UPLC-Q-TOF测定化妆品中9种硝基苯类化合物

doi:10.3969/j.issn.2097-2806.2024.06.016

摘要/Abstract

摘要：

建立了超高效液相色谱-四极杆-飞行时间质谱筛查确证化妆品中9种硝基苯类化合物的分析方法。样品经乙酸乙酯提取后，钯碳5% Pd催化氢化，以0.1%（V/V）甲酸水-乙腈为流动相在Poroshell 120 EC-C₁₈（100 mm×4.6 mm, 2.7 µm）色谱柱上进行梯度洗脱，正离子模式下采用信息依赖性扫描（Auto MS/MS CID）模式采集图谱，以保留时间、一级母离子精确质量数、同位素丰度比、二级子离子精确质量数构建筛查数据库并对检测结果检索，实现化妆品中9种硝基苯类化合物的筛查确证，以分子离子精确质量数提取色谱峰面积定量。结果表明，9种硝基苯类化合物的氢化产物线性关系良好，相关系数（r）大于0.999，方法的检出限为0.01~0.3 mg/kg，定量限为0.04~2.0 mg/kg。膏霜、化妆水、爽身粉、唇膏基质在三个加标水平下的回收率为85.2%~113%，RSD为0.23%~3.61%。该法准确、灵敏、专属性好，适用于化妆品中硝基苯类化合物的筛查和定量分析。

关键词: 超高效液相色谱, 四极杆-飞行时间质谱, 硝基苯类化合物, 化妆品

Abstract:

An ultra performance liquid chromatography-quadrupole-time-flight mass spectrometric method was developed for the simultaneous screening and determination of 9 nitrobenzene compounds, including nitrobenzene （NB）, 3, 4-dinitrotoluene （3, 4-DNT）, 2, 3-dinitrotoluene （2, 3-DNT）, 2, 4-dinitrotoluene （2, 4-DNT）, 2, 6-dinitrotoluene （2, 6-DNT）, 2, 5-dinitrotoluene （2, 5-DNT）, 3, 5-dinitrotoluene （3, 5-DNT）, 2-nitrotoluene （2-NT） and 1-chloro-4-nitrobenzene （ChNB） in cosmetics. Samples were extracted with ethyl acetate, and the extracts were further hydrogenated using 5% Pd/C catalyst. The target analytes were separated on a Poroshell 120 EC-C18 chromatographic column （100 mm×4.6 mm, 2.7 µm）. Gradient elution was carried out with 0.1% （V/V） formic acid aqueous solution and acetonitrile as the mobile phases. The eluent from the column was further detected using Q-tof MS with information dependent acquisition （Auto MS/MS） mode for MS data acquisition. A database, containing retention time, precise mass of parent ion, isotope abundance ratio and precise mass of fragment ion, was established for screening and confirming the nitrobenzene compounds. The quantitation analysis was carried out by extracting peak area with precise mass. Under optimal conditions, the analytes show good linear relationship within the range, with the correlation coefficient （r） not less than 0.999. The limits of detection are in the range of 0.01-0.3 mg/kg, and the limits of quantification are in the range of 0.04-2.0 mg/kg. Samples, such as cream, lotion, powder and lip balm, are fortified at three levels. The average spiked recoveries range from 85.2% to 113%, with the relative standard deviations （RSDs） ranging from 0.23% to 3.61%. The optimized method is accurate, sensitive, specific and suitable for the detection and screening of nitrobenzene compounds in cosmetics.

Key words: ultra performance liquid chromatography, quadrupole-time-flight mass spectrometry, nitrobenzene compounds, cosmetics

中图分类号:

TQ658

张科明, 刘雪年, 邓鸣, 鲁毅翔, 许杨彪. UPLC-Q-TOF测定化妆品中9种硝基苯类化合物[J]. 日用化学工业（中英文）, 2024, 54(6): 744-750.

Keming Zhang, Xuenian Liu, Ming Deng, Yixiang Lu, Yangbiao Xu. Determination of nine nitrobenzene compounds in cosmetics by ultra performance liquid chromatography quadrupole-time-of-flight mass spectrometry[J]. China Surfactant Detergent & Cosmetics, 2024, 54(6): 744-750.

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参考文献 20

[1]	Toxic Chemicals Management Office of the National Environmental Protection Administration, Environmental Protection Research Institute of Beijing Institute of Chemical Engineering, Ministry of Chemical Industry. Data manual for chemical toxicity, regulation & environment[M]. Beijing: China Environmental Science Press, 1992: 389-399.
[2]	Official Journal of the European Union. Regulation (EC) No 1223/2009 of the European Parliament and of the Council of 30 November 2009 on cosmetic products[S/OL]. Official Journal of the European Union, 2009: 59-209. http://eur-lex.europa.eu/legal-content/EN/TXT/?uri=celex%3A32009R1223.
[3]	National Medical Products Adiministration. Safety and Technical Standards for Cosmetics[S/OL]. Beijing: People’s Medical Publishing House, 2015: 12-13. http://www.nmpa.gov.cn/hzhp/hzhpfgwj/hzhpgzwj/20151223120001986.html.
[4]	Xue Zhifeng, Hu Zhijie, Yang Chun, et al. Determination of nitrobenzene compounds in water by liquid-liquid extraction and gas chromatography[J]. Analytical Instrumentation, 2021 (3) : 24-27.
[5]	Sun Bo. Method optimization of liquid-liquid extraction-gas chromatography for the determination of ten nitrobenzene compounds in water[J]. Zhejiang Chemical Industry, 2022, 53 (7) : 45-48.
[6]	Pan Jianjun, Zhang Xiaoting, Min Jie, et al. Determination of 15 kinds of nitrobenzene compounds in leather products by ASE-SPE-GC/MS[J]. China Leather, 2019, 48 (12) : 5-11.
[7]	Sun Ming. Rapid determination of nitrobenzene compounds in ambient air by GC-MS combined with NTD[J]. Chemical Industry Times, 2021, 35 (9) : 6-11.
[8]	Yuan Yanli, Zhang Shuyu, Liu Cheng, et al. Determination of aniline and nitrobenzene in soil by ultrasonic extraction-GC-MS[J]. Shandong Chemical Industry, 2021, 48 (23) : 115-116, 121.
[9]	Bai Jiang, Xiao Jianwei, Bai Mei, et al. Determination of 3 kinds of nitrobenzene compounds in water by purge and trap gas chromatography-mass spectrometry[J]. Environmental Protection and Circular Economy, 2021, 41 (8) : 77-80.
[10]	Cui Jun, Zhang Qiang, Gu Hua, et al. Determination of 15 kinds of nitrobenzene in water using dispersive liquid-liquid microextraction and gas chromatography-mass spectrometry[J]. Environmental Monitoring in China, 2020, 36 (6) : 127-133.
[11]	Gu Yanbin, Kou Liqing. Determination of dinitrobenzene in surface water by GC-MS[J]. Analytical Instrumentation, 2020 (4) : 42-44.
[12]	Lin Ningting, Xue Jianping, Chen Shanying, et al. Determination of 5 kinds of nitrobenzene compounds in textiles by gas chromatography-mass spectrometry[J]. The Light & Textile Industries of Fujian, 2020 (8) : 29-34.
[13]	Pan Jianjun, Zhang Xiaoting, Min Jie, et al. Determination of nitrobenzene compounds in textiles by accelerated solvent extraction-high performance liquid chromatography[J]. Textile Auxiliaries, 2019, 36 (12) : 57-60.
[14]	He Dong. Simultaneous determination of thirteen nitrobenzenes in cosmetics by gas chromatography-mass spectrometry[J]. Flavour Fragrance Cosmetics, 2014 (6) : 42-46.
[15]	Wang Xiaofang, Jin Quan, Ren Ren, et al. Simultaneous determination of 8 nitrobenzenes in cosmetics by high performance liquid chromatography[J]. Chinese Journal of Health Laboratory Technology, 2014, 24 (8) : 1094-1097.
[16]	Inspection and Quarantine of the People’s Republic of China. Determination of chloroform, benzene, carbon tetrachloride, chloropicrine, nitrobenzene and dichlorotoluene in cosmetics: SN/T 2933—2011[S]. Beijing: National Certification and Accreditation Administration, 2011.
[17]	Inspection and Quarantine of the People’s Republic of China. Determination of nitrobenzene, nitrotuluene and dinitrotoluene in cosmetics for import and export: SN/T 4442—2016[S]. Beijing: National Certification and Accreditation Administration, 2016.
[18]	Liu Xianxiang, Yang Yongjun, Yin Dulin, et al. Hydrogenation performance of o-chloronitrobenzene over Pd/C under atmospheric press[J]. Chemical Industry and Engineering Progress, 2016, 35 (2) : 524-527.
[19]	Yan Lijuan, Zhang Jie, Pan Chensong, et al. High throughput screening of tranquilizers in dairy products using ultra performance liquid chromatography coupled to high resolution time-of-flight mass spectrometry[J]. Chinese Journal of Analytical Chemistry, 2013, 41 (1) : 31-35.
[20]	Li Yangjie, Huang Jiaying, Fang Jihui, et al. Fast screening and confirmation of 73 common prohibited compounds in cosmetics by ultra performance liquid chromatography-quadrupole-time-of-flight high resolution mass spectrometry[J]. Chinese Journal of Chromatography, 2022, 40 (5) : 433.

化合物	氢化产物化学分子式	保留时间/min	母离子（m/z）			子离子（m/z）
化合物	氢化产物化学分子式	保留时间/min	理论值	实测值	偏差（10^-6）	子离子（m/z）
NB	C₆H₇N	4.36	94.065 1	94.065 3	2.1	—
3, 4-DNT	C₇H₁₀N₂	8.02	123.091 7	123.091 9	1.6	106.065 3, 108.067 9
2, 3-DNT	C₇H₁₀N₂	8.36	123.091 7	123.091 8	0.8	106.065 9, 108.068 5
2, 4-DNT	C₇H₁₀N₂	3.82	123.091 7	123.091 9	1.6	106.064 6, 108.067 6
2, 6-DNT	C₇H₁₀N₂	2.21	123.091 7	123.092 1	3.2	106.065 3, 108.068 0
2, 5-DNT	C₇H₁₀N₂	2.67	123.091 7	123.091 9	1.6	106.065 4, 108.068 2
3, 5-DNT	C₇H₁₀N₂	3.64	123.091 7	123.092 0	2.4	106.065 3, 108.068 2
2-NT	C₇H₉N	8.19	108.080 8	108.081 2	3.7	91.054 2, 93.057 3
ChNB	C₆H₆NCl	10.27	128.026 2	128.026 5	2.3	110.999 5, 93.057 7

化合物	溶剂线性方程	基质效应
		膏霜		化妆水		爽身粉		唇膏
		线性方程	η/%	线性方程	η/%	线性方程	η/%	线性方程	η/%
NB	y=6.21×10⁵x+1.06×10⁵	y=1.10×10⁶x+7.54×10⁴	78.0	y=5.28×10⁵x+6.49×10⁴	-14.9	y=6.57×10⁵x+1.92×10⁵	5.8	y=6.41×10⁵x+9.37×10⁴	3.3
3, 4-DNT	y=3.28×10⁶x-8.44×10⁵	y=5.93×10⁶x-8.52×10⁵	80.8	y=4.48×10⁶x-3.75×10⁵	36.4	y=3.34×10⁶x-4.52×10⁵	1.7	y=3.76×10⁶x-6.63×10⁵	14.5
2, 3-DNT	y=3.30×10⁶x-8.52×10⁵	y=5.92×10⁶x-8.16×10⁵	79.4	y=4.50×10⁶x-3.88×10⁵	36.5	y=3.36×10⁶x-5.21×10⁵	1.8	y=3.76×10⁶x-6.94×10⁵	14.1
2, 4-DNT	y=1.14×10⁶x+3.61×10⁴	y=1.09×10⁶x-6.28×10⁴	-4.4	y=1.28×10⁶x+2.36×10⁵	12.3	y=1.28×10⁶x+5.21×10⁴	12.0	y=6.91×10⁵x+7.65×10⁴	-39.4
2, 6-DNT	y=1.13×10⁶x+1.15×10⁵	y=1.74×10⁶x+1.87×10⁵	53.2	y=1.63×10⁶x+8.95×10⁴	43.8	y=1.37×10⁶x+8.09×10⁴	20.4	y=1.08×10⁶x+1.74×10⁵	-4.8
2, 5-DNT	y=1.79×10⁶x+1.21×10⁵	y=2.33×10⁶x+1.97×10⁵	30.5	y=1.68×10⁶x-1.98×10⁵	-5.7	y=1.95×10⁶x+7.73×10⁴	9.3	y=1.41×10⁶x+5.74×10⁴	-20.9
3, 5-DNT	y=5.53×10⁵x+3.97×10⁴	y=6.31×10⁵x+1.28×10⁵	14.1	y=5.35×10⁵x-1.16×10⁵	-3.3	y=6.25×10⁵x-9.71×10³	12.9	y=3.55×10⁵x+1.18×10³	-35.8
2-NT	y=6.77×10⁶x-1.04×10⁶	y=1.35×10⁷x+1.08×10⁶	99.1	y=1.86×10⁶x-5.18×10⁵	-72.5	y=7.31×10⁶x+1.52×10⁶	8.1	y=5.74×10⁶x+5.50×10⁵	-15.2
ChNB	y=1.34×10⁶x-1.44×10⁵	y=2.38×10⁶x-5.71×10⁵	77.9	y=3.54×10⁵x-1.42×10⁵	-73.6	y=1.46×10⁶x+3.17×10⁵	8.6	y=5.00×10⁵x-1.82×10⁴	-62.7

化合物	线性范围/（mg/L）	线性方程	相关系数（r）	检出限/（mg/kg）				定量限/（mg/kg）
化合物	线性范围/（mg/L）	线性方程	相关系数（r）	膏霜	化妆水	爽身粉	唇膏	膏霜	化妆水	爽身粉	唇膏
NB	0.3~15	y=6.21×10⁵x+1.06×10⁵	1.000 0	0.06	0.07	0.06	0.07	0.2	0.3	0.2	0.3
3, 4-DNT	1.0~50	y=3.28×10⁶x-8.44×10⁵	0.999 9	0.2	0.08	0.2	0.2	0.7	0.3	0.7	0.7
2, 3-DNT	1.0~50	y=3.30×10⁶x-8.52×10⁵	0.999 9	0.2	0.08	0.2	0.2	0.7	0.3	0.7	0.7
2, 4-DNT	0.5~25	y=1.14×10⁶x+3.61×10⁴	1.000 0	0.2	0.04	0.06	0.06	0.4	0.2	0.2	0.2
2, 6-DNT	0.2~10	y=1.13×10⁶x+1.15×10⁵	1.000 0	0.04	0.03	0.03	0.04	0.2	0.1	0.1	0.2
2, 5-DNT	0.2~10	y=1.79×10⁶x+1.21×10⁵	1.000 0	0.05	0.03	0.03	0.03	0.2	0.1	0.1	0.1
3, 5-DNT	1.0~50	y=5.53×10⁵x+3.97×10⁴	1.000 0	0.2	0.3	0.2	0.2	0.5	1.0	0.4	0.5
2-NT	0.1~5.0	y=6.77×10⁶x-1.04×10⁶	1.000 0	0.02	0.01	0.01	0.01	0.07	0.04	0.04	0.05
ChNB	1.0~50	y=1.34×10⁶x-1.44×10⁵	0.999 7	0.3	0.6	0.05	0.3	1.0	2.0	0.2	0.8

化合物	加标量/ （mg/kg）	膏霜		化妆水		爽身粉		唇膏
化合物	加标量/ （mg/kg）	回收率/%	精密度/%	回收率/%	精密度/%	回收率/%	精密度/%	回收率/%	精密度/%
NB	0.3	94.6	2.61	93.4	0.60	86.8	1.06	91.5	1.27
	0.6	113	0.67	101	2.94	104	2.34	97.7	0.53
	3.0	102	1.03	101	1.92	97.4	1.39	100	1.43
3, 4-DNT	1.0	98.7	0.48	96.5	1.82	93.4	1.05	100	0.90
	2.0	94.6	2.40	93.5	2.00	91.9	2.08	95.7	1.00
	10	104	0.67	90.5	3.17	97.7	0.53	96.4	1.01
2, 3-DNT	1.0	101	1.09	98.2	1.48	103	0.42	104	0.87
	2.0	98.9	2.28	93.4	2.36	94.0	1.88	96.6	1.45
	10	105	1.39	90.3	3.14	97.0	0.72	96.5	0.32
2, 4-DNT	0.5	95.7	1.08	93.1	1.52	99.2	0.42	98.1	2.27
	1.0	99.1	1.66	106	1.89	100	1.45	102	0.81
	5.0	105	2.46	102	0.74	87.3	1.36	97.2	2.35
2, 6-DNT	0.2	92.8	0.54	92.5	2.54	96.0	0.16	100	0.94
	0.4	96.2	2.65	103	0.69	102	0.64	104	0.75
	2.0	95.5	1.50	98.1	2.81	85.2	0.36	105	1.01
2, 5-DNT	0.2	89.0	2.04	99.6	1.19	100	0.78	94.7	1.43
	0.4	87.6	1.22	109	0.23	103	0.54	97.7	0.41
	2.0	94.7	1.31	104	1.43	92.6	1.19	102	0.46
3, 5-DNT	1.0	89.6	2.25	101	0.96	97.5	1.48	101	1.04
	2.0	90.5	0.67	101	1.19	103	0.26	101	1.14
	10	92.7	2.21	99.0	1.62	91.2	1.37	99.8	1.57
2-NT	0.1	94.6	2.68	111	2.36	101	0.58	85.2	0.98
	0.2	101	2.57	105	1.61	99.9	1.51	97.8	2.27
	1.0	92.8	2.91	97.2	2.47	105	0.44	89.0	1.61
ChNB	1.0	106	1.62	107	1.40	98.7	0.41	96.9	2.19
	2.0	106	1.59	103	2.15	102	1.04	97.7	1.59
	10	94.5	3.61	93.4	1.82	94.7	1.46	90.1	2.07