高效液相色谱串联质谱法测定化妆品中15种喹诺酮类抗生素

doi:10.3969/j.issn.1001-1803.2019.06.010

Abstract

Abstract:

A high performance liquid chromatography tandem mass spectrometry（HPLC-MS/MS） method was established for the determination of 15 quinolone antibiotics in cosmetics. The samples were extracted with 0.1% formic acid acetonitrile solution, degreased with n-hexane, separated by Thermo Hypersil GOLD C₁₈（2.1 mm×100 mm, 1.9 μm） column, then detected by triple quadrupole mass spectrometry multi-reaction monitoring mode（MRM） to determine retention time and relative ion abundance, and quantified by external standard method. The results show that all of the 15 quinolone antibiotics show good linearity in the range of 5.0-200 μg/L with the correlation coefficients greater than 0.995 0. The limit of detection and quantification of the method are 0.15 and 0.50 mg/kg, respectively. The average recoveries of the spiked samples were ranged from 80.1% to 104.9% and the relative standard deviations（RSD, n=6） were in the range of 1.0%-7.4%. The method is accurate and reliable, which meets the requirements of the determination of quinolone antibiotics in cosmetics.

Key words: high performance liquid chromatography tandem mass spectrometry, cosmetics, antibiotics, quinolones

CLC Number:

TQ658

LU Jian,XUN Zhi-qing,WANG Chen-xia,GUO Xin-dong,YANG Yang,WU Zhong-ping. Determination of 15 quinolone antibiotics in cosmetics by liquid chromatography tandem mass spectrometry[J].China Surfactant Detergent & Cosmetics, 2019, 49(6): 403-409.

Figures/Tables 5

Tab. 1

Fig. 1

Tab. 2

Tab. 3

Tab. 4

Recoveries and RSDs of the analytes in cosmetics（n=6）"

化妆品基质	添加量/（mg·kg^-1）	爽肤水		乳液		非蜡基膏霜
化妆品基质	添加量/（mg·kg^-1）	回收率/%	RSD/%	回收率/%	RSD/%	回收率/%	RSD/%
依诺沙星	0.5	82.5	2.1	81.7	1.8	84.8	3.3
	1.0	87.8	1.5	88.6	2.6	91.6	4.5
	5.0	96.5	1.2	103.3	3.4	93.8	2.6
麻保沙星	0.5	81.8	1.4	81.7	1.6	85.8	3.8
	1.0	90.7	2.8	88.7	2.1	87.3	2.7
	5.0	96.7	2.1	97.9	3.4	93.2	1.8
诺氟沙星	0.5	80.8	3.4	81.1	2.8	85.8	4.5
	1.0	92.5	2.4	87.2	1.8	89.1	2.6
	5.0	94.1	2.9	96.3	2.7	99.2	3.1
氧氟沙星	0.5	81.1	3.6	82.2	3.6	87.6	2.7
	1.0	89.5	2.8	88.2	5.1	87.4	1.9
	5.0	90.6	3.1	100.5	4.8	101.9	3.4
氟罗沙星	0.5	86.1	3.1	84.1	5.7	87.4	2.8
	1.0	91.3	2.5	91.4	4.2	93	1.7
	5.0	94.1	1.2	103.4	3.6	95.1	2.8
培氟沙星	0.5	81.7	3.6	86.6	3.7	86.9	2.8
	1.0	90.3	5.2	89.2	2.5	90.4	3.8
	5.0	94.2	6.1	104.6	5.8	101.1	4.5
环丙沙星	0.5	84.4	4.8	80.1	1.6	86.4	1.8
	1.0	91.6	4.6	87.5	4.1	91.6	5.5
	5.0	90.2	6.2	104.9	5.6	92.8	4.8
洛美沙星	0.5	80.7	4.9	84.8	3.6	84.8	6.4
	1.0	90.6	2.7	87.4	1.0	88.5	3.1
	5.0	100.9	2.8	99.7	1.8	91.2	1.2
丹诺沙星	0.5	83.5	4.9	81.7	5.1	86.9	4.8
	1.0	90.2	2.7	90.2	3.2	90.6	5.1
	5.0	96.3	3.0	91.6	2.1	103.7	2.4
恩诺沙星	0.5	84.5	2.9	81.8	3.3	87.3	3.9
	1.0	88.4	3.4	89.2	5.3	87.5	1.2
	5.0	91.8	4.9	94.7	1.0	100.7	3.5
奥比沙星	0.5	82.6	3.6	80.8	3.8	81.4	6.2
	1.0	88.8	3.9	87.6	2.3	92.1	3.0
	5.0	100.5	2.7	94.7	2.9	94.9	1.1
沙拉沙星	0.5	87.8	3.6	80.2	6.4	83.6	7.4
	1.0	92.4	4.8	89.1	1.8	89.1	3.8
	5.0	99.2	2.9	104.5	3.0	104.6	3.5
司帕沙星	0.5	86.4	3.3	81.4	1.9	85.4	1.6
	1.0	90.7	5.2	92.6	3.9	88.5	3.3
	5.0	96.4	4.7	93.2	5.3	94.3	2.1
双氟沙星	0.5	80.3	6.6	84.1	2.1	81.1	2.5
	1.0	90.5	2.4	92.3	5.7	90.6	1.3
	5.0	100.1	5.1	93.2	2.8	101.0	3.2
莫西沙星	0.5	84.9	6.0	86.1	4.4	86.8	4.5
	1.0	87.4	4.5	88.1	2.4	90.5	2.1
	5.0	99.1	5.3	102.3	3.5	100.8	2.4

Tab. 4

References 10

[1]	Song Ying, Jiang Zhenzhou, Zhang Luyong . Advances in studies on quinolone resistance and its mechanisms[J]. Drug Evaluation Research, 2012,35(3) : 199-203.
[2]	Sheng Zhaojun, Chen Xiaole, Zhang Yan , et al. Research progress of quinolones[J]. Shandong Chemical Industry, 2018,47(13) : 42-43, 45.
[3]	Yang Yanwei, Liu Siran, Zhang Weiqiang , et al. Investigation of substances prohibited in cosmetic products[J]. Journal of Environmental and Health, 2017,34(1) : 48-52.
[4]	Chen Qiang, Bing Naici, Xie Hongyong , et al. A study on antibiotics pollution status in different environment media and research progress of detection methods[J]. Environmental Monitoring and Forewarning, 2017,9(5) : 24-31.
[5]	Dong Hengtao, Yao Jinting, Hao Hongyuan , et al. Determination of 14 quinolones residues in surface water by UHPLC-MS /MS[J]. Environmental Chemistry, 2018,37(6) : 1436-1439.
[6]	Zong Jingjing, Zhang Xiaojun, Yan Zhongyong , et al. Detection of 15 quinolones in aquatic products by colloidal gold immunochromatography assay[J]. PTCA (Part B: Chem Anal) , 2018,54(5) : 591-595.
[7]	Li Peipei, Guo Yuanming, Chen Xuechang , et al. Chromatographic detection of quinolones residues in animal tissues[J]. Food Science, 2013,34(3) : 303-307.
[8]	Zhang Yuan, Zhou Weie, Li Shaohui , et al. Research progress in pretreatment technologies and detection methods of quinolones residues in foods[J]. Science and Technology of Food Industry, 2016,37(5) : 378-383.
[9]	Chen Jing, Zheng Rong, Ji Shen , et al. Determination of 19 quinolone antibiotics in cosmetics by ultra performance liquid chromatography[J]. Chinese Journal of Analytical Chemistry, 2013,41(6) : 931-935.
[10]	Zheng Yanming, Guo Xindong, Xian Yanping , et al. Determination of seven fluoroquinolones in cosmetics by reversed-phase high performance liquid chromatography[J]. Journal of Instrumental Analysis, 2009,28(2) : 235-238.

化合物	保留时间/min	母离子（m/z）	子离子（m/z）	DP/V	CE/V	CXP/V
依诺沙星	4.13	321.0	303.0*	50	30	15
依诺沙星	4.13	321.0	232.0	50	26	15
麻保沙星	4.14	363.1	320.2*	55	23	15
麻保沙星	4.14	363.1	345.2	55	29	15
诺氟沙星	4.45	320.1	276.0*	50	25	16
诺氟沙星	4.45	320.1	233.0	50	35	16
氧氟沙星	4.46	362.3	318.2*	75	27	9
氧氟沙星	4.46	362.3	261.0	75	38	9
氟罗沙星	4.47	370.0	326.0*	80	19	15
氟罗沙星	4.47	370.0	269.0	80	26	15
培氟沙星	4.58	334.2	316.2*	60	25	12
培氟沙星	4.58	334.2	290.3	60	27	15
环丙沙星	4.65	332.3	288.1*	80	30	18
环丙沙星	4.65	332.3	245.0	80	25	18
洛美沙星	4.89	352.3	265.2*	65	33	15
洛美沙星	4.89	352.3	308.3	65	26	15
丹诺沙星	4.93	358.1	340.2*	50	27	15
丹诺沙星	4.93	358.1	283.2	50	34	15
恩诺沙星	5.21	360.3	316.3*	55	37	9
恩诺沙星	5.21	360.3	245.0	55	25	18
奥比沙星	5.32	396.2	352.3*	50	25	15
奥比沙星	5.32	396.2	295.3	50	30	15
沙拉沙星	6.11	386.1	342.2*	70	34	15
沙拉沙星	6.11	386.1	299.1	70	27	15
司帕沙星	6.21	393.5	349.2*	65	29	15
司帕沙星	6.21	393.5	292.2	65	35	15
双氟沙星	6.22	400.3	356.2*	80	34	15
双氟沙星	6.22	400.3	299.1	80	28	15
莫西沙星	6.81	402.5	384.5*	70	30	15
莫西沙星	6.81	402.5	364.5	70	30	15

化合物	线性方程	线性范围/ （μg·L^-1）	相关系数	方法检出限/（mg·kg^-1）	方法定量限/（mg·kg^-1）
依诺沙星	y=2 377.7x+17 432	5.0~200	0.999 1	0.15	0.50
麻保沙星	y=7 091.1x-44 365	5.0~200	0.996 1	0.15	0.50
诺氟沙星	y=2 073.7x+3 172.9	5.0~200	0.999 7	0.15	0.50
氧氟沙星	y=17 449x+17 992	5.0~200	0.999 8	0.15	0.50
氟罗沙星	y=2 651.6x+4 737.1	5.0~200	0.999 3	0.15	0.50
培氟沙星	y=9 925.0x-70 357	5.0~200	0.998 4	0.15	0.50
环丙沙星	y=1 930.8x+1 120.1	5.0~200	0.999 9	0.15	0.50
洛美沙星	y=9 569.3x+47 256	5.0~200	0.999 2	0.15	0.50
丹诺沙星	y=10 722x+82 434	5.0~200	0.998 9	0.15	0.50
恩诺沙星	y=2 915.9x+5 331.5	5.0~200	0.999 1	0.15	0.50
奥比沙星	y=21 171x-136 322	5.0~200	0.999 2	0.15	0.50
沙拉沙星	y=1 776.5x+733.29	5.0~200	0.998 7	0.15	0.50
司帕沙星	y=11 188x-76 514	5.0~200	0.999 6	0.15	0.50
双氟沙星	y=5 519.5x-917.71	5.0~200	0.999 7	0.15	0.50
莫西沙星	y=10 290x-83 638	5.0~200	0.998 9	0.15	0.50

化合物	基质效应
化合物	爽肤水	乳液	非蜡基膏霜
依诺沙星	0.818	0.746	0.715
麻保沙星	1.020	0.868	0.779
诺氟沙星	0.818	0.729	0.703
氧氟沙星	0.921	0.838	0.718
氟罗沙星	1.010	0.838	0.701
培氟沙星	0.918	0.844	0.749
环丙沙星	0.912	0.882	0.805
洛美沙星	0.965	0.780	0.741
丹诺沙星	0.926	0.863	0.814
恩诺沙星	0.971	0.837	0.812
奥比沙星	1.030	0.844	0.768
沙拉沙星	0.994	0.889	0.792
司帕沙星	0.910	0.860	0.708
双氟沙星	0.953	0.897	0.780
莫西沙星	0.913	0.830	0.736

[1]	Jingxuan Liu, Jianming Jin, Hua Wu. Botanical cosmetic ingredients （VII）Research and development of plant antifungal [J]. China Surfactant Detergent & Cosmetics, 2024, 54(3): 259-266.
[2]	Wu Bi, Xiaohong Pan, Xiaoqin Tu, Shuai Yin, Hui Sun. Analysis of the mechanism of anti-sensitive skin effect of cosmetic raw material Stephania tetrandra based on network pharmacology [J]. China Surfactant Detergent & Cosmetics, 2024, 54(3): 305-312.
[3]	Yaoyao Li. Study on the anti-aging and antioxidant effects of isosinensetin [J]. China Surfactant Detergent & Cosmetics, 2024, 54(3): 313-319.
[4]	Liyuan Zhang, Linqi Yan, Qiaoyuan Cheng, Lvye Qi, Rong Wang, Liuqian Huang. Determination of 14 kinds of α-hydroxy acids and hydroxy esters in cosmetics [J]. China Surfactant Detergent & Cosmetics, 2024, 54(3): 353-359.
[5]	Wei Xu, Po Zou, Changyu Li, Ming Yang, Yan Lu, Huiliang Li. Determination of 36 stimulants in cosmetics by ultra performance liquid chromatography-tandem mass spectrometry [J]. China Surfactant Detergent & Cosmetics, 2024, 54(3): 360-368.
[6]	Kangfu Zhou, Yixuan Zhi, Feifei Wang, Yazhuo Shang. New emulsion system and its application in cosmetics （VI）Microemulsion [J]. China Surfactant Detergent & Cosmetics, 2024, 54(2): 139-148.
[7]	Zhen Xie, Wei Huang, Jinsong Zhang, Shuhuai Chen, Linji Qu, Rong Kuang. Study on biomarkers of corneal injury in the evaluation of eye irritation of cosmetics [J]. China Surfactant Detergent & Cosmetics, 2024, 54(2): 161-167.
[8]	Xiaohong Pan, Ziqi Gao, Zhen Chen, Shuai Yin, Haiping Huang, Bin Hu. Discussion on the current situation of research and management on the stability of cosmetic products in China [J]. China Surfactant Detergent & Cosmetics, 2024, 54(2): 201-208.
[9]	Li Lu, Fang Fang, Youlong Feng, Ling Cao. Screening for illegal addition of sulfonamides in cosmetic products using ultra-performance liquid chromatographytriple quadrupoletandem mass spectrometry with precursor ion scanning [J]. China Surfactant Detergent & Cosmetics, 2024, 54(2): 216-223.
[10]	Ren Wang, Yuanyang Wu, Jia Qiao, Linqi Yan, Cen Chen, Liyuan Zhang. Study on phenoxyethanol content in children’s cosmetics on the mark and preliminary risk assessment [J]. China Surfactant Detergent & Cosmetics, 2024, 54(2): 224-230.
[11]	Yixiang Lu, Liting Wu, Jimin Jiang, Hailu Chen, Xuan Huang. Determination of tolnaftate and liranaftate in cosmetics by high performance liquid chromatography and verification by high performance liquid chromatography-tandem mass spectrometry [J]. China Surfactant Detergent & Cosmetics, 2024, 54(2): 231-238.
[12]	Liyuan Zhang, Qiaoyuan Cheng, Cen Chen, Zehua Li, Liuqian Huang, Lvye Qi. Determination of 3 kinds of α-hydroxy acids and their esters in cosmetics by high performance liquid chromatography [J]. China Surfactant Detergent & Cosmetics, 2024, 54(1): 102-106.
[13]	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.
[14]	Xu Han, Jiajia Wu, Na Wu, Yazhuo Shang. New emulsion system and its application in cosmetics （V） Janus emulsion [J]. China Surfactant Detergent & Cosmetics, 2024, 54(1): 24-31.
[15]	Feng Liu, Yuanchang Deng, Guohong Ying, Xiaowei Wang. Establishment of duplex-PCR method for rapid detection of Pluralibacter gergoviae [J]. China Surfactant Detergent & Cosmetics, 2024, 54(1): 45-50.

Determination of 15 quinolone antibiotics in cosmetics by liquid chromatography tandem mass spectrometry

RichHTML

PDF (PC)

Like

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 5

References 10

Related Articles 15

Metrics

Comments

Recommended 10