超高效液相色谱-串联质谱法快速测定化妆品中14种性激素

doi:10.3969/j.issn.1001-1803.2020.02.011

摘要/Abstract

摘要：

建立了化妆品中14种性激素无基质效应影响的超高效液相-串联质谱分析方法。样品经饱和氯化钠分散后,采用乙腈提取,冷冻离心处理,用乙腈10倍稀释以消除基质效应影响后,以水-甲醇为流动相,梯度洗脱,采用多反应监测进行分析。结果显示,14种性激素在10~200 μg/L质量浓度范围内线性关系良好,相关系数（r）均在0.995以上,平均回收率为90.8%~115.2%。本方法准确,灵敏度高,专属性好,检出限低,可用于化妆品中14种性激素的定性及定量测定。

关键词: 超高效液相色谱-串联质谱, 化妆品, 性激素

Abstract:

A method of ultra high performance liquid chromatography-tandem mass spectrometry was developed for simultaneous determination of 14 sexual hormones in cosmetics without matrix effects. After the sample was dispersed in saturated sodium chloride, it was extracted with acetonitrile, frozen and centrifuged, and diluted 10 times with acetonitrile to eliminate the matrix effect. The extracts were separated using gradient elution of water and methanol as mobile phase. The analysis of the target compounds was performed under multiple reaction monitoring. The results show that the 14 sexual hormones have a good linearity in the range of 10-200 μg/L with correlation coefficients （r） more than 0.995, and the average recoveries of the method are 90.8%-115.2%. This method is accurate, sensitive, specific, low detection limit and can be used for the qualitative and quantitative determinations of 14 kinds of sexual hormones in cosmetics.

Key words: ultra high performance liquid chromatography-tandem mass spectrometry, cosmetics, sexual hormones

中图分类号:

TQ658

李卓,饶雅琨,张荻悦,张亚锋,高安成,张海龙. 超高效液相色谱-串联质谱法快速测定化妆品中14种性激素[J]. 日用化学工业, 2020, 50(2): 137-142.

LI Zhuo,RAO Ya-kun,ZHANG Di-yue,ZHANG Ya-feng,GAO An-cheng,ZHANG Hai-long. Rapid determination of 14 sexual hormones in cosmetics by ultra high performance liquid chromatography-tandem mass spectrometry[J]. China Surfactant Detergent & Cosmetics, 2020, 50(2): 137-142.

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参考文献 16

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序号	化合物	离子化模式	保留时间/min	母离子（m/z）	子离子（m/z）		传输电压/V	碰撞能量/V
1	雌三醇	ESI-	1.91	287.2	145.0,	171.1*	120	41,36
2	雌二醇	ESI-	4.85	271.2	143.1,	183.1*	115	52,40
3	睾丸酮	ESI+	5.84	289.2	97.1*,	253.2	64	22,17
4	炔诺酮	ESI+	5.91	299.2	91.1*,	231.2	68	40,18
5	甲睾酮	ESI+	6.79	303.3	97.1*,	285.2	64	24,15
6	己烯雌酚	ESI-	7.21	267.2	222.0,	251.1*	92	34,24
7	甲炔诺酮	ESI+	7.51	313.2	245.2*,	295.2	68	18,14
8	醋酸羟孕酮	ESI+	8.41	373.3	271.2,	313.2*	68	18,14
9	醋酸甲地孕酮	ESI+	9.05	385.3	224.2,	325.2*	65	26,13
10	醋酸氯地孕酮	ESI+	9.09	405.2	267.1,	345.1*	65	20,12
11	孕酮	ESI+	9.15	315.2	97.1*,	297.2	66	21,15
12	醋酸甲羟孕酮	ESI+	9.23	387.3	123.1,	327.2*	68	27,13
13	甲烯雌醇醋酸酯	ESI+	9.28	397.2	279.2,	337.2	65	19,13
14	己酸羟孕酮	ESI+	13.56	429.3	271.2,	313.2*	68	18,14

化合物	ME₁/%	ME₂/%	ME₃/%
雌三醇	33.1	94.0	99.2
雌二醇	103.5	97.5	101.8
睾丸酮	96.9	107.1	107.2
炔诺酮	95.2	104.3	108.3
甲睾酮	90.0	102.7	105.4
己烯雌酚	96.4	98.6	101.5
甲炔诺酮	97.5	107.8	108.3
醋酸羟孕酮	100.0	104.3	100.1
醋酸甲地孕酮	105.3	105.8	106.3
醋酸氯地孕酮	105.2	107.4	107.8
孕酮	102.7	104.0	101.8
醋酸甲羟孕酮	98.1	108.2	106.4
甲烯雌醇醋酸酯	94.5	108.4	107.1
己酸羟孕酮	69.0	98.9	98.4

序号	化合物	线性范围/（μg·L^-1）	线性方程	相关系数r	定量限/（mg·kg^-1）	检出限/（mg·kg^-1）
1	雌三醇	10~200	y =5.900×10³x + 2.928×10⁴	0.999 2	0.3	0.1
2	雌二醇	10~200	y =3.177×10³x + 1.944×10⁴	0.999 1	0.3	0.1
3	睾丸酮	10~200	y =6.267×10⁴x + 1.599×10⁴	0.999 9	0.02	0.005
4	炔诺酮	10~200	y =1.931×10⁴x + 6.331×10⁴	0.999 6	0.03	0.01
5	甲睾酮	10~200	y =6.139×10⁴x + 3.191×10⁵	0.997 6	0.03	0.01
6	己烯雌酚	10~200	y =1.440×10⁴x + 6.939×10⁴	0.999 7	0.2	0.05
7	甲炔诺酮	10~200	y =1.425×10⁵x + 4.133×10⁴	0.999 9	0.03	0.01
8	醋酸羟孕酮	10~200	y =2.555×10⁴x + 1.284×10⁴	0.999 7	0.03	0.01
9	醋酸甲地孕酮	10~200	y =8.266×10⁴x + 6.389×10⁵	0.998 5	0.006	0.002
10	醋酸氯地孕酮	10~200	y =6.778×10³x + 7.990×10⁴	0.995 5	0.03	0.01
11	孕酮	10~200	y =3.379×10⁴x + 1.149×10⁵	0.999 3	0.02	0.005
12	醋酸甲羟孕酮	10~200	y =3.756×10⁴x + 2.771×10⁵	0.998 6	0.006	0.002
13	甲烯雌醇醋酸酯	10~200	y =8.884×10⁴x + 5.147×10⁵	0.999 7	0.02	0.005
14	己酸羟孕酮	10~200	y =4.595×10⁴x + 1.065×10⁵	0.999 7	0.006	0.002

基质类型	添加水平/（μg·L^-1）	回收率/%					RSD/%
水	10	98.5	,	97.9	,	105.9	4.4
	50	93.9	,	101.7	,	90.8	5.8
	100	98.3	,	95.7	,	104.5	4.5
乳	10	107.8	,	96.8	,	95.9	6.9
	50	101.2	,	94.7	,	104.9	5.1
	100	98.5	,	103.5	,	94.2	4.7
霜	10	102.8	,	106.3	,	94.7	5.7
	50	93.8	,	101.4	,	103.7	5.2
	100	108.4	,	105.5	,	115.2	4.5