HPLC-MS/MS法测定育发类化妆品中22种禁用物质

doi:10.3969/j.issn.1001-1803.2021.09.015

Abstract

Abstract:

A method of high performance liquid chromatography-tandem mass spectrometry （HPLC-MS/MS）was developed for simultaneous determination of 22 prohibited substances in hair growth cosmetics. After dispersed in saturated sodium chloride solution, the samples were ultrasonically extracted with acetonitrile, and separated by gradient elution. The analysis was performed under multiple reaction monitoring （MRM）. Matrix-matched standard curve was used for quantitative analysis. The results show that the 22 prohibited substances show good linear relationship within the range of corresponding mass concentrations with the correlation coefficients （r） more than 0.995. The limits of detection （LODs） are 4.9-49.7 ng/g. The average recoveries are within the range of 80.7%-110.3% with the RSD （n=6） less than 15% in the two matrices. With the advantages of simplicity, sensitivity and accuracy, the established method is suitable for the analysis of the 22 prohibited substances in hair growth cosmetics.

Key words: HPLC-MS/MS, hair growth cosmetics, prohibited drug

CLC Number:

TQ658

Gong Xu,Fang Fang. Determination of 22 prohibited substances in hair growth cosmetics by HPLC-MS/MS method[J].China Surfactant Detergent & Cosmetics, 2021, 51(9): 910-917.

Figures/Tables 5

Tab. 1

Fig. 1

Tab. 2

Linear range, correlation coefficients, LODs and LOQs of the 22 compounds in water aqua and shampoo"

化合物	水剂		香波		线性范围/（ng·mL^-1）	检出限/（ng·g^-1）	定量限/ （ng·g^-1）
化合物	线性方程	相关系数r	线性方程	相关系数r	线性范围/（ng·mL^-1）	检出限/（ng·g^-1）	定量限/ （ng·g^-1）
米诺地尔	y=365 488.0x-22 004.0	0.999 9	y=261 151.0x-69 434.4	0.997 5	0.2~12.4	5.0	12.4
氢化可的松	y=26 732.0x+7 962.6	0.995 9	y=9 314.7x+2 381.0	0.998 4	0.5~24.7	9.9	24.7
螺内酯	y=33 434.8x+5 265.0	0.998 9	y=7 607.9x+3 478.7	0.997 9	1.0~49.9	20.0	49.9
雌酮	y=12 856.2x+925.0	0.999 9	y=394.5x+201.8	0.997 8	2.5~124.3	49.7	124.3
坎利酮	y=52 696.1x+1 977.3	0.999 6	y=11 268.7x+2 826.9	0.997 2	0.5~23.9	9.6	23.9
醋酸曲安奈德	y=45 225.1x+14 781.3	0.998 3	y=21 046.6x+5 066.0	0.995 6	0.5~24.5	9.8	24.5
黄体酮	y=36 058.0x+5 651.8	0.999 5	y=6 684.3x-758.2	0.999 9	0.5~24.4	9.8	24.4
非那雄胺	y=85 672.9x+32 056.6	0.996 1	y=29 720.3x-3 616.0	0.998 6	0.2~12.4	5.0	12.4
度他雄胺	y=821.1x+270.9	0.999 7	y=1 086.4x+226.3	0.999 3	2.5~123.0	49.2	123.0
雌三醇	y=193.0x+32.9	0.999 2	y=1 149.6x+1 335.4	0.999 5	2.5~123.7	49.5	123.7
雌二醇	y=3 374.9x+451.0	0.999 9	y=11.0x+25.1	0.997 4	2.5~121.9	48.8	121.9
睾酮	y=262 346.0x+6 140.3	0.999 9	y=11 063.0x-1 318.8	0.999 1	0.5~24.7	9.9	24.7
甲睾酮	y=146 573.0x+38 571.7	0.997 3	y=18 031.0x+11 006.1	0.995 7	0.5~24.9	9.9	24.9
己烯雌酚	y=4 012.2x-268.3	0.999 4	y=56.8x+19.4	0.999 2	0.5~24.9	9.9	24.9
孕三烯酮	y=185 056.0x+25 725.0	0.999 9	y=9 892.9x+588.9	0.999 6	0.5~24.7	9.9	24.7
炔诺孕酮	y=64 275.6x+8 746.3	0.998 3	y=19 343.8x-1 846.3	0.998 5	0.5~24.7	9.9	24.7
醋酸环丙孕酮	y=29 985.2x-2 147.4	0.999 7	y=4 660.8x+557.7	0.999 2	0.5~24.5	9.8	24.5
地塞米松	y=10 817.1x+3 253.9	0.999 9	y=5 079.7x+3 294.1	0.997 7	0.5~24.5	9.8	24.5
醋酸甲地孕酮	y=95 950.5x+26 177.8	0.999 5	y=17 279.3x-2 418.8	0.997 9	0.2~12.3	4.9	12.3
醋酸氯地孕酮	y=30 139.9x+4 350.4	0.998 3	y=5 595.4x+637.5	0.998 3	0.5~24.1	9.6	24.1
醋酸甲羟孕酮	y=72 289.7x+5 377.2	0.999 9	y=18 242.8x+2 947.3	0.999 6	0.2~12.3	4.9	12.3
己酸羟孕酮	y=27 616.4x+4 785.6	0.998 7	y=15 896.9x+3 191.2	0.997 2	0.5~24.5	9.8	24.5

Tab. 2

Tab. 3

Fig. 2

References 12

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编号	化合物	离子化模式	母离子（m/z）	碎片离子（m/z）	碰撞能量/eV	去簇电压/V
1	米诺地尔	ESI⁺	210.0	193.0^*	20	60
1	米诺地尔	ESI⁺	210.0	164.0	31	60
2	氢化可的松	ESI⁺	363.1	121.0^*	35	90
2	氢化可的松	ESI⁺	363.1	327.1	24	90
3	螺内酯	ESI⁺	341.0	91.0^*	80	107
3	螺内酯	ESI⁺	341.0	107.0	45	107
4	雌酮	ESI^-	269.1	145.0^*	-47	-100
4	雌酮	ESI^-	269.1	183.0	-47	-100
5	坎利酮	ESI⁺	341.1	107.0^*	45	107
5	坎利酮	ESI⁺	341.1	91.0	80	107
6	醋酸曲安奈德	ESI⁺	477.1	457.2^*	15	80
6	醋酸曲安奈德	ESI⁺	477.1	339.0	20	80
7	黄体酮	ESI⁺	315.1	97.1^*	25	135
7	黄体酮	ESI⁺	315.1	109.1	27	135
8	非那雄胺	ESI⁺	373.2	317.1^*	32	110
8	非那雄胺	ESI⁺	373.2	305.1	40	110
9	度他雄胺	ESI⁺	529.2	461.2^*	46	150
9	度他雄胺	ESI⁺	529.2	511.3	45	150
10	雌三醇	ESI^-	287.1	170.9^*	-48	-100
10	雌三醇	ESI^-	287.1	145.0	-51	-100
11	雌二醇	ESI^-	271.1	145.0^*	-50	-105
11	雌二醇	ESI^-	271.1	182.9	-50	-105
12	睾酮	ESI⁺	289.2	97.1^*	28	100
12	睾酮	ESI⁺	289.2	109.0	31	100
13	甲睾酮	ESI⁺	303.2	109.0^*	31	100
13	甲睾酮	ESI⁺	303.2	97.0	28	100
14	己烯雌酚	ESI^-	267.1	251.0^*	-34	-100
14	己烯雌酚	ESI^-	267.1	237.0	-35	-100
15	孕三烯酮	ESI⁺	309.1	241.0^*	30	100
15	孕三烯酮	ESI⁺	309.1	199.1	42	100
16	炔诺孕酮	ESI⁺	313.1	245.1^*	25	100
16	炔诺孕酮	ESI⁺	313.1	109.0	31	100
17	醋酸环丙孕酮	ESI⁺	417.1	357.1^*	24	100
17	醋酸环丙孕酮	ESI⁺	417.1	321.2	28	100
18	地塞米松	ESI⁺	393.1	373.0^*	18	85
18	地塞米松	ESI⁺	393.1	355.0	13	85
19	醋酸甲地孕酮	ESI⁺	385.2	325.1^*	20	90
19	醋酸甲地孕酮	ESI⁺	385.2	267.0	25	90
20	醋酸氯地孕酮	ESI⁺	405.1	345.1^*	18	95
20	醋酸氯地孕酮	ESI⁺	405.1	309.1	22	95
21	醋酸甲羟孕酮	ESI⁺	387.2	327.2^*	20	85
21	醋酸甲羟孕酮	ESI⁺	387.2	123.1	31	85
22	己酸羟孕酮	ESI⁺	429.3	313.1^*	18	80
22	己酸羟孕酮	ESI⁺	429.3	271.1	27	80

化合物	加入量/（ng·g^-1）	回收率/%		RSD/%
化合物	加入量/（ng·g^-1）	水剂	香波	水剂	香波
米诺地尔	49.7	100.1	92.6	1.6	2.0
米诺地尔	497.2	99.5	101.4	1.4	1.3
氢化可的松	98.7	100.9	89.5	8.5	5.3
氢化可的松	986.7	99.3	97.6	11.6	3.2
螺内酯	199.6	97.5	100.7	13.8	5.9
螺内酯	1 996.0	94.5	83.4	5.7	3.4
雌酮	497.2	107.4	97.8	7.6	5.7
雌酮	4 971.7	89.1	103.0	8.8	3.9
坎利酮	95.8	90.3	88.5	5.5	10.2
坎利酮	957.7	96.0	94.8	11.3	4.8
醋酸曲安奈德	98.1	98.6	105.0	2.6	3.9
醋酸曲安奈德	981.4	91.4	103.4	3.6	2.3
黄体酮	97.7	98.3	104.7	3.0	8.2
黄体酮	977.1	98.4	103.4	5.5	8.3
非那雄胺	49.7	102.3	91.6	2.9	12.8
非那雄胺	496.7	99.4	102.6	5.5	4.4
度他雄胺	491.8	102.0	92.9	7.9	4.9
度他雄胺	4 918.5	93.1	104.7	4.2	2.6
雌三醇	495.0	96.6	92.6	4.8	5.4
雌三醇	4 949.9	99.2	91.6	4.5	5.2
雌二醇	487.8	103.4	96.6	5.5	8.4
雌二醇	4 877.6	96.8	103.8	5.9	3.4
睾酮	98.7	95.5	110.3	3.3	12.7
睾酮	987.4	96.9	93.2	2.7	9.5
甲睾酮	99.4	99.0	93.8	7.1	12.4
甲睾酮	994.0	89.7	101.2	2.1	5.0
己烯雌酚	99.4	94.5	84.5	2.3	12.9
己烯雌酚	994.3	105.2	100.2	6.0	5.1
孕三烯酮	98.6	86.2	104.5	5.1	7.8
孕三烯酮	986.0	102.7	94.0	1.3	1.8
炔诺孕酮	98.7	95.1	95.1	6.3	10.1
炔诺孕酮	987.0	96.6	99.6	2.5	3.0
醋酸环丙孕酮	97.8	100.4	93.0	5.8	1.7
醋酸环丙孕酮	978.1	95.4	97.1	2.0	2.3
地塞米松	97.9	86.4	86.6	5.7	5.8
地塞米松	978.8	98.0	92.6	1.9	2.4
醋酸甲地孕酮	49.4	94.9	88.4	9.8	6.9
醋酸甲地孕酮	493.9	95.2	84.3	3.4	2.5
醋酸氯地孕酮	96.4	89.1	91.6	6.7	4.9
醋酸氯地孕酮	964.2	90.7	104.6	4.2	3.6
醋酸甲羟孕酮	49.1	80.7	97.3	9.5	8.9
醋酸甲羟孕酮	491.2	97.7	87.7	12.6	6.3
己酸羟孕酮	98.0	92.4	92.0	2.3	4.9
己酸羟孕酮	980.4	91.3	90.4	4.1	8.1

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Determination of 22 prohibited substances in hair growth cosmetics by HPLC-MS/MS method

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