高效液相色谱-串联质谱法测定化妆品中9种禁用生物碱

Determination of Nine Banned Alkaloids in Cosmetics by High Performance Liquid Chromatography-Tandem Mass Spectrometry

建立了高效液相色谱-串联质谱(HPLC-MS/MS)法同时测定化妆品中9种禁用生物碱。采用水作为样品分散剂,氨水-甲醇(2∶98,V/V)作为提取剂,使用正己烷除脂,实现一步完成提取与净化;用Poroshell 120 Bonus-RP色谱柱分离,以0.2%甲酸水溶液-乙腈为流动相进行梯度洗脱;在电喷雾正离子模式下,以多反应监测(MRM)模式测定,推测生物碱的质谱碎裂机理。结果表明,9种生物碱在相应的浓度范围内线性关系良好,线性相关系数r^2为0.997 8~0.999 8。方法的检出限和定量限分别为0.03~0.36μg/kg和0.1~1.2μg/kg,3种加标浓度的回收率为85.3%~135.3%,相对标准偏差为1.0%~13.4%。该方法前处理简便高效、测定结果准确、灵敏度高,适用于化妆品中禁用生物碱的检测及化妆品的安全性评价。

A method of high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS)was developed for the simultaneous determination of nine banned alkaloids in cosmetics,including strychnine,pilocarpine,veratrine,noscapine,lobeline,atropine,hyoscine,ephedrine and physostigmine.Water was selected as dispersant agent,a mixture of ammonia-methanol(2∶98,V/V)solution was selected as extracting agent,meanwhile,n-hexane was adopted for defat treatment,so the purification and extraction could be accomplished in one step.The chromatographic separation was achieved by using a Poroshell 120 Bonus-RP column in combination with a gradient elution with 0.2%formic acid in water and acetonitrile.The qualitative and quantitative analysis of the nine alkaloids were operated by electrospray ionization at positive ion mode using multiple reaction monitoring(MRM)mode.The mass spectrometric fragmentation rule of the alkaloids was also studied.The results showed that the linear relationships are good corresponding to concentration ranges,and the correlation coefficients are 0.9978-0.9998.The limits of detection(LODs)and the limits of quantitation(LOQs)range from 0.03 to 0.36μg/kg and 0.1 to 1.2μg/kg,respectively.The recoveries are 85.3%-135.3%at three spiked concentrations,and the relative standard deviations(RSDs)are 1.0%-13.4%.The method is fast,accurate and sensitive,and it is suitable for the detection of the banned alkaloids in cosmetics and the evaluation of the safety of cosmetics.