Simultaneous Analysis of Seventeen Chemical Ingredients of Ligusticum chuanxiong by On-Line High Performance Liquid Chromatography-Diode Array Detector-Mass Spectrometry

Abstract

An on-line high performance liquid chromatography (HPLC)-diode array detector (DAD)-mass spectrometry (MS) analytical method has been developed to simultaneously separate and identify seventeen main constituents of Chuanxiong (Ligusticum chuanxiong Hort.), a traditional Chinese medicinal herb. In three Chuanxiong samples, nine compounds were unequivocally determined as vanillin (1), ferulic acid (2), senkyunolide I (4), senkyunolide H (5), senkyunolide A (6), coniferyl ferulate (7), Z-ligustilide (8), neocnidilide (9) and 3-butylidenephthalide (10) by comparing their t_R, UV, and MS data with those obtained for the authentic compounds. Furthermore, additional eight compounds were tentatively identified as senkyunolide J (11), senkyunolide F (12), 3-butylphthalide (13), cnidilide (14), riligustilide (15) or Z,Z′-6,8′,7,3′-diligustilide (16), tokinolide B (17), levistolide A (18) and senkyunolide P (19), based on their MS data and the comparison of their UV spectra with the published references. This is the first report to describe the development of an on-line HPLC-DAD-MS method to simultaneously analyse seventeen main constituents present in Chuanxiong and to construct the chemical profiles of various Chuanxiong samples.

HPLC-DAD-MS - Chuanxiong - phthalides - Ligusticum chuanxiong - Umbelliferae

References

• 1 The State Pharmacopoeia Commission of P. R. China. Pharmacopoeia of the People’s Republic of China. Vol. 1 Beijing; Chemical Industry Press 2000: 37
• 2 Sun S R, Huang X, Zhang L. Quantitative analysis of ferulic acid in serum after oral administration of decoction of both Ligusticum chuanxiong and Salvia miltiorrhiza root in patients with blood stasis by HPLC.  Journal of Chinese Material Medica. 2002;  33 223-5
• 3 Wang P S, Gao Y X, Wang Y X, Yoshiyasu F, Iwao M, Michiharu S. Phthalides from the rhizome of Ligusticum wallichi .  Phytochemistry. 1984;  23 2033-8
• 4 Wang P S. Survey of investigation on chemical principles and biological activities of Ligusticum wallichi .  Chinese Pharmaceutical Industry. 1988;  19 553-9
• 5 Kobayashi M, Fujita M, Mitsuhashi H. Studies on the constituents of Umbelliferae plants. XV. Constituents of Cnidium officinale: Occurrence of pregnenolone, coniferyl ferulate and hydroxyphthalides.  Chem Pharm Bull. 1987;  35 1427-33
• 6 Kobayashi M, Mitsuhashi H. Studies on the constituents of Umbelliferae plants. XVII. Structures of three new ligustilide derivatives from Ligusticum wallichi .  Chem Pharm Bull. 1987;  35 4789-92
• 7 Kaouadji M, De Pachtere F, Pouget C, Chulia A J. Three additional phthalide derivatives, an epoxymonomer and two dimers, from Ligusticum wallichi rhizomes.  J Nat Prod. 1986;  49 872-7
• 8 Naito T, Katsuhara T, Niitsu K, Ikeya Y, Okada M, Mitsuhashi L H. Phthalide dimers from Ligusticum chuanxiong Hort.  Heterocycles. 1991;  32 2433-42
• 9 Naito T, Kubota K, Shimoda Y, Sato T, Ikeya Y, Okada M ,. et al . Effects of constituents in a Chinese crude drug, ligustici chuanxiong rhizoma on vasocontraction and blood viscosity.  Nat Med. 1995;  49 288-92
• 10 Sun X G, Wang T, Zhu J S. Determination of tetramethylpyrazine in Ligusticum chuanxiong Hort. by RP-HPLC coupled with countercurrent extraction.  Acta Univ Med Tongji. 2001;  30 209-10
• 11 Zhao Z C, Yu H Q, Lu K P, Yang S N. Determination of tetramethylpyrazine in traditional Chinese medicines by HPLC.  J Tradit Chin Med. 1991;  16 7299-300
• 12 Naito T, Sakata M, Ikeya Y, Okada M, Maruno M. Quantitative analysis of effective constituents for blood circulation in cnidii rhizoma and ligustici rhizoma - Comparison of the contents of constituents in commercial cnidii rhizoma and ligustici rhizoma.  Nat Med. 1995;  49 425-30
• 13 Chen Y, Yang X, Han F M, Cheng Z Y. Determination of ligustrazin and ferulic acid in Chuanxiong rhizome by capillary electrophoresis.  Acta Pharmaceutica Sin. 1999;  34 699-701
• 14 Li H X, Ding M Y, Lu K, Yu J Y. Determination of the active ingredients in Chuanxiong by HPLC, HPLC-MS, and EI-MS.  J Liq Chromatogr R T. 2001;  24 2017-31
• 15 Li H X, Ding M Y, YU J Y. Separation and identification of the phthalic anhydride derivatives of Liguticum chuanxiong Hort. by GC-MS, TLC, HPLC-DAD, and HPLC-MS.  J Chromatogr Sci. 2002;  40 156-61
• 16 Li Z W, Zhang Q. Separation and identification of lactone components in Ligusticum chuanxiong Hort. and Cnidium officinale Mak. by GC-MS.  Chinese Journal of Pharmaceutical Analysis. 1993;  13 187-9
• 17 Lin L Z, He X G, Lian L Z, King W, Elliott J. Liquid chromatographic-electrospray mass spectrometric study of the phthalides of Angelica sinensis and chemical changes of Z-ligustilide.  J Chromatogr A. 1998;  810 71-9
• 18 He X G. On-line identification of phytochemical constituents in botanical extracts by combined high-performance liquid chromatographic-diode array detection-mass spectrometric techniques.  J Chromatogr A. 2000;  880 203-32
• 19 Naito T, Katsuhara T, Niitsu K, Ikeya Y, Okada M, Mitsuhashi H. Two phthalides from Ligusticum chuanxiong .  Phytochemistry. 1992;  31 639-42
• 20 Peking Institute of Pharmaceutical I ndustries. Structure elucidation and synthesis of tetramethylpyrazine.  Journal of Chinese Material Medica. 1977;  8 150-2