Determination of Flavonoids Compounds of Three Species and Different Harvesting Periods in Crataegi folium Based on LC-MS/MS
Abstract
:1. Introduction
2. Results and Discussion
2.1. The Results of Qualitative Analysis
2.1.1. Identification of Unique Compounds in Three Species of Crataegi folium
2.1.2. The Main Fragmentation Patterns of Representative Flavonoids Compounds
2.2. The Results of the Quantitative Analysis
2.2.1. Validated Method Data
2.2.2. The Content of Eight Flavonoids Compounds in Different Species of Crataegi folium
2.2.3. Comparative Analysis of Different Harvesting Periods of Crataegi folium
2.2.4. Comparison with the Content of Eight Flavonoids in Different Parts of CS and CK
2.2.5. The Content of Eight Flavonoids in the Leaves of CS and C. pinnatifida
3. Materials and Methods
3.1. Reagents and Materials
3.2. UPLC–Q-TOF–MS Analysis
3.3. UPLC–TQ–MS Analysis
3.4. Sample Preparation
3.5. Quantitative Method Validation
3.6. Data Analysis
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Sample Availability
References
- Liu, P.; Kallio, H.; Lü, D.; Zhou, C.; Yang, B. Quantitative analysis of phenolic compounds in Chinese hawthorn (Crataegus spp.) fruits by high performance liquid chromatography-electrospray ionisation mass spectrometry. Food Chem. 2011, 127, 1370–1377. [Google Scholar] [CrossRef]
- Liu, P.; Kallio, H.; Yang, B. Phenolic compounds in hawthorn (Crataegus grayana) fruits and leaves and changes during fruit ripening. J. Agric. Food Chem. 2011, 59, 11141–11149. [Google Scholar] [CrossRef]
- Wang, T.; An, Y.; Zhao, C.; Han, L.; Boakye-Yiadom, M.; Wang, W.; Zhang, Y. Regulation effects of Crataegus pinnatifida leaf on glucose and lipids metabolism. J. Agric. Food Chem. 2011, 59, 4987–4994. [Google Scholar] [CrossRef]
- Akila, M.; Devaraj, H. Synergistic effect of tincture of Crataegus and Mangifera indica L. extract on hyperlipidemic and antioxidant status in atherogenic rats. Vasc. Pharmacol. 2008, 49, 173–177. [Google Scholar] [CrossRef] [PubMed]
- Pittler, M.H.; Schmidt, K.; Ernst, E. Hawthorn extract for treating chronic heart failure: Meta-analysis of randomized trials. Am. J. Med. 2003, 114, 665–674. [Google Scholar] [CrossRef]
- Elango, C.; Devaraj, S.N. Immunomodulatory effect of Hawthorn extract in an experimental stroke model. J. Neuroinflammation. 2010, 30, 7–97. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Walker, A.F.; Marakis, G.; Simpson, E.; Hope, J.L.; Robinson, P.A.; Hassanein, M.; Simpson, H.C. Hypotensive effects of hawthorn for patients with diabetes taking prescription drugs: A randomised controlled trial. Br. J. Gen. Pract. 2006, 56, 437–443. [Google Scholar]
- Melikoğlu, G.; Bitiş, L.; Meriçli, A.H. Flavonoids of Crataegus microphylla. Nat. Prod. Res. 2004, 18, 211–213. [Google Scholar] [CrossRef]
- Ying, X.; Wang, R.; Xu, J.; Zhang, W.; Li, H.; Zhang, C.; Li, F. HPLC determination of eight polyphenols in the leaves of Crataegus pinnatifida Bge. var. major. J. Chromatogr. Sci. 2009, 47, 201–205. [Google Scholar] [CrossRef] [Green Version]
- Zhang, P.C.; Xu, S.X. C-glucoside flavonoids from the leaves of Crataegus pinnatifida Bge. var. major N.E.Br. J. Asian Nat. Prod. Res. 2003, 5, 131–136. [Google Scholar] [CrossRef]
- Veveris, M.; Koch, E.; Chatterjee, S.S. Crataegus special extract WS 1442 improves cardiac function and reduces infarct size in a rat model of prolonged coronary ischemia and reperfusion. Life Sci. 2004, 74, 1945–1955. [Google Scholar] [CrossRef]
- Dong, P.; Pan, L.; Zhang, X.; Zhang, W.; Wang, X.; Jiang, M.; Chen, Y.; Duan, Y.; Wu, H.; Xu, Y.; et al. Hawthorn (Crataegus pinnatifida Bunge) leave flavonoids attenuate atherosclerosis development in apoE knock-out mice. J. Ethnopharmacol. 2017, 198, 479–488. [Google Scholar] [CrossRef] [PubMed]
- Li, P.; Wang, J.; Lu, S.; Fu, J.; Liu, J. Protective effect of hawthorn leaf procyanidins on cardiomyocytes of neonatal rats subjected to simulated ischemia-reperfusion injury. Zhongguo Zhong Yao Za Zhi. 2009, 34, 96–99. [Google Scholar] [PubMed]
- Asgary, S.; Naderi, G.H.; Sadeghi, M.; Kelishadi, R.; Amiri, M. Antihypertensive effect of Iranian Crataegus curvisepala Lind.: A randomized, double-blind study. Drugs Exp. Clin. Res. 2004, 30, 221–225. [Google Scholar]
- Fu, J.H.; Zheng, Y.Q.; Li, P.; Li, X.Z.; Shang, X.H.; Liu, J.X. Hawthorn leaves flavonoids decreases inflammation related to acute myocardial ischemia/reperfusion in anesthetized dogs. Chin. J. Integr. Med. 2013, 19, 582–588. [Google Scholar] [CrossRef] [PubMed]
- Tadić, V.M.; Dobrić, S.; Marković, G.M.; Dordević, S.M.; Arsić, I.A.; Menković, N.R.; Stević, T. Anti-inflammatory, gastroprotective, free-radical-scavenging, and antimicrobial activities of hawthorn berries ethanol extract. J. Agric. Food Chem. 2008, 56, 7700–7709. [Google Scholar] [CrossRef] [PubMed]
- Pittler, M.H.; Guo, R.; Ernst, E. Hawthorn extract for treating chronic heart failure. Cochrane Database Syst. Rev 2008, 1, CD005312. [Google Scholar]
- Ma, G.; Jiang, X.H.; Chen, Z.; Ren, J.; Li, C.R.; Liu, T.M. Simultaneous determination of vitexin-4”-O-glucoside and vitexin-2”-O-rhamnoside from Hawthorn leaves flavonoids in rat plasma by HPLC method and its application to pharmacokinetic studies. J. Pharm. Biomed. Anal. 2007, 44, 243–249. [Google Scholar] [CrossRef] [PubMed]
- Ying, X.; Gao, S.; Zhu, W.; Bi, Y.; Qin, F.; Li, X.; Li, F. High-performance liquid chromatographic determination and pharmacokinetic study of vitexin-2”-O-rhamnoside in rat plasma after intravenous administration. J. Pharm. Biomed. Anal. 2007, 44, 802–806. [Google Scholar] [CrossRef]
- Liu, W.; Chen, G.; Cui, T. Determination of flavones in Crataegus pinnatifida by capillary zone electrophoresis. J. Chromatogr. Sci. 2003, 41, 87–91. [Google Scholar] [CrossRef] [Green Version]
- Wen, L.; Lin, Y.; Lv, R.; Yan, H.; Yu, J.; Zhao, H.; Wang, X.; Wang, D. An Efficient Method for the Preparative Isolation and Purification of Flavonoids from Leaves of Crataegus pinnatifida by HSCCC and Pre-HPLC. Molecules 2017, 22, 767. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Ying, X.; Lu, X.; Sun, X.; Li, X.; Li, F. Determination of vitexin-2”-O-rhamnoside in rat plasma by ultra-performance liquid chromatography electrospray ionization tandem mass spectrometry and its application to pharmacokinetic study. Talanta 2007, 72, 1500–1506. [Google Scholar] [CrossRef] [PubMed]
- Liu, H.; Liao, K.; Xiaoqin, A.; Shirong, Z.; Xiaolong, L. Pollen Viability in Three Xinjiang Hawthorn Species. J. Agric. Sci. & Tech. 2014, 15, 550–553. [Google Scholar]
- Plazas, E.; Casoti, R.; Avila, M.; Batista Da Costa, F.; Cuca, L.E. Metabolomic profiling of Zanthoxylum species: Identification of anti-cholinesterase alkaloids candidates. Phytochemistry 2019, 168, 112128. [Google Scholar] [CrossRef]
- Wiklund, S.; Johansson, E.; Sjöström, L.; Mellerowicz, E.J.; Edlund, U.; Shockcor, J.P.; Gottfries, J.; Moritz, T.; Trygg, J. Visualization of GC/TOF-MS-based metabolomics data for identification of biochemically interesting compounds using OPLS class models. Anal. Chem. 2008, 80, 115–122. [Google Scholar] [CrossRef] [PubMed]
- Arapitsas, P.; Ugliano, M.; Marangon, M.; Piombino, P.; Rolle, L.; Gerbi, V.; Versari, A.; Mattivi, F. Use of Untargeted Liquid Chromatography-Mass Spectrometry Metabolome To Discriminate Italian Monovarietal Red Wines, Produced in Their Different Terroirs. J. Agric. Food Chem. 2020, 68, 13353–13366. [Google Scholar] [CrossRef] [PubMed]
- Prinz, S.; Ringl, A.; Huefner, A.; Pemp, E.; Kopp, B. 4”-Acetylvitexin-2”-O-rhamnoside, isoorientin, orientin, and 8-methoxykaempferol-3-O-glucoside as markers for the differentiation of Crataegus monogyna and Crataegus pentagyna from Crataegus laevigata (Rosaceae). Chem. Biodivers. 2007, 4, 2920–2931. [Google Scholar] [CrossRef] [PubMed]
- Løvdal, T.; Olsen, K.M.; Slimestad, R.; Verheul, M.; Lillo, C. Synergetic effects of nitrogen depletion, temperature, and light on the content of phenolic compounds and gene expression in leaves of tomato. Phytochemistry 2010, 71, 605–613. [Google Scholar] [CrossRef]
NO | Compound | RT (min) | Adducts | Formula | Fragmentation Ions | Mass Error (ppm) | m/z |
---|---|---|---|---|---|---|---|
1 | α-D-Gal-(→3)-α-D-Gal-OMe | 0.64 | M-H2O-H | C13H24O11 | 309(13), 191(100), 137(12), 125(7) | −2.53 | 337.1131 |
2 | (2S)-Hex-2-ulofuranosyl-4,6-dideoxyhexopyranoside | 0.96 | M-H | C12H22O9 | 309(100), 179(62), 129(97), 119(54), 89(53) | 2.92 | 309.1200 |
3 | Glucogallin | 1.24 | M-H | C13H16O10 | 331(89), 168(49), 149(100), 125(61), 107(1) | 6.54 | 331.0692 |
4 | Eucomic acid | 2.50 | M+FA-H | C11H12O6 | 285(80), 208(13), 152(52), 121(1), 108(100) | 3.75 | 285.0625 |
5 | 2-succinyl-6-hydroxycyclohexa-2,4-diene-1-carboxylic acid | 4.01 | M-H | C11H12O6 | 203(3), 179(7), 163(22), 119(100) | 3.62 | 239.0573 |
6 | (3R,5S,6S,7E,9S)-Megastigman-7-ene-3,5,6,9-tetrol-9-O-β-D-glucopyranoside | 4.49 | M+FA-H | C19H34O9 | 395(1), 167(28), 153(14), 145(100) | 0.12 | 451.2185 |
7 | Procyanidin B1 | 4.69 | M-H | C30H26O12 | 451(10), 425(86), 407(100), 289(91), 245(39), 125(60) | −3.90 | 577.1354 |
8 | Chlorogenic acid | 5.52 | M-H | C16H18O9 | 289(100), 205(18), 191(88), 123(51), 109(54) | 2.39 | 353.0887 |
9 | Procyanidin C1 | 7.00 | M-H | C45H38O18 | 695(15), 577(23), 451(23), 289(99), 125(66) | 4.79 | 865.2027 |
10 | (Z)-3-Hexenyl-O-β-D-xylopyranosyl-(1”→6’)-β-D-glucopyranoside | 8.02 | M+FA-H | C17H30O10 | 221(1), 172(100), 131(2), 101(27), 89(8) | 0.27 | 439.1822 |
11 | Rutin | 8.88 | M-H | C27H30O16 | 563(8), 463(9), 446(81), 299(100), 271(10) | 0.94 | 609.1467 |
12 | 2-O-{(2S,3R,4R)-4-[(α-L-arabinopyranosyloxy)methyl]-3,4-dihydroxytetrahydro-2-furanyl}-β-D-galactopyranoside | 9.15 | M-H2O-H | C32H38O21 | 739(100), 579(10), 569(30), 307(3) | −5.18 | 739.1688 |
13 | 7-O-rhamnogalactoside quercetin | 9.48 | M-H | C27H30O16 | 300(100), 271(17), 255(6), 243(1) | 0.42 | 609.1464 |
14 | 6-C-glucoside-8-C-xylsoyl apigenin | 10.00 | M+FA-H | C26H28O14 | 500(6), 446(60), 251(100), 117(82), 89(3) | 1.36 | 609.1469 |
15 | vitexin-2”-O-rhamnoside | 10.68 | M-H | C27H30O14 | 413(20), 341(1), 311(4), 293(100), 269(1), 173(1) | 0.30 | 577.1565 |
16 | vitexin | 10.70 | M-H2O-H | C21H20O10 | 341(1), 311(8), 293(100), 269(1), 117(1) | 4.34 | 413.0897 |
17 | Vitexin-2”-O-glucoside | 10.72 | M-H | C27H30O15 | 577(44), 413(19), 341(1), 311(8), 293(100), 117(1) | 0.66 | 593.1516 |
18 | 3-O-β-D-6”-acetylglucopyranoside quercetin | 12.10 | M-H | C23H22O13 | 463(1), 300(100), 271(51), 255(23), 243(6),151(5) | 0.86 | 505.0992 |
19 | Vitexin-3”-O-acetyl | 13.04 | M-H | C23H22O11 | 473(86), 413(23), 341(9), 311(96), 283(100), 161(9), 117(6) | 1.01 | 473.1094 |
20 | Picroside III | 14.49 | M-H | C25H30O13 | 462(2), 431(9), 316(1), 181(9), 153(100), 136(1) | −2.14 | 583.1674 |
21 | Vitexin-6”-O-acetyl | 15.53 | M-H | C23H22O11 | 413(27), 311(68), 283(100), 268(4) | 2.62 | 473.1102 |
22 | Linalyl rutinoside | 16.43 | M-H | C22H38O10 | 413(26), 371(5), 211(7), 197(7), 145(100) | 0.07 | 461.2393 |
23 | Madecassic acid | 18.31 | M-H | C30H48O6 | 503(100), 485(17), 441(23), 235(1) | −0.73 | 549.3435 |
24 | 2α,3β,19α-thihydroxyl ursolic acid | 19.14 | M-H | C30H48O5 | 487(100), 469(8), 443(1), 423(1) | 0.07 | 487.3429 |
25 | 3-O-t-p-Coumaroyltormentic acid | 19.60 | M-H | C39H54O7 | 633(100), 589(1),145(7), 119(1) | 2.22 | 679.3878 |
26 | (2α,3β)-2,19-Dihydroxy-3-{[(2Z)-3-(4-hydroxyphenyl)-2-propenoyl]oxy}urs-12-en-28-oic acid | 19.81 | M+FA-H | C39H54O7 | 633(100), 589(2),513(1), 145(16), 119(1) | 2.98 | 679.3871 |
27 | Jacoumaric acid | 20.03 | M-H | C39H54O6 | 617(100), 497(4), 472(49) | −1.09 | 617.3841 |
28 | (3β,5ξ,9ξ,14β)-3-Hydroxy-27-{[(2E)-3-(4-hydroxyphenyl)-2-propenoyl]oxy}urs-12-en-28-oic acid | 20.30 | M-H | C39H54O6 | 617(100),573(1), 497(2), 453(1), 145(22),117(2) | 1.56 | 617.3857 |
Analytes | Calibration Curves | r | Linear Range (μg/g) | Accuracy (n = 6) | Repeatability (n = 6) | Recovery (n = 6) | LOD (μg/g) | LOQ (μg/g) | |
---|---|---|---|---|---|---|---|---|---|
RSD% | RSD% | Mean | RSD% | ||||||
Epicatechin | y = 9.79038x + 2.87783 | 0.9998 | 0.50–500 | 1.88 | 2.07 | 99.9 | 2.21 | 0.10 | 0.25 |
Quercetin | y = 42.0891x + 107.983 | 0.9990 | 0.10–100 | 1.96 | 1.83 | 100.9 | 1.71 | 0.05 | 0.10 |
Vitexin | y = 37.7813x − 29.4584 | 0.9997 | 0.50–500 | 1.30 | 3.78 | 99.4 | 3.17 | 0.25 | 0.50 |
Isoquercetin | y = 12.0094x − 36.7965 | 0.9997 | 0.50–500 | 1.99 | 3.73 | 99.4 | 3.56 | 0.25 | 0.50 |
Hyperoside | y = 23.6934x − 14.5733 | 0.9991 | 0.50–500 | 1.65 | 1.59 | 98.3 | 3.66 | 0.25 | 0.50 |
vitexin-2”-O-rhamnoside | y = 25.0249x − 91.4384 | 0.9997 | 0.50–500 | 1.26 | 1.51 | 98.1 | 2.43 | 0.25 | 0.50 |
Vitexin-2”-O-glucoside | y = 22.8099x − 59.7038 | 0.9991 | 0.50–500 | 1.69 | 3.06 | 100.5 | 3.06 | 0.10 | 0.25 |
Rutin | y = 24.1448x − 28.9144 | 0.9997 | 0.25–500 | 1.87 | 1.41 | 100.4 | 1.53 | 0.10 | 0.25 |
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations. |
© 2021 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
Share and Cite
Guo, Y.-P.; Yang, H.; Wang, Y.-L.; Chen, X.-X.; Zhang, K.; Wang, Y.-L.; Sun, Y.-F.; Huang, J.; Yang, L.; Wang, J.-H. Determination of Flavonoids Compounds of Three Species and Different Harvesting Periods in Crataegi folium Based on LC-MS/MS. Molecules 2021, 26, 1602. https://doi.org/10.3390/molecules26061602
Guo Y-P, Yang H, Wang Y-L, Chen X-X, Zhang K, Wang Y-L, Sun Y-F, Huang J, Yang L, Wang J-H. Determination of Flavonoids Compounds of Three Species and Different Harvesting Periods in Crataegi folium Based on LC-MS/MS. Molecules. 2021; 26(6):1602. https://doi.org/10.3390/molecules26061602
Chicago/Turabian StyleGuo, Ya-Ping, Hong Yang, Ya-Li Wang, Xiao-Xiang Chen, Ke Zhang, Yan-Li Wang, Yi-Fan Sun, Jian Huang, Lu Yang, and Jin-Hui Wang. 2021. "Determination of Flavonoids Compounds of Three Species and Different Harvesting Periods in Crataegi folium Based on LC-MS/MS" Molecules 26, no. 6: 1602. https://doi.org/10.3390/molecules26061602