UPLC-LTQ/Orbitrap MS快速筛查确证化妆品中89种禁用物质  

Fast Screening and Confirmation of 89 Prohibited Compounds in Cosmetics Using UPLC-LTQ/Orbitrap MS

作　　者：牛增元[1] 罗忻[1] 王凤美[1] 张丽[1,2] 李兆永[3] 陈静[1] 

机构地区：[1]山东出入境检验检疫局检验检疫技术中心,山东青岛266002 [2]中国海洋大学化学化工学院,山东青岛266100 [3]国家海洋局第一研究所,海洋生态研究中心,山东青岛266061

出　　处：《质谱学报》2016年第3期201-212,共12页Journal of Chinese Mass Spectrometry Society

基　　金：国家质检总局科研项目(2011IK224、2013IK015、2011IK037);质检公益性科研专项(201310062)资助

摘　　要：采用超高效液相色谱-线性离子阱/静电场轨道阱结合高分辨质谱法（UPLC-LTQ/Orbitrap MS）同时测定化妆品中抗生素、激素、邻苯二甲酸酯、农药以及孔雀石绿和结晶紫等5大类共89种化合物。不同剂型的化妆品基质用甲醇超声提取,以Waters Acquity UPLC BEH C18色谱柱（2.1mm×100mm×1.7μm）分离;正离子模式下,以含0.1%甲酸的5mmol/L乙酸铵溶液和乙腈为流动相;负离子模式下,以5mmol/L乙酸铵溶液和乙腈为流动相,进行梯度洗脱。以保留时间和Orbitrap获得的一级母离子精确质量数以及同位素丰度比,实现对化妆品中多种类物质的快速筛查;以Orbitrap碰撞诱导解离（CID）获得的碎片离子精确质量数进行确证。结果表明：化合物的线性关系良好,线性相关系数R2〉0.99;除邻苯二甲酸二苯酯外,其他化合物的最低检出限（LOQ）均在5~10μg/kg之间;在添加浓度为1倍、2倍、10倍LOQ 3个水平下,绝大多数化合物的平均回收率在60%~117%之间,相对标准偏差小于13%。该方法简便、快速、可靠性高,适用于化妆品中多种类别禁用物质的检测。A multi-target method of ultra high performance liquid chromatography-linear ion trap/Orbitrap high resolution mass spectrometry （UPLC-LTQ/Orbitrap MS） was established and validated for the detection of 89 prohibited compounds regulated by （EC） No 1223/2009 on cosmetic products, including antibiotics, hormones, phthalie acid esters （PAEs）, pesticide residuals, malachite green and violet. The target com- pounds were extracted with methanol using ultrasonic extraction. The separation was carried out on a Waters Acquity UPLC BEH C18 column （2.1 mm×100 mm×1.7 μm） with a mobile phase consisting of 5 mmol/L ammonium acetate （0.1% formic acid） and aeetonitrile in positive mode and 5 mmol/L ammonium acetate and acetonitrile in negative mode. The retention time, accurate mass of parent ion and relative isotope abundance were used for fast screening, while the generated fragments by collision- induced dissociation （CID） were used for comfirmation. With the assistance of Mass Frontier software, fragments generated in MS2 collision were deduced and their theoreti- cal assignments were used, which can greatly improve the confirmative accuracy of com- pounds. The results show that each target has good linearity in its own concentration range and the correlation coefficients is higher than 0.99. The limit of quantification （LOQ） for most compounds are in the range of 5-10 μg/kg except for diphenyl phthalate. For the most compounds, the average recovery at three spiked levels of 1 LOQ, 2 LOQ and 10 LOQ range from 600/00 to 117%, and the relative standard devia- tion （RSD） is less than 13%. This method is simple, rapid and reliable, which can be used for determination of multi-class prohibited compounds in cosmetics.

关 键 词：化妆品 禁用物质 超高效液相色谱(UPLC) 线性离子阱/静电场轨道阱高分辨质谱(LTQ/Orbitrap MS) 

分 类 号：O657.63[理学—分析化学]