气相色谱串联质谱法测定中药酒剂中16种邻苯二甲酸酯类化合物的残留量

Determination of 16 Kinds of Phthalate Esters Residues in Chinese Medicine Health Wine by GC-MS/MS

目的 建立测定中药酒剂中16种邻苯二甲酸酯类化合物残留量的气相色谱串联质谱法。方法 样品经正己烷超声提取后,采用分流进样,色谱柱为Aglient ZB-5MS毛细管柱(30 m×0.25 mm,0.25μm),程序升温分离,选择反应监测(MRM)模式下的质谱扫描分析,以外标法定量。结果 16种邻苯二甲酸酯类化合物的质量浓度在0.02~1.0μg/mL范围内与峰面积线性关系良好(r≥0.999 1);检测限为0.1μg/kg,定量限为0.3μg/kg;精密度、稳定性、重复性试验结果的RSD均小于3.0%(n=6);平均加样回收率为81.92%~103.90%,RSD为1.11%~7.23%。12种中药酒剂样品中均未检出邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二烯丙酯(DAP)、邻苯二甲酸二(2-甲氧基)乙酯(DMEP)、邻苯二甲酸二乙氧基乙基酯(DEEP)、邻苯二甲酸二-4-甲基-2-戊基酯(BMPP)、邻苯二甲酸二正戊酯(DPP)、邻苯二甲酸二己酯(DHXP)、邻苯二甲酸丁苄酯(BBP)、邻苯二甲酸二丁氧基乙基酯(DBEP)、邻苯二甲酸二环己酯(DCHP)、邻苯二甲酸二苯酯(DPHP)、邻苯二甲酸二正辛酯(DNOP);1种中药酒剂样品(编号为G)中检出邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二异丁酯(DIBP),检出量分别为8.89,2.14 mg/kg;主要检出邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二-2-乙基己酯(DEHP),含量分别介于0.12~5.73 mg/kg和0.10~1.52 mg/kg。结论 该方法简便快速、定量准确、灵敏度高,可用于中药酒剂中邻苯二甲酸酯类化合物残留量的测定。

Objective To establish a gas chromatography-tandem mass spectrometry(GC-MS/MS) method for the determination of 16 kinds of phthalate ester residues in Chinese medicine health wine.Methods The samples were extracted with n-hexane,and the split injection was adopted.The chromatographic column was AgClient ZB-5MS capillary column(30 m ×0.25 mm,0.25 μm) with temperature programming.Mass spectrometry scanning analysis was performed in multi-reaction monitoring(MRM) mode,and quantification was performed by the external standard method.Results The linear range of 16phthalate esters was 0.02-1.0 μg/mL(r ≥ 0.999 1).The limit of detection(LOD) was 0.1 μg/kg,and the limit of quantification(LOQ) was 0.3 μg/kg.The RSDs of precision,stability,and repeatability test results were all lower than 3.0%(n = 6).The average recovery rate was in the range of 81.92%-103.90%,with RSD of 1.11%-7.23%.No dimethyl phthalate(DMP),diallyl phthalate(DAP),bis(2-methoxyethyl) phthalate(DMEP),diethoxyethyl phthalate(DEEP),bis(4-methyl-2-pentyl) phthalate(BMPP),di-n-butyl phthalate(DPP),dihexyl phthalate(DHXP),butyl benzyl phthalate(BBP),dibutyloxyethyl phthalate(DBEP),dicyclohexyl phthalate(DCHP),diphenyl phthalate(DPHP),or di-n-octyl phthalate(DNOP)were detected in 12 samples of Chinese medicine health wine preparations.Diethyl phthalate(DEP) and diisobutyl phthalate(DIBP) were detected in one sample of Chinese medicine health wine(designated as G),with detection contents of 8.89 mg/kg and 2.14 mg/kg,respectively;the main detected substances were dibutyl phthalate(DBP) and di(2-ethylhexyl) phthalate(DEHP) with contents of 0.12-5.73 mg/kg and 0.10-1.52 mg/kg,respectively.Conclusion The method is simple,rapid,accurate,and highly sensitive,which can be used for the determination of phthalate ester residues in Chinese medicine health wine.