超高效液相色谱-线性离子阱/静电场轨道阱质谱对化妆品中抗生素类成分的快速筛查和确证

Screening and confirmation of antibiotics in cosmetics by high performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry

目的建立化妆品中抗生素快速筛查和确证的超高效液相色谱-线性离子阱/静电场轨道阱高分辨质谱法(ultra high performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry)。方法采用超声波辅助提取化妆品中的抗生素类化合物,提取液经ACQUITY BEH C18色谱柱分离,以水(含5 mmol/L乙酸铵和0.1%甲酸)-乙腈为流动相,梯度洗脱分离。静电场轨道阱一级全扫描得到的准分子离子的精确质量数用于快速筛选分析,保留时间和离子阱的二级质谱数据用于进一步定性确证。结果 36种抗生素的精确质量相对偏差小于5×10-6(5 ppm),线性相关系数r2大于0.994,方法检出限(limit of detection)均≤10μg/kg,方法的加标回收率为54.15%~117.55%,相对标准偏差(relative standard deviation)为1.19%~13.25%。结论应用该方法对不同剂型的50余种化妆品实际样品筛查的分析结果良好,说明该方法是化妆品中抗生素类成分快速筛选和确证的有效方法。

Objective To screen and confirm common antibiotics in cosmetics by ultra high performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry (UPLC-LTQ/orbitrap MS).Methods Cosmetic samples were extracted with methanol, the elutes were separated on a Waters ACQUITY UPLC BEH C18 column (2.1 mm×100 mm, 1.7μm) using gradient elution with aqueous containing 5 mmol/L ammonium acetate and 0.1% formic acid/acetonitrile. The accurate mass of quasi-molecular ion were acquired by full scanning of electrostatic field orbitrap, the rapid screening were carried out by the accurate mass of quasi-molecular ion. The confirmatory analysis for target compounds was performed with the retention time and qualitative fragments obtained by data dependent scan mode.Results Under the optimal conditions, 36 antibiotics were routinely detected with mass accuracy error below 5×10-6(5 ppm), and they all showed a good linearity in their respective linear ranges with correlation coefficients all higher than 0.99. The limit of detection (LOD) for all of 36 determined compounds were≤10μg/kg, the recoveries were in the range of 54.15%-117.55% with the relative standard deviations (RSDs) between 1.19%~13.25%.Conclusion The developed method was applied to screen the antibiotics in 50 kinds of cosmetic samples which demonstrated that the method was a useful tool for the rapid screening and qualitative identification of antibiotics in cosmetics.