超高效液相色谱-串联质谱法定性定量检测中成药及保健食品中非法添加的17种化学药物

Qualitative and quantitative determination of 17 added into Chinese patent medicine and health food by UPLC-MS/MS

目的建立一种快速、准确检测中成药及保健品中非法添加17种抗消化性溃疡化学药物(丙谷胺、米索前列醇、西咪替丁、雷尼替丁、法莫替丁、尼扎替丁、奥美拉唑、兰索拉唑、泮托拉唑、雷贝拉唑、阿托品、山莨菪碱、东莨菪碱、溴丙胺太林、甲硝唑、克拉霉素、阿莫西林)的方法。方法采用超高效液相色谱串联三重四级杆质谱仪(UPLC⁃MS/MS),色谱条件:Shim⁃pack XR⁃ODSⅡ(2.0 mm×75 mm,2.2μm)色谱柱,柱温20℃,以乙腈-0.1%甲酸溶液(含7 mmol/L的乙酸铵)为流动相梯度洗脱(ESI+)或乙腈⁃15mmol/L的乙酸铵为流动相等度洗脱(ESI-),流速0.25 ml/min。质谱条件:ESI源,多反应检测(MRM)模式,以保留时间和定性离子对之间的相对丰度定性,以定量离子对峰面积定量。结果在上述色谱及质谱条件下,17种化学药物分离度良好并在一定检测范围内呈现良好的线性关系(r>0.9951),平均加样回收率在81.5%~102.7%,17种化学药物含量重复性试验RSD<3.0%。结论该方法简便准确,灵敏度高,可作为抗消化性溃疡类中成药及保健食品中非法添加化学药的定性定量测定方法。

Objective To establish a rapid and accurate method for the determination of 17 anti⁃peptic ulcer chemicals(progluta⁃mine,misoprostol,cimetidine,ranitidine,famotidine,nizatidine,omeprazole,lansoprazole,pantoprazole,rabeprazole,atropine,anisoda⁃mine,scopolamine,propantheline bromide,metronidazole,clarithromycin,amoxicillin)which were illegally added into the Chinese patent medicines(CPM)and health food.Method Ultra performance liquid chromatography tandem quadrupole mass spectrome⁃ter was adopted.LC condition:A Shim⁃pack XR⁃ODSⅡ(2.0 mm×75 mm,2.2μm)column was used with acetonitrile and 0.1%for⁃mic acid containing 7 mmol/L ammonium acetate as the mobile phase for gradient elution(ESI+)or acetonitrile and 15 mmol/L am⁃monium acetate as the mobile phase for isocratic elution(ESI-).The flow rate was 0.25ml/min.MS condition:adopted electrospray ionization(ESI),and multiple reaction monitoring(MRM);The retention time and relative intensities of the detected qualitative ion pairs was adopted for qualitative analysis,while integrating the signals of the detected quantitative ion pairs was used for quanti⁃tative analysis.Results The 17 chemicals were well separated and showed a good linearity within a certain range of detection(cor⁃relation coefficient>0.9951)under this UPLC and MS/MS condition.The average recoveries were 81.5%⁃102.7%.Repeatability ex⁃periments showed that RSD values of content were less than 3.0%.Conclusion The method is simple,accurate and has high sensi⁃tivity,which can be used for the qualitative and quantitative determination of illegally added chemicals in CMP and health foods.