HPLC-DAD-ESI-MSn技术对橘叶(福橘叶)中96个化学成分的快速分离和鉴定

doi:10.5246/jcps.2016.02.010

摘要/Abstract

摘要：

为了对橘叶(福橘叶)中的化学成分进行较为系统地研究,我们首次采用液质联用技术((HPLC-DAD-ESI-MSⁿ)系统地分离和鉴定了橘叶中的化学成分。最终,我们在橘叶中解析了96个化学成分,包括: 31个酚酸类化合物, 4个黄酮苷元, 6个黄酮单氧苷, 10个黄酮双氧苷, 5个黄酮单碳苷和5个黄酮双碳苷化合物,以及6个黄酮碳氧苷, 5个3-羟基-3-甲基戊二酰基取代的黄酮苷, 1个黄烷-3-醇和2个生物碱类化合物,并且初步鉴定出了21个多甲基黄酮类化合物(PMFs)。在上述解析的96个化合物中, 52个化合物为首次在橘叶中发现, 15个化合物为首次在柑橘属植物中发现。同时,我们在橘叶中也发现了9个潜在的新化合物。

关键词: 橘叶(福橘叶), HPLC-DAD-ESI-MSn, 黄酮碳氧苷, 多甲基黄酮类化合物

Abstract:

In order to systematically investigate the chemical constituents of Citri Reticulatae Folium (leaves of ‘Fuju’), an analytical method that included high-performance liquid chromatography, diode array detection, electrospray ionization, and ion-trap time-of-flight mass spectrometry (HPLC-DAD-ESI-MSⁿ) was used to separate and identify the individual chemical components of Citri Reticulatae Folium. As a result, 96 compounds were tentatively identified in this study: including 31 phenolic acids, 4 flavonoid aglycones, 6 flavonoid mono-O-glycosides, 10 flavonoid-O-diglycosides, 5 flavonoid mono-C-glycosides, 5 flavonoid di-C-glycosides, 6 flavonoid O,C-glycosides, 5 (3-hydroxy-3-methylglutaryl) glycosyl flavonoids, 1 flavan-3-ol,and 2 alkaloids. In addition, 21 polymethoxy flavonoids (PMFs) were identified in this paper. Among these compounds, 52 compounds, which were previouslyfound in other Citrus plants, have been identified for the first time in Citri Reticulatae Folium. 15 compounds have not been previously found in theCitrusgenus were identified. Moreover, 9 potentially new compounds have also been detected in this paper. This is the first report of the full characterization of chemical components of Citri Reticulatae Folium (leaves of ‘Fuju’) by HPLC-DAD-ESI-MSⁿ.

Key words: Citri Reticulatae Folium (leaves of ‘Fuju’), HPLC-DAD-ESI-MSn, Flavonoid, O,C-Glycosides, PMFs

中图分类号:

R284

Supporting:

曹规划, 付庆荣, 张藏曼, 王弘, 陈世忠. HPLC-DAD-ESI-MSn技术对橘叶(福橘叶)中96个化学成分的快速分离和鉴定[J]. 中国药学(英文版), 2016, 25(2): 91-110.

Guihua Cao, Qingrong Fu, Cangman Zhang, Hong Wang, Shizhong Chen. Rapid characterization of 96 chemical constituents in Citri Reticulatae Folium (leaves of ‘Fuju’) using HPLC-DAD-ESI-MSn[J]. Journal of Chinese Pharmaceutical Sciences, 2016, 25(2): 91-110.

参考文献

[1] Roowi, S.; Crozier, A. J. Agric. Food Chem. , 59, 12217-12225.2011

[2] Tripoli, E.; Guardia, M.L.; Giammanco, S.; Majo, D.D.; Giammanco, M. Food Chem. , 104, 466-479.2007

[3] Khan, M.K.; Huma, Z.E.; Dangles, O. J. Food Compos. Anal. , 33, 85-104.2014

[4] Duan, L.; Guo, L.; Liu, K.; Liu, E.H.; Li, P. J. Chromatogr. A. , 1339, 118-127.2014

[5] He, X.G.; Lian, L.Z.; Lin, L.Z.; Bernart, M.W. J. Chromatogr. A. 1997, 791, 127-134.

[6] Bocco, A.; Cuvelier, M.E.; Richard, H.; Berset, C. J. Agric. Food Chem. 1998, 46, 2123-2129.

[7] Jeong, S.M.; Kim, S.Y. J. Agric. Food Chem. 2004, 52, 3389-3393.

[8] Manthey, J.A.; Grohmann, K. J. Agric. Food Chem. 2001, 49, 3268-3273.

[9] Stuetz, W.; Prapamontol, T. J. Agric. Food Chem. 2010, 58, 6069-6074.

[10] Barreca, D.; Bisignano, C; Ginestra, G. Food Chem. 2013, 141, 1481-1488.

[11] Zhang, J.Y.; Zhang, Q.; Zhang, H.X. J. Agric. Food Chem. 2012, 60, 9023-9034.

[12] Xiao, H.; Yang, C.S.; Li, S.; Jin, H.; Ho, C.T.; Patel, T. Mol. Nutr. Food Res. 2009, 53, 398-406.

[13] Nakagawa, H.; Takaishi, Y.; Tanaka, N. J. Nat. Prod. 2006, 69, 1177-1179.

[14] Zheng, G.D.; Zhou, P.; Yang, H.; Li, Y.S.; Li, P.; Liu, E.H. Food Chem. 2013, 136, 604-611.

[15] Ding, L.; Luo, X.B.; Tang, F.; Yuan, J.B.; Liu, Q.; Yao, S.Z. J. Chromatogr. B. 2007, 857, 202-209.

[16] Wang, S.F.; Chen, P.H.; Jiang, W.; Wu, L.H.; Chen, L.L. J. Chromatogr. A. 2014, 1348, 105-124.

[17] Kawaii, S.; Tomono, Y.; Katase, E. J. Agric. Food Chem. 2000, 48, 3865-3871.

[18] Manthey, J.A.; Grohmann, K.; Berhow, M.A.; Tisserat, B. Plant Physiol. Biochem. 2000, 38, 333-343.

[19] Chen, J.; Montanari, A.M. J. Agric. Food Chem. 1998, 46, 1235-1238.

[20] Lin, L.Z.; Harnly, J.M. J. Agric. Food Chem. 2007, 55, 1084-1096.

[21] Bengoechea, L.; Hernandez, T.; Quesada, C. Chromatographia. 1995, 41, 94-98.

[22] Lorenz, P.; Conrad, J.; Bertrams, J. Phytochem. Anal. 2012, 23, 60-71.

[23] Duenas, M.; Fernandez, D.; Hernandez, T.; Estrella, I.; Munoz, R. J. Sci. Food Agric. 2005, 85, 297-304.

[24] Risch, B.; Herrmann, K.; Wray, V.; Grotjahn, L. Phytochemistry. 1987, 26, 509-510.

[25] Zhao, H.Y.; Fan, M.X.; Wu, X.; Wang, H.J.; Yang, J.; Si, N.; Bian, B.L. J. Chromatogr. Sci. 2013, 51, 273-285.

[26] Jaiswal, R.; Kuhnert, N. J. Agric. Food Chem. 2014, 62, 1261-1271.

[27] Abrosca, B.D.; Fiorentino, A.; Ricci, A.; Scognamiglio, M. Phytochem. Lett. 2010, 3, 38-44.

[28] Pacifico, S.; Gallicchio, M.; Lorenz, P. Chem. Res. Toxicol. 2014, 27, 611-626.

[29] Zhao, X.; Long, Z.M.; Dai, J.N.; Bi, K.S.; Chen, X.H. Rapid Commun. Mass Spectrom. 2012, 26, 2443-2453.

[30] Seo, O.N.; Kim, G.S.; Kim, Y.H. J. Funct. Foods. 2013, 5, 1741-1750.

[31] Clifford, M.N.; Johnston, K.L.; Knight, S.; Kuhnert, N. J. Agric. Food Chem. 2003, 51, 2900-2911.

[32] Vilaplana, A.G.; Valentao, P.; Moreno, D.A. J. Agric. Food Chem. 2012, 60, 6571-6580.

[33] Kuhnert, N.; Jaiswal, R.; Matei, M.F.; Sovdat, T.; Deshpande, S. Rapid Commun. Mass Spectrom. 2010, 24, 1575-1582.

[34] Parveen, I.; Threadgill, M.D.; Hauck, B.; Donnison, I.; Winters, A. Phytochemistry. 2011, 72, 2376-2384.

[35] Arroyo, S.F.; Catalan, E.B.; Micol, V.; Carretero, A.S.; Gutierrez, A.F. Phytochem. Anal. 2010, 21, 307-313.

[36] Hvattum, E.; Ekeberg, D. J. Mass Spectrom. 2003, 38, 43-49.

[37] Cuyckens, F.; Rozenberg, R.; Hoffmann, E.; Claeys, M. J. Mass Spectrom. 2001, 36, 1203-1210.

[38] March, R.; Lewars, E.G.; Stadey, C.J.; Miao, X.S.; Zhao, X.M.; Metcalfe, C.D. Int. J. Mass Spectrom. 2006, 248, 61-85.

[39] Cuyckens, F.; Claeys, M. Phytochem. Anal. 2001, 12, 159-165.

[40] Voirin, B. Phytochemistry. 1984, 23, 2237-2251.

[41] Voirin, B. Phytochemistry. 1983, 22, 2107-2145.

[42] Mandalari, G.; Bennett, R.N.; Bisiganno, G. J. Agric. Food Chem. 2006, 54, 197-203.

[43] Garcia, B.A.; Berrueta, L.A.; Lobato, S.G.; Urkaregi, A.; Gallo, B.; Vicente, F. J. Agric. Food Chem. 2012, 60, 3635-3644.

[44] Dugo, P.; Presti, M.L.; Ohman, M. J. Sep. Sci. 2005, 28, 1149-1156.

[45] Kim, G.O.; Han, J.H.; Ko, G.H. Repub. Korean Kongkae Taeho Kongbo KR 2009081287 A 20090728, 2009.

[46] Wang, Z.D.; Shang, Q.K.; Wang, W.L.; Feng, X.J. J. Food Process Eng. 2011, 34, 844-859.

[47] Kuroyanagi, M.; Ishii, H.; Kawahara, N. J. Nat. Med. 2008, 62, 107-111.

[48] Garcia, B.A.; Lobato, S.G.; Berrueta, L.A.; Gallo, B.; Vicente, F. Talanta. 2012, 99, 213-224.

[49] Ferreres, F.; Izquierdo, A.G.; Andrade, P.B.; Valentao, P.; Barberan, F.A.T. J. Chromatogr. A. 2007, 1161, 214-223.

[50] Ferreres, F.; Izquierdo, A.G.; Vinholes, J. Rapid Commun. Mass Spectrom. 2011, 25, 700-712.

[51] Jhoo, J.W.; Ang, C.Y.W.; Heinze, T.M. J. Food Sci. 2007, 72, 120-125.

[52] Anagnostopoulou, M.A.; Kefalas, P. Biomed. Chromatogr. 2012. 26, 1252-1268.

[53] Piccinelli, A.L.; Mesa, M.G. J. Agric. Food Chem. 2008, 56, 1574-1581.

[54] Reidah, I.M.A.; Contreras, M.D.M.; Roman, D.A. Electrophoresis. 2014, 35, 1571-1581.

[55] Anagnostopoulou, M.A.; Kefalas, P.; Kokkalou, E. Biomed. Chromatogr. 2005, 19, 138-148.

[56] Wu, L.Z.; Zhang, X.P.; Xu, X.D.; Zheng, Q.X.; Yang, J.S.; Ding, W.L. J. Pharm. Biomed. Anal. 2013, 75, 55-63.

[57] Mastubara, Y.; Sawabe, A.; Mizuno, T. Kinki Daigaku Igaku Zasshi. 1987, 12, 89-101.

[58] Matsubara, Y.; Kumamoto, H. Tennen Yuki Kagobutsu Toronkai Koen Yoshishu. 1985, 27, 702-709.

[59] Hou, B.; Li, Z.L.; Li, X. Acta Pharm. Sin. 2005, 40, 533-535.

[60] Liu, G.Q.; Dong, J.; Wang, H. Chem. J. Chinese U. 2009, 30, 1566-1570.

[61] Ferracin, R.J. Phytochemistry. 1998, 47, 393-396.

[62] Ribeiro, A.B.; Abdelnur, P.V. J. Agric. Food Chem. 2008, 56, 7815-7822.

[63] Chen, H.F.; Zhang, W.G.; Yuan, J.B. J. Pharm. Biomed. Anal. 2012, 59, 90-95.

[64] Nielsen, S.; Breinholt, V.; Cornett, C.; Dragsted, L.O. Food Chem. Toxicol. 2000, 38, 739-746.

[65] Sugiyama, S.; Umehara, K.; Kuroyanagi, M.; Ueno, A.; Taki, T. Chem. Pharm. Bull. 1993, 41, 714-719.

[66] Haggag, E.G.; Mahmoud, I.I.; Abou, M.E.A.; Mabry, T.J. Asian J. Chem. 1999, 11, 707-714.

[67] Hyon, J.S.; Kang, S.M.; Han, S.W. Hanˊguk Sikpˊum Yongyang Kwahak Hoechi. 2009, 38, 1310-1316.

[68] Wollenweber, E.; Roitman, J.N. Biochem. Syst. Ecol. 1996, 24, 479-480.

[69] Lichius, J.J.; Thoison, O.; Montagnac, A. J. Nat. Prod. 1994, 57, 1012-1016.

[70] Horie, T.; Tsukayama, M.; Nakayama, M. Bull. Chem. Soc. Jpn. 1982, 55, 2928-2932.

[71] Lin, Z.T.; Wang, H.; Xu, Y.; Dong, J. Food Chemistry. 2012, 134, 1181-1191.