液相色谱-电喷雾电离-离子迁移谱联用法测定中药口服液中7种指标性成分
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摘要
采用液相色谱-电喷雾电离-离子迁移谱联用技术,研究建立了中药口服液中丹参素、甘草酸、天麻素、绿原酸、葛根素、黄芩苷、芦丁等7种指标性成分的二维分离分析方法。样品溶液首先经ACQUITY UPLC BEH C_(18)色谱柱(50 mm×1 mm, 1.7μm)分离后,导入可调节式分流器(分流比50∶1),柱后流出液分别进入离子迁移谱和三重四极杆质谱检测。分别详细优化了液相色谱、喷雾电压、迁移管和气体预加热温度、漂移气流速等实验条件,同时建立了指标性成分的液相色谱-三重四极杆质谱确证方法。7种中药指标性成分的检出限为2～10μg/mL,定量限为5～25μg/mL。采用本方法对中药口服液实际样品进行了检测分析。通过将液相色谱和离子迁移谱进行偶联,可实现目标化合物同时基于疏水性和离子迁移率差异的二维分离,获得更为丰富的测试信息。
A two-dimensional separation and analysis method, based on liquid chromatography-electrospray ionization-ion mobility spectrometry(LC-ESI-IMS), is developed for the determination of seven indicative ingredients(danshensu, glycyrrhizic acid, gastrodin, chlorogenic acid, puerarin, baicalin, and rutin) in oral liquids of Chinese medicine. The sample was first separated on an ACQUITY UPLC BEH C_(18) column(50 mm×1 mm, 1.7 μm). The post-column effluent was directed to an adjustable flow splitter with a split ratio of 50∶1. The low-flow and high-flow outlets were connected to an ion mobility spectrometer and a triple quadrupole mass spectrometer, respectively. The experimental conditions for LC, spray voltage, drift tube temperature, gas pre-heating temperature, and drift gas velocity were systematically optimized. The limits of detection(LODs) and quantitation(LOQs) for the seven analytes were 2-10 μg/mL and 5-25 μg/mL, respectively. The proposed method was applied for the analysis of real oral liquids of Chinese medicine samples. By coupling LC and IMS, two-dimensional separation could be achieved based on hydrophobicity difference and ionic mobility disparity, thus providing more comprehensive measurement information than LC or IMS used alone.
A two-dimensional separation and analysis method, based on liquid chromatography-electrospray ionization-ion mobility spectrometry(LC-ESI-IMS), is developed for the determination of seven indicative ingredients(danshensu, glycyrrhizic acid, gastrodin, chlorogenic acid, puerarin, baicalin, and rutin) in oral liquids of Chinese medicine. The sample was first separated on an ACQUITY UPLC BEH C_(18) column(50 mm×1 mm, 1.7 μm). The post-column effluent was directed to an adjustable flow splitter with a split ratio of 50∶1. The low-flow and high-flow outlets were connected to an ion mobility spectrometer and a triple quadrupole mass spectrometer, respectively. The experimental conditions for LC, spray voltage, drift tube temperature, gas pre-heating temperature, and drift gas velocity were systematically optimized. The limits of detection(LODs) and quantitation(LOQs) for the seven analytes were 2-10 μg/mL and 5-25 μg/mL, respectively. The proposed method was applied for the analysis of real oral liquids of Chinese medicine samples. By coupling LC and IMS, two-dimensional separation could be achieved based on hydrophobicity difference and ionic mobility disparity, thus providing more comprehensive measurement information than LC or IMS used alone.
引文
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[2] Sun R S,Zhao M J,Meng J.Ginseng Research,2018,30(2):52 孙仁爽,赵敏婧,孟军.人参研究,2018,30(2):52
[3] Xiang J L,Wang W,Ren F Y,et al.Guide of China Medicine,2018,16(11):237 向金莲,王伟,任飞宇,等.中国医药指南,2018,16(11):237
[4] Fan Y,Li Y,Wu Y,et al.Evid Based Complement Alternat Med,2017,2017:6781593
[5] Costa G M,Gazola A C,Zucolotto S M,et al.Rev Bras Farmacogn,2016,26(4):451
[6] Peng J J,Li D X,Huang J Y,et al.Chin Herb Med,2017,9(3):267
[7] Bai X W.Heilongjiang Science and Technology Information,2014,(23)7 柏新闻.黑龙江科技信息,2014(23):7
[8] Zhang Y,Yan J Q,Liu M,et al.China Pharmacy,2018,29(2):283 张元,闫加庆,刘敏,等.中国药房,2018,29(2):283
[9] Dussy F E,Berchtold C,Briellmann T A,et al.Forensic Sci Int,2008,177(2/3):105
[10] Najarro M,Dávila Morris M E,Staymates M E,et al.Analyst,2012,137(11):2614
[11] Dai J X,Zhao Z J,Zhu S,et al.Chinese Journal of Analytical Chemistry,2018,46(8):1238 代渐雄,赵忠俊,朱爽,等.分析化学,2018,46(8):1238
[12] Wang J F.[PhD Dissertation],Beijing:Beijing University of Chemical Technology,2012 王建凤.[博士学位论文].北京:北京化工大学,2012
[13] Li D,Qiu J,Qian Y Z,et al.Quality and Safety of Agro-products,2012(5):41 李丹,邱静,钱永忠,等.农产品质量与安全,2012(5):41
[14] Lu Y T,Hu S,Lu P,et al.Journal of Food Safety and Quality,2014,5(4):1087 陆娅婷,胡双,陆鹏,等.食品安全质量检测学报,2014,5(4):1087
[15] Guo X Y,Zhai J F,Ma L H,et al.Chinese Journal of Chromatography,2019,37(2):233 郭项雨,翟俊峰,马龙华,等.色谱,2019,37(2):233
[16] Meng X S,Ma Q,Ma L H,et al.Chinese Journal of Chromatography,2016,34(6):596 孟宪双,马强,马龙华,等.色谱,2016,34(6):596
[17] Zarejousheghani M,Schrader S,M?der M,et al.Talanta,2018,190:47
[18] Liu X Y,Kong X H,Ji R D,et al.Journal of Atomic and Molecular Physics,2007,24(1):163 刘宪云,孔祥和,季仁东,等.原子与分子物理学报,2007,24(1):163
[19] Mans D J,Callahan R J,Dunn J D,et al.J Pharm Biomed Anal,2013,75(5):153
[20] Jafari M T,Saraji M,Ameri A H.Anal Chim Acta,2015,853:460
[21] Hashemian Z,Khayamian T,Saraji M.Anal Bioanal Chem,2015,407:1615
[22] Zargar T,Khayamian T,Jafari M T.J Pharm Biomed Anal,2017,132:232
[23] Saraji M,Khayamian T,Hashemian Z.J Sep Sci,2014,37(23):3518
[24] Kong J L,Liu W W,Ding J J,et al.Chinese Journal of Analytical Chemistry,2017,45(11):1583 孔景临,刘卫卫,丁俊杰,等.分析化学,2017,45(11):1583
[25] Chen C,Wang W G,Liang X X,et al.Chinese Journal of Chromatography,2013,31(4):386 陈创,王卫国,梁茜茜,等.色谱,2013,31(4):386
[26] Feng X,Yin L H,Jin S H,et al.Chinese Journal of Pharmaceutical Analysis,2013,33(7):1109 冯雪,尹利辉,金少鸿,等.药物分析杂志,2013,33(7):1109
[27] Guo C H,Cao S Y.Ion Mobility Spectrometry.Beijing:National Defense Industry Press,2010 郭成海,曹树亚.离子迁移谱.北京:国防工业出版社,2010
[28] Kong J L,Liu W W,Qin M L,et al.Modern Instruments and Medical Treatment,2018,24(3):99 孔景临,刘卫卫,秦墨林,等.现代仪器与医疗,2018,24(3):99
[29] Zhang Z Y,Sha M,Song C,et al.Shandong Journal of Traditional Chinese Medicine,2017,36(7):601 张正勇,沙敏,宋超,等.山东中医杂志,2017,36(7):601
[30] Zhang Z Y,Song C,Sha M,et al.Spectroscopy and Spectral Analysis,2016,36(10):441 张正勇,宋超,沙敏,等.光谱学与光谱分析,2016,36(10):441
[31] Zhang Z Y,Sha M,Liu J,et al.Hunan Journal of Traditional Chinese Medicine,2017,33(6):168 张正勇,沙敏,刘军,等.湖南中医杂志,2017,33(6):168
[32] Zhang Z Y,Sha M,Gui D D,et al.Liaoning Journal of Traditional Chinese Medicine,2017,44(11):2365 张正勇,沙敏,桂冬冬,等.辽宁中医杂志,2017,44(11):2365
[33] Wang Z,Kang D,Jia X,et al.J Chromatogr B,2018,1096:73
[34] Budimir N,Weston D J,Creaser C S.Analyst,2007,132:34
[35] Shen H L,Meng Q Y,Jia X,et al.Chinese Journal of Analytical Chemistry,2017,45(6):809 沈红玲,孟庆艳,贾旭,等.分析化学,2017,45(6):809
[36] Lee D S,Wu C,Hill H H Jr.J Chromatogr A,1998,822:1
[37] Matz L M,Dion H M,Hill H H Jr.J Chromatogr A,2002,946:59
[38] Clemmer D E,Jarrold M F.J Mass Spectrom,1997,32:577
[39] Chen M,Guo X Y,Cao W,et al.Journal of Analytical Science,2018,34(3):342 陈萌,郭项雨,操卫,等.分析科学学报,2018,34(3):342
[40] Lian X H,Guo X Y,Xue H Y,et al.Physical Testing and Chemical Analysis Part B:Chemical Analysis,2018,54(5):529 连显会,郭项雨,薛宏宇,等.理化检验-化学分册,2018,54(5):529