色谱

色谱 ›› 2024, Vol. 42 ›› Issue (1): 75-83.DOI: 10.3724/SP.J.1123.2023.04010

• 研究论文 • 上一篇    下一篇

气相色谱-串联质谱法测定化妆品中15种防腐剂类过敏原物质

韩伟娜1,2, 刘彤彤1, 王露露1, 侯筱宇2,*(), 曹进1,*()   

  1. 1.国家市场监督管理总局食品质量与安全重点实验室, 中国食品药品检定研究院, 北京 100050
    2.中国药科大学, 江苏 南京 210009
  • 收稿日期:2023-04-13 出版日期:2024-01-08 发布日期:2024-01-10
  • 通讯作者: *Tel:(010)67095078,E-mail:caojin@nifdc.org.cn(曹进);Tel:(025)86185415,E-mail:xyhou@cpu.edu.cn(侯筱宇).

Determination of 15 preservative allergens in cosmetics by gas chromatography-tandem mass spectrometry

HAN Weina1,2, LIU Tongtong1, WANG Lulu1, HOU Xiaoyu2,*(), CAO Jin1,*()   

  1. 1. Key Laboratory of Food Quality and Safety, State Administration for Market Regulation, National Institutes for Food and Drug Control, Beijing 100050, China
    2. China Pharmaceutical University, Nanjing 210009, China
  • Received:2023-04-13 Online:2024-01-08 Published:2024-01-10

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摘要：

防腐剂成分大多具有刺激性,容易造成皮肤过敏,国内外对其在化妆品中的使用有明确的禁、限量规定。研究通过气相色谱-串联质谱(GC-MS/MS)同时测定化妆品中15种防腐剂类过敏原物质的含量,建立了基于“两柱保留指数、一个质谱匹配度”的精确鉴定方法,通过外标法定量。样品经过乙腈涡旋超声提取,无水硫酸镁除水后,分别采用DB-5MS和DB-WAX色谱柱分离检测,以电子轰击离子(EI)源为离子源,通过多反应监测模式(MRM)采集数据信息,使用保留指数对15种防腐剂类过敏原物质进行定性。经两次检测,15种防腐剂类过敏原物质在DB-5MS色谱柱上方法的检出限为0.02~0.2 mg/kg, 12种防腐剂类过敏原物质在DB-WAX色谱柱上方法的检出限为0.01~20 mg/kg。防腐剂类过敏原物质在DB-5MS和DB-WAX色谱柱上均在一定范围内线性关系良好,相关系数均大于0.99。以水、乳、面膜、膏霜为代表基质,在低、中、高3个加标水平下,15种防腐剂过敏原物质在DB-5MS和DB-WAX色谱柱上的回收率在70.1%~129.8%范围内,相对标准偏差(RSD)均小于15%(n=6)。采用建立的方法对80批实际样品进行检测,在DB-5MS和DB-WAX色谱柱条件下,有两批样品中均检测出禁用防腐剂4-羟基苯甲酸异丙酯;DB-5MS色谱柱条件下,有11种限用防腐剂被检出,DB-WAX色谱柱条件下,10种限用防腐剂被检出。检测结果表明:该方法使用双柱系统,准确性高,能有效避免假阳性和假阴性的检测结果,可用于化妆品中15种防腐剂类过敏原物质的检测,使用保留指数对15种防腐剂类过敏原物质进行定性,为非定向筛查提供了思路,满足监管需求。

关键词: 气相色谱-串联质谱, 多反应监测模式, 保留指数, 防腐剂类过敏原物质, 化妆品

Abstract:

Most preservatives are irritating and can easily induce skin sensitivities. Therefore, both domestic and international regulations impose clear restrictions on the use of preservatives in cosmetics. Herein, gas chromatography-tandem mass spectrometry (GC-MS/MS) was employed to simultaneously analyze the levels of 15 preservative allergens in cosmetics. Further, a precise identification approach based on a two-column retention index and mass spectrometry matching degree was developed. Cosmetic samples were extracted via acetonitrile vortex ultrasound extraction and then dehydrated with anhydrous MgSO4. The preservative allergens were separated on two columns, namely, DB-5MS and DB-WAX. Targets were identified using electron impact ionization (EI) source and the multiple reaction monitoring (MRM) mode and characterized using a retention index calibrated by a series of n-alkane standards. Following two tests, the LODs for the 15 preservative allergens on the DB-5MS column were in the range of 0.02-0.2 mg/kg, while those for 12 preservative allergens on the DB-WAX column were in the range of 0.01-20 mg/kg. The preservative allergens on the DB-5MS and DB-WAX columns demonstrated strong correlations, with all correlation coefficients exceeding 0.99. The recoveries for the 15 preservative allergens were in the range of 70.1%-129.8% at low, medium, and high levels, and the relative standard deviations (RSDs) were all below 15% (n=6) when using water, lotion, facial mask, and cream as the representative matrix. Next, 80 batches of genuine samples were tested using the established method. Isopropyl 4-hydroxybenzoate, a prohibited preservative, was detected in two sample batches using the DB-5MS and DB-WAX columns. Additionally, 11 and 10 restricted preservative allergens were identified on the DB-5MS and DB-WAX columns, respectively. The test results indicate that the double-column system approach offers excellent accuracy, effectively preventing false-positive and false-negative results, and can detect the 15 preservative allergens in cosmetics. The use of the retention index for the qualitative detection of these preservative allergens offers valuable options for non-targeted screening and meeting regulatory criteria.

Key words: gas chromatography-tandem mass spectrometry (GC-MS/MS), multiple reaction monitoring (MRM), retention index (RI), preservative allergens, cosmetics

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