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  

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

作　　者：刘芸[1] 丁涛[1] 廖雪晴[2] 沈崇钰[1] 姜珊[1] 吕辰 桂茜雯[1] 柳菡[1] 费晓庆[1] 吴斌[1] 张睿[1] 王艳[1] 季美泉 王栩璐 黄志强[4] 

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

出　　处：《分析化学》2016年第3期423-429,共7页Chinese Journal of Analytical Chemistry

基　　金：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~~

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 C（18）色谱柱（100 mm×4.6 mm,2.6μm）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。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 ultrasonicassisted 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 C（18）（ 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 than8. 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.

关 键 词：保健食品 化学药物 非法添加 高效液相色谱-四极杆/静电场轨道阱质谱 高分辨率质谱 

分 类 号：R286.0[医药卫生—中药学] O657.63[医药卫生—中医学] TS218[理学—分析化学]