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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OACSTPCD

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

中文摘要英文摘要

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.

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 em-ployed 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 ultra-sound 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 elec-tron 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 recover-ies 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 pro-hibited preservative,was detected in two sample batches using the DB-5MS and DB-WAX col-umns.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 re-sults,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-targe-ted screening and meeting regulatory criteria.

韩伟娜;刘彤彤;王露露;侯筱宇;曹进

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||中国药科大学,江苏 南京 210009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中国药科大学,江苏 南京 210009

化学

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

gas chromatography-tandem mass spectrometry(GC-MS/MS)multiple reaction monitoring(MRM)retention index(RI)preservative allergenscosmetics

《色谱》 2024 (001)

75-83 / 9

10.3724/SP.J.1123.2023.04010

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