QuEChERS-HPLC-MS/MS法测定4种化妆品基质中15种硝基咪唑类非法添加药物的基质效应研究

doi:10.3969/j.issn.1001-1803.2020.04.011

摘要/Abstract

摘要：

建立了QuEChERS-HPLC-MS/MS法测定4种化妆品基质中15种硝基咪唑类非法添加药物的方法,研究了在该方法下水剂、散粉、乳液和膏霜对15种硝基咪唑类药物的基质效应,并探讨了基质种类、基质质量浓度和药物质量浓度对基质效应的影响。结果表明：4种基质对15种硝基咪唑类药物均存在不同程度的基质效应,且多呈基质抑制效应,基质种类、基质质量浓度和药物质量浓度均会影响基质效应。因此,在日常检测化妆品中硝基咪唑类非法添加药物时要考虑基质效应对检测结果的影响。对于呈现弱基质效应的水剂和散粉类基质,可根据实际需求忽略其基质效应的影响;而对于基质效应明显的乳液和膏霜类基质,建议采用基质匹配标准曲线进行定量分析,以确保检测结果的准确性。

关键词: 基质效应, 高效液相色谱-串联质谱法, 化妆品, 硝基咪唑类, 非法添加

Abstract:

A QuEChERS coupled with high performance liquid chromatography tandem mass spectrometry （HPLC-MS/MS） method was developed for the detection of 15 nitroimidazole drugs illegally added in 4 kinds of cosmetic matrices. The matrix effects of 15 nitroimidazole drugs in water aqua, powder, lotion and cream, together with the influences of matrix type, matrix mass concentration and drug mass concentration on the matrix effects were discussed. The result show that the 4 kinds of cosmetic have different degrees of matrix effects on 15 nitroimidazole drugs, and most of them are matrix inhibitory effects, which are impacted by matrix type, matrix mass concentration and drug mass concentration. Therefore, it’s crucial to take matrix effect into consideration during the detection of the nitroimidazoles illegally added in cosmetic products. For some matrices with weak matrix effects, such as water aqua and powder, the matrix effects can be ignored according to actual needs. For emulsions and cream substrates with significant matrix effects, it is recommended to use a matrix-matched standard curve for quantitative analysis to ensure the accuracy of the test results.

Key words: matrix effect, HPLC-MS/MS, cosmetics, nitroimidazoles, illegally added

中图分类号:

TQ658

陈岑,颜琳琦,程巧鸳. QuEChERS-HPLC-MS/MS法测定4种化妆品基质中15种硝基咪唑类非法添加药物的基质效应研究[J]. 日用化学工业, 2020, 50(4): 275-281.

CHEN Cen,YAN Ling-qi,CHENG Qiao-yuan. Research of matrix effect of 15 nitroimidazole drugs illegally added in 4 kinds of cosmetic matrices by QuEChERS-HPLC-MS/MS methods[J]. China Surfactant Detergent & Cosmetics, 2020, 50(4): 275-281.

图/表 9

表 1

图 1

表 2

图 2

图 3

图 4

图 5

图 6

图 7

参考文献 19

[1]	Cronly M, Behan P, Foley B , et al. Rapid confirmatory method for the determination of 11 nitroimidazoles in egg using liquid chromatography tandem mass spectrometry[J]. Journal of Chromatography A, 2009,1216(46) : 8101-8109. doi: 10.1016/j.chroma.2009.04.074 pmid: 19446819
[2]	Xia Xi, Li Xiaowei, Zhang Suxia , et al. Simultaneous determination of 5-nitroimidazoles and nitrofurans in pork by high-performance liquid chromatography-tandem mass spectrometry[J]. Journal of Chromatography A, 2008,1208:101-108. doi: 10.1016/j.chroma.2008.08.055 pmid: 18762299
[3]	Ministry of Health of the People’s Republic of China. Hygienic standard for cosmetics [M]. Beijing: Military Medical Science Press, 2007: 39.
[4]	Lu Jian, Wu Zhongping, Che Wenjun , et al. Determination of nitroimidazoles in acne dispelling cosmetics with solid phase extraction and high performance liquid chromatography-tandem mass spectrometry[J]. China Surfactant Detergent & Cosmetics, 2014,44(11) : 652-660.
[5]	Zhang Xinxin, Gao Yuanhui, Hua Jin , et al. Determination of five kinds of nitroimidazole compound in whelk dispelling cosmetics by liquid chromatography-tandem mass spectrometry[J]. China Surfactant Detergent & Cosmetics, 2016,46(11) : 661-670.
[6]	Meng Qian, Zheng Rong, Wang Ke . Determination of 16 anti-ungal and nitroimidazole compounds in cosmetics by HPLC-MS-MS[J]. Chinese Journal of Health Laboratory Technology, 2016,26(6) : 784-788.
[7]	Meng Xianshuang, Bai Hua, Zhang Qing , et al. Simultaneous determination of 15 nitroimidazoles in cosmetics by HPLC coupled with electrospray ionization-tandem mass spectrometry[J]. Journal of AOAC International, 2014,97(6) : 1538-1545. doi: 10.5740/jaoacint.13-314
[8]	Shah V P, Midha K K, Findlay J W , et al. Bioanalytical method validation-a revisit with a decade of progress[J]. Pharmaceutical Research, 2001,17(12) : 1551-1557. doi: 10.1023/a:1007669411738 pmid: 11303967
[9]	Anastassiades M, Lehotay S J, Stajnbaher D , et al. Fast and easy multiresidue method employing acetonitrile extraction/partitioning and “dispersive solid-phase extraction” for the determination of pesticide residues in produce[J]. Journal of AOAC International, 2003,86(2) : 412-421. pmid: 12723926
[10]	Guo Haixia, Xiao Guiying, Zhang Xiqing , et al. Simultaneous determination of 121 veterinary drugs in pork by QuEChERS and ultra performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2015,33(12) : 1242-1250. doi: 10.3724/SP.J.1123.2015.09016
[11]	Ding Ho, Wang Zhiyuan, Xie Jianjun , et al. Determination of 24 antihyperglycemic, antihypotensive and antihyperlipidemic drugs illegaly added in health food samples by liquid chromatography-quadrupole-time of flight mass spectrometry[J]. Chinese Journal of Chromatography, 2016,34(6) : 583-590. doi: 10.3724/SP.J.1123.2016.02016
[12]	Chen Shaobo, Pu Yunyue, Wang Hairui , et al. Simultaneous and rapid screening of 112 prohibited drugs in cosmetics by high performance liquid chromatography-tandem mass spectrometry[J]. Journal of Instrumental Analysis, 2018,37(11) : 1302-1310.
[13]	Xu Wenjuan, Wang Zhengang, Ding Kuiying , et al. Detection of matrix effects of 17 carbamate pesticides in 5 vegetables by QuEChERS/LC-MS/MS method[J]. Journal of Instrumental Analysis, 2017,36(1) : 54-60.
[14]	Zhao Jinli, Wang Chenglong, Liu Jia , et al. Matrix effects of different vegetables in pesticide residue analysis by using QuEChERS combined with high-performance liquid chromatograph-tandem mass spectrometry[J]. Agrochemicals, 2018,57(10) : 742-746.
[15]	Qiu Shiting, Pu Fenglin, Hou Xue , et al. Matrix effects in the analysis of 36 pesticides residues in nine kinds of green leafy vegetables by ultra performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Pesticide Science, 2018,20(5) : 661-667.
[16]	Li Lichun, Liu Shugui, Yin Yi , et al. The amphenicols residues analysis in aquatic products and their matrix effects by QuEChERS method and UPLC-MS/MS[J]. Chinese Fishery Quality and Standards, 2018,8(6) : 32-39.
[17]	Yang Tingting, Yi Luyao, Xiong Wen , et al. Determination of matrix effects of nitrofuran metabolites residues in seven kinds of eggs and egg products by QuEChERS-quadrupole time-of-flight series mass spectrometry[J]. Meat Industry, 2018 ( 4) : 45-50.
[18]	Meng Minghui, He Zeying, Xu Yaping , et al. Simultaneous extraction and determination of antibiotics in soils using a QuEChERS-based method and liquid chromatography-tandem mass spectrometry[J]. Journal of Agro-Environment Science, 2017,36(8) : 1672-1679.
[19]	Liu Jinxi, Qin Shanshan, Feng Shuhui , et al. Matrix effects in the analysis of pesticides residues in edible fungi by HPLC-MS/MS[J]. Food Science, 2016,37(18) : 171-177.

序号	化合物	保留时间/min	母离子（m/z）	子离子（m/z）		碰撞能量/V
1	4-HMZ	3.07	114.2	68.2*,	84.2	15,12
2	MNI	4.15	128.2	82.1*,	111.1	15,15
3	MNZOH	4.29	188.2	123.2*,	126.2	15,14
4	MNZ	5.33	172.2	82.1*,	128.2	20,15
5	HMMNI	5.37	158.2	140.2*,	55.2	15,15
6	DMZ	5.95	142.2	96.2*,	81.2	15,20
7	RNZ	6.81	201.2	140.2*,	55.2	12,20
8	TerNDZ	7.00	186.2	82.2*,	128.2	25,15
9	NBI	7.46	164.2	118.2*,	91.1	18,30
10	SNZ	7.94	186.2	128.2*,	82.1	15,20
11	CMNI	8.81	162.2	116.1*,	145.1	17,15
12	TNZ	9.26	248.2	121.2*,	128.2	15,20
13	IPZOH	10.45	186.2	168.2*,	122.2	15,20
14	ONZ	10.88	220.2	82.1*,	128.2	25,15
15	IPZ	13.00	170.2	124.2*,	109.2	17,24

化合物	ME
	水剂		散粉		乳液		膏霜
	MC	DC	MC	DC	MC	DC	MC	DC
4-HMZ	0.84~0.96	0.66~0.98	0.81~0.85	0.83~0.97	0.42~0.63	0.54~0.66	0.86~0.91	0.89~0.95
MNI	0.89~1.00	0.97~1.07	0.93~0.96	0.90~1.05	0.39~0.44	0.40~0.51	0.94~0.96	0.95~0.98
MNZOH	0.90~0.92	0.89~1.07	0.90~0.93	0.77~0.92	0.57~0.61	0.65~0.72	0.91~0.93	0.97~1.01
MNZ	0.96~1.01	0.96~1.05	1.06~1.09	0.90~1.09	0.41~0.48	0.44~0.55	0.85~0.95	0.90~1.13
HMMNI	0.95~0.98	0.90~0.98	0.98~1.04	0.86~1.12	0.74~0.78	0.78~0.90	0.95~0.98	0.93~1.04
DMZ	0.97~1.01	0.93~1.07	0.98~1.02	0.97~1.08	0.91~0.96	0.95~0.97	0.92~0.95	0.94~1.05
RNZ	0.97~1.02	0.94~1.05	0.93~0.96	0.93~1.11	0.88~0.93	0.95~1.07	0.90~0.98	0.98~1.10
TerNDZ	0.95~1.02	0.92~1.04	0.95~1.01	0.94~1.15	0.93~0.95	0.92~0.97	0.95~0.98	0.99~1.21
NBI	0.92~0.97	0.93~1.08	0.87~0.90	0.90~1.01	0.93~0.95	0.95~1.01	0.92~0.96	0.98~1.07
SNZ	0.95~0.99	0.93~1.10	0.98~1.02	0.96~1.08	0.92~0.95	0.95~0.98	0.94~0.99	0.99~1.13
CMNI	0.96~0.98	0.95~1.10	0.98~1.02	0.91~1.17	0.89~0.92	0.91~1.09	0.96~1.02	0.91~1.07
TNZ	0.85~0.93	0.78~0.93	0.97~0.99	0.89~1.07	0.85~0.90	0.77~0.94	0.80~0.82	0.81~0.98
IPZOH	0.85~0.87	0.85~0.94	0.96~0.97	0.99~1.08	0.91~0.94	0.93~0.99	0.90~0.95	0.97~1.12
ONZ	0.96~1.00	1.00~1.21	0.99~1.02	0.87~1.17	1.01~1.07	1.06~1.17	0.65~0.74	0.71~0.80
IPZ	0.92~0.94	0.94~1.00	0.98~1.01	0.95~1.10	0.51~0.59	0.59~0.62	0.87~0.94	0.91~0.95