超高效液相色谱-四极杆-飞行时间高分辨质谱用于化妆品中18种非甾体抗炎药筛查和测定  

Rapid Screening and Determination of 18 Non-steroidal Anti-inflam⁃matory Drugs in Cosmetics by Ultra Performance Liquid Chromatog⁃raphy-Quadrupole-Time-of-flight High-resolution Mass Spectrometry

作　　者：黄佳颖 李杨杰[2] 方继辉[2] 肖树雄[2] 徐新军[1] HUANG Jia-ying;LI Yang-jie;FANG Ji-hui;XIAO Shu-xiong;XU Xin-jun(School of Pharmaceutical Scieces,Sun Yat-sen University,Guangzhou 510006,China;National Medical Products Administration Key Laboratory for Safety Risk Assessment of Cosmetics,Guangdong Institute for Drug Control,Guangzhou 510163,China)

机构地区：[1]中山大学药学院,广东广州510006 [2]广东省药品检验所,国家药品监督管理局化妆品风险评估重点实验室,广东广州510163

出　　处：《分析测试学报》2024年第2期269-277,共9页Journal of Instrumental Analysis

摘　　要：建立了超高效液相色谱-四极杆-飞行时间高分辨质谱(UPLC-Q-TOF MS)快速筛查和测定化妆品中18种非甾体抗炎药(NSAIDs)的方法。样品采用60%乙腈水溶液超声提取,以ACQUITY UPLC BEH C_(18)(100 mm×2.1 mm,1.7μm)色谱柱分离,0.1%甲酸水和0.1%甲酸乙腈为流动相梯度洗脱。在ESI正离子扫描模式下,采用Target MS/MS模式采集化合物的质谱信息构建筛查数据库,以保留时间、一级母离子精确质量数、同位素丰度比和二级子离子谱库匹配进行快速筛查,以基质匹配外标法进行定量分析。结果表明18种化合物的线性关系良好,相关系数(r^(2))均大于0.99;检出限为0.001~0.050μg/g,定量下限为0.004~0.150μg/g。低、中、高3个加标水平下,膏霜及水剂两种化妆品基质的平均回收率为70.7%~116%,日内相对标准偏差(RSD,n=6)为0.70%~7.5%,日间RSD(n=3)为3.0%~14%。该方法前处理简单高效、准确度好、分析速度快,筛查结果准确,可用于化妆品中非甾体抗炎药的定性确证和定量分析,为化妆品风险识别提供技术手段。In this study,an ultra performance liquid chromatography-quadrupole-time-of-flight high-resolution mass spectrometry(UPLC-Q-TOF MS)method was developed for the rapid screening and quantitative analysis of 18 non-steroidal anti-inflammatory drugs(NSAIDs)in cosmetics.The chromatographic and mass spectrometric conditions were optimized in detail.The samples were firstly extracted by ultrasonic extraction with 60%acetonitrile aqueous solution,then separated on an ACQUITY UPLC BEH C_(18) column(100 mm×2.1 mm,1.7μm)by gradient elution,with water and acetonitrile both containing 0.1%formic acid as the mobile phases.The 18 NSAIDs were detected by positive ion electrospray ionization(ESI)in the Target MS/MS mode.The retention time,exact mass number of primary parent ions,isotope abundance ratio and secondary sub-ion library matching were collected to construct a screening library with the software.The results of matching were used to rapid identification of 18 NSAIDs in cosmetics.The quantification of primary parent ions was performed by matrix-matched external standard method.The 18 NSAIDs were all well separated,with good linearity.The linear correlation coefficients(r^(2))were more than 0.99.The limits of detection(LODs)ranged from 0.001-0.050μg/g and the limits of quantitation(LOQs)ranged from 0.004-0.150μg/g.The mean spiked recoveries at three spiked levels in cream and lotion matrices ranged from 70.7%to 116%,with intra-day relative standard deviations(RSDs,n=6)of 0.70%-7.5%and inter-day RSDs(n=3)of 3.0%-14%.The 500 batches of cosmetic samples were detected and screened under the same conditions.The TOF MS information,including the retention time,exact mass number of primary parent ions,isotope abundance ratio and secondary sub-ion library,were compared between the cosmetic samples and the standard MS information with PCDL software.Finally,three batches of samples added with acetamidophen were indentified.The amounts of the added drug were very high,indicating high safety risk for cosumers using such cosmetics.W

关 键 词：化妆品 非甾体抗炎药 超高效液相色谱-四极杆-飞行时间高分辨质谱 

分 类 号：O657.63[理学—分析化学] TQ658[理学—化学]