UHPLC-MS/MS法测定甘草类化妆品中光甘草定的研究

doi:10.3969/j.issn.1001-1803.2021.02.013

摘要/Abstract

摘要：

建立了超高效液相色谱-三重四极杆串联质谱（UHPLC-MS/MS）法用于检测含甘草类化妆品中的光甘草定。针对膏霜乳液基质和液态水基样品,分别采用乙酸乙酯和甲醇作为提取溶剂,对前处理条件、色谱条件、质谱条件进行了考察,在多反应监测模式（MRM）下建立了UHPLC-MS/MS法,并考察了方法学参数。该方法线性关系良好,检出限为0.006 mg/kg,在两种基质中三个质量浓度水平的加标回收率范围为83.1%~113%。对31批标识含有甘草提取物、光果甘草（根、叶）提取物的样品进行检测,其中13批检出光甘草定,含量范围为低于定量限至944 mg/kg。该研究工作可用于评价化妆品中光果甘草提取物有效成分的含量水平。

关键词: 超高效液相色谱-串联质谱, 甘草, 光甘草定, 化妆品

Abstract:

An UHPLC-MS/MS method was developed for the determination of glabridin in cosmetic containing licorice. The glabridin in facial cream and toner samples was extracted with ethyl acetate and methanol, respectively. After optimizing the sample pretreatment and chromatography conditions, as well as mass spectrometry parameters, UHPLC-MS/MS analysis method was performed with MRM mode. The methodological parameters were investigated in detail. The results showed that the linear relationship is good and the detection limit is 0.006 mg/kg. The average recoveries of the two substrates ranged from 83.1% to 113% at low, medium and high mass concentrations. 31 Batches of samples labeled with licorice extracts were tested. Glabridin was detected in 13 batches with the content ranging from lower than LOQ to 944 mg/kg. The study can be used to evaluate the content of the active components of glycyrrhiza extract in cosmetics.

Key words: UHPLC-MS/MS, licorice, glabridin, cosmetic

中图分类号:

TQ658

董亚蕾,乔亚森,王启林,李莉,黄传峰,王海燕,孙磊. UHPLC-MS/MS法测定甘草类化妆品中光甘草定的研究[J]. 日用化学工业, 2021, 51(2): 161-165.

DONG Ya-lei,QIAO Ya-sen,WANG Qi-lin,LI Li,HUANG Chuan-feng,WANG Hai-yan,SUN Lei. Determination of glabridin in cosmetic by UHPLC-MS/MS method[J]. China Surfactant Detergent & Cosmetics, 2021, 51(2): 161-165.

图/表 5

图 1

图2

表1

表2

表3

参考文献 14

[1]	Ma Yongpeng, Zhang Hongxia, Du Zhizhi. Application of essential oils from aromatic plants of yunnan plateau in cosmetics[J]. Natural Product Research and Development, 2018,30:146-154.
[2]	Zhang Fenglan, Wu Jing, Wang Gangli, et al. Investigation on the using of whitening ingredients in skin whitening cosmetics[J]. Chinese Journal of Health Laboratory Technology, 2017,27:3012-3015.
[3]	Mourboul Ablise, Rena Kasimu, Ma Shuyan, et al. Isolation and antioxidant property of glabridin[J]. Natural Product Research and Development, 2007,19:675-677.
[4]	Tomohiro Yokota, Hiroyuki Nishio, Yasuo Kubota, et al. The inhibitory effect of glabridin from licorice extracts on melanogenesis and inflammation[J]. Pigment Cell Res, 1998,11:355-361. doi: 10.1111/j.1600-0749.1998.tb00494.x pmid: 9870547
[5]	Kim Y J, Uyama H. Tyrosinase inhibitors from natural and synthetic sources:structure, inhibition mechanism and perspective for the future[J]. CMLS, 2005,62:1707-1723. pmid: 15968468
[6]	Wang Ruixue, Zhao Zhen, Zhong Yan, et al. Synergistic effect of several kinds of whitening agent on inhibition of tyrosinase activity[J]. China Surfactant Deterg & Cosmetics, 2014,44:572-576.
[7]	Li Yuhui, Xu Deping, Zhang Lianfu. Simultaneous extraction of glabridin and glycyrrhizic acid from Glycyrrhiza glabra L.[J]. Natural Product Research and Development, 2011,23:547-550.
[8]	Wang Jianguo, Zhou Zhong, Liu Haifeng, et al. Application of active glycyrrhizic constituents to cosmetics[J]. China Surfactant Deterg & Cosmetics, 2004,34:249-251.
[9]	Kamal Y T, Singh Mhaveer, Tamboli E T, et al. Rapid RP-HPLC method for the quantification of glabridin in crude drug and in polyherbal formulation[J]. Journal of Chromatographic Science, 2012,50:779-784. doi: 10.1093/chromsci/bms063 pmid: 22661460
[10]	Lu Jun, Li Ying. Determination of 7 licorice components in cosmetics by HPLC[J]. Phys Testing Chem Anal part B: Chem Anal, 2015,51:655-658.
[11]	Gao Junfei, Zhu Quan, Duan Tingting, et al. Determination of 11 kinds of plant whitening ingredients in cosmetics by ultra performance liquid chromatography[J]. China Surfactant Deterg & Cosmetics, 2019,49:480-484.
[12]	Du Ruyun, Lu Zhiyun, Yu Chenghua. Determination of glabridin in cosmetics by high performance liquid chromatography[J]. Flavour Fragrance Cosmetics, 2014 (4) : 35-37.
[13]	Xi Shaofeng, Li Huiyong, Tan Jianhua, et al. Determination of active constituents of ginseng and glycyrrhizae in hair growth cosmetics by SPE-UPLC-Q-TOF MS[J]. Journal of Chinese Mass Spectrometry Society, 2015,36:341-349.
[14]	Hu Xinhua, Chen Ranshan, Yuan Jinsong. Content determination of glabridin in clycyrrhizae radix et rhizoma from different regions by HPLC[J]. China Pharmacy, 2016,27:824-826.

序号	前处理方式	检测方法	保留时间/min	检出限	参考文献
1	70%甲醇提取两次,旋蒸浓缩二倍	HPLC-DAD	24	0.9 ng	[10]
2	50%甲醇直接提取	UPLC-DAD	10	0.032 1 ng	[11]
3	甲醇直接提取	HPLC-PDA	7.83	0.15 mg/L	[12]
4	甲醇提取,SPE净化	UPLC-Q-TOF MS	5.45	0.03 mg/kg	[13]
5	膏霜乳液和面膜,乙酸乙酯提取;液态水基样品,甲醇直接提取	UHPLC-MS/MS	5.12	0.006 mg/kg	本文

样品基质	本底值	加标值/（ng·mL^-1）	实测值/（ng·mL^-1）	回收率/%	RSD/%
膏霜乳液	0	4.92	4.09	83.1	4.3
		9.85	9.37	95.2	4.5
		19.7	16.0	91.6	0.9
液态水基质	0	4.92	4.93	100	1.8
		19.7	22.3	113	2.1
		49.2	55.1	112	1.0

序号	样品名称	是否特殊用途化妆品	标识成分	含量/（mg·kg^-1）
1	光果甘草焕颜霜	否	光果甘草根提取物	0.033 4
2	滋润倍护乳	否	光果甘草根提取物	0.037 3
3	美白嫩肤面膜	否	光果甘草提取物	0.585
4	雪肌精华水	否	光果甘草根提取物	1.67
5	美白嫩肤睡眠面膜	是	光果甘草根提取物	12.3
6	滋养霜	否	光果甘草根提取物	13.2
7	美白祛斑精华乳	是	光果甘草根提取物	26.0
8	修护眼唇霜	否	光果甘草根提取物	27.1
9	渗透乳	否	光果甘草根提取物	31.8
10	美白修复霜	是	光果甘草根提取物	520
11	雪肌精华液	否	光果甘草根提取物	944
12	健肤沐浴露	否	甘草根提取物	0.020 4
13	美白保湿柔肤水	是	甘草根提取物	检出,低于定量限

[1]	柳婧璇, 金建明, 吴华. 化妆品植物原料（Ⅶ）——抗真菌的植物原料的研究与开发[J]. 日用化学工业（中英文）, 2024, 54(3): 259-266.
[2]	毕武, 潘小红, 涂晓琴, 殷帅, 孙辉. 基于网络药理学的化妆品原料粉防己抗敏作用机制分析[J]. 日用化学工业（中英文）, 2024, 54(3): 305-312.
[3]	李瑶瑶. 异橙黄酮的抗衰老及抗氧化功效研究[J]. 日用化学工业（中英文）, 2024, 54(3): 313-319.
[4]	许梦然, 赵华. 化妆品晒后修护功效评价方法研究进展[J]. 日用化学工业（中英文）, 2024, 54(3): 329-336.
[5]	张丽媛, 颜琳琦, 程巧鸳, 戚绿叶, 王容, 黄柳倩. 高效液相色谱法测定化妆品中14种α-羟基酸和羟基酸酯[J]. 日用化学工业（中英文）, 2024, 54(3): 353-359.
[6]	徐炜, 邹坡, 李长于, 杨铭, 鹿燕, 李慧良. 超高效液相色谱-串联质谱法测定化妆品中36种兴奋剂[J]. 日用化学工业（中英文）, 2024, 54(3): 360-368.
[7]	周康夫, 支奕轩, 王飞飞, 尚亚卓. 新型乳化体系及其在化妆品中的应用（Ⅵ）——微乳液[J]. 日用化学工业（中英文）, 2024, 54(2): 139-148.
[8]	谢珍, 黄微, 张劲松, 陈舒怀, 瞿霖吉, 匡荣. 化妆品眼刺激性评价中角膜损伤生物标志物研究[J]. 日用化学工业（中英文）, 2024, 54(2): 161-167.
[9]	潘小红, 高梓琪, 陈真, 殷帅, 黄海萍, 胡斌. 我国化妆品产品稳定性研究与管理现状的探讨[J]. 日用化学工业（中英文）, 2024, 54(2): 201-208.
[10]	芦丽, 方方, 冯有龙, 曹玲. 前体离子扫描超高效液相色谱-三重四级杆串联质谱法快速筛查化妆品中非法添加的磺胺类药物[J]. 日用化学工业（中英文）, 2024, 54(2): 216-223.
[11]	王任, 吴鸳鸯, 乔佳, 颜琳琦, 陈岑, 张丽媛. 市售儿童化妆品中苯氧乙醇的测定及初步风险特征评估[J]. 日用化学工业（中英文）, 2024, 54(2): 224-230.
[12]	鲁毅翔, 伍丽婷, 蒋济民, 陈海露, 黄璇. 化妆品中托萘酯、利拉萘酯的高效液相色谱定量及高效液相色谱-串联质谱确证[J]. 日用化学工业（中英文）, 2024, 54(2): 231-238.
[13]	张丽媛, 程巧鸳, 陈岑, 李泽桦, 黄柳倩, 戚绿叶. 高效液相色谱法测定化妆品中3种α-羟基酸及其酯[J]. 日用化学工业（中英文）, 2024, 54(1): 102-106.
[14]	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.
[15]	龙慧端, 鲁毅翔, 覃江兰, 张科明. 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[J]. 日用化学工业（中英文）, 2024, 54(1): 114-122.