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

Abstract

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

CLC Number:

TQ658

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.

Figures/Tables 7

Tab. 1

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Tab. 5

References 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

Rapid determination of 14 sexual hormones in cosmetics by ultra high performance liquid chromatography-tandem mass spectrometry

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