超高效液相色谱法测定化妆品中11种香豆素类化合物及质谱确证

doi:10.3969/j.issn.1001-1803.2020.11.012

摘要/Abstract

摘要：

建立了同时测定化妆品中11种香豆素类化合物（8-羟基补骨脂素、补骨脂素、6-甲基香豆素、异补骨脂素、8-甲氧基补骨脂素、5-甲氧基补骨脂素、补骨脂二氢黄酮、新补骨脂异黄酮、三甲沙林、欧前胡素和异欧前胡素）的超高效液相色谱方法及液相色谱-串联质谱确证方法。样品用甲醇超声提取20 min,离心后取上清液经微孔滤膜过滤后测定。采用ACQUITY UPLC HSS T₃色谱柱（2.1 mm×50 mm,1.8 μm）,以乙腈-水为流动相进行梯度洗脱,流速为0.3 mL/min,柱温为30 ℃,检测波长为246和278 nm。以超高效液相色谱法的结果进行定性筛查,并采用标准曲线法定量,以液相色谱-串联质谱法的结果进行确证。结果表明,11种香豆素类化合物的线性范围均为1.0~10 mg/L,相关系数均大于0.999 7。方法检出限为0.1~0.6 mg/kg。在低、中、高3种加标水平下,平均回收率为95.3%~110.0%,RSD为0.4%~2.6%。该方法简便、快速、准确,适用于化妆品中11种香豆素类化合物的同时检测。

关键词: 化妆品, 超高效液相色谱法, 液相色谱-串联质谱法, 香豆素类化合物

Abstract:

A method for the simultaneous determination of eleven coumarins （8-hydroxypsoralen, psoralen, 6-methylcoumarin, isopsoralen, 8-methoxypsoralen, 5-methoxypsoralen, bavachin, neobavaisoflavone, trioxsalen, imperatorin and isoimperatorin） in cosmetics by ultra high performance liquid chromatography verification by liquid chromatography-tandem mass spectrometry was established. The cosmetic samples were ultrasonically extracted with methanol for 20 min, centrifuged, and the supernatant was filtered through a microporous membrane for determination. An ACQUITY UPLC HSS T₃ chromatographic columns （2.1 mm×50 mm, 1.8 μm） was used for gradient elution at a flow rate of 0.3 mL/min with acetonitrile-water as the mobile phases. The wavelengths of detection were 246 and 278 nm. The column temperature was set at 30 ℃. The results of ultra high performance liquid chromatography were used for qualitative screening, the standard curve method was used for quantification, and the results of liquid chromatography-tandem mass spectrometry were used for verification. The results show that the linear ranges of the eleven coumarins were 0.1-10 mg/L, and the correlation coefficients were all greater than 0.999 7. The detection limits are 0.1-0.6 mg/kg. The average recoveries are 95.3%-110.0% with RSDs of 0.4%-2.6% at low, medium and high spiked levels. The method is simple, rapid and accurate for the simultaneous determination of eleven coumarins in cosmetics.

Key words: cosmetics, ultra high performance liquid chromatography, liquid chromatography-tandem mass spectrometry, coumarins

中图分类号:

TQ658

陈卫,张斌,陈丽波,钱叶飞,赵琪,贾昌平. 超高效液相色谱法测定化妆品中11种香豆素类化合物及质谱确证[J]. 日用化学工业, 2020, 50(11): 804-808.

CHEN Wei,ZHANG Bin,CHEN Li-bo,QIAN Ye-fei,ZHAO Qi,JIA Chang-ping. Simultaneous determination of eleven coumarins in cosmetics by ultra high performance liquid chromatography and verification by liquid chromatography-tandem mass spectrometry[J]. China Surfactant Detergent & Cosmetics, 2020, 50(11): 804-808.

图/表 5

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参考文献 7

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序号	化合物名称	一级母离子（m/z）	二级子离子（m/z）	碰撞能量/eV
1	8-羟基补骨脂素	203.03	131.05,147.04,175.04	25
2	补骨脂素	187.04	115.05,131.05,143.05	25
3	6-甲基香豆素	161.06	79.05, 91.05,105.07	25
4	异补骨脂素	187.04	115.05,131.05,143.05	25
5	8-甲氧基补骨脂素	217.05	118.04,174.03,202.03	35
6	5-甲氧基补骨脂素	217.05	118.04,174.03,202.03	35
7	新补骨脂异黄酮	323.10	137.02,199.07,255.07	35
8	补骨脂二氢黄酮	325.10	149.02,205.09,269.08	25
9	三甲沙林	229.10	142.08,173.10,201.09	25
10	欧前胡素	271.10	131.05,147.04,203.03	25
11	异欧前胡素	271.10	131.05,147.04,203.03	35

化合物	保留时间/min	线性范围/（mg·L^-1）	回归方程	相关系数	方法检出限/（mg·kg^-1）
8-羟基补骨脂素	6.12	0.1~10	A=44 523 ρ+113	0.999 8	0.4
补骨脂素	11.25	0.1~10	A=83 546 ρ+205	0.999 7	0.3
6-甲基香豆素	11.57	0.1~10	A=41 812 ρ-468	0.999 7	0.6
异补骨脂素	12.04	0.1~10	A=74 359 ρ+680	0.999 7	0.3
8-甲氧基补骨脂素	12.64	0.1~10	A=63 149 ρ+539	0.999 7	0.3
5-甲氧基补骨脂素	14.77	0.1~10	A=42 110 ρ+882	0.999 8	0.3
新补骨脂异黄酮	16.38	0.1~10	A=45 046 ρ+674	0.999 8	0.1
补骨脂二氢黄酮	16.59	0.1~10	A=21 795 ρ+387	0.999 8	0.2
三甲沙林	17.00	0.1~10	A=62 437 ρ+1166	0.999 7	0.1
欧前胡素	17.21	0.1~10	A=48 705 ρ+ 246	0.999 7	0.1
异欧前胡素	17.77	0.1~10	A=37 029 ρ+ 595	0.999 8	0.2

化合物	平均回收率/%			RSD/%
化合物	低水平	中水平	高水平	低水平	中水平	高水平
8-羟基补骨脂素	103.4	105.0	106.7	1.4	0.8	0.5
补骨脂素	104.0	106.5	108.6	1.5	0.6	0.5
异补骨脂素	99.1	105.6	108.7	1.9	0.6	0.6
8-甲氧基补骨脂素	100.7	105.6	109.0	1.7	0.4	0.6
5-甲氧基补骨脂素	99.0	106.3	108.1	1.5	0.9	0.8
新补骨脂异黄酮	100.0	104.3	108.5	1.4	0.8	0.7
补骨脂二氢黄酮	96.6	99.2	105.7	2.2	0.6	1.0
三甲沙林	95.3	103.3	107.8	1.8	0.8	0.9
欧前胡素	101.7	102.2	107.6	2.6	0.7	0.6
异欧前胡素	100.4	105.8	108.2	2.3	0.8	1.1
6-甲基香豆素	99.7	106.6	110.0	1.5	0.7	0.6

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