毛怡宁;武文奇;康莹;王方方;刘勇;
MAO Yi-ning;WU Wen-qi;KANG Ying;WANG Fang-fang;LIU Yong;Beijing University of Chinese Medicine;

• 1:北京中医药大学中药学院

摘要(Abstract)：

基于UHPLC-LTQ-Orbitrap-MS技术对酸枣仁中化学成分进行定性分析。采用Waters Acquity UPLC BEH-C18色谱柱(2. 1 mm×50 mm,1. 7μm),以乙腈(A)-0. 1%甲酸水溶液(B)为流动相梯度洗脱,体积流量0. 3 m L·min-1;在电喷雾负离子模式下采集数据。将母离子列表(parent ion list,PIL)-MS2和高能碰撞(high energy collision dissociation,HCD)技术,用于酸枣仁中三萜皂苷成分的鉴别。结合质谱数据和文献数据,共鉴定、推断出24个化合物,4个未知化合物;其中包括21个黄酮类化合物,5个皂苷类化合物,2个三萜类化合物。采用UHPLC-LTQ-Orbitrap-MS技术,为酸枣仁中化学成分的定性分析及质量控制提供了一种高效、快速的分析方法,为今后进一步阐明其药效物质基础及资源开发利用提供了数据基础。
This study aimed to analyze the chemical components of Zizyphi Spinosae Semen by using ultra high performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry( UHPLC-LTQ-Orbitrap-MS). The chromatographic separation of the components was achieved on a Waters Acquity UPLC BEH-C18 column( 2. 1 mm × 50 mm,1. 7 μm),with acetonitrile-water( 0. 1% formic acid) as mobile phase at a flow rate of 0. 3 m L·min-1. Electrospray ionization-( ESI) source was applied and operated in negative ion mode. The parent ion list( PIL)-MS2 and high energy collision dissociation( HCD) techniques were used to identify triterpene saponins in Zizyphi Spinosae Semen. Through analysis of the mass spectrometry data and literature data,24 compounds and 4 unknown compounds were identified and inferred,including 21 flavonoids,5 saponins and 2 triterpenoids. The use of UHPLC-LTQ-Orbitrap-MS technology provide an efficient and rapid analytical method for the qualitative analysis and quality control of the chemical components in Zizyphi Spinosae Semen. It can also provide reference data for the research on the material basis of pharmacodynamics and the resources development and utilization.

关键词(KeyWords)： 酸枣仁;UHPLC-LTQ-Orbitrap-MS;化学成分
Zizyphi Spinosae Semen;UHPLC-LTQ-Orbitrap-MS;chemical components

Abstract:

Keywords:

基金项目(Foundation):

作者(Authors): 毛怡宁;武文奇;康莹;王方方;刘勇;
MAO Yi-ning;WU Wen-qi;KANG Ying;WANG Fang-fang;LIU Yong;Beijing University of Chinese Medicine;

DOI: 10.19540/j.cnki.cjcmm.20180915.001

参考文献(References)：

• [1]中国药典.一部[S]. 2015.
• [2]刘世军,唐志书,崔春利,等.酸枣仁化学成分的研究进展[J].西部中医药,2016,29(9):143.
• [3]黄之镨,马伟光.酸枣仁及活性物质的药理研究进展[J].中国民族民间医药,2018,27(3):57.
• [4]谭云龙,孙晖,孙文军,等.酸枣仁化学成分及其药理作用研究进展[J].时珍国医国药,2014,25(1):1868.
• [5]杨冲,李宪松,刘孟军.酸枣的营养成分及开发利用研究进展[J].北方园艺,2017(5):184.
• [6]张巧月,史贺,杨浩天,等.药食两用酸枣仁研究近况与开发前景[J].时珍国医国药,2016,27(6):1476.
• [7]马进杰,刘萍,马百平.酸枣仁化学成分及其镇静催眠作用研究进展[J].国际药学研究杂志,2011,38(3):206.
• [8]王晴,卢志威,刘月红,等. UPLC-Q-TOF/MSE结合诊断离子过滤方法快速分析大黄中酚类成分[J].中国中药杂志,2017,42(10):1922.
• [9]李强.酸枣仁潜在效应成分研究[D].太原:山西大学,2017.
• [10]王卫记,罗建光,孔令义. HPLC-ESI-MSn分析酸枣仁有效部位的化学成分[J].中国中药杂志,2009,34(21):2768.
• [11]吴新安,都模勤.黄酮碳苷类化合物ESIMS-MS裂解规律初探[J].天然产物研究与开发,2011,23(6):1085.
• [12] Zhang F X,Li M,Qiao L R,et al. Rapid characterization of Ziziphi Spinosae Semen by UPLC/Qtof MS with novel informatics platform and its application in evaluation of two seeds from Ziziphus species[J]. J Pharm Biomed Anal,2016,122:59.
• [13] Niu C Y,Wu C S,Sheng Y X,et al. Identification and characterization of flavonoids from Semen Ziziphi Spinosae by high-performance liquid chromatography/linear ion trap FTICR hybrid mass spectrometry[J]. J Asian Nat Prod Res,2010,12(4):300.
• [14] Ma J J,Kang L P,Zhou W B,et al. Identification and characterization of saponins in extract of Ziziphi Spinosae Semen(ZSS)by ultra-performance liquid chromatography-electrospray ionization-quadrupole time-of-ight tandem mass spectrometry(UPLCESI-QTOF-MSE)[J]. J Med Plants Res,2011,5(26):6152.
• [15] Yang B,Yang H,Chen F,et al. Phytochemical analyses of Ziziphus jujuba Mill. var. spinosa seed by ultrahigh performance liquid chromatography-tandem mass spectrometry and gas chromatography-mass spectrometry[J]. Analyst,2013,138(22):6881.
• [16]于国华,杨洪军,李俊芳,等.基于UHPLC-LTQ-Orbitrap-MS/MS技术分析枳实中的化学成分[J].中国中药杂志,2016,41(18):3371.
• [17]康安,郭锦瑞,谢彤,等. UPLC-LTQ-Orbitrap质谱联用技术分析茯苓中的化学成分[J].南京中医药大学学报,2014,30(6):561.
• [18]周立分,赵栋云,刘霞,等. LTQ-Orbitrap MS在中药研发中的应用[J].江西中医药,2017,48(12):75.
• [19]侯改芳.海洋天然产物的电喷雾电离质谱(ESI-MS)及其乙酰胆碱酯酶抑制活性构效关系分析[D].青岛:中国海洋大学,2013.
• [20]孙大赢,赵文法,李广华,等. LC-MS/MS法同时测定参芍胶囊中人参皂苷和芍药苷的含量[J].药物分析杂志,2018,38(1):186.
• [21]张瑜,杨健,詹志来,等. UPLC-MS/MS测定不同产地吊石苣苔中苯乙醇苷类成分含量[J].中国现代中药,2017,19(4):504.
• [22]单鸣秋,钱雯,高静,等. UPLC-MS分析侧柏叶中黄酮类化合物[J].中国中药杂志,2011,36(12):1626.
• [23]陈金梅,廖锦红,高金薇,等. UPLC-Q-TOF-MS/MS研究胆木药材水提物的化学成分[J].中国实验方剂学杂志,2018,24(18):49.
• [24]王子健,刘颖,刘思燚,等. UPLC-HRMSn结合高能诱导裂解快速鉴定麦冬中高异黄酮类成分[J].质谱学报,2016,37(06):481.
• [25]刘颖,蔡伟,李宁,等. UHPLC-LTQ-Orbitrap MS结合高能碰撞诱导裂解技术快速鉴定大鼠口服麦冬甾体皂苷后的血中移行成分[J].药学学报,2016,51(11):1751.
• [26]张权,齐梦蝶,康莹,等. UHPLC-LTQ Orbitrap MS快速鉴别无患子果皮中部分苷及苷元成分[J].质谱学报,2018,39(2):224.
• [27]杨瑞,唐思,董晓茜,等.基于UPLC-Q-TOF-MS分析雷公藤配伍甘草治疗肾病综合征大鼠的尿液代谢组学[J].中国实验方剂学杂志,2018,24(12):150.