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    高效液相色谱-串联质谱法同时测定化妆品中9种对羟基苯甲酸酯类防腐剂的含量

    Simultaneous Determination of 9 p-Hydroxybenzoic Acid Ester Preservatives in Cosmetics by High Performance Liquid Chromatography-Tandem Mass Spectrometry

    • 摘要: 取样品0.25 g,加入甲醇30 mL,超声提取30 min,用甲醇稀释至50 mL。用0.22 μm有机滤膜过滤,续滤液进入高效液相色谱-串联质谱仪,4-羟基苯甲酸甲酯、4-羟基苯甲酸乙酯、4-羟基苯甲酸丙酯、4-羟基苯甲酸异丙酯、4-羟基甲酸丁酯、4-羟基苯甲酸异丁酯、4-羟基甲酸戊酯、4-羟基苯甲酸苯酯和4-羟基苯甲酸苄酯等9种对羟基苯甲酸酯类防腐剂在Waters ACQUITY UPLC BEH C18色谱柱上用不同体积比的0.1%(体积分数)甲酸溶液-乙腈混合溶液进行梯度洗脱分离,在电喷雾离子源负离子模式和多反应监测模式下检测。结果显示,9种目标物的质量浓度在0.5~200.0 μg·L-1内与峰面积呈线性关系,检出限为0.015~0.092 μg·g-1。对空白样品进行加标回收试验,回收率为88.6%~106%,测定值的相对标准偏差(n=6)为0.90%~11%。调整检测仪器、色谱柱、流动相比例和柱温等,9种目标物的分离效果仍较好,说明方法耐用性较好。方法用于15批不同化妆品的分析,检出了4-羟基苯甲酸甲酯、4-羟基苯甲酸乙酯、4-羟基苯甲酸丙酯和4-羟基苯甲酸苄酯,4-羟基苯甲酸苄酯为禁用防腐剂(检出量为0.104~0.125 μg·g-1),可能由原料残留引入,其他目标物的检出量均未超过《化妆品安全技术规范》(2015年版)规定的限值。

       

      Abstract: Samples (0.25 g) were taken, and 30 mL of methanol was added. The mixture was extracted by ultrasound for 30 min, diluted to 50 mL with methanol, and filtered through a 0.22 μm organic filter membrane, and the subsequent filtrate was introduced into high performance liquid phase chromatography-tandem mass spectrometer. Methyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, isopropyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate, isobutyl 4-hydroxybenzoate, pentyl 4-hydroxybenzoate, phenyl 4-hydroxybenzoate, and benzyl 4-hydroxybenzoate of the 9 p-hydroxybenzoic acid ester preservatives were separated on Waters ACQUITY UPLC BEH C18 column by gradient elution with mixed solutions of 0.1% (volume fraction) formic acid solution and acetonitrile at different volume ratios, and detected in negative ion mode of electric spray ion source and multiple reaction monitoring mode. It was shown that mass concentrations of the 9 targets were linearly related with response values in the ranges of 0.5-200.0 μg·L-1, and detection limits ranged from 0.015 μg·g-1 to 0.092 μg·g-1. Test for recovery was made on blank samples by standard addition method, giving recoveries in the range of 88.6%-106%, and RSDs of the determined values (n=6) ranged from 0.90% to 11%. After adjusting the detection instrument, column, mobile phase ratio and column temperature, the 9 targets were well separated, which indicated that the method had a good durability. The proposed method was applied to the analysis of 15 batches of different cosmetic products, and methyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate and benzyl 4-hydroxybenzoate were detected. Benzyl 4-hydroxybenzoate with detection amounts of 0.104-0.125 μg·g-1 was a prokibited perservative, which might be introduced by raw material residues, and detection amounts of the other targets were not more than limits specified by Safety and Technical Standards for Cosmetics (2015 edition).

       

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