−): 299, 284
F6112.72Norwogonin-8-O-glucuronide isomer447.09344447.09219−2.81C21H19O11445.07693445.077631.57C21H17O11(−): 269
F6212.74Dihydroxyflavone-O-glucopyranoside417.11905417.11801−2.50C21H21O9415.10311415.103460.83C21H19O9(+): 255
F6312.75Kaempferin433.11420433.11292−2.94C21H21O10431.09791431.098371.06C21H19O10(+): 271
F6412.79Tricin 7-O-glucoside----491.11895491.119501.11C23H23O12(−): 329, 313
F6512.82Quercetin----301.03524301.035380.45C15H9O7(−): 151
F6612.97Oroxylin A-7-O-glucuronide461.10755461.107840.62C22H21O11459.09257459.093291.55C22H19O11(+): 285, 270
F6713.00Chrysin-7-O-glucuronide431.09825431.09727−2.26C21H19O10429.08215429.082721.34C21H17O10(−): 253
F6813.08Hydroxyl wogonoside477.10320477.10275−0.94C22H21O12475.08742475.088201.65C22H19O12(−): 299
F6913.35Norwogonin-8-O-glucuronide447.09296447.09219−1.73C21H19O11445.07720445.077630.97C21H17O11(−): 269
F7013.48Oroxin A isomer433.11342433.11292−1.15C21H21O10431.09809431.098370.64C21H19H10(+): 271
F7113.62Wogonoside *461.10765461.107840.40C22H21O11459.09255459.093291.60C22H19O11(−): 283, 268
F7213.84Dihydrooroxylin A287.09159287.09140−0.65C16H15O5285.07658285.076850.94C16H13O5-
F7313.85(2S)-5-hydroxy-6-methoxyflavanone 7-O-β-D-glucuronide463.12401463.12349−1.12C22H23O11461.10839461.108941.18C22H21O11(−): 285, 270
F7413.91Trihydroxy-methoxyflavanone303.08658303.08631−0.89C16H15O6301.07153301.071760.78C16H13O6(+): 147, 135
F7513.94Oroxin A isomer433.11357433.11292−1.49C21H21O10431.09808431.098370.66C21H19H10(+): 271
F7613.975,7-dihydroxy-6,8-dimethoxyflavone-7-O-glucuronide491.11836491.118400.09C23H23O12489.10335489.103851.03C23H21O12(+): 315, 300, 285
F7714.08Viscidulin II isomer331.08144331.08123−0.63C17H15O7329.06652329.066680.48C17H13O7(+): 316, 301
F7814.08(2S)-5-hydroxy-6-methoxyflavanone 7-O-β-D-glucuronide isomer463.12409463.12349−1.30C22H23O11461.10851461.108940.93C22H21O11(−): 285, 270
F7914.10Baicalin ethyl ester or isomer475.12392475.12349−0.92C23H23O11473.10881473.108940.26C23H21O11(+): 271
F8014.20Skullcapflavone II isomer375.10761375.10744−0.45C19H19O8373.09286373.092890.08C19H17O8(+): 360, 345, 327
F8114.50Mosloflavone isomer299.09137299.091400.10C17H15O5297.07684297.076850.02C17H13O5(+): 238
F8214.58Epimedoside C or isomer517.17064517.17044−0.39C26H29O11515.15542515.155890.90C26H27O11(+): 355
F8314.68Chrysosplenin or isomer537.16057537.16027−0.57C25H29O13----(+): 375, 345
F8414.80Baicalin ethyl ester or isomer475.12353475.12349−0.09C23H23O11473.10828473.108941.38C23H21O11(+): 271
F8514.82Phellamurin519.18583519.186090.50C26H31O11563.17651563.177010.89 aC27H31O13(−): 517
F8614.88Trihydroxy-methoxyflavanone303.08625303.086310.21C16H15O6301.07157301.071760.64C16H13O6(+): 147, 135
F8714.95Alpinetin271.09657271.09649−0.32C16H15O4----(+): 167
F8815.06Tenaxin II301.07046301.070660.69C16H13O6299.05588299.056110.77C16H11O6(−): 284
F8915.14Apigenin *271.05992271.060100.65C15H11O5269.04529269.045550.96C15H9O5(−): 237, 225, 201, 175, 151, 149
F9015.145,2′,5′-trihydroxy-6,7,8-trimethoxyflavone or isomer361.09173361.091790.17C18H17O8359.07692359.077240.90C18H15O8(+): 346, 331, 328, 313
F9115.15Kaempferol isomer287.05503287.05501−0.06C15H11O6285.04027285.040460.67C15H9O6(−): 227, 211
F9215.235,2′,6′-dihydroxy-6,7,8-trimethoxyflavone-2′-O-glucoside isomer523.14464523.14462−0.05C24H27O13521.12962521.130060.86C24H25O13(+): 361
F9315.31Viscidulin II isomer331.08119331.081230.12C17H15O7329.06642329.066680.78C17H13O7(+): 316, 301
F9415.47Tectorigenin301.07062301.070660.14C16H13O6299.05586299.056110.86C16H11O6(+): 286
F9515.52Kaempferol287.05507287.05501−0.18C15H11O6285.04023285.040460.80C15H9O6(+): 269, 258, 241, 231, 213
F9615.73Norwogonin271.06005271.060100.18C15H11O5269.04531269.045550.89C15H9O5(+): 253, 225
F9715.78Viscidulin II isomer331.08125331.08123−0.07C17H15O7329.06661329.066680.21C17H13O7(+): 316
F9815.85Baicalin ethyl ester or isomer475.12347475.123490.05C23H23O11473.10934473.10894−0.86C23H21O11(+): 271
F9916.00Trihydroxyflavanone273.07572273.075750.12C15H13O5271.06100271.061200.74C15H11O5(+): 153
F10016.074′-hydroxyl wogonin301.07044301.070660.75C16H13O6299.05577299.056111.15C16H11O6(+): 286
F10116.105,2′,5′-trihydroxy-6,7,8-trimethoxyflavone or isomer361.09207361.09179−0.77C18H17O8359.07696359.077240.78C18H15O8(+): 346, 331, 328, 313
F10216.16Viscidulin II331.08127331.08123−0.13C17H15O7329.06645329.066680.69C17H13O7(+): 316
F10316.32Baicalein *271.05990271.060100.72C15H11O5269.04525269.045551.11C15H9O5(+): 253, 225
F10416.35Fisetin isomer287.05543287.05501−1.45C15H11O6285.04034285.040460.42C15H9O6(+): 241
F10516.36Skullcapflavone II isomer375.10807375.10744−1.66C19H19O8373.09286373.092890.08C19H17O8(+): 360, 345, 327
F10616.40Kaempferide isomer301.07060301.070660.21C16H13O6299.05586299.056110.86C16H11O6(+): 286
F10716.405,2′,5′-trihydroxy-6,7,8-trimethoxyflavone or isomer361.09177361.091790.07C18H17O8359.07724359.077240.00C18H15O8(+): 346, 331, 328, 313
F10816.68Trihydroxyflavanone273.07580273.07575−0.19C15H13O5271.06095271.061200.90C15H11O5(+): 153
F10916.75Tricin331.08117331.081230.19C17H15O7329.06638329.066680.92C17H13O7(−): 314, 299
F11017.145,8,2′-trihydroxy-7-methoxyflavone301.07071301.07066−0.14C16H13O6299.05608299.056110.12C16H11O6(+): 286
F11117.235,8,2′-trihydroxy-6,7-dimethoxyflavone331.08112331.081230.32C17H15O7329.06661329.066680.21C17H13O7(+): 316, 301
F11217.40Trihydroxy-methoxyflavanone303.08621303.086310.36C16H15O6301.07156301.071760.68C16H13O6(+): 147, 135
F11318.465,7-dihydroxy-8,2′,3′,6-tetramethoxyflavone or isomer391.10200391.102360.92C19H19O9389.08755389.087810.66C19H17O9(+): 361
F11418.63Trimethoxyflavone313.10681313.107050.76C18H17O5----(+): 298, 283
F11518.70Trihydroxy-dimethoxyflavone331.08108331.081230.46C17H15O7329.06646329.066680.66C17H13O7(+): 316, 301
F11619.68Dihydrooroxylin A isomer287.09142287.09140−0.07C16H15O5285.07672285.076850.46C16H13O5-
F11719.715,7,3′-trihydroxy-6,4′,5′-trimethoxyflavone361.09172361.091790.21C18H17O8359.07710359.077240.39C18H15O8(−): 344, 329, 314
F11820.12Rivularin345.09650345.096881.10C18H17O7343.08212343.082330.59C18H15O7(−): 328, 313, 298, 285, 270
F11920.41Wogonin *285.07536285.075751.35C16H13O5283.06071283.061201.72C16H11O5(+): 270
F12020.61Amentoflavone isomer539.09726539.097270.02C30H19O10537.08211537.082721.14C30H17O10(−): 391, 373, 268, 245
F12120.63Chrysin255.06516255.065190.11C15H11O4253.05045253.050630.73C15H9O4(−): 209
F12220.78Skullcapflavone II isomer375.10723375.107440.58C19H19O8373.09290373.09289−0.03C19H17O8(+): 360, 345, 327
F12320.82Dihydrooroxylin A isomer287.09149287.09140−0.30C16H15O5285.07676285.076850.30C16H13O5-
F12420.88Skullcapflavone I315.08618315.086310.44C17H15O6313.07148313.071760.89C17H13O6(−): 298, 283, 255, 239, 227, 211, 201, 199, 183, 173, 155
F12521.21Skullcapflavone II375.10743375.107440.03C19H19O8373.09252373.092890.99C19H17O8(−): 358, 343, 328, 315, 300, 285, 272, 269, 257, 213
F12621.33Oroxylin A285.07557285.075750.62C16H13O5283.06108283.061200.43C16H11O5(+): 270
F12721.53Dihydrooroxylin A isomer287.09137287.091400.10C16H15O5285.07677285.076850.25C16H13O5-
F12821.595,8-dihydroxy-6,7-dimethoxyflavone315.08612315.086310.63C17H15O6313.07150313.071760.84C17H13O6(−): 298, 283, 255, 239, 227, 211, 183
F12921.67Amentoflavone isomer539.09716539.097270.20C30H19O10537.08265537.082720.13C30H17O10-
F13022.605,2′-dihydroxy-6,7,8-trimethoxyflavone345.09651345.096881.08C18H17O7343.08199343.082330.98C18H15O7(−): 328, 313, 298, 295, 270
F13123.717-O-methylscutellarein-O-baicalein553.11268553.112920.44C31H21O10551.09789551.098370.87C31H19O10(−): 281, 269
F13224.09Mosloflavone isomer299.09128299.091400.40C17H15O5----(+): 284
F13324.77Moslosooflavone299.09130299.091400.32C17H15O5----(+): 284, 266, 238
F13425.46Mosloflavone299.09133299.091400.22C17H15O5----(+): 284, 255
a: [M + HCOO]−. -: not detected. * Compared with a reference standard.
Table 2. Alkaloids identified in Lanqin oral liquid by UHPLC-FT-ICR MS.
Table 2. Alkaloids identified in Lanqin oral liquid by UHPLC-FT-ICR MS.
No.RT (min)Identification[M-H]+[M-H]−Product Ion (m/z)
ObservedCalculatedError (ppm)FormulaObservedCalculatedError (ppm)Formula
A11.62Candicine180.13838180.13829−0.51C11H18NO+----(+): 121
A22.51N-methylhigenamine 7-glucopyranoside isomer448.19671448.19659−0.25C23H30NO8----(+): 286
A33.43Juziphine isomer300.15938300.159420.13C18H22NO3----(+): 107
A43.99N-methylhigenamine 7-glucopyranoside isomer448.19649448.196590.23C23H30NO8----(+): 286
A54.05Laudanosoline 6-mether-4′-O-glucopyranoside isomer478.20728478.20716−0.26C24H32NO9----(+): 316
A64.37Higenamine272.12795272.128120.64C16H18NO3----(+): 107
A74.42Laudanosoline 6-mether-4′-O-glucopyranoside478.20735478.20716−0.40C24H32NO9----(+): 316
A84.43Juziphine-4′-O-glucopyranoside462.21227462.21224−0.06C24H32NO8----(+): 300
A94.57Govadine328.15405328.154330.87C19H22NO4----(+): 178
A104.71Coclaurine isomer286.14372286.143770.16C17H20NO3-----
A115.07Isaindigodione isomer327.13367327.133930.80C18H19N2O4----(+): 201
A125.16Protosinomenine-3′-O-glucopyranoside492.22311492.22281−0.62C25H34NO9----(+): 330, 299, 192
A135.28Unknown328.15414328.154330.58C19H22NO4----(+): 192
A145.34Corypalmine342.17025342.16998−0.78C20H24NO4----(+): 297
A155.37Isaindigodione327.13345327.133931.47C18H19N2O4----(+): 201
A165.41Lotusine314.17516314.17507−0.29C19H24NO3----(+): 269, 237
A175.43lndole-3-acetonitrile-6-O-β-D-glucopyranoside335.12407335.12376−0.92C16H19N2O6379.11463379.114690.16 aC17H19N2O8(−): 333, 306, 144
A185.46Protosinomenine isomer330.17006330.16998−0.23C19H24NO4-----
A195.51(E)-3-(3′,5′-dimethoxy-4′-hydroxy-benzylidene)-2-indolinone298.10770298.10738−1.06C17H16NO4-----
A205.57Protosinomenine-3′-O-glucopyranoside isomer492.22283492.22281−0.04C25H34NO9----(+): 300
A215.63Indican296.11296296.11286−0.33C14H18NO6340.10358340.103790.61 aC15H18NO8(−): 294, 161, 132
A225.65Unknown356.14910356.149250.43C20H22NO5----(+): 206
A235.743,4-dihydro-[(4-hydroxyphenyl)methyl]-7-methoxy-2-methyl-8-isoquinolinol298.14366298.143770.35C18H20NO3----(+): 283, 282, 254
A245.80Magnocurarine314.17486314.175070.66C19H24NO3----(+): 269, 237
A255.812,3-dihydro-1H-pyrrolo[2,1-c][1,4]benzodiazepine-5,11(10H,11ah)-dione217.09734217.09715−0.85C12H13N2O2----(+): 144
A265.85Juziphine-4′-O-glucopyranoside462.21275462.21224−1.10C24H32NO8----(+): 300
A275.95Unknown356.14938356.14925−0.36C20H22NO5----(+): 206
A286.05Phellodendrine342.16909342.169982.62C20H24NO4----(+): 192
A296.15N-methylhigenamine 7-glucopyranoside448.19537448.196592.72C23H30NO8446.18187446.182040.37C23H28NO8(+): 286, 255
A306.20Anthranilic acid-7-O-β-D-glucopyranose ester300.10827300.10778−1.64C13H18NO7----(+): 282, 264, 246, 138
A316.40Tembetarine344.18565344.18563−0.03C20H26NO4----(+): 175, 137
A326.438-O-methyloblongine328.19083328.19072−0.33C20H26NO3----(+): 313, 283
A336.46(1S)-1,2,3,4-tetrahydro-7-hydroxy-1-[(4-hydroxybenzyl)methyl]-2,2-dimethyl-8-O-isoquinolinyl-[3-hydroxy-3-methylglutaryl]-β-D-glucopyranoside592.23893592.23885−0.13C29H38NO12590.22428590.224300.03C29H36NO12(+): 530, 490, 448, 286
A346.52Magnoflorine342.16988342.169980.31C20H24NO4----(+): 297, 282, 265, 237
A356.61Piperlonguminine274.14417274.14377−1.46C16H20NO3----(+): 256, 227
A366.66Unknown312.12357312.12303−1.72C18H18NO4----(+): 297
A376.87Protosinomenine330.17032330.16998−1.01C19H24NO4----(+): 192
A387.11Fuzitine342.16969342.169980.86C20H24NO4----(+): 192
A397.13Oblongine314.17491314.175070.51C19H24NO3----(+): 269, 237, 175, 143
A407.19Laudanosine358.20120358.201280.24C21H28NO4----(+): 327, 189
A417.29Deoxyvasicinone187.08643187.086590.83C11H11N2O----(+): 146
A427.35Unknown358.20108358.201280.56C21H28NO4----(+): 189
A437.43Menisperine356.18596356.18563−0.92C21H26NO4+----(+): 311, 296, 279
A447.74Tetrahydroberberine isomer340.15482340.15433−1.41C20H22NO4-----
A457.85Tembetarine isomer344.18582344.18563−0.54C20H26NO4+----(+): 137
A467.85Methylcorydine356.18579356.18563−0.43C21H26NO4+----(+): 311, 279
A477.93Pilocarpine isomer260.12826260.12812−0.53C15H18NO3-----
A488.098-O-methyloblongine isomer328.19121328.19072−1.50C20H26NO3----(+): 283
A498.27Tetrahydroberberine isomer340.15452340.15433−0.55C20H22NO4----(+): 309, 192
A508.281-Methoxyindole-3-acetamide205.09713205.097150.11C11H13N2O2----(+): 188
A518.30Cryptopine370.16531370.16490−1.11C21H24NO5-----
A528.49Isaindigodione isomer327.13486327.13393−2.83C18H19N2O4----(+): 201
A538.665,8,13,13a-tetrahydro-2,9,10,11-tetrahydro-3-methoxy-7-methy-6H-dibenz[a,g]quinoline324.12323324.12303−0.60C19H18NO4----(+): 294, 280
A548.79Dasycarpamin304.15478304.15433−1.46C17H22NO4-----
A558.85Armepavine314.17539314.17507−1.00C19H24NO3----(+): 269, 237
A569.02Rotundine356.18565356.18563−0.03C21H26NO4----(+): 192
A579.03Platydesmine260.12836260.12812−0.91C15H18NO3----(+): 242
A589.15Demethyleneberberine324.12337324.12303−1.03C19H18NO4----(+): 309, 308, 294, 280
A599.70Indole-3-acetonitrile-2-S-β-D-glucopyranoside----349.08596349.086371.17C16H17N2O5S(−): 187, 160
A609.91Platydesmine isomer260.12817260.12812−0.19C15H18NO3-----
A6110.0011-hydroxypalmatine or 13-hydroxypalmatine368.14971368.14925−1.25C21H22NO5----(+): 352, 323, 322
A6210.001-hydroxyberberine352.11789352.117950.17C20H18NO5----(+): 308
A6310.103-(2′-carboxyphenyl)-4(3H)-quinazolinone267.07661267.07642−0.73C15H11N2O3----(+): 249
A6410.14N-methylcanadine isomer354.17009354.16998−0.28C21H24NO4----(+): 190
A6510.30Cryptopine isomer370.16510370.16490−0.55C21H24NO5-----
A6610.69Indole-3-acetonitrile-4-methoxy-2-S-β-D-glucopyranoside or N-Methoxyindole-3-acetonitrile-2-S-β-D-glucopyranoside381.11206381.11148−1.51C17H21N2O6S379.09657379.096930.95C17H19N2O6S(+): 219
A6711.10Berberrubine322.10757322.10738−0.57C19H16NO4----(+): 307
A6811.10Tetrahydrocorysamine338.13873338.13868−0.13C20H20NO4----(+): 323, 322, 308, 294
A6911.11N-methyltetrahydropalmatine370.20188370.20128−1.60C22H28NO4----(+): 206
A7011.21Tetrahydroberberine340.15458340.15433−0.73C20H22NO4----(+): 176
A7111.253-(2′-hydroxyphenyl)-4-(3H)-quinazolinone239.08162239.08150−0.50C14H11N2O2----(+): 221
A7211.26N-p-Coumaroyltyramine284.12834284.12812−0.79C17H18NO3----(+): 147
A7311.30N-methylcanadine354.17029354.16998−0.87C21H24NO4----(+): 190
A7411.97Palmatine *352.15457352.15433−0.67C21H22NO4----(+): 336, 308
A7512.25Berberine336.12277336.123030.79C20H18NO4----(+): 320, 292
A7612.909-hydroxy-10-methoxy-13-methyl-5,6-dihydro-[1,3]dioxolo[4,5-g]isoquinolino[3,2-a]isoquinolin-7-ium336.12296336.123030.22C20H18NO4----(+): 292
A7714.15Unknown486.19116486.19111−0.09C29H28NO6----(+): 336
A7814.388-oxopalmatine368.14933368.14925−0.22C21H22NO5----(+): 338
A7914.72Canthin-6-one221.07097221.07094−0.13C14H9N2O----(+): 193, 167, 140
A8015.25Skimmianine260.09171260.091730.10C14H14NO4----(+): 227
A8115.69γ-fagarine230.08119230.08117−0.07C13H12NO3----(+): 215
A8217.21Dictamnine200.07066200.07060−0.30C12H10NO2----(+): 185
A8318.567-hydroxyrutaecarpine304.10797304.108050.26C18H14N3O2-----
A8419.368-oxopalmatine368.14907368.149250.49C21H22NO5----(+): 338
A8521.56Oxyberberine352.11792352.117950.07C20H18NO5----(+): 337, 322, 294
A8621.69Indigo *263.08146263.081500.18C16H11N2O2----(+): 245, 235, 219
A8722.72N-methylflindersine242.11759242.11756−0.15C15H16NO2-----
A8823.49Indirubin *263.08145263.081500.21C16H11N2O2----(+): 245, 235, 219
a: [M + HCOO]−. -: not detected. * Compared with a reference standard.
Table 3. Terpenoids identified in Lanqin oral liquid by UHPLC-FT-ICR MS.
Table 3. Terpenoids identified in Lanqin oral liquid by UHPLC-FT-ICR MS.
No.RT (min)Identification[M-H]+[M-H]−Product Ion (m/z)
ObservedCalculatedError (ppm)FormulaObservedCalculatedError (ppm)Formula
T11.75Gardoside----373.11372373.114020.80C16H21O10(−): 211, 193, 167, 149, 123
T21.96Aldoxoside383.13136383.13125−0.28 aC16H24NaO9405.13976405.140241.17 bC17H25O11(−): 359
T31.98Deacetylasperulosidic acid----389.10856389.108940.96C16H21O11(−): 345, 227, 209, 183, 165
T42.05Shanzhiside393.13904393.139140.25C16H25O11391.12397391.124591.56C16H23O11(−): 229, 211, 185, 167, 149
T52.34Geniposidic acid375.12859375.12857−0.04C16H23O10373.11374373.114020.76C16H21O10(−): 211, 193, 167, 149, 123
T62.43Ixoroside383.13112383.131250.36 aC16H24NaO9405.13997405.140240.65 bC17H25O11(−): 359
T72.546-oxo demethylgenipin 1-O-glucopyranoside----387.09334387.09329−0.14C16H19O11(−): 343
T82.80Deacetyl asperulosidic acid methyl ester427.12108427.121080.00 aC17H24NaO11449.12935449.130061.58 bC18H25O13(−): 241
T93.07Deacetylasperulosidic acid isomer391.12351391.12349−0.06C16H23O11389.10898389.10894−0.12C16H21O11(−): 345
T103.21Gardenoside427.12095427.121080.32 aC17H24NaO11449.12939449.130061.50 bC18H25O13(−): 241
T113.49Jasminoside G347.17007347.17004−0.09C16H27O8345.15527345.155490.63C16H25O8(−): 165
T123.65Scandoside methyl ester427.12100427.121080.19 aC17H24NaO11449.12977449.130060.66 bC18H25O13(−): 241
T134.02Shanzhiside methyl ester isomer407.15474407.154790.13C17H27O11405.13998405.140240.64C17H25O11(−): 361, 225
T144.53Jasminoside B isomer347.16989347.170040.44C16H27O8391.16066391.160970.81 bC17H27O10(−): 165
T154.56Galioside427.12080427.121080.66 aC17H24NaO11449.13007449.13006−0.01 bC18H25O13(−): 241
T164.66Loganic acid----375.12974375.12967−0.19C16H23O10(−): 213
T174.89Jasminoside C329.15945329.159480.09C16H25O7327.14492327.144930.01C16H23O7(−): 165
T184.96Jasminoside B347.16974347.170040.89C16H27O8391.16044391.160971.36 bC17H27O10(−): 345, 179, 165, 161
T195.31Shanzhiside methyl ester----405.14012405.140240.29C17H25O11(−): 243
T205.327-epiloganin--- 389.14535389.14532−0.09C17H25O10(−): 181, 166
T215.65Mussaenosidic acid----375.12956375.129670.29C16H23O10(−): 191
T225.70Genipin-1-O-β-D-gentiobioside551.19677551.197050.51C23H35O15595.18735595.187971.04 bC24H35O17(−): 549, 225, 207, 147, 123, 101
T235.728-Epiapodantheroside389.14434389.14422−0.31C17H25O10387.12895387.129671.86C17H23O10-
T246.00Genameside C551.19796551.19705−1.66C23H35O15595.18720595.187971.30 bC24H35O17(−): 549, 225, 123
T256.067,8-dihydro-genipin-1-O-β-gentiobioside----597.20326597.203620.61 bC24H37O17(−): 551, 389, 227
T266.07Jasminoside I493.22826493.22795−0.62C22H37O12537.21830537.218881.08 bC23H37O14(−): 491, 167
T276.17Asperulosidic acid----431.11920431.119500.68C18H23O12-
T286.18Genipin 1-O-apiofuranosyl glucopyranoside----565.17704565.177410.65 bC23H33O16(−): 519, 225
T296.28Geniposide411.12648411.12617−0.76 aC17H24NaO10433.13452433.135151.45 bC18H25O12(−): 387, 225, 207, 123, 101
T306.39Genameside D551.19796551.19705−1.66C23H35O15595.18773595.187970.41 bC24H35O17(−): 549, 387, 225
T316.44Genipin 1-O-xylopyranosyl glucopyranoside----565.17731565.177410.17 bC23H33O16(−): 519, 225, 207
T326.60Dihydrogeniposide----435.15050435.150800.68 bC18H27O12-
T336.69Jasminoside O463.21823463.21739−1.81C21H35O11461.20303461.20284−0.42C21H33O11(+): 331, 169
T346.81Epijasminoside A or Jasminoside A/E/K331.17512331.175130.03C16H27O7375.16572375.166060.90 bC17H27O9(+): 169
T356.88Epijasminoside A or Jasminoside A/E/K331.17507331.175130.17C16H27O7375.16591375.166060.39 bC17H27O9(+): 169
T367.07Epijasminoside A or Jasminoside A/E/K331.17569331.17513−1.69C16H27O7375.16573375.166060.87 bC17H27O9(+): 169
T377.34Jasminoside C329.15980329.15948−0.96C16H25O7373.15019373.150410.59 bC17H25O9(−): 165
T387.36Genipin----225.07668225.076850.75C11H13O5(−): 147
T397.61Jasminodiol----183.10241183.102671.42C10H15O3(−): 139
T407.666″-O-trans-p-coumaroylgenipin gentiobioside isomer697.23369697.233830.20C32H41O17695.21832695.219271.37C32H39O17(−): 163
T417.8310-O-succinoylgeniposide isomer----487.14544487.145710.56C21H27O13(−): 207
T428.23(1R,7R,8S,10R)-7,8,11-trihydroxyguai-4-en-3-one-8-β-D-glucopyranside431.22786431.22756−0.70C21H35O9429.21274429.213010.62C21H33O9(+): 269
T438.2410-O-acetylgeniposide453.13736453.13673−1.39 aC19H26NaO11475.14536475.145710.75 bC20H27O13(−): 209
T448.372′-O-trans-p-coumaroylgardoside----519.15007519.150801.41C25H27O12(−): 163, 145, 123
T458.596′-O-trans-sinapoylgardoside581.18719581.18648−1.21C27H33O14579.17142579.171930.87C27H31O14(−): 325, 223, 205
T468.676″-O-trans-caffeoylgenipin gentiobioside----711.21306711.214191.58C32H39O18(−): 179, 123
T478.786′-O-trans-p-coumaroylgeniposidic acid----519.15061519.150800.37C25H27O12(−): 211, 163, 145, 123
T488.8810-O-succinoylgeniposide----487.14528487.145710.89C21H27O13(−): 207
T498.9510-(6-O-trans-sinapoylglucopyranosyl)-gardendiol567.20828567.20722−1.87C27H35O13565.19190565.192661.35C27H33O13(−): 325, 295, 265, 223
T508.996′-O-trans-sinapoylgardoside isomer581.18726581.18648−1.34C27H33O14579.17130579.171931.08C27H31O14(−): 325, 223, 205
T519.09Jasminoside R513.19610513.19425−3.61 aC22H34NaO12535.20260535.203231.18 bC23H35O14-
T529.096″-O-trans-p-coumaroylgenipin gentiobioside isomer----695.21812695.219271.66C32H39O17(−): 469, 163
T539.3111-(6-O-trans-sinapoylglucopyranosyl)-gardendiol567.20835567.20722−1.99C27H35O13565.19236565.192660.55C27H33O13(−): 265, 223
T549.4110-O-acetylgeniposide isomer453.13754453.13673−1.78 aC19H26NaO11475.14530475.145710.87 bC20H27O13(−): 209
T559.726″-O-trans-p-coumaroylgenipin gentiobioside697.23461697.23383−1.12C32H41O17695.21845695.219271.18C32H39O17(−): 469, 367, 349, 307, 265, 235, 207, 163, 145, 123
T569.75Jasminoside I/S/H----537.21830537.218881.08 bC23H37O14(−): 491
T579.916″-O-trans-sinapoylgenipin gentiobioside----755.23881755.240402.11C34H43O19(−): 427, 325, 265, 223, 205
T5810.056″-O-trans-feruloylgenipin gentiobioside727.24630727.24439−2.63C33H43O18725.22867725.229841.61C33H41O18(−): 397, 295, 235, 225, 207, 193, 175, 123
T5910.33Jasminoside R----489.19730489.197750.92C22H33O12-
T6010.34Crocin I----975.37046975.371481.04C44H63O24(−): 651
T6110.686′-trans-sinapoylgeniposide isomer617.18520617.18408−1.82 aC28H34NaO14593.18700593.187580.97C28H33O14(−): 367, 223
T6210.756′-O-trans-sinapoyljasminoside L553.22916553.22795−2.19C27H37O12551.21267551.213401.32C27H35O12(−): 223
T6311.366′-trans-sinapoylgeniposide595.20406595.20213−3.24C28H35O14593.18666593.187581.55C28H33O14(−): 367, 223, 205, 123
T6411.476′-O-trans-coumaroylgeniposide535.18261535.18100−3.00C26H31O12533.16592533.166451.00C26H29O12(−): 307, 145
T6511.70Jasminoside I/S/H----491.21363491.21340−0.47C22H35O12-
T6611.726″-O-trans-p-coumaroylgenipin gentiobioside isomer----695.21805695.219271.75C32H39O17(−): 207, 163
T6712.06Jasminoside I/S/H----491.21248491.213401.87C22H35O12-
T6812.10Rehmapicrogenin or isomer----183.10239183.102671.50C10H15O3-
T6912.42Rutaevin487.19808487.19626−3.74C26H31O9485.18117485.181711.10C26H29O9(−): 467, 423
T7013.276″-O-trans-p-cinnamoylgenipin gentiobioside703.22355703.22086−3.83 aC32H40NaO16725.22811725.229842.38 bC33H41O18(−): 679, 531, 355, 225, 207, 147, 123
T7113.976′-O-trans-sinapoyljasminoside A537.23366537.23304−1.15C27H37O11535.21809535.218490.74C27H35O11(−): 223
T7214.44Obacunoic acid473.21640473.216991.26C26H33O8471.20217471.202440.59C26H31O8(−): 325
T7314.47Crocin I acid----1007.374861007.376561.69C48H63O23(−): 683
T7414.636′-trans-sinapoylgeniposide isomer617.18462617.18408−0.89 aC28H34NaO14593.18691593.187581.14C28H33O14(−): 367, 223, 205, 123
T7514.756′-O-trans-sinapoyjasminoside C535.21774535.21739−0.65C27H35O11533.20202533.202841.53C27H33O11(−): 223, 205
T7615.4012α-hydroxylimonin487.19607487.196260.38C26H31O9-----
T7716.49Neocrocin E----975.37036975.371481.15C44H63O24(−): 651
T7816.86Crocin-Ⅲ or 13-cis-crocetin-8′-O-β-D-gentiobioside or isomer653.28032653.280380.09C32H45O14651.26523651.265830.92C32H43O14(−): 327, 283, 239
T7917.91Crocin II837.31452837.315150.75 aC38H54NaO19813.31723813.318651.75C38H53O19(−): 651
T8017.93beta-D-glucosyl crocetin491.22716491.227560.82C26H35O9489.21276489.213010.50C26H33O9(−): 327
T8118.356′-O-trans-sinapoyljasminoside A----535.21815535.218490.62C27H35O11(−): 223
T8218.37beta-D-glucosyl crocetin491.22719491.227560.76C26H35O9489.21277489.213010.48C26H33O9(−): 327
T8319.146′-O-trans-sinapoyljasminoside A isomer----535.21823535.218490.49C27H35O11(−): 223
T8419.60Obaculactone471.20104471.201340.64C26H31O8469.18655469.186790.51C26H29O8(+): 453, 427, 425, 409, 367, 339, 161
T8520.34Crocin II837.31579837.31515−0.77 aC38H54NaO19813.31960813.31865−1.17C38H53O19(−): 651
T8620.35Obacunoic acid473.21675473.216990.52C26H33O8471.20245471.20244−0.02C26H31O8(−): 325, 307
T8720.70Crocin-Ⅲ or 13-cis-crocetin-8′-O-β-D-gentiobioside or isomer675.26198675.262330.52 aC32H44NaO14651.26503651.265831.22C32H43O14(−): 327, 283, 239
T8821.09Obacunoic acid isomer473.21690473.216990.20C26H33O8471.20262471.20244−0.39C26H31O8(−): 325
T8921.19Neocrocin B----987.35048987.35035−0.14C48H59O22-
T9021.38Crocin-Ⅲ or 13-cis-crocetin-8′-O-β-D-gentiobioside or isomer653.28052653.28038−0.21C32H45O14651.26515651.265831.04C32H43O14(−): 327
T9121.95Dehydrolimonin469.18526469.185690.93C26H29O8513.17635513.176620.53 bC27H29O10(−): 467, 449
T9222.05Crocin-Ⅲ or 13-cis-crocetin-8′-O-β-D-gentiobioside or isomer653.27972653.280381.02C32H45O14651.26462651.265831.86C32H43O14(−): 327
T9322.90beta-D-glucosylcrocetin491.22735491.227560.43C26H35O9489.21272489.213010.58C26H33O9(−): 327
T9423.14beta-D-glucosylcrocetin491.22726491.227560.61C26H35O9489.21268489.213010.68C26H33O9(−): 327
T9523.47beta-D-glucosylcrocetin491.22722491.227560.69C26H35O9489.21265489.213010.72C26H33O9(−): 327
T9624.02Obacunone455.20596455.206431.04C26H31O7453.19169453.191880.40C26H29O7(+): 437, 419, 409, 391, 359, 349, 331, 315
T9725.09Crocetin329.17453329.174740.63C20H25O4327.15993327.160180.77C20H23O4(−): 283
T9825.36Erubigenin489.35728489.357450.35C30H49O5487.34244487.342900.93C30H47O5(−): 469
T9925.68Dikamaliartanes A501.32111501.32107−0.08C30H45O6499.30640499.306510.23C30H43O6-
T10025.83Crocetin isomer329.17472329.174740.04C20H25O4327.15992327.160180.81C20H23O4(−): 283
T10125.95Obacunone isomer455.20628455.206430.33C26H31O7453.19150453.191880.83C26H29O7(+): 437, 411, 409, 359
T10225.96Gardenic acid B487.34171487.341800.19C30H47O5485.32690485.327250.71C30H45O5-
T10326.56Crocetin isomer329.17474329.174740.00C20H25O4327.15986327.160180.99C20H23O4(−): 283
T10427.17Crocetin isomer329.17470329.174740.10C20H25O4327.15981327.160181.14C20H23O4(−): 283
T10527.7827-O-p-(E)-coumaroyloxyursolic acid----617.38369617.384761.73C39H54O6-
T10629.029,19-cyclolanost-24-ene-3,23-dione----469.33097469.332332.91C30H45O4-
T10729.52Quadrangularic acid E----471.34652471.347983.10C30H47O4-
T10830.44Betulinic acid----455.35162455.353073.19C30H47O3(−): 407
a: [M + Na]+; b: [M + HCOO]−. -: not detected.
Table 4. Organic acids identified in Lanqin oral liquid by UHPLC-FT-ICR MS.
Table 4. Organic acids identified in Lanqin oral liquid by UHPLC-FT-ICR MS.
No.RT (min)Identification[M-H]+[M-H]−Product Ion (m/z)
ObservedCalculatedError (ppm)FormulaObservedCalculatedError (ppm)Formula
O10.94Quinic acid----191.05582191.056111.55C7H11O6(−): 173, 127
O21.27Succinic acid----117.01917117.019331.37C4H5O4-
O31.32Malic acid----133.01404133.014251.59C4H5O5(−): 115
O41.69Quinic acid 3-hydroxy-3-methylpentanedioate337.11289337.112920.10C13H21O10335.09793335.098371.31C13H19O10(−): 191
O52.19Dihydroxybenzoic acid glucoside----315.07186315.072160.93C13H15O9(−): 153, 109
O62.27Vanillic acid hexose331.10239331.10236−0.09C14H19O9329.08737329.087811.32C14H17O9(−): 167
O72.513-({3-[4-(β-glucopyranosyloxy)-3-methoxyphenyl]-2-propenoyl}oxy)-1,4,5-trihydroxycyclohexanecarboxylic acid531.17052531.170830.58C23H31O14529.15607529.156280.40C23H29O14(−): 193, 191
O82.59Dihydroxybenzoic acid glucoside isomer317.08701317.08671−0.95C13H17O9315.07189315.072160.85C13H15O9(−): 153, 109
O93.41Neochlorogenic acid355.10206355.102360.83C16H19O9353.08749353.087810.91C16H17O9(−): 191, 179, 173, 135
O103.814-O-caffeoyl-3-O-feruloylquinic acid531.17059531.170830.45C23H31O14529.15610529.156280.34C23H29O14(−): 191, 179, 173
O115.194-O-caffeoyl-3-O-feruloylquinic acid isomer531.17049531.170830.64C23H31O14529.15606529.156280.41C23H29O14(−): 191, 179, 173
O125.273-p-coumaroylquinic acid339.10747339.10744−0.08C16H19O8337.09277337.092890.35C16H17O8(−): 191, 163
O135.60Chlorogenic acid *355.10232355.102360.11C16H19O9353.08757353.087810.67C16H17O9(−): 191, 179, 173, 135
O145.835-O-feruloylquinic acid369.11802369.11801−0.02C17H21O9367.10306367.103461.08C17H19O9(−): 193, 191, 173, 149, 134
O155.85Cryptochlorogenic acid355.10257355.10236−0.59C16H19O9353.08759353.087810.62C16H17O9(−): 191, 179, 173, 135
O166.044-sinapoylquinic acid----397.11376397.114020.65C18H21O10(−): 223, 191, 169, 146
O176.17Caffeic acid *----179.03487179.034980.64C9H7O4(−): 135
O186.584-p-coumaroylquinic acid339.10753339.10744−0.25C16H19O8337.09281337.092890.26C16H17O8(−): 191, 163
O196.603,4-dicaffeoyl quinic acid isomer517.13521517.13405−2.24C25H25O12515.11895515.119501.07C25H23O12(−): 353, 191, 179, 135
O206.624-O-β-D-glucosyl-cis-p-coumaric acid----325.09285325.092890.13C15H17O8-
O216.672-hydroxy-1,4-phthalic acid----181.01400181.014251.39C8H5O5(−): 137
O226.923-O-feruloylquinic acid369.11805369.11801−0.12C17H21O9367.10342367.103460.10C17H19O9(−): 193, 191, 173, 134
O237.063-Sinapoylquinic acid399.12895399.12857−0.94C18H23O10397.11398397.114020.11C18H21O10(−): 223, 191, 169, 146
O247.23Dicaffeoyl quinic acid-glucopyranoside----677.17142677.172321.33C31H33O17-
O257.574-O-feruloylquinic acid369.11813369.11801−0.34C17H21O9367.10337367.103460.24C17H19O9(−): 193, 191, 173
O267.75Dicaffeoyl quinic acid-glucopyranoside----677.17156677.172321.13C31H33O17(−): 515
O278.05Dicaffeoyl quinic acid-glucopyranoside----677.17136677.172321.42C31H33O17(−): 515
O288.14Ferulic acid195.06547195.06519−1.46C10H11O4193.05029193.050631.79C10H9O4(−): 149
O298.42Ferulic acid isomer----193.05041193.050631.16C10H9O4(−): 149
O308.733,4-dicaffeoyl quinic acid517.13626517.13405−4.27C25H25O12515.11906515.119500.86C25H23O12(−): 353, 191, 179, 135
O319.133,5-dicaffeoyl quinic acid517.13648517.13405−4.69C25H25O12515.11893515.119501.11C25H23O12(−): 353, 191, 179, 135
O329.654,5-dicaffeoyl quinic acid517.13521517.13405−2.24C25H25O12515.11877515.119501.42C25H23O12(−): 353, 191, 179, 135
O339.993-O-caffeoyl-4-O-sinapoylquinic acid561.16097561.16027−1.26C27H29O13559.14509559.145711.12C27H27O13(−): 379, 364, 353, 335, 223, 205, 191, 179, 173, 164, 161, 155, 149, 137, 135
O3410.024-p-coumaroylquinic acid isomer339.10758339.10744−0.39C16H19O8-----
O3510.173,5-di-O-caffeoyl-4-O-(3-hydroxy-3-methyl) glutarylquinic acid661.17765661.17631−2.02C31H33O16659.16151659.161760.38C31H31O16(−): 353, 191
O3610.825-O-caffeoyl-4-O-sinapoylquinic acid561.16144561.16027−2.09C27H29O13559.14515559.145711.00C27H27O13(−): 379, 364, 353, 335, 223, 205, 191, 179, 173, 164, 161, 155, 149, 137, 135
O3711.175-O-caffeoyl-4-O-sinapoylquinic acid isomer561.16144561.16027−2.09C27H29O13559.14501559.145711.26C27H27O13(−): 379, 364, 353, 335, 223, 205, 191, 179, 173, 164, 161, 155, 149, 137, 135
O3812.55Phellinsin A or isomer359.07730359.07614−3.22C18H15O8357.06125357.061590.96C18H13O8(−): 339, 321, 313, 295
O3915.599,12-dihydroxy-13-oxooctadec-14-enoic acid329.23207329.232250.55C18H33O5327.21739327.217700.94C18H31O5(−): 291, 273, 247, 239, 229, 211, 209, 203, 197, 193, 183, 171
O4015.879,12-dihydroxy-13-oxooctadec-14-enoic acid isomer329.23259329.23225−1.03C18H33O5327.21725327.217701.37C18H31O5(−): 291, 273, 247, 239, 229, 211, 209, 203, 197, 193, 183, 171
O4117.049,12-dihydroxy-13-oxooctadecanoic acid353.22966353.229840.51 aC18H34NaO5329.23302329.233351.01C18H33O5(−): 311, 229, 211, 183, 171
O4218.719,12-dihydroxy-13-oxooctadecanoic acid isomer353.22964353.229840.59 aC18H34NaO5329.23322329.233350.40C18H33O5(−): 311, 229, 211
O4318.949,12-dihydroxy-13-oxooctadecanoic acid isomer353.22958353.229840.75 aC18H34NaO5329.23317329.233350.54C18H33O5(−): 311, 229, 211
O4419.649,12-dihydroxy-13-oxooctadecanoic acid isomer353.22977353.229840.20 aC18H34NaO5329.23308329.233350.80C18H33O5(−): 311, 229, 211
O4520.549,12-dihydroxy-13-oxooctadecanoic acid isomer353.22972353.229840.37 aC18H34NaO5329.23337329.23335−0.08C18H33O5(−): 311, 229, 211
O4623.27(9Z,12Z)-15,16-dihydroxyoctadeca-9,12-dienoic acid335.21901335.219280.80 aC18H32NaO4311.22236311.222781.36C18H31O4(−): 293, 275, 223, 205
O4725.009/12-Octadecanedioic acid or isomer337.23464337.234930.87 aC18H34NaO4313.23799313.238431.42C18H33O4(−): 295, 277
O4825.309/12-Octadecanedioic acid or isomer337.23471337.234930.65 aC18H34NaO4313.23821313.238430.71C18H33O4(−): 295
O4929.94γ-Linolenic acid----277.21655277.217302.73C18H29O2(−): 233
O5030.69Linoleic acid----279.23222279.232952.62C18H31O2(−): 261
O5131.59Oleic acid283.26315283.263160.02C18H35O2281.24796281.248602.30C18H33O2-
a: [M + Na]+. -: not detected. * Compared with a reference standard.
Table 5. Phenylpropanoids and other compounds identified in Lanqin oral liquid by UHPLC-FT-ICR MS.
Table 5. Phenylpropanoids and other compounds identified in Lanqin oral liquid by UHPLC-FT-ICR MS.
No.RT (min)Identification[M-H]+[M-H]−Product Ion (m/z)
ObservedCalculatedError (ppm)FormulaObservedCalculatedError (ppm)Formula
OC10.90Arginine175.11906175.11895−0.61C6H15N4O2173.10429173.104400.63C6H13N4O2(+): 158
OC21.16Cytidine244.09273244.092800.28C9H14N3O5----(+): 112
OC31.37Tyrosine182.08116182.081170.07C9H12NO3----(+): 165, 147, 136
OC41.37Uridine245.07684245.07681−0.11C9H13N2O6243.06197243.062261.21C9H11N2O6(−): 110
OC51.39Adenosine268.10389268.104030.53C10H14N5O4----(+): 136
OC61.41Guanosine284.09891284.098940.11C10H14N5O5282.08390282.084391.74C10H12N5O5(−): 150, 133
OC71.60Unknown363.16472363.164960.66C16H27O9361.15007361.150410.94C16H25O9(−): 181, 137
OC82.05Phenylalanine hexose328.13890328.139080.55C15H22NO7326.12431326.124530.66C15H20NO7(−): 164
OC92.11Phenylalanine166.08639166.08626−0.82C9H12NO2----(+): 149
OC102.36Unknown363.16535363.16496−1.08C16H27O9361.15003361.150411.05C16H25O9(−): 181, 137
OC112.824-(2-hydroxyethyl)phenyl 6-O-apiofuranosyl-β-D-glucopyranoside433.17064433.17044−0.47C19H29O11477.16109477.161360.57 cC20H29O13(−): 431, 293
OC122.881-O-syringoyl-β-D-glucopyranoside361.11286361.112920.18C15H21O10359.09821359.098370.43C15H19O10(−): 197
OC133.81Tryptophan205.09704205.097150.57C11H13N2O2203.08247203.082600.67C11H11N2O2(+): 188, 146
P14.40Esculin341.08642341.086710.85C15H17O9339.07211339.072160.13C15H15O9(+): 179, 151, 133, 123
OC144.80Osmanthuside H----431.15579431.155890.23C19H27O11(−): 191, 149
P25.03Coniferin365.12059365.120690.27 aC16H22NaO8387.12932387.129670.90 cC17H23O10(−): 341, 179
OC155.13Darendoside A433.17064433.17044−0.47C19H29O11431.15566431.155890.52C19H27O11(−): 299, 191, 149
P35.18Liriodendrin isomer----787.26642787.266620.25 cC35H47O20(−): 741
OC165.39Darendoside A isomer433.17153433.17044−2.52C19H29O11431.15558431.155890.71C19H27O11(−): 299, 191, 149
P45.61Syringin390.17599390.17586−0.34 bC17H28NO9417.13995417.140240.68 cC18H25O11(−): 209
P56.09Esculetin *----177.01901177.019331.82C9H5O4(−): 149, 133
P66.18Clemastanin B----729.26007729.261141.46 cC33H45O18(−): 683, 521, 359, 329
OC176.41Unknown----563.16146563.161760.52 cC23H31O16(−): 517, 225
P76.42Lariciresinol-4′-O-β-D-glucoside----521.20303521.20284−0.37C26H33O11(−): 359
OC186.59Sinapyglucoside387.12897387.12857−1.03C17H23O10385.11395385.114020.17C17H21O10(−): 205
OC197.022-methyl-L-erythritol-4-O-(6-O-transsinapoyl)-β-D-glucopyranoside527.17422527.17351−1.34 aC22H32NaO13503.17659503.177010.85C22H31O13(−): 205
P87.09Liriodendrin----787.26595787.266620.85 cC35H47O20(−): 741
P97.275,5′-dimethoxy lariciresinol-4′-O-glucoside isomer605.22181605.22046−2.22 aC28H38NaO13581.22325581.223961.23C28H37O13(−): 415
P107.40(−)-Secoisolariciresinol 4-O-β-D-glucopyranoside----523.21827523.218490.41C26H35O11(−): 361
OC207.43Darendroside B----475.18169475.182100.87C21H31O12(−): 329
OC217.531-O-feruloyl heptopyranose409.11089409.11052−0.91 aC17H22NaO10385.11362385.114021.05C17H21O10(+): 387
P117.973,3′,4-trihydroxy-4-methoxy-7,7-epoxylignan or isomer331.15427331.15400−0.82C19H23O5329.13885329.139451.81C19H21O5(+): 316
P127.97Lariciresinol-4-O-β-D-glucoside----521.20218521.202841.27C26H33O11(−): 359
P138.065,5′-dimethoxy lariciresinol-4′-O-glucoside----581.22346581.223960.87C28H37O13(−): 419
P148.15Staunoside C----595.20287595.203230.60C28H35O14-
P158.16Prinsepiol----389.12383389.124190.92C20H21O8(−): 374, 359, 175, 151, 136
OC228.22Acteoside isomer647.19555647.19464−1.40 aC29H36NaO15623.19736623.198141.25C29H35O15(−): 461, 315, 179, 161
P168.23Conicaoside575.21087575.20990−1.69 aC27H36NaO12551.21302551.213400.70C27H35O12-
OC238.82Acteoside----623.19721623.198141.49C29H35O15(−): 461, 315, 179, 161
P178.87Isolariciresinol361.16492361.16456−0.98C20H25O6405.15502405.155491.16 cC21H25O8(−): 359
P188.91Pinoresinol-4-O-glucoside----519.18674519.187190.86C26H31O11(−): 357, 342, 151, 136
P199.08Aschantin401.16042401.15948−2.34C22H25O7----(−): 383
P209.12Acanthoside B603.20697603.20481−3.58 aC28H36NaO13579.20790579.208310.72C28H35O13(−): 417, 402, 387, 181, 166
P2110.308-hydroxypinoresinol375.14347375.143830.95C20H23O7373.12925373.129280.07C20H21O7(−): 313
P2210.388-hydroxysyringaresinol435.16542435.16496−1.07C22H27O9433.15003433.150410.87C22H25O9(−): 403, 385, 373, 358, 343, 325
P2310.38Pinoresinol-4-O-glucoside isomer----519.18688519.187190.58C26H31O11(−): 357
P2410.41Secoisolariciresinol----361.16543361.165660.65C20H25O6(−): 346, 165
P2510.47Hydroxymedioresinol----403.13921403.139841.58C21H23O8(−): 343
OC2410.52Leucosceptoside A or isomer639.22994639.22835−2.49C30H39O15637.21278637.213791.60C30H37O15(−): 461
F4010.60Syringetin347.07655347.07614−1.17C17H15O8345.06107345.061591.50C17H13O8(+): 332
P2610.93Lariciresinol-9-O-β-D-glucopyranoside523.21844523.21739−2.00C26H35O11521.20242521.202840.80C26H33O11(−): 506
P2711.243,3′,4-trihydroxy-4-methoxy-7,7-epoxylignan or isomer331.15428331.15400−0.85C19H23O5329.13936329.139450.27C19H21O5-
P2811.26Hydroxymedioresinol isomer----403.13953403.139840.77C21H23O8-
OC2511.58Cistanoside D----651.22826651.229441.81C31H39O15(−): 505
OC2612.49Isomartynoside----651.22861651.229441.27C31H39O15(−): 505
OC2713.28Ethyl caffeate----207.06606207.066281.08C11H11O4(−): 179, 161, 135
OC2813.49Variolaric acid315.05025315.04993−1.03C16H11O7313.03517313.035380.66C16H9O7(−): 269
P2914.09Unknown329.06581329.06558−0.71C17H13O7327.05071327.051030.95C17H11O7(−): 299, 283, 265, 255, 237, 222, 209
OC2916.83Lariciresinol361.16492361.16456−0.98C20H25O6359.14979359.150010.61C20H23O6(−): 329
OC3017.58Unknown729.14456729.145010.62C37H29O16727.12966727.130461.10C37H27O16(+): 553, 283
OC3119.81Unknown729.14475729.145010.35C37H29O16727.12995727.130460.70C37H27O16(+): 553, 283
a: [M + Na]+; b: [M + NH4]+; c: [M + HCOO]−. -: not detected. * Compared with a reference standard. P: phenylpropanoid; OC: other compound.
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Liu, T.; Lin, S. Systematic Screening of the Chemical Constituents of Lanqin Oral Liquid by Ultra-High-Performance Liquid Chromatography Combined with Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. Molecules 2023, 28, 7053. https://doi.org/10.3390/molecules28207053

AMA Style

Liu T, Lin S. Systematic Screening of the Chemical Constituents of Lanqin Oral Liquid by Ultra-High-Performance Liquid Chromatography Combined with Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. Molecules. 2023; 28(20):7053. https://doi.org/10.3390/molecules28207053

Chicago/Turabian Style

Liu, Ting, and Shu Lin. 2023. "Systematic Screening of the Chemical Constituents of Lanqin Oral Liquid by Ultra-High-Performance Liquid Chromatography Combined with Fourier Transform Ion Cyclotron Resonance Mass Spectrometry" Molecules 28, no. 20: 7053. https://doi.org/10.3390/molecules28207053

APA Style

Liu, T., & Lin, S. (2023). Systematic Screening of the Chemical Constituents of Lanqin Oral Liquid by Ultra-High-Performance Liquid Chromatography Combined with Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. Molecules, 28(20), 7053. https://doi.org/10.3390/molecules28207053

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