Analysis of the chemical composition of Angelicae Pubescentis Radix by ultra-performance liquid chromatography and quadrupole time-of-flight tandem mass spectrometry

doi:10.5246/jcps.2019.03.014

Abstract

Abstract:

Angelicae Pubescentis Radix(APR, Duhuo) is a commonly used traditional Chinese medicine and usually used for the treatments of rheumatic diseases. To assess the chemical composition of APR extract, a sensitive and reliable UPLC-Q-TOF-MS method was used for qualitative analysis. The separation was achieved on an Agilent SB-C₁₈ column (1.8 μm, 2.1 mm×50 mm) with a gradient elution system consisting of acetonitrile and water containing 0.1% formic acid. An electrospray ionization (ESI) was used for mass spectrometer, and the data were collected in the positive ion mode, which was operated in a full-scan mode at m/z 100–800. A total of 49 compounds including 46 coumarins were identified according to the MS and MS/MS data. Among them, two were new compounds, and isoangenomalin, scoparone, 4-methyl-umbelliferyl acetate, suberenol, trans-dehydroosthol, and oroselone were first reported in APR.

Key words: Angelicae Pubescentis Radix, UPLC/Q-TOF-MS, Chemical composition

CLC Number:

R284

Supporting:

Meiqi Wan, Youbo Zhang, Yanfang Yang, Xiaoyan Liu, Lingyun Jia, Xiuwei Yang. Analysis of the chemical composition of Angelicae Pubescentis Radix by ultra-performance liquid chromatography and quadrupole time-of-flight tandem mass spectrometry[J]. Journal of Chinese Pharmaceutical Sciences, 2019, 28(3): 145-159.

References

[1] Chinese Pharmacopoeia Commission. Pharmacopoeia of the People’s Republic of China. Volume I. Bejing, China: China Medical Science and Technology Press. 2015, 263.

[2] Li, X.R.; Wang, J.N.; Gao, L. Anti-inflammatory and analgesic activity of R.A.P. (Radix Angelicae Pubescentis) ethanol extracts. Afr. J. Tradit. Complement. Altern. Med. 2013, 10, 422-426.

[3] Li, R.L.; Zhao, C.; Yao, M.N.; Song, Y.; Wu, Y.; Wen, A.D. Analgesic effect of coumarins from Radix angelicae pubescentis is mediated by inflammatory factors and TRPV1 in a spared nerve injury model of neuropathic pain. J. Ethnopharmacol. 2017, 195, 81-88.

[4] Pei, Y.; Ma, X.D.; Yi, J.; Li, S.; Wang, S.Y.; Ma, J. Effects of Angelica pubescens coumarins on anti-oxidation function and excitatory amino acid glutamic acid content of Parkinson’s rat model. Chin. J. Gerontol. 2014, 34, 1272-1274.

[5] Liu, J.H.; Zschocke, S.; Reininger, E.; Bauer, R. Inhibitory effects of Angelica pubescens f. biserrata on 5-lipoxygenase and cyclooxygenase. Planta Med. 1998, 64, 525-529.

[6] Liao, J.F.; Jan, Y.M.; Huang, S.Y.; Wang, H.H.; Yu, L.L.; Chen, C.F. Evaluation with receptor binding assay on the water extracts of ten CNS-active Chinese herbal drugs. Proc. Natl. Sci. Counc. Repub. China B. 1995, 19, 151-158.

[7] Pei, Y.; Li, D.X.; Sun, S.H. Experimental study on the effect of Radix Angelicae Pubescentis and its alcohol extract on apoptosis of brain cells in nature aging mice. Chin. J. Gerontol. 2005, 8, 959.

[8] Hu, Y.; Zhao, D.; Zhang, X.D.; Sun, D.; Hao, H.G.; Yang, J.X. Different extracts of Angelica pubescens inhibit H2O2-induced SH-SY5Y cells injury. Chin. J. Exp. Tradit. Med. Form. 2013, 19, 184-188.

[9] Zhu, M.D.; Cui, J.P.; Wang, C.X. The experimental study of the intervention effect of Duhuo on immune damage of model rats suffering from Alzheimer. Liaoning J. Tradit. Chin. Med. 2011, 38, 2085-2086.

[10] Lyu, S.; Ji, B.; Gao, W.W.; Chen, X.Q.; Xie, X.T.; Zhou, J.J. Effects of Angelicae Pubescentis and Loranthi Decotion on repairing knee joint cartilages in rats. J. Orthop. Surg. Res. 2017, 12, 189.

[11] Liu, J.H.; Zschocke, S.; Bauer, R. A Polyacetylenic acetate and a coumarin from Angelica pubescens f. biserrata. Phytochemistry. 1998, 49, 211-213.

[12] Mirunalini, S.; Krishnaveni, M. Coumarin: a plant derived polyphenol with wide biomedical applications. Int. J. Pharm. Technol. Res. 2011, 3, 1693-1696.

[13] Kao, S.J.; Su, J.L.; Chen, C.K.; Yu, M.C.; Bai, K.J.; Chang, J.H.; Bien, M.Y.; Yang, S.F.; Chien, M.H. Osthole inhibits the invasive ability of human lung adenocarcinoma cells via suppression of NF-κB-mediated matrix metalloproteinase-9 expression. Toxicol. Appl. Pharmacol. 2012, 261, 105-115.

[14] Sumiyoshi, M.; Sakanaka, M.; Taniguchi, M.; Baba, K.; Kimura, Y. Anti-tumor effects of various furocoumarins isolated from the roots, seeds and fruits of Angelica and Cnidium species under ultraviolet A irradiation. J. Nat. Med. 2014, 68, 83-94.

[15] Hornick, A.; Lieb, A.; Vo, N.P.; Rollinger, J.M.; Stuppner, H.; Prast, H. The coumarin scopoletin potentiates acetylcholine release from synaptosomes, amplifies hippocampal long-term potentiation and ameliorates anticholinergic- and age-impaired memory. Neuroscience. 2011, 197, 28092.

[16] Jeong, H.J.; Na, H.J.; Kim, S.J.; Rim, H.K.; Myung, N.Y.; Moon, P.D.; Han, N.R.; Seo, J.U.; Kang, T.H.; Kim, J.J.; Choi, Y.; Kang, I.C.; Hong, S.H.; Kim, Y.A.; Seo, Y.W.; Kim, H.M.; Um, J.Y. Anti-inflammatory effect of Columbianetin on activated human mast cells. Biol. Pharm. Bull. 2009, 32, 1027-1031.

[17] Panno, M.L.; Giordano, F.; Mastroianni, F.; Palma, M. G.; Bartella, V.; Carpino, A.; Aquila, S.; Andò, S. Breast cancer cell survival signal is affected by bergapten combined with an ultraviolet irradiation. FEBS Lett. 2010, 584, 2321-2326.

[18] Wang, B.; Liu, X.H.; Zhou, A.; Meng, M.; Li, Q.L. Simultaneous analysis of coumarin derivatives in extracts of Radix Angelicae pubescentis (Duhuo) by HPLC-DAD-ESI-MSn technique. Anal. Methods. 2014, 6, 7996-8002.

[19] Shipchandler, M.; Soine, T.O. Coumarins. VI. A revised structure of columbianin and pertinent mass spectral studies. J. Pharm. Sci. 1968, 57, 747-752.

[20] Ge, A.H.; Ma, W.F.; Wang, C.P.; Li, J.; He, J.; Liu, E.W.; Adelakum, T.A.; Zhang, B.L.; Gao, X.M.; Chang, Y.X. Ultra high performance liquid chromatography with photodiode array detector and quadrupole time-of-flight tandem mass spectrometry coupled with discriminant analysis to evaluate Angelicae pubescentis radix from different regions. J. Sep. Sci. 2014, 37, 2523-2534.

[21] Wang, X.J.; Lv, H.; Sun, H.; Liu, L.; Sun, W.J.; Cao, H.X. Development of a rapid and validated method for investigating the metabolism of scoparone in rat using ultra-performance liquid chromatography/electrospray ionization quadruple time-of-flight mass spectrometry. Rapid. Commun. Mass Spectrom. 2007, 21, 3883-3890.

[22] Avula, B.; Chittiboyina, A.G.; Wang, Y.H.; Sagi, S.; Raman, V.; Wang, M.; Khan, I.A. Simultaneous Determination of Aegeline and Six Coumarins from Different Parts of the Plant Aegle marmelos Using UHPLC-PDA-MS and Chiral Separation of Aegeline Enantiomers Using HPLC-ToF-MS. Planta. Med. 2016, 82, 580-588.

[23] Ammar, S.; del Mar Contreras, M.; Belguith-Hadrich, O.; Segura-Carretero, A.; Bouaziz, M. Assessment of the distribution of phenolic compounds and contribution to the antioxidant activity in Tunisian fig leaves, fruits, skins and pulps using mass spectrometry-based analysis. Food Funct. 2015, 6, 3663-3677.

[24] Gao, D.; Wang, B.J.; Huo, Z.P.; He, Y.; Polachi, N.; Lei, Z.D.; Liu, X.X.; Song, Z.H.; Qi, L.W. Analysis of chemical constituents in an herbal formula Jitong Ning Tablet. J. Pharm. Biomed. Anal. 2017, 140, 301-312.

[25] Yang, Y.F.; Zhang, L.; Yang, X.W. Distribution Assessments of Coumarins from Angelicae Pubescentis Radix in Rat Cerebrospinal Fluid and Brain by Liquid Chromatography Tandem Mass Spectrometry Analysis. Molecules. 2018, 23, E225.

[26] Yang, Y.F.; Zhang, L.; Zhang, Y.B.; Yang, X.W. Simultaneous assessment of absorption characteristics of coumarins from Angelicae Pubescentis Radix: In vitro transport across Caco-2 cell and in vivo pharmacokinetics in rats after oral administration. J. Chromatogr. B Analyt. Technol. Biomed. Life Sci. 2017, 1060, 308-315.

[27] Li, J.; Chan, W. Investigation of the biotransformation of osthole by liquid chromatography/tandem mass spectrometry. J. Pharm. Biomed. Anal. 2013, 74, 156-161.

[28] Liu, J.H.; Zschocke, S.; Reininger, E.; Bauer, R. Comparison of Radix Angelicae pubescentis and Substitutes-Constituents and Inhibitory Effect on 5-lipoxygenase and Cyclooxygenase. Pharmaceutical. Biology. 1998, 36, 207-216.

[29] Liu, J.H.; Xu, S.X.; Yao, X.S.; Kobayashi, H. Angelol-type coumarins from Angelica pubescence F. biserrata and their inhibitory effect on platelet aggregation. Phytochemistry. 1995, 39, 1099-1101.

[30] Liu, Z.G.; Jiang, M.Y.; Lu, X.M.; Qin, F.; Song, Y.; Wen, J.; Li, F.M. Simultaneous determination of pimpinellin, isopimpinellin and phellopterin in rat plasma by a validated UPLC-MS/MS and its application to a pharmacokinetic study after administration of Toddalia asiatica extract. J. Chromatogr. B Analyt. Technol. Biomed. Life Sci. 2012, 891-892, 102-108.

[31] Smyth, T.J.; Ramachandran, V.; Brooks, P.; Smyth, W.F. Investigation of antibacterial phytochemicals in the bark and leaves of Ficus coronata by high-performance liquid chromatography-electrospray ionization-ion trap mass spectrometry (HPLC-ESI-MSn) and ESI-MS(n). Electrophoresis. 2012, 33, 713-718.

[32] Lee, M.K.; Ling, J.H.; Chun, M.H.; Jeong, J.H.; Na, Y.C.; Lee, K.W.; Jung, J.H.; Hong, J. Simultaneous determination of biological marker compounds in Ostericum koreanum by HPLC method and discrimination by principal component analysis. Bull Korean Chem. Soc. 2008, 29, 2465-2470.

[33] Chen, Y.; Fan, G.; Zhang, Q.; Wu, H.; Wu, Y. Fingerprint analysis of the fruits of Cnidium monnieri extract by high-performance liquid chromatography-diode array detection-electrospray ionization tandem mass spectrometry. J. Pharm. Biomed. Anal. 2007, 43, 926-936.

[34] Chen, Y.; Fan, G.R.; Zhang, Q.Y.; Wu, H.L.; Wu, Y.T. Determination of volatile flavor components in danggui cultivars by solvent free injection and hydrodistillation followed by gas chromatographic-mass spectrometric analysis. J. Chromatogr. A. 2006, 1116, 259-264.

[35] Song, G.S.; Jin, M.M.; Du, Y.F.; Cao, L.; Xu, H. UPLC-QTOF-MS/MS based screening and identification of the metabolites in rat bile after oral administration of imperatorin. J. Chromatogr. B Analyt. Technol. Biomed. Life Sci. 2016, 1022, 21-29.

[36] Ngo, L.; Tran, P.; Ham, S.H.; Cho, J.H.; Cho, H.Y.; Lee, Y.B. Simultaneous determination of imperatorin and its metabolite xanthotoxol in rat plasma and urine by LC-MS/MS and its application to pharmacokinetic studies. J. Chromatogr. B Analyt. Technol. Biomed. Life Sci. 2017, 1044-1045, 30-38.

[37] Huo, H.L.; Jia, P.P.; Zhang, X.X.; Zhang, Z.Y.; Yang, H.T.; Zhang, Q.Y.; Shi, H.; Zhang, L.T. Tentative identification of new metabolites of cnidilin by liquid chromatography-mass spectrometry. J. Chromatogr. B Analyt. Technol. Biomed. Life Sci. 2015, 995-996, 85-92.

[38] Yang, X.W.; Liu, Y.F.; Tao, H.Y.; Yang, Z.; Xiao, S.Y. GC-MS analysis of essential oils from Radix Angelicae Pubescentis. China J. Chin. Mater. Med. 2006, 31, 663-666.

[39] Yang, X.W.; Zhang, P.; Tao, H.Y.; Jiang, S.Y.; Zhou, Y. GC-MS analysis of essential oil constituents from Rhizome and Root of Notopterygium incisum. J. Chin. Pharm. Sci. 2006, 15, 172-177.

[40] Wu, X.W.; Zhang, Y.B.; Zhang, L.; Yang, X.W. Simultaneous quantification of 33 active components in Notopterygii Rhizoma et Radix using ultra high performance liquid chromatography with tandem mass spectrometry. J. Chromatogr. B Analyt. Technol. Biomed. Life Sci. 2018, 1092, 244-251.

[41] Yang, Y.F.; Xu, W.; Song, W.; Ye, M.; Yang, X.W. Transport of Twelve Coumarins from Angelicae Pubescentis Radix across a MDCK-pHaMDR Cell Monolayer-An in Vitro Model for Blood-Brain Barrier Permeability. Molecules. 2015, 20, 11719-11732.

[42] Dresler, S.; Bogucka-Kocka, A.; Kováčik, J.; Kubrak, T.; Strzemski, M.; Wójciak -Kosior, M.; Rysiak, A.; Sowa, I. Separation and determination of coumarins including furanocoumarins using micellar electrokinetic capillary chromatography. Talanta. 2018, 187, 120-124.

[43] Deng, G.G.; Yang, X.W.; Zhang, Y.B.; Xu, W.; Wei, W.; Chen, T.L. Chemical constituents from lipophilic parts in roots of Angelica dahurica var. formosana cv. Chuanbaizhi. China J. Chin. Mater. Med. 2015, 40, 2148-2156.