色谱 ›› 2021, Vol. 39 ›› Issue (5): 552-557.DOI: 10.3724/SP.J.1123.2020.11003

• 技术与应用 • 上一篇    

气相色谱-质谱法测定化妆品中13种防晒剂

吕稳*(), 李红英, 刘杰, 韩玮, 黄伟   

  1. 湖北省药品监督检验研究院, 湖北 武汉 430075
  • 收稿日期:2020-11-02 出版日期:2021-05-08 发布日期:2021-03-31
  • 通讯作者: 吕稳
  • 作者简介:Tel:(027)87705269,E-mail:lvwenhbyjy@163.com.

Determination of 13 sunscreen agents in cosmetics by gas chromatography-mass spectrometry

LÜ Wen*(), LI Hongying, LIU Jie, HAN Wei, HUANG Wei   

  1. Hubei Institute for Drug Control, Wuhan 430075, China
  • Received:2020-11-02 Online:2021-05-08 Published:2021-03-31
  • Contact: LÜ Wen

摘要:

防晒剂广泛应用于化妆品中,是目前化妆品监管的重点。建立了同时测定化妆品中13种防晒剂的气相色谱-质谱(GC-MS)方法。化妆品样品经二氯甲烷提取后,涡旋超声后稀释。采用程序升温模式,经HP-5ms毛细管色谱柱(30 m×250 μm×0.25 μm)在30 min内对13种防晒剂实现分离,经电子轰击(EI)源电离后采用选择离子监测模式(SIM)扫描测定,外标法定量。比较了6种常用有机溶剂的基质效应和平均回收率,二氯甲烷的基质效应弱,平均回收率较高。13种防晒剂在相应的线性范围内线性关系良好,相关系数均大于0.998,检出限(LOD, S/N=3)为0.04~0.63 mg/g,定量限(LOQ, S/N=10)为0.12~2.10 mg/g。实验选取了两种基质,在3个水平下验证方法的回收率和精密度,13种防晒剂在霜类基质中的加标回收率为88.7%~103.6%,相对标准偏差(RSD, n=6)为1.7%~4.9%,在乳类基质中的加标回收率为88.4%~102.3%, RSD(n=6)为1.2%~3.9%。美白类化妆品常添加防晒剂成分,为监管盲区,采用该方法检测了5批含有防晒剂的美白类化妆品,其所含5种防晒剂的含量为0.8%~5.2%,符合相关要求。该方法操作简单,灵敏度高,回收率好,测定的13种防晒剂均为我国《化妆品安全技术规范》2015版规定的常用的限用组分,可以用于各类化妆品中13种防晒剂的定性定量测定,为市场监管和实验室检测提供新的技术支持。

关键词: 气相色谱-质谱法, 防晒剂, 化妆品

Abstract:

Sunscreens can be categorized as physical and chemical types. Chemical sunscreens are widely used in cosmetics, and hence, their concentration in the desired products should be strictly monitored. Gas chromatography-mass spectrometry (GC-MS) is widely used for the analysis of cosmetics as it does not require organic mobile phases and allows for accurate qualitative and quantitative analyses. In this study, a method based on GC-MS was established for the determination of 13 sunscreen agents in cosmetics: ethylhexyl salicylate, homosalate, 4-methylbenzylidene camphor, ethylhexyl dimethyl para-aminobenzoic acid, ethylhexyl methoxycinnamate, octocrylene, butyl methoxydibenzoylmethane, diethylamino hydroxybenzoyl hexyl benzoate, 3-benzylidene camphor, benzophenone-3, camphor benzalkonium methosulfate, drometrizole trisiloxane, and isopentyl-4-methoxycinnamate. Accordingly, 0.5 g of the cosmetic product was dissolved in dichloromethane in a 50 mL volumetric flask and extracted ultrasonically for 15 min. Then, 1.0 mL of the extracting solution was withdrawn and diluted to 50.0 mL with dichloromethane. The mixture was filtered through a 0.22-μm membrane. A 1 μL aliquot of the dichloromethane solution was introduced onto the HP-5ms chromatographic column (30 m×250 μm×0.25 μm). The 13 components were separated under programed temperature elevation in the interval from 150 ℃ to 290 ℃. These components could be analyzed within 30 min after being ionized by the EI source, and their determination was achieved in selected ion monitoring (SIM) mode. The external standard method was employed for quantitative determination. Linear equations, linear correlation coefficients, and linear ranges were obtained by analyzing a series of mixed standard working solutions. The limits of detection (LODs, S/N=3) and limits of quantification (LOQs, S/N=10) of the 13 sunscreen agents were determined. The matrix effect and average recoveries of the 13 agents with six extraction solvents (dichloromethane, tetrahydrofuran, methanol, acetonitrile, n-hexane, and acetone) were compared. Among these, dichloromethane showed a weak matrix effect and high average recovery. The matrix effect of dichloromethane was 90.1%-100.5%, and the average recovery was 96.3%. All the 13 sunscreen agents showed good linearity in their corresponding ranges. The correlation coefficients (r 2) were higher than 0.998. The LODs and LOQs were in the ranges of 0.04 to 0.63 mg/g and 0.12 to 2.10 mg/g, respectively. Two types of cosmetics were selected to verify the accuracy and precision of the method at three levels. The average spiked recoveries of the 13 sunscreen agents in cream and lotion were 88.7%-103.6%, and 88.4%-102.3%, respectively; the corresponding relative standard deviations (RSDs, n=6) were 1.7%-4.9% and 1.2%-3.9%. Whitening cosmetics are frequently added with sunscreen agents, which is a regulatory blind spot. Five batches of skin whitening products containing sunscreen agents were detected using this method. The contents of five sunscreen agents in skin whitening cosmetics ranged from 0.8% to 5.2%, which were lower than the relevant limits in China. Owing to its advantages of simple operation, high sensitivity, and good recovery, the proposed method is suitable for the qualitative and quantitative determination of 13 sunscreen agents in cosmetics. This method provides technical support for market supervision and laboratory testing.

Key words: gas chromatography-mass spectrometry (GC-MS), sunscreen agents, cosmetics

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