响应曲面优化-固相萃取-超高效液相色谱-串联质谱法测定霜膏类化妆品中的联苯胺和对氨基偶氮苯

Determination of 4,4′-Diaminobiphenyl Benzidine and p-Aminoazobenzene in Cream Cosmetics by Solid Phase Extraction Purification Combined with Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry and Response Surface Methodology

建立超高效液相色谱-串联质谱法(UPLC-MS/MS)测定霜膏类化妆品中的联苯胺和对氨基偶氮苯。样品经叔丁基甲醚提取后,氮气浓缩,正己烷复溶,硅胶和中性氧化铝固相萃取剂进行净化。使用乙腈和0.1%甲酸-水溶液(V/V)等度洗脱,Agilent poroshell EC C_(18)色谱柱分离,最后电喷雾电离源正离子模式电离,多反应监测模式进行测定,确定一级母离子和二级子离子,建立质谱测定方法。采用三因素三水平响应曲面优化测定的最佳条件,并建立数学模型预测最佳测得值,预测值和实际值吻合。最佳的测定条件为:硅胶用量200 mg,中性氧化铝用量500 mg,叔丁基甲醚用量10 mL,在该条件组合下,测得联苯胺回收率为89.85%。基质曲线在2.0~200μg/L范围内线性关系良好,相关系数R 2大于0.999,平均回收率范围在86.4%~92.7%,相对标准偏差在1.96%~7.05%之间,方法检出限为4.0~10.0μg/kg,定量限为10.0~20.0μg/kg。该方法操作简便、回收率好,具有较高的灵敏度和精密度,适用于测定霜膏类化妆品中的联苯胺和对氨基偶氮苯。

An ultra performance liquid chromatography-tandem mass spectrometry method was established for the determination of 4,4′-diaminobiphenyl benzidine and p-aminoazobenzene in cream cosmetics.The samples were extracted with tert-butyl methyl ether and concentrated with nitrogen and redissolved in n-hexane,then purified with silica gel and alumina-N solid phase extractant.The separation was performed on Agilent poroshell EC C_(18) chromatographic column with isocratic elution using acetonitrile and 0.1%formic acid-water solution(V/V).Finally,electrospray ionization source was used for positive ion mode ionization and multiple reaction monitoring mode was used for determination.Parent ions and secondary product ions were identified to establish the mass spectrometry method.Optimization was conducted using three factors and three levels response surface for the best conditions of determination,in addition,a mathematical model was established to predict the best trial values.The predicted values were consistent with the trial values.The optimum determination conditions were silica gel amount:200 mg,alumina-N amount:500 mg,Tert-butyl methyl ether amount:10 mL.Under this combination of conditions,the recovery of 4,4′-diaminobiphenyl benzidine was 89.85%.The matrix curve exhibited a good linear relationship in the range of 2.0-200μg/L,while the correlation coefficients R 2 were greater than 0.999.The average recovery rates ranged from 86.4%to 92.7%and the relative standard deviations(RSDs)were in the range of 1.96%-7.05%.The limit of detection(LOD)and limit of quantification(LOQ)were 4.0-10.0μg/kg and 10.0-20.0μg/kg,respectively.The method was simple operation,accurate quantification,good recovery,high sensitivity and high precision and suitable for the determination of 4,4′-diaminobiphenyl benzidine and p-aminoazobenzene in cream cosmetics.