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

Abstract

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

CLC Number:

TQ658

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.

Figures/Tables 7

Fig. 1

Tab. 1

Fig. 2

Fig. 3

Tab. 2

Tab. 3

Tab. 4

References 20

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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

Determination of nine nitrobenzene compounds in cosmetics by ultra performance liquid chromatography quadrupole-time-of-flight mass spectrometry

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