高效液相色谱法同时测定化妆品中24种香豆素类化合物及质谱确证

Simultaneous determination of 24 coumarin compounds in cosmetics by high performance liquid chromatography and verification by liquid chromatography-tandem mass spectrometry

采用高效液相色谱法,建立了同时测定化妆品中24种香豆素类化合物含量的分析方法。乳液、膏霜、水基类样品和唇膏、粉饼等固态类样品分别采用甲醇、四氢呋喃-甲醇(1∶1)混合溶液超声提取后,经色谱柱分离,以甲醇-0.02 mol/L磷酸二氢钠缓冲液(pH 3.5)为流动相进行梯度洗脱,流速1.0 mL/min,二极管阵列检测器多波长检测,外标法定量。经高效液相色谱法检出的疑似阳性样品,采用液相色谱-串联质谱法进行确证。结果表明,24种香豆素类化合物在各自的质量浓度范围内呈良好的线性关系,相关系数r均≥0.9996,检出限为2~19 mg/kg,定量限为5~63 mg/kg。在低、中、高三个加标水平下,方法回收率为94.4%~106.4%,相对标准偏差为0.5%~3.3%。该方法操作简便、准确性好,可用于化妆品中香豆素类化合物的定性筛查和定量测定。

An analytical method for simultaneous determination of 24 coumarin compounds in cosmetics was established by high performance liquid chromatography.Samples with certain fluidity,such as lotions,creams,and waterbased samples,were directly extracted with methanol by ultrasonic treatment,while solid samples(lipsticks,pressed powders,etc.)were ultrasonically extracted with mixed solvent of tetrahydrofuran-methanol(1∶1).The compounds were separated on a CAPCELL CORE MGII C18(4.6×250 mm,5μm)column,and gradient elution was carried out with methanol and 0.02 mol/L sodium dihydrogen phosphate buffer(pH 3.5)as the mobile phase.The flow rate was 1.0 mL/min.The quantification was done by external standard method,with PDA detector at multi-wavelength,and the suspected positive samples were confirmed by liquid chromatography-tandem mass spectrometry.The results showed that the 24 coumarin compounds showed good linearity,with correlation coefficient≥0.9996 in their respective mass concentration range.The limits of detection and limits of quantification were 2-19 mg/kg and 5-63 mg/kg,respectively.At the three spiked levels of low,medium and high,the average recoveries ranged from 94.4%to 106.4%,and the relative standard deviations were between 0.5%and 3.3%.This method was simple,accurate and suitable for the determination of 24 coumarin compounds in cosmetics.