UHPLC-MS/MS法测定面膜化妆品中甘草、人参和黄芩类功效成分

doi:10.3969/j.issn.2097-2806.2024.01.015

摘要/Abstract

摘要：

建立了超高效液相色谱-三重四极杆质谱法（UHPLC-MS/MS）测定面膜化妆品中甘草功效成分（甘草苷、甘草酸）、人参功效成分（人参皂苷Rg1、人参皂苷Rb1、人参皂苷Re）和黄芩功效成分（黄芩苷）的方法，并用该方法对市售20批面膜样品进行风险监测。样品采用0.1%甲酸甲醇超声提取法，以0.1%甲酸水溶液-乙腈溶液为流动相，梯度洗脱，ACQUITY UPLC HSS T₃（2.1 mm×100 mm，1.8 μm）色谱柱分离，以UHPLC-MS/MS负离子模式检测。同时对样品前处理条件及色谱-质谱条件进行优化，并对方法学进行验证。结果表明：甘草苷、黄芩苷在0.25~100 ng/mL及人参皂苷Rg1、人参皂苷Rb1、人参皂苷Re和甘草酸在0.50~200 ng/mL质量浓度范围内呈良好线性关系，相关系数大于0.998;检出限为0.41~6.4 μg/kg（S/N=3）;基质中加标回收率为95.9%~109.1%，相对标准偏差小于4.9%（n=6）。该方法适用于面膜化妆品中甘草、人参和黄芩功效成分的测定。

关键词: 面膜化妆品, 甘草, 人参, 黄芩, 功效成分, 液质联用

Abstract:

An analytical method was established for the determination of Glycyrrhizae functional components （liquiritin and glycyrrhizic acid）, Ginseng functional components （ginsenoside Rg1, ginsenoside Rb1, ginsenoside Re） and Scutellariae functional components （baicalin） in facial mask cosmetics with ultra-high performance liquid chromatography triple quadrupole mass spectrometry （UHPLC-MS/MS）. This method was used to monitor the risk of 20 batches of samples sold on the market. The samples were extracted by ultrasonic method using 0.1% formic acid in methanol. The mobile phase was 0.1% formic acid aqueous solution-acetonitrile solution, and the gradient elution was carried out. The samples were separated on the ACQUITY UPLC HSS T₃（2.1 mm×100 mm, 1.8 μm） column and detected by UHPLC-MS/MS negative ion mode. At the same time, the pretreatment conditions and UHPLC-MS/MS conditions were optimized and the method was verified. The results show that the method shows good linearity in the mass concentration range of 0.25-100 ng/mL for liquiritin and baicalin, and 0.50-200 ng/mL for ginsenoside Rg1, ginsenoside Rb1, ginsenoside Re and glycyrrhizic acid, with R no less than 0.998. The limits of detection are in the range of 0.41-6.4 μg/kg （S/N=3）. The average recoveries in the sample matrix of facial masks are from 95.9% to 109.1%, with the relative standard deviations （RSDs） less than 4.9% （n=6）. This method is suitable for the determination of ginseng functional components in the ginseng cosmetics.

Key words: facial masks cosmetics, Glycyrrhizae, Ginseng, Scutellariae, functional components, UHPLC-MS/MS

中图分类号:

TQ658

陆林玲, 鲁辉, 闵春艳, 钱叶飞. UHPLC-MS/MS法测定面膜化妆品中甘草、人参和黄芩类功效成分[J]. 日用化学工业（中英文）, 2024, 54(1): 107-113.

Linling Lu, Hui Lu, Chunyan Min, Yefei Qian. Determination of functional components of Glycyrrhizae, Ginseng and Scutellariae in facial masks by UHPLC-MS/MS[J]. China Surfactant Detergent & Cosmetics, 2024, 54(1): 107-113.

图/表 7

图1

表1

图 2

表2

表3

表4

宣称含有甘草、人参、黄芩成分的面膜化妆品样品测定结果"

序号	名称	标识成分	检出成分	含量	检出成分与标识成分是否一致
1	凝芝水润滋养保湿面膜	甘草酸铵	甘草苷甘草酸	1.99 ng/g 29.88 μg/g	否
2	德胜本草水嫩亮肤透润面膜	甘草酸二钾、甘草根提取物、人参根提取物	甘草苷甘草酸人参皂苷Rg1	25.73 ng/g 108.17 μg/g 检出，低于定量限	是
3	希诺丝大米舒缓面膜	甘草酸二钾	甘草苷甘草酸	3.16 ng/g 221.57 μg/g	否
4	希诺丝黄金亮肤面膜	光果甘草提取物、黄芩根提取物	甘草苷甘草酸黄芩苷	2.53 ng/g 检出，低于定量限 46.53 ng/g	是
5	希诺丝芦荟保湿舒缓面膜	甘草酸二钾	甘草苷甘草酸	83.92 ng/g 162.78 μg/g	否
6	方嗅玻尿酸多肽水光精华蚕丝面膜	甘草根提取物	甘草酸	0.08 μg/g	是
7	八女仙容薰衣草舒缓柔肤面膜	甘草酸二钾	甘草苷甘草酸	6.88 ng/g 267.17 μg/g	否
8	丁家宜烟酰胺水光提亮面膜	甘草酸二钾、光果甘草提取物、黄芩根提取物	甘草苷甘草酸 —	5.43 ng/g 578.93 μg/g —	否
9	兰薇欧墨角藻柔润面膜	甘草酸二钾	甘草酸	200.41 μg/g	是
10	芮朵缤纷蔷薇盈柔面膜	甘草酸二钾	甘草酸	183.06 μg/g	是
11	相宜本草补水面膜	甘草酸二钾	甘草苷甘草酸	检出，低于定量限 287.08 μg/g	否
12	摩肌博士胶原水盈修护面膜	甘草酸二钾	甘草苷甘草酸	2.62 ng/g 1.81 mg/g	否
13	绿叶多肽提拉紧致面膜	甘草酸二钾、光果甘草提取物、黄芩提取物	甘草苷甘草酸 —	1.66 ng/g 206.12 μg/g —	否
14	辣木籽清洁净透黑膜	—	—	—	是
15	欣兰亭芍药靓肤舒缓面膜	—	—	—	是
16	安菲奈尔灵芝青春焕肤面膜	—	—	—	是
17	欣兰亭小分子肽嫩肤面膜	—	—	—	是
18	维他命C盈润焕采面膜	—	—	—	是
19	七分妆水果面膜	—	甘草酸	3.32 μg/g	否
20	悠莱软磷脂源生舒缓面膜	—	甘草酸	0.10 μg/g	否

表4

图 3

参考文献 15

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编号	物质名称	母离子（m/z）	DP/V	子离子（m/z）	CE/V
1	甘草苷	417.1	-95	255.1^*/135.1	-26/-38
2	黄芩苷	445.1	-50	269.1^*/175.0	-26/-16
3	人参皂苷Rg1	845.5	-150	799.4^*/637.5	-38/-38
4	人参皂苷Rb1	1 153.6	-80	1 107.6^*/945.5	-26/-60
5	人参皂苷Re	991.5	-150	945.5^*/637.5	-40/-55
6	甘草酸	821.1	-120	351.0^*/645.4	-58/-60

物质名称	线性方程	相关系数r	线性范围/ （ng/mL）	检出质量浓度/ （ng/mL）	LOD/ （ng/g）	定量质量浓度/ （ng/mL）	LOQ/ （ng/g）
甘草苷	Y=7.98×10⁴X+1.81×10³	0.999 3	0.27~108.37	0.02	0.42	0.07	1.4
黄芩苷	Y=4.73×10⁴X-1.23×10³	0.999 4	0.26~102.25	0.02	0.41	0.07	1.4
人参皂苷Rg1	Y=9.37×10³X-1.27×10³	0.998 2	0.53~210.90	0.12	2.3	0.39	7.8
人参皂苷Re	Y=1.28×10⁴X+2.99×10³	0.998 4	0.63~250.29	0.09	1.9	0.32	6.3
人参皂苷Rb1	Y=8.23×10³X+1.01×10³	0.998 1	0.63~251.78	0.17	3.4	0.56	11
甘草酸	Y=1.53×10⁴X+3.05×10³	0.999 0	0.45~179.45	0.08	1.6	0.26	5.2

编号	物质名称	加入量/（μg/g）	平均回收率/%	RSD/%
1	甘草苷	0.1，0.5，2.0	106.6，103.9，107.1	1.2，2.5，1.9
2	黄芩苷	0.1，0.5，2.0	105.4，100.3，104.1	2.6，4.1，2.3
3	人参皂苷Rg1	0.2，1.0，4.0	102.5，100.9，105.3	2.6，2.7，0.7
4	人参皂苷Rb1	0.2，1.0，4.0	98.1， 95.9，103.5	3.2，5.3，4.9
5	人参皂苷Re	0.2，1.0，4.0	102.5，101.4，109.1	3.8，4.5，3.0
6	甘草酸	0.2，1.0，4.0	102.9，102.8，112.6	3.2，1.2，3.3