UPLC-MS/MS测定化妆品中15种禁用物质

doi:10.3969/j.issn.1001-1803.2020.01.012

摘要/Abstract

摘要：

建立了同时测定化妆品中苯海拉明、曲吡那敏和氯苯那敏等15种禁用物质的超高效液相色谱-串联质谱（UPLC-MS/MS）分析方法。采用Waters Acquity UPLC ?BEH C₁₈色谱柱（1.7 μm×2.1 mm×50 mm）进行分离,以甲醇和乙酸铵-甲酸水溶液为流动相梯度洗脱,流速为0.4 mL/min,进样量为3 μL,在电喷雾正离子模式下（ESI ⁺）,采用多反应监测（MRM）模式进行定性和定量。结果表明,所建立的方法在相应的浓度范围内线性关系良好,线性相关系数为0.999 3~0.999 9,加标回收率在87.21%~99.39%（n=3）之间,相对标准偏差为2.28%~5.27%（n=6）,检出限为0.004 3~0.239 2 mg/kg,定量限为0.014 3~0.797 2 mg/kg。本方法准确、可靠,适用于化妆品中多种禁用物质的同时测定。

关键词: 禁用物质, 化妆品, 超高效液相色谱-串联质谱法

Abstract:

An analytical method of ultra performance liquid chromatography-triple quadrupole mass spectrometry （UPLC-MS/MS） was developed for the simultaneous determination of 15 prohibited substances （diphenhydramine, tripelennamine, chlorpheniramine, etc.） in cosmetics. The UPLC separation was carried out on a Waters Acquity UPLC? BEH C₁₈ column （1.7 μm × 2.1 mm × 50 mm） by gradient elution using methanol and ammonium acetate-formic acid solution. The flow rate was 0.4 mL/min and the sample injection amount was 3 μL. The electrospray ionization source in positive ion mode （ESI ⁺） was used for qualitative analysis and quantitative analysis of fifteen prohibited drugs in the multiple reaction monitoring （MRM） mode. The established method exhibited a good linear relationship in the corresponding concentration range. The linear correlation coefficient is 0.999 3-0.999 9; the recoveries of standard addition are between 87.21%-99.39% （n=3）; the relative standard deviation is 2.28%-5.27% （n=6）; the detection limit range is 0.014 3-0.239 2 mg/kg; the limit of quantification range is 0.004 3-0.797 2 mg/kg. The method is accurate and reliable, and is suitable for simultaneous determination of various prohibited substances in cosmetics.

Key words: prohibited substance, cosmetics, ultra performance liquid chromatography-triple quadrupole mass spectrometry

中图分类号:

TQ658

曹海荣,李晓宇,薛晓康. UPLC-MS/MS测定化妆品中15种禁用物质[J]. 日用化学工业, 2020, 50(1): 64-70.

CAO Hai-rong,LI Xiao-yu,XUE Xiao-kang. Determination of fifteen prohibited substances in cosmetics by ultra performance liquid chromatography-triple quadrupole mass spectrometry[J]. China Surfactant Detergent & Cosmetics, 2020, 50(1): 64-70.

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参考文献 16

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组分名称	母离子（m/z）	子离子（m/z）	锥孔电压/V	子离子的碰撞气能量/V
盐酸苯海拉明	256.2	167.1	26	12
盐酸曲吡那敏	256.2	211.1	26	14
马来酸氯苯那敏	275.1	230.1	34	15
盐酸异丙嗪	285.1	86.2	34	18
盐酸赛庚啶	288.2	96.2	34	28
地氯雷他定	311.1	259.1	35	24
盐酸氯丙嗪	319.1	86.2	34	21
马来酸溴苯那敏	319.1	274.0	34	18
盐酸羟嗪	375.2	201.0	34	19
氯雷他定	383.1	337.0	34	22
盐酸西替利嗪	389.1	201.0	34	20
奋乃静	404.2	171.1	34	24
盐酸氟奋乃静	438.2	143.1	34	30
阿司咪唑	459.3	135.1	34	35
特非那定	472.3	436.3	40	26

组分名称	线性范围/ （μg·L^-1）	回归方程	r	检出限/（mg·kg^-1）	定量限/（mg·kg^-1）
盐酸苯海拉明	5~100	y = 5 296.8x - 3 586.1	0.999 0	0.007 9	0.026 2
盐酸曲吡那敏	5~100	y = 8 508.2x -7 771.3	0.999 9	0.023 0	0.076 7
马来酸氯苯那敏	5~100	y = 3 593.8x -2 925.0	0.999 8	0.037 6	0.125 3
盐酸异丙嗪	5~100	y = 4 596.2x - 1 266.2	0.999 9	0.011 4	0.038 0
盐酸赛庚啶	5~100	y = 1 305.8x - 434.0	0.999 9	0.039 5	0.131 6
地氯雷他定	5~100	y = 306.6x - 225.1	0.999 8	0.061 7	0.205 6
盐酸氯丙嗪	5~100	y = 4 250.4x - 968.8	0.999 9	0.018 5	0.061 6
马来酸溴苯那敏	5~100	y = 2 290.4x - 6 689.9	0.999 6	0.239 2	0.797 2
盐酸羟嗪	5~100	y = 2 700.4x + 9 165.1	0.999 9	0.084 4	0.281 5
氯雷他定	5~100	y = 908.5x + 155.2	0.999 9	0.004 3	0.014 3
盐酸西替利嗪	5~100	y = 741.8x + 205.2	0.999 3	0.084 9	0.282 9
奋乃静	5~100	y = 851.0x + 73.6	0.999 9	0.032 5	0.108 2
盐酸氟奋乃静	5~100	y = 621.2x + 2.8	0.999 9	0.004 5	0.015 1
阿司咪唑	5~100	y = 2 057.3x - 1 029.6	0.999 8	0.054 2	0.180 7
特非那定	5~100	y = 1 134.2x + 1 957.1	0.999 9	0.010 1	0.033 7

组分名称	ρ（添加）/（μg·L^-1）	ρ（实际）/（μg·L^-1）	加标回收率/%	平均加标回收率/%	组分名称	ρ（添加）/（μg·L^-1）	ρ（实际）/（μg·L^-1）	加标回收率/%	平均加标回收率/%
盐酸苯海拉明	41.39	36.73	88.74	94.15	盐酸曲吡那敏	45.25	40.40	89.27	93.05
	62.08	58.32	93.93			67.88	62.25	91.71
	82.78	82.59	99.78			90.51	88.86	98.18
马来酸氯苯那敏	41.41	34.25	82.71	89.24	盐酸异丙嗪	42.25	39.13	92.62	99.39
	62.12	55.53	89.39			63.38	63.01	99.41
	82.83	79.20	95.63			84.51	89.70	106.15
盐酸赛庚啶	42.37	37.20	87.79	93.58	地氯雷他定	39.98	34.58	86.47	92.70
	63.55	58.81	92.54			59.98	56.01	93.39
	84.74	85.09	100.41			79.97	78.55	98.22
盐酸氯丙嗪	40.59	34.91	86.03	89.84	马来酸溴苯那敏	42.50	35.77	84.16	90.40
	60.88	54.78	89.98			63.76	56.41	88.48
	81.17	75.91	93.52			85.01	83.78	98.56
盐酸羟嗪	41.90	35.40	84.49	89.96	氯雷他定	40.45	35.63	88.08	93.55
	62.86	54.16	86.17			60.68	56.52	93.14
	83.81	83.16	99.23			80.91	80.44	99.42
盐酸西替利嗪	39.87	34.44	86.39	91.40	奋乃静	42.22	35.46	83.99	87.66
	59.80	53.71	89.81			63.33	55.34	87.39
	79.73	78.15	98.01			84.44	77.33	91.58
盐酸氟奋乃静	40.06	35.08	87.57	92.76	阿司咪唑	36.81	29.75	80.82	87.21
	60.09	55.35	92.10			55.21	47.74	86.46
	80.12	79.00	98.59			73.62	69.45	94.34
特非那定	40.14	35.04	87.30	92.83
	60.21	55.42	92.05
	80.28	79.59	99.14

组分名称	ρ（添加）/（μg·L^-1）	精密度/%	平均精密度/%	组分名称	ρ（添加）/（μg·L^-1）	精密度/%	平均精密度/%
盐酸苯海拉明	40	8.46	3.97	盐酸曲吡那敏	40	7.10	5.27
	60	2.33			60	5.66
	80	1.13			80	3.06
马来酸氯苯那敏	40	6.23	5.16	盐酸异丙嗪	40	5.03	2.87
	60	3.65			60	2.17
	80	5.59			80	1.42
盐酸赛庚啶	40	4.91	3.06	地氯雷他定	40	6.71	3.45
	60	2.34			60	2.26
	80	1.94			80	1.38
盐酸氯丙嗪	40	4.49	2.80	马来酸溴苯那敏	40	3.96	4.03
	60	1.97			60	3.65
	80	1.95			80	4.48
盐酸羟嗪	40	5.85	2.92	氯雷他定	40	3.32	2.82
	60	2.03			60	2.34
	80	0.87			80	2.79
盐酸西替利嗪	40	6.60	3.52	奋乃静	40	7.42	4.24
	60	2.47			60	2.93
	80	1.49			80	2.37
盐酸氟奋乃静	40	6.48	3.65	阿司咪唑	40	5.03	3.53
	60	2.08			60	3.15
	80	2.40			80	2.42
特非那定	40	3.14	2.28
	60	1.64
	80	2.05