SUN Jing-hui, WU Wei, GUO Ying-ying, QIN Qiu-jie, LIU Shu-ying. Differentiation of Ginsenoside Isomers Rh2 and CK Using ESI-Q-TOF-MS/MS[J]. Journal of Chinese Mass Spectrometry Society, 2014, 35(2): 158-162. DOI: 10.7538/zpxb.2014.35.02.0158
Citation: SUN Jing-hui, WU Wei, GUO Ying-ying, QIN Qiu-jie, LIU Shu-ying. Differentiation of Ginsenoside Isomers Rh2 and CK Using ESI-Q-TOF-MS/MS[J]. Journal of Chinese Mass Spectrometry Society, 2014, 35(2): 158-162. DOI: 10.7538/zpxb.2014.35.02.0158

Differentiation of Ginsenoside Isomers Rh2 and CK Using ESI-Q-TOF-MS/MS

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  • A rapid analysis method of electrospray-quadrupole-time-of-flight mass spectrometry (ESI-Q-TOF-MS/MS) was established to differentiate ginsenoside isomers Rh2 and compound K (CK). Based on the analysis of MS/MS product ions with different collision energy in both negative and positive ion mode, ginsenoside isomers Rh2 and CK are distinguished. The results show that the fragmentation pathway of Rh2 and CK in negative ion mode is similar. The difference is that the fragment ion abundance of Rh2 is significantly lower than that of CK with the same collision energy. The fragmentation behavior of Rh2 is different from CK in positive ion mode, specific fragment ions m/z 465 and m/z 203 are produced with collision energy 20, 40 and 60 eV in CK, but Rh2 produces the similar specific fragment ions only with collision energy 60 eV in MS/MS. The MS/MS fragmentation pathway is particularly useful in the identification of ginsenoside isomers Rh2 and CK.
  • [1]
    ATTELE A S, WU J A, YUAN C S. Ginseng pharmacology: Multiple constituents and multiple actions[J]. Biochemical Pharmacology, 1999, 58(11): 1685-1693.
    [2]
    CHRISTENSEN L P. Ginsenosides: Chemistry, biosynthesis, analysis, and potential health effects[J]. Advances in Food and Nutrition Research, 2008, 55: 1-99.
    [3]
    程慧,宋新波,张丽娟. 人参皂苷Rg3与Rh2的研究进展[J]. 药物评价研究,2010, 33(4): 307-311.CHENG Hui, SONG Xinbo, ZHANG Lijuan. Advances in research on the ginsenoside Rg3 and ginsenoside Rh2[J]. Drug Evaluation Research, 2010, 33(4): 307-311(in Chinese).
    [4]
    MUSENDE A G, EBERDING A, WOOD C, et al.Preclinical evaluation of Rh2 in PC-3 human xenograft model for prostate cancer in vivo: Formulation, pharmacokinetics, biodistribution and efficacy[J]. Cancer Chemother Pharmacol, 2009, 64(60): 1085-1095.
    [5]
    于雷,李成龙,于珊珊. 人参皂苷CK的研究进展[J]. 生物技术通报,2013, 1(1): 31-35.YU Lei, LI Chenglong, YU Shanshan. Advance on research of ginsenoside CK[J]. Biotechnology Bulletin, 2013, 1(1): 31-35(in Chinese).
    [6]
    CHAE S, KANG K A, CHANG W Y, et al. Effect of compound K, a metabolite of ginseng saponin, combined with gamma-ray radiation in human lung cancer cells in vitro and in vivo[J]. J Agric Food Chem, 2009, 57(13): 5777-5782.
    [7]
    杨金玲,高丽丽,朱平. 人参皂苷生物合成研究进展[J]. 药学学报,2013, 48(2): 170-178.YANG Jinling, GAO Lili, ZHU Ping. Advances in the biosynthesis research of ginsenosides[J]. Acta Pharmaceutica Sinica, 2013, 48(2): 170-178(in Chinese).
    [8]
    CHO S H, CHUNG K S, CHOI J H, et al. Compound K, a metabolite of ginseng saponin, induces apoptosis via caspase-8-dependent pathway in HL-60 human leukemia cells[J]. BMC Cancer, 2009, 9(1): 449-461.
    [9]
    杨元超,王英平,闫梅霞,等. 人参皂苷compound K转化菌株的筛选[J]. 中国中药杂志,2011, 36(12): 1596-1598.YANG Yuanchao, WANG Yingping, YAN Meixia, et al. Screening of plant pathogenic fungi by ginsenoside compound K production[J]. China Journal of Chinese Material Medica, 2011, 36(12): 1596-1598(in Chinese).
    [10]
    赵立亚,鱼红闪,金凤燮. 酶法生产稀有人参皂甙及其产物成分的分析[J]. 大连轻工学院学报,2002, 21(2): 112-115.ZHAO Liya, YU Hongshan, JIN Fengxie. Preparing rare ginsenoside from enzyme reaction and composition analysis of its products[J]. Journal of Dalian Institute of Light Industry, 2002, 21(2): 112-115(in Chinese).
    [11]
    YOO M H, YEOM S J, PARK C S, et al. Production of aglycon protopanaxadiol via compound K by a themostable β-glycosidase from Pyroc occus furiosus[J]. Appl Microbiol Biotechnol, 2011, 89(4): 1019-1028.
    [12]
    金鑫,张振海,孙娥,等. 炮制、体内转化过程与人参皂苷潜在构效关系相关性的探讨[J]. 中国中药杂志,2013, 38(3): 307-313.JIN Xin, ZHANG Zhenhai, SUN E, et al. Discussion on correlation between preparation, in vivo conversion process and potential structure-activity relationship of ginsenoside[J]. China Journal of Chinese Material Medica, 2013, 38(3): 307-313(in Chinese).
    [13]
    QIAN T X, CAI Z W, WONG RNS, et al. In vivo rat metabolism and pharmacokinetic studies of ginsenoside Rg3[J]. Journal of Chromatography B, 2005; 816(1): 223-232.
    [14]
    WANG C Z, KIM K E, DU G J, et al. Ultra-performance liquid chromatography and time-of-flight mass spectrometry analysis of ginsenoside metabolites in human plasma[J]. Am J Chin Med, 2011, 39(6): 1161-1171.
    [15]
    CUI M, SONG F R, ZHOU Y, et al. Rapid identification of saponins in plant extracts by electrospray ionization multi-stage tandem mass spectrometry and liquid chromatography/tandem mass spectrometry[J]. Rapid Commun Mass Spectrom, 2000, 14(14): 1280-1286.
    [16]
    FUZZATI N, GABETTA B, JAYAKAR K, et al.Liquid chromatography-electrospray mass spectrometric identification of ginsenosides in Panax ginseng roots[J]. Chromatogr A, 1999, 854(1): 69-79.
    [17]
    郑重,宋凤瑞,刘淑莹,等. 人参、红参皂苷类成分指纹图谱研究[J]. 质谱学报,2012, 33(6): 327-333.ZHENG Zhong, SONG Fengrui, LIU Shuying, et al. Fingerprint study on ginsenoside in ginseng and red ginseng[J]. Journal of Chinese Mass Spectrometry Society, 2012, 33(6): 327-333(in Chinese).
    [18]
    刘燕,聂黎行,陈方军,等. 高分离度快速液相色谱-离子阱质谱分析参麦注射液化学成分[J]. 药物分析杂志,2011, 31(9): 1672-1677.LIU Y, NIE L X, CHEN F J, et al. Analysis on chemical constitutes of Shenmai injection by RRLC-ion trap mass spectrometry[J]. Chin J Pharm Anal, 2011, 31(9): 1672-1677(in Chinese).
    [19]
    SONG F R, LIU Z Q, LIU S Y, et al. Differentiation and identification of ginsenoside isomers by electrospray ionization tandem mass spectrometry[J]. Analytica Chimica Acta, 2005, 531(1): 69-77.
    [20]
    YU Q, YU B, YANG H M, et al. Silver (Ι)-assisted enantiomeric analysis of ginsenosides using electrospray ionization tandem mass spectrometry[J]. Journal of Mass Spectrometry, 2012, 47(10): 1313-1321.
    [21]
    张语迟,刘志强,宋凤瑞,等. 利用高效液相色谱和电喷雾质谱指纹图谱鉴别人参与桔梗[J]. 质谱学报,2008, 29(4): 203-208.ZHANG Y C, LIU Zhiqiang, SONG Fengrui, et al. Identification of Panax Ginseng and Platycodon Grandiflorum by the Fingerprint of HPLC and ESI-MS[J]. Journal of Chinese Mass Spectrometry Society, 2008, 29(4): 203-208(in Chinese).
    [22]
    WANG X M, SAKUMA T, ASAFU-ADJAYE E, et al. Determination of ginsenosides in plant extracts from Panax ginseng and Panax quinquefolius L. by LC/MS/MS[J]. Analytical Chemistry, 1999, 71(8): 1579-1584.
    [23]
    CHAN T W D, BUT P P H, CHENG S W, et al.Differentiation and authentication of Panax ginseng, Panax quinquefolius, and ginseng products by using HPLC/MS[J]. Analytical Chemistry, 2000, 72(6): 1281-1287.
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