关键词: 超高效液相色谱-串联质谱, 禁用原料, 化妆品

Abstract:

The methods of detecting numerous prohibited components are not included in the Technical Specifications for Cosmetic Safety (2015 Edition). Recently, owing to its high speed, sensitivity, and anti-interference properties, ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) became the preferred method of detecting banned substances in cosmetics. In this study, a UPLC-MS/MS method was developed for use in determining 87 prohibited ingredients in cosmetics, including 33 sex hormones, 20 anti-infective drugs, 15 antihistamines, 7 coumarins, 4 sedative-hypnotic drugs, 4 antipyretic and analgesic drugs, 2 allergenic fragrances, and 2 drugs with vasoconstriction effects. The main factors affecting the response, recovery, and sensitivity of the method, such as the type of extraction solvent, extraction time, ratio of the mobile phases, and MS conditions, were optimized during sample pretreatment and instrumental analysis. Accordingly, approximately 0.2 g of the toner or cream sample was dispersed in 2 mL acetonitrile in a 10 mL colorimetric tube. After diluting to 10 mL with 50% acetonitrile aqueous solution, the sample was ultrasonically extracted for 20 min and centrifuged, and the mixture was then filtered through a 0.22 μm membrane. Approximately 0.2 g of the oil sample was dispersed in 2 mL n-hexane in a 15 mL polypropylene centrifuge tube and extracted twice with 3 mL 70% acetonitrile aqueous solution. The extracts were transferred into a 10 mL colorimetric tube and diluted to 10 mL with 50% acetonitrile aqueous solution, and the mixture was then filtered through a 0.22 μm membrane. The samples were separated using a CORTECS C₁₈ column (150 mm×2.1 mm, 2.7 μm), employing a gradient elution program with acetonitrile and 0.1% formic acid aqueous solution as the mobile phases. The flow rate, column temperature, and injection volume were respectively set at 0.3 mL/min, 40 ℃, and 2 μL. The 87 compounds were monitored in multiple reaction monitoring (MRM) mode with electrospray ionization (ESI) under positive and negative conditions. Matrix-matched external standard calibration was used for quantification, and the analysis was completed within 33 min. The prohibited compounds exhibited good linear relationships, with r values of >0.99, and the limits of detection (LODs) and quantification (LOQs) for the 87 compounds were 0.07-0.38 and 0.21-1.15 μg/g, respectively. Three types of cosmetic matrices were selected to verify the recovery and precision of the method at LOQ, 2 LOQ, and 10 LOQ levels. The average recoveries of the 87 prohibited compounds were in the range of 81.7%-115.4%, and the relative standard deviations (RSDs, n=6) were 0.4%-9.9%. The reliability of the developed method was demonstrated by applying it to 349 commercial cosmetics obtained from the market, and 8 positive samples were identified. The positive components included trimethoprim, terbinafine, naphazoline, 7-methoxycoumarin, and 7-methylcoumarin. The established method displays the advantages of simple operation and rapidness and a high sensitivity and good recovery. And, this method provides technical support for rapid risk screening and the revision of national standards for cosmetics.

Key words: ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), prohibited ingredients, cosmetics