高效液相色谱-四极杆/静电场轨道阱高分辨率质谱法快速筛查中成药和保健食品中非法添加的42种化学药物

引用本文: 刘芸, 丁涛, 廖雪晴, 沈崇钰, 姜珊, 吕辰, 桂茜雯, 柳菡, 费晓庆, 吴斌, 张睿, 王艳, 季美泉, 王栩璐, 黄志强. 高效液相色谱-四极杆/静电场轨道阱高分辨率质谱法快速筛查中成药和保健食品中非法添加的42种化学药物[J]. 分析化学, 2016, 44(3): 423-429. doi: 10.11895/j.issn.0253-3820.150726 shu

Citation: LIU Yun, DING Tao, LIAO Xue-Qing, SHEN Chong-Yu, JIANG Shan, LV Chen, GUI Qian-Wen, LIU Han, FEI Xiao-Qing, WU Bin, ZHANG Rui, WANG Yan, JI Mei-Quan, WANG Xu-Lu, HUANG Zhi-Qiang. Direct Determination of 42 Chemical Drugs Illegally Added in Herbal Medicines and Dietary Supplement by High Performance Liquid Chromatography-Quadrurpole/Electrostatic Field Orbitrap High Resolution Mass Spectrometry[J]. Chinese Journal of Analytical Chemistry, 2016, 44(3): 423-429. doi: 10.11895/j.issn.0253-3820.150726 shu

高效液相色谱-四极杆/静电场轨道阱高分辨率质谱法快速筛查中成药和保健食品中非法添加的42种化学药物

刘芸 ,
丁涛 ^{1,
,} ,
廖雪晴 ^2, ,
沈崇钰 ^1, ,
姜珊 ^1, ,
吕辰 ^3, ,
桂茜雯 ^1, ,
柳菡 ^1, ,
费晓庆 ^1, ,
吴斌 ^1, ,
张睿 ^1, ,
王艳 ^1, ,
季美泉 ^1, ,
王栩璐 ^1, ,
黄志强 ^4,

1.
¹ 江苏出入境检验检疫局, 南京 210001;
2.
² 中国药科大学, 南京 210001;
3.
³ 赛默飞世尔科技(中国)有限公司, 上海 201206;
4.
⁴ 湖南出入境检验检疫局, 长沙 410004

通讯作者: 丁涛

基金项目:
本文系江苏出入境检验检疫局科技计划(No.2015KJ29) (No.2015KJ29)

国家科技支撑计划课题(No.2012BAK08B01)基金资助项目 (No.2012BAK08B01)

摘要: 建立了高效液相色谱-四极杆/静电场轨道阱高分辨率质谱法快速筛查中成药和保健品中非法添加化学药物的方法。中成药和保健品样品,经提取溶剂提取,以12000 r/min离心后进行质谱分析。采用Phenomenex C₁₈色谱柱(100 mm×4.6 mm,2.6 μm)进行分离,以乙腈和0.1%甲酸溶液作为流动相,进行梯度洗脱。质谱采用正离子和负离子同时扫描,Fullms-dd-MS²模式进行分析。在所建立的色谱条件下,42种化学药物能够得到较好分离,在线性范围内线性关系良好,相关系数均大于0.99。通过加标验证,在20, 50和100 ng/g加标水平下, 所有分析物的平均回收率为69.3%~105.2%,相对标准偏差(RSD)小于8.9%。运用本方法对31种保健品和中成药进行快速筛查,发现其中3种添加了盐酸二甲双胍,1种添加了西地那非,1种添加了羟基莫豪西地那非。本方法样品处理过程简单,分析时间短,准确可靠,灵敏度高。适用于中成药和保健品中非法添加化学药品的定性与定量检测,可用于非法添加药物的筛查。

关键词:

English

Direct Determination of 42 Chemical Drugs Illegally Added in Herbal Medicines and Dietary Supplement by High Performance Liquid Chromatography-Quadrurpole/Electrostatic Field Orbitrap High Resolution Mass Spectrometry

1.
¹ Jiangsu Entry-Exit Inspection and Quarantine Bureau, Nanjing 210001, China;
2.
² China Pharmaceutical University, Nanjing 210001, China;
3.
³ Thermol Fisher Scientific, Shanghai 201206, China;
4.
⁴ Hunan Entry-Exit Inspection and Quarantine Bureau, Changsha 410004, China

Corresponding author: 丁涛

Received Date: 14 September 2015
Fund Project:
本文系江苏出入境检验检疫局科技计划(No.2015KJ29)

国家科技支撑计划课题(No.2012BAK08B01)基金资助项目

Abstract: A method of high performance liquid chromatography-quadrurpole/electrostatic field orbitrap high resolution mass spectrometry (HPLC-Q/Qrbitrap MS) was developed to determine 42 chemical drugs illegally added in herbal medicines and dietary supplements. The samples were pretreated based on the ultrasoni-cassisted extraction by the solvent of methanol-water (6:4, V/V), and centrifuged under 12000 r/min. Subsequently, the solution was filtered by a polytetrafluoroethylene (PTFE) membrane with pore size of 0.22 μm. The analytes were separated on a Phenomenex C₁₈ (100 mm×4.6 mm, 2.6 μm) column through gradient elution with acetonitrile and 0.1% formic acid aqueous solution. The mass spectrometer was operated under Full MS/dd-MS2 experiment using positive and negative mode, respectively. Under the optimal conditions, 42 chemical drugs were well separated. Good linearity was obtained in their respective linear ranges with correlation coefficients higher than 0.99. The average recoveries at three spiked levels (20, 50 and 100 ng/g) were in the range of 69.3%-105.2% and the relative standard deviations (RSDs) lower than 8.9%. Based on the above method, 31 kinds of herbal medicines and dietary supplements were analyzed, in which metformin was found in three samples while sildenafil and hydroxyhomosildenafil were found in one sample, respectively. The proposed method is simple, time saving, high accuracy and sensitive. The method is suitable for confirmation and quantification of 42 chemical drugs in herbal medicines and dietary supplements. The research provides an effective method to control the quality and illegal addition for herbal medical and dietary supplements.

Key words:

Dietary supplements
/ Chemical drug
/ Illegal add
/ High performance liquid chromatography-quadrurpole/electrostatic field orbitrap mass spectrometry
/ High resolution mass spectrometry

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沈阳化工大学材料科学与工程学院沈阳 110142

高效液相色谱-四极杆/静电场轨道阱高分辨率质谱法快速筛查中成药和保健食品中非法添加的42种化学药物

通讯作者: 丁涛

English

Direct Determination of 42 Chemical Drugs Illegally Added in Herbal Medicines and Dietary Supplement by High Performance Liquid Chromatography-Quadrurpole/Electrostatic Field Orbitrap High Resolution Mass Spectrometry

Corresponding author: 丁涛

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

高效液相色谱-四极杆/静电场轨道阱高分辨率质谱法快速筛查中成药和保健食品中非法添加的42种化学药物

通讯作者: 丁涛

English

Direct Determination of 42 Chemical Drugs Illegally Added in Herbal Medicines and Dietary Supplement by High Performance Liquid Chromatography-Quadrurpole/Electrostatic Field Orbitrap High Resolution Mass Spectrometry

Corresponding author: 丁涛

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs