超高效液相色谱-串联质谱法测定化妆品中15种N-亚硝胺化合物

Determination of Fifteen N-nitrosamine Compounds in Cosmetics by Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry

采用超高效液相色谱-串联质谱(UPLC-MS/MS)建立了化妆品中15种痕量N-亚硝胺化合物的分析方法。水剂样品以水或乙腈分组超声提取,膏霜乳液样品采用亚铁氰化钾-乙酸锌溶液沉淀大分子或者饱和氯化钠-乙腈盐析分组处理后,以Agilent Poroshell 120 SB-Aq(100 mm×3.0 mm,2.7μm)色谱柱分离,经大气压化学电离源(APCI)电离,多反应监测模式检测,以同位素内标法定量。结果表明,15种N-亚硝胺化合物在相应质量浓度范围内线性关系良好(r^(2)>0.995),检出限和定量下限分别为5~15 ng/g和15~45 ng/g。水、乳、膏霜3种化妆品基质在25、50、100 ng/g加标水平下的平均回收率为88.0%~111%,相对标准偏差(RSD,n=6)为1.4%~9.8%。该方法用于市售化妆品检测,发现13批次样品检出N-亚硝基二乙醇胺(NDELA),其中1批次超限量值。方法的专属性强,灵敏度高,精密度好,解决了N-亚硝胺化合物稳定性差、易被干扰等问题,适用于化妆品中15种N-亚硝胺化合物的痕量测定。

An ultra performance liquid chromatography-tandem mass spectrometric(UPLC-MS/MS)method was established for detecting 15 trace N-nitrosamine compounds in cosmetics.The final established method involved ultrasonic extraction of cosmetics using water or acetonitrile for different compounds.The samples were treated with potassium ferrocyanide-zinc acetate solution for precipitating macromolecules or saturated sodium chloride-acetonitrile for salting out.An Agilent Poroshell 120 SB-Aq(100 mm×3.0 mm,2.7μm)chromatography column was used for separation,followed by atmospheric pressure chemical ionization(APCI)source and multiple reaction monitoring mode detection in the isotope internal standard method for quantification.The result showed good linearity(r^(2)>0.995)for the 15 N-nitrosamine compounds in their respective concentration ranges,with detection and quantitation limits of 5-15 ng/g and 15-45 ng/g,respectively.The average recoveries for the three cosmetic matrices(aqueous,emulsion,cream)at spiked levels of 25,50,100 ng/g were between 88.0%and 111%,with relative standard deviations(RSD,n=6)of 1.4%-9.8%.The method was applied to the detection of commercial cosmetics and N-nitrosodiethanolamine(NDELA)was detected in 13 batches,with one batch exceeding the limit.The strong specificity,high sensitivity,and good precision made the method could solve the problems of poor stability and easy interference of N-nitrosamine compounds,and was suitable for the trace determination of 15 N-nitrosamine compounds in cosmetics.