UHPLC-MS/MS法同时测定面膜类化妆品中63种激素

doi:10.3969/j.issn.1001-1803.2021.12.014

摘要/Abstract

摘要：

建立了准确测定面膜类化妆品中63种激素类药物的超高效液相色谱-串联质谱（UHPLC-MS/MS）检测方法。对样品前处理条件进行了优化,采用乙腈为提取试剂进行超声辅助液液萃取。对色谱和质谱条件进行考察,在Scheduled MRM模式下,通过正负离子同时采集,建立了面膜类化妆品中63种糖皮质激素和性激素的检测方法。对该方法进行方法学考察,63种激素在线性范围之内的线性相关系数均不低于0.99。加标回收试验结果表明,各化合物的平均回收率范围为71.5%~119.5%,RSD均小于19.2%,证明本方法具有灵敏度高、测定准确、结果可靠的优点,能用于市售面膜类化妆品中63种激素的检测,满足化妆品中禁用物质高通量检测的要求。

关键词: 超高效液相色谱-串联质谱, 非法添加, 激素, 面膜, 化妆品

Abstract:

An UHPLC-MS/MS method for the determination of 63 hormone drugs in facial mask cosmetics was established. The pretreatment conditions and mass spectrometry parameters were optimized. The samples were extracted with acetonitrile by ultrasonic-assisted liquid-liquid extraction. Acetonitrile and water were employed as mobile phases and gradient elution was performed. The UHPLC separation was carried out on a Shim-pack XR-ODSⅢ column （2.0 mm×150 mm）. The samples were detected by tandem mass spectrometry detector with scheduled multiple reaction monitoring （Scheduled MRM） scanning method. And 63 kinds of glucocorticoids and sex hormones were scanned through simultaneous collection of positive and negative ions. Quantitative analysis was carried out by matrix standard curve with the peak areas of the daughter ions on high intensity. The detection limit, quantitative limit and linear equation of 63 hormone drugs were confirmed. The average recoveries are 71.5%-119.5%, and the RSD are less than 19.2%, indicating good recovery and high precision. This method is simple, sensitive and accurate, which can be employed to simultaneously detect illegal addition of hormone drugs in facial mask cosmetics. It is suitable for high through-put detection of prohibited substances in cosmetics. This research work provides technical support for the safety and quality supervision of facial mask cosmetics.

Key words: UHPLC-MS/MS, illegal addition, hormones, facial mask, cosmetics

中图分类号:

TQ658

乔亚森,董亚蕾,黄传峰,王海燕,孙磊. UHPLC-MS/MS法同时测定面膜类化妆品中63种激素[J]. 日用化学工业, 2021, 51(12): 1259-1268.

Qiao Yasen,Dong Yalei,Huang Chuanfeng,Wang Haiyan,Sun Lei. Simultaneous determination of 63 hormone drugs in facial masks by UHPLC-MS/MS[J]. China Surfactant Detergent & Cosmetics, 2021, 51(12): 1259-1268.

图/表 5

表 1

63种激素的质谱参数"

序号	化合物名称	母离子（m/z）	子离子（m/z）	DP	CE	RT/min
1	曲安西龙	395.2	357.1^*, 225.1	80	20, 27	7.70
2	泼尼松龙	361.2	343.1^*, 147.4	80	14, 38	10.51
3	泼尼松	359.2	341.1^*, 147	80	14, 35	10.49
4	异氟泼尼松	379.1	359^*, 341	70	12, 16	10.49
5	氢化可的松	363.2	121^*, 105.1	80	33, 67	10.66
6	可的松	361.2	163.1^*, 121	80	30, 40	10.77
7	甲基泼尼松龙	375.2	357.1^*, 161.1	66	15, 29	11.77
8	倍他米松	393.2	355^*, 146.8	80	18, 37	12.02
9	地塞米松	393.2	355^*, 146.8	80	17, 40	12.10
10	氟米松	411.2	253^*, 121.1	80	25, 47	12.12
11	倍氯米松	409.2	279.1^*, 147.1	80	28, 32	12.51
12	曲安奈德	435.2	338.9^*, 396.9	80	20, 15	12.81
13	地索奈德	417.2	323.3^*, 225.1	70	17, 30	12.86
14	氟尼缩松	435.2	321.2^*, 397.1	80	20, 16	12.95
15	氟轻松	453.2	121^*, 337.2	80	40, 20	13.13
16	曲安西龙双醋酸酯	479.2	440.9^*, 321	81	14, 22	13.13
17	氟氢缩松	437.2	361^*, 285.2	80	26, 30	13.28
18	泼尼松龙醋酸酯	403.2	147^*, 307.1	80	32, 17	13.33
19	氟米龙	377.2	278.9^*, 320.9	80	20, 16	13.61
20	氢化可的松醋酸酯	405.2	309.1^*, 120.8	80	24, 44	13.58
21	氟氢可的松醋酸酯	423.2	238.9^*, 120.9	80	39, 41	13.63
22	地夫可特	442.2	141.9^*, 123.9	80	40, 40	13.97
23	泼尼松醋酸酯	401.2	295^*, 146.8	80	23, 39	13.85
24	可的松醋酸酯	403.2	162.8^*, 343	80	37, 26	14.12
25	卤美他松	445.1	154.8^*, 287	80	32, 20	14.03
26	甲基泼尼松龙醋酸酯	417.2	399.2^*, 253.2	80	12, 25	14.63
27	倍他米松醋酸酯	435.21	309^*, 337	80	22, 16	14.68
28	睾酮	289.2	97.1^*, 109	113	35, 30	14.67
29	地塞米松醋酸酯	435.2	309^*, 337	80	20, 19	15.04
30	布地奈德	431.2	413.1^*, 146.9	80	15, 31	15.09
31	氢化可的松丁酸酯	433.2	345^*, 120.8	80	19, 31	15.23
32	孕三烯酮	309.1	241.1^*, 199.2	120	30, 44	15.33
33	氟米龙醋酸酯	419.2	279^*, 321	80	26, 21	15.58
34	甲基睾丸酮	303.2	108.9^*, 97	110	29, 30	15.58
35	氢化可的松戊酸酯	447.3	345.2^*, 120.8	80	21, 31	16.61
36	曲安奈德醋酸酯	477.2	338.9^*, 320.8	80	22, 25	16.52
37	二氟拉松双醋酸酯	495.2	316.8^*, 278.8	80	23, 27	16.71
38	氟轻松醋酸酯	495.2	120.8^*, 337	80	52, 25	16.69
39	炔诺孕酮	313.2	245.3^*, 109	115	24, 33	16.62
40	倍他米松戊酸酯	477.3	354.9^*, 278.8	80	14, 28	17.58
41	哈西奈德	455.2	104.9^*, 121	80	63, 38	18.19
42	泼尼卡酯	489.2	380.9^*, 114.8	80	13, 25	18.24
43	氯替泼诺	467.2	359.1^*, 265.1	80	18, 44	18.32
44	阿氯米松双丙酸酯	521.2	301^*, 279	80	25, 24	18.51
45	安西奈德	503.2	338.9^*, 321	80	22, 23	18.51
46	卤倍他索丙酸酯	485.2	391.2^*, 353.1	90	17, 20	18.44
47	氯倍他索丙酸酯	467.2	372.9^*, 354.9	80	17, 20	18.61
48	氟替卡松丙酸酯	501.2	312.9^*, 292.9	80	19, 21	18.76
49	莫米他松糠酸酯	521.1	503^*, 263	80	13, 38	18.90
50	醋酸甲地孕酮	385.1	325.1^*, 267.3	90	20, 24	18.89
51	醋酸氯地孕酮	405.1	309.3^*, 267.3	90	23, 30	19.21
52	倍他米松双丙酸酯	505.2	318.9^*, 278.9	80	20, 35	19.23
53	黄体酮	315.2	109^*, 97.3	100	30, 30	19.09
54	醋酸甲羟孕酮	387.2	327^*, 122.9	91	18, 35	19.36
55	倍氯米松双丙酸酯	521.2	503^*, 319	80	14, 20	19.93
56	双氟可龙戊酸酯	479.2	375.3^*, 439.4	80	18, 17	20.32
57	氯倍他松丁酸酯	479.2	342.8^*, 278.9	80	24, 24	20.44
58	己酸羟孕酮	429.1	313.2^*, 271.3	76	19, 27	23.36
59	环索奈德	541.3	523.2^*, 323.2	80	18, 25	24.83
60	雌二醇	271.2	182.9^*, 145.2	-120	-50, -50	14.10
61	雌三醇	287.1	171^*, 143.2	-110	-50, -60	9.39
62	雌酮	269.1	145^*, 183.1	-120	-50, -50	15.41
63	己烯雌酚	267.1	251.2^*, 222.2	-100	-35, -42	16.02

表 1

图 1

图 2

表 2

面膜基质中63种激素的线性回归方程、相关系数及检出限和定量限"

序号	化合物名称	线性方程	线性相关系数	检出浓度/（μg·L^-1）	定量浓度/（μg·L^-1）	检出限/（μg·g^-1）	定量限/（μg·g^-1）
1	曲安西龙	y=3.56×10³x-2.46×10³	0.999 8	0.6	2	0.03	0.1
2	泼尼松龙	y=1.33×10⁴x+1.61×10⁴	0.997 7	0.6	2	0.03	0.1
3	泼尼松	y=4.81×10⁴x+8.50×10⁴	0.992 4	0.6	2	0.03	0.1
4	异氟泼尼松	y=9.64×10³x+1.67×10⁴	0.996 0	0.6	2	0.03	0.1
5	氢化可的松	y=1.64×10⁴x+9.19×10³	0.997 0	0.6	2	0.03	0.1
6	可的松	y=2.68×10⁴x+1.93×10⁴	0.997 3	0.6	2	0.03	0.1
7	甲基泼尼松龙	y=2.27×10⁴x+4.28×10⁴	0.995 9	0.6	2	0.03	0.1
8	倍他米松	y=3.64×10³x+1.21×10⁴	0.998 8	0.6	2	0.03	0.1
9	地塞米松	y=5.02×10³x+1.17×10³	0.999 7	0.6	2	0.03	0.1
10	氟米松	y=5.93×10³x+6.26×10³	0.991 9	0.6	2	0.03	0.1
11	倍氯米松	y=1.28×10³x+6.84×10²	0.993 2	0.6	2	0.03	0.1
12	曲安奈德	y=5.74×10³x-1.07×10³	0.999 1	0.6	2	0.03	0.1
13	地索奈德	y=1.03×10⁴x+1.33×10³	0.995 7	0.6	2	0.03	0.1
14	氟尼缩松	y=7.48×10³x+2.62×10³	0.999 5	0.6	2	0.03	0.1
15	氟轻松	y=6.30×10³x-1.16×10⁴	0.996 4	0.6	2	0.03	0.1
16	曲安西龙双醋酸酯	y=1.76×10²x+2.76×10³	0.991 9	0.6	2	0.03	0.1
17	氟氢缩松	y=5.24×10³x+2.64×10³	0.998 6	2	6	0.1	0.3
18	泼尼松龙醋酸酯	y=2.32×10³x+2.34×10³	0.995 8	0.6	2	0.03	0.1
19	氟米龙	y=9.06×10³x+3.78×10³	0.997 5	0.6	2	0.03	0.1
20	氢化可的松醋酸酯	y=1.71×10⁴x+1.27×10⁴	0.993 3	0.6	2	0.03	0.1
21	氟氢可的松醋酸酯	y=5.67×10³x+1.56×10³	0.996 2	0.6	2	0.03	0.1
22	地夫可特	y=1.03×10⁴x+1.64×10⁴	0.992 8	0.6	2	0.03	0.1
23	泼尼松醋酸酯	y=1.39×10⁴x-8.21×10³	0.995 6	0.6	2	0.03	0.1
24	可的松醋酸酯	y=1.61×10⁴x-9.71×10³	0.996 0	0.6	2	0.03	0.1
25	卤美他松	y=9.30×10²x+1.49×10³	0.994 8	2	6	0.1	0.3
26	甲基泼尼松龙醋酸酯	y=9.71×10³x+3.55×10³	0.999 2	0.6	2	0.03	0.1
27	倍他米松醋酸酯	y=1.22×10³x+1.71×10³	0.991 3	0.6	2	0.03	0.1
28	睾酮	y=5.56×10⁴x+3.08×10⁴	0.997 3	0.6	2	0.03	0.1
29	地塞米松醋酸酯	y=2.94×10³x+4.67×10²	0.997 6	0.6	2	0.03	0.1
30	布地奈德	y=1.10×10⁴x+7.65×10²	0.990 0	0.6	2	0.03	0.1
31	氢化可的松丁酸酯	y=8.87×10³x-7.88×10³	0.990 2	0.6	2	0.03	0.1
32	孕三烯酮	y=5.07×10⁴x+4.62×10⁴	0.995 1	0.6	2	0.03	0.1
33	氟米龙醋酸酯	y=2.70×10⁴x+2.87×10⁴	0.994 4	0.6	2	0.03	0.1
34	甲基睾丸酮	y=3.91×10⁴x+1.57×10⁴	0.996 5	0.6	2	0.03	0.1
35	氢化可的松戊酸酯	y=8.51×10³x-3.37×10³	0.990 2	0.6	2	0.03	0.1
36	曲安奈德醋酸酯	y=6.92×10³x+9.37×10³	0.995 3	0.6	2	0.03	0.1
37	二氟拉松双醋酸酯	y=2.60×10³x+6.85×10³	0.998 9	0.6	2	0.03	0.1
38	氟轻松醋酸酯	y=5.78×10³x+1.97×10⁴	0.998 4	0.6	2	0.03	0.1
39	炔诺孕酮	y=9.61×10³x+4.91×10³	0.998 4	0.6	2	0.03	0.1
40	倍他米松戊酸酯	y=3.84×10³x-5.30×10³	0.991 6	0.6	2	0.03	0.1
41	哈西奈德	y=2.45×10³x+1.85×10³	0.993 9	2	6	0.1	0.3
42	泼尼卡酯	y=5.37×10³x+5.53×10³	1.000 0	0.6	2	0.03	0.1
43	氯替泼诺	y=2.16×10⁴x+2.54×10³	0.998 1	0.6	2	0.03	0.1
44	阿氯米松双丙酸酯	y=2.11×10³x+5.09×10³	0.999 1	0.6	2	0.03	0.1
45	安西奈德	y=4.42×10³x+1.19×10⁴	0.999 2	0.6	2	0.03	0.1
46	卤倍他索丙酸酯	y=2.64×10³x+3.57×10³	0.992 1	0.6	2	0.03	0.1
47	氯倍他索丙酸酯	y=7.30×10³x-4.34×10²	0.991 9	0.6	2	0.03	0.1
48	氟替卡松丙酸酯	y=9.77×10³x+5.78×10³	0.996 7	0.6	2	0.03	0.1
49	莫米他松糠酸酯	y=8.48×10³x+8.98×10³	0.994 2	0.6	2	0.03	0.1
50	醋酸甲地孕酮	y=7.58×10⁴x+3.80×10⁴	0.996 6	0.6	2	0.03	0.1
51	醋酸氯地孕酮	y=1.96×10⁴x+8.60×10³	0.998 1	0.6	2	0.03	0.1
52	倍他米松双丙酸酯	y=4.35×10³x+5.43×10³	0.998 4	0.6	2	0.03	0.1
53	黄体酮	y=5.37×10⁴x+8.24×10³	0.999 3	0.6	2	0.03	0.1
54	醋酸甲羟孕酮	y=5.61×10⁴x+1.55×10⁴	0.999 0	0.6	2	0.03	0.1
55	倍氯米松双丙酸酯	y=1.11×10⁴x+7.23×10³	0.996 8	0.6	2	0.03	0.1
56	双氟可龙戊酸酯	y=5.68×10³x+6.12×10³	0.994 5	0.6	2	0.03	0.1
57	氯倍他松丁酸酯	y=1.29×10⁴x+4.39×10³	0.999 7	0.6	2	0.03	0.1
58	己酸羟孕酮	y=4.54×10⁴x+8.44×10³	0.999 5	0.6	2	0.03	0.1
59	环索奈德	y=1.56×10⁴x+6.39×10³	0.997 7	0.6	2	0.03	0.1
60	雌二醇	y=1.16×10³x+8.30×10²	0.993 6	2	6	0.1	0.3
61	雌三醇	y=2.86×10³x-1.11×10³	0.998 2	2	6	0.1	0.3
62	雌酮	y=1.01×10⁴x+3.11×10²	0.999 4	2	6	0.1	0.3
63	己烯雌酚	y=2.33×10⁴x-7.61×10³	0.999 7	0.6	2	0.03	0.1

表 2

表 3

面膜基质中63种激素的平均回收率和精密度"

序号	化合物名称	加标含量/（μg·g^-1）	测定含量/（μg·g^-1）	平均回收率/%	RSD/%
1	曲安西龙	1.01	1.00	99.7	6.9
1	曲安西龙	5.03	4.73	94.0	6.0
2	泼尼松龙	1.51	1.52	101.0	12.8
2	泼尼松龙	5.03	4.65	92.5	13.4
3	泼尼松	1.51	1.40	93.1	8.3
3	泼尼松	5.03	4.91	97.5	8.7
4	异氟泼尼松	1.51	1.22	80.6	9.9
4	异氟泼尼松	5.03	5.52	109.7	8.0
5	氢化可的松	1.51	1.64	108.4	15.2
5	氢化可的松	5.03	4.95	98.3	16.9
6	可的松	1.51	1.48	98.0	7.7
6	可的松	5.03	5.21	103.6	12.2
7	甲基泼尼松龙	1.51	1.63	107.9	12.0
7	甲基泼尼松龙	5.03	5.67	112.8	13.7
8	倍他米松	1.51	1.48	98.4	13.0
8	倍他米松	5.03	5.25	104.3	12.1
9	地塞米松	1.51	1.48	98.4	10.0
9	地塞米松	5.03	4.83	96.0	10.5
10	氟米松	1.01	1.10	109.2	5.7
10	氟米松	5.03	4.55	90.5	6.5
11	倍氯米松	1.01	1.08	107.1	15.6
11	倍氯米松	5.03	4.90	97.3	6.4
12	曲安奈德	1.51	1.57	104.3	11.0
12	曲安奈德	5.03	4.49	89.2	12.7
13	地索奈德	1.51	1.36	90.0	5.5
13	地索奈德	5.03	4.13	82.1	5.6
14	氟尼缩松	1.51	1.33	88.1	7.1
14	氟尼缩松	5.03	4.56	90.6	3.2
15	氟轻松	2.01	2.31	114.8	8.5
15	氟轻松	7.04	7.42	105.4	11.5
16	曲安西龙醋酸酯	1.01	1.06	105.6	18.5
16	曲安西龙醋酸酯	5.03	4.37	86.9	6.4
17	氟氢缩松	1.01	1.14	113.0	8.1
17	氟氢缩松	5.03	5.24	104.2	3.8
18	泼尼松龙醋酸酯	0.30	0.30	97.8	18.1
18	泼尼松龙醋酸酯	5.03	5.36	106.6	18.5
19	氟米龙	1.01	1.03	102.0	12.2
19	氟米龙	5.03	5.20	103.4	4.5
20	氢化可的松醋酸酯	0.30	0.30	100.3	10.4
20	氢化可的松醋酸酯	5.03	4.60	91.5	18.4
21	氟氢可的松醋酸酯	0.30	0.33	110.9	11.0
21	氟氢可的松醋酸酯	5.03	4.30	85.5	17.5
22	地夫可特	0.20	0.19	94.7	14.8
22	地夫可特	3.02	3.20	106.2	14.2
23	泼尼松醋酸酯	0.20	0.16	79.5	11.2
23	泼尼松醋酸酯	5.03	4.99	99.1	18.3
24	可的松醋酸酯	0.20	0.17	86.1	12.9
24	可的松醋酸酯	5.03	4.67	92.8	18.3
25	卤美他松	1.01	1.16	114.8	15.1
25	卤美他松	5.03	5.33	105.9	7.3
26	甲基泼尼松龙醋酸酯	1.51	1.46	96.9	5.7
26	甲基泼尼松龙醋酸酯	5.03	4.36	86.7	7.7
27	倍他米松醋酸酯	0.50	0.61	102.9	9.1
27	倍他米松醋酸酯	5.03	4.93	98.1	15.5
28	睾酮	1.01	1.11	110.3	6.3
28	睾酮	5.03	5.31	105.6	2.5
29	地塞米松醋酸酯	0.40	0.42	104.0	12.6
29	地塞米松醋酸酯	5.03	3.64	80.5	14.3
30	布地奈德	1.01	1.05	104.2	4.8
30	布地奈德	5.03	4.87	96.8	8.2
31	氢化可的松丁酸酯	0.20	0.22	108.2	3.3
31	氢化可的松丁酸酯	5.03	4.24	84.2	4.4
32	孕三烯酮	1.01	1.12	111.1	6.2
32	孕三烯酮	5.03	5.07	100.8	1.1
33	氟米龙醋酸酯	1.01	1.16	115.0	8.1
33	氟米龙醋酸酯	5.03	4.83	95.9	4.3
34	甲睾酮	1.01	1.07	106.3	6.2
34	甲睾酮	5.03	5.11	101.6	2.8
35	氢化可的松戊酸酯	0.20	0.17	86.8	3.8
35	氢化可的松戊酸酯	3.02	3.07	101.7	5.8
36	曲安奈德醋酸酯	0.50	0.41	81.3	16.4
36	曲安奈德醋酸酯	5.03	4.03	80.2	16.7
37	二氟拉松双醋酸酯	0.75	0.65	85.7	13.7
37	二氟拉松双醋酸酯	5.03	4.55	90.5	18.6
38	氟轻松醋酸酯	0.50	0.55	108.8	9.7
38	氟轻松醋酸酯	5.03	4.00	79.6	13.6
39	炔诺孕酮	1.01	1.10	109.5	6.1
39	炔诺孕酮	5.03	5.04	100.3	2.7
40	倍他米松戊酸酯	0.20	0.19	93.9	2.0
40	倍他米松戊酸酯	5.03	4.76	94.6	5.9
41	哈西奈德	1.01	1.09	108.6	6.6
41	哈西奈德	5.03	5.01	99.5	3.4
42	泼尼卡酯	0.50	0.51	101.6	12.7
42	泼尼卡酯	5.03	5.46	108.6	15.3
43	氯替泼诺	1.01	0.97	96.0	12.0
43	氯替泼诺	5.03	4.71	93.7	3.5
44	阿氯米松双丙酸酯	1.01	0.93	92.4	14.7
44	阿氯米松双丙酸酯	5.03	4.83	96.1	9.0
45	安西奈德	1.01	0.72	71.5	12.4
45	安西奈德	5.03	4.82	95.8	13.2
46	卤倍他索丙酸酯	1.01	1.16	115.6	5.7
46	卤倍他索丙酸酯	5.03	5.26	104.6	5.1
47	氯倍他索丙酸酯	1.01	1.01	100.3	7.8
47	氯倍他索丙酸酯	5.03	4.35	86.6	7.4
48	氟替卡松丙酸酯	1.01	1.00	98.9	13.4
48	氟替卡松丙酸酯	5.03	4.62	91.9	8.5
49	莫米他松糠酸酯	1.01	0.74	73.9	19.2
49	莫米他松糠酸酯	5.03	4.98	99.1	7.8
50	醋酸甲地孕酮	1.01	1.09	108.2	5.3
50	醋酸甲地孕酮	5.03	5.00	99.4	2.3
51	醋酸氯地孕酮	1.01	1.08	107.8	5.7
51	醋酸氯地孕酮	5.03	4.93	98.0	2.6
52	倍他米松双丙酸酯	1.01	0.96	95.3	18.9
52	倍他米松双丙酸酯	5.03	4.70	93.5	8.6
53	黄体酮	1.01	1.03	102.6	5.2
53	黄体酮	5.03	5.10	101.5	2.8
54	醋酸甲羟孕酮	1.01	1.05	104.8	6.3
54	醋酸甲羟孕酮	5.03	5.13	102.0	2.0
55	倍氯米松双丙酸酯	1.01	0.78	77.8	14.8
55	倍氯米松双丙酸酯	5.03	4.65	92.5	9.0
56	双氟可龙戊酸酯	1.01	1.01	100.4	11.6
56	双氟可龙戊酸酯	5.03	4.67	92.9	9.2
57	氯倍他松丁酸酯	1.01	1.02	101.5	9.2
57	氯倍他松丁酸酯	5.03	4.96	98.7	3.1
58	己酸羟孕酮	1.51	1.23	81.8	4.6
58	己酸羟孕酮	5.03	4.44	88.2	2.5
59	环索奈德	1.01	1.09	108.7	12.4
59	环索奈德	5.03	4.85	96.4	17.0
60	雌二醇	1.01	1.20	119.2	9.5
60	雌二醇	5.03	6.01	119.5	1.5
61	雌三醇	1.01	1.12	111.5	8.4
61	雌三醇	5.03	5.50	109.3	2.1
62	雌酮	1.01	1.07	105.9	6.0
62	雌酮	5.03	5.51	109.5	3.0
63	己烯雌酚	1.01	0.95	94.8	5.2
63	己烯雌酚	5.03	5.02	99.7	2.2

表 3

参考文献 18

[1]	Li Shuo, Zhao Qianru, Hei Zhenzhen, et al. Investigation and analysis of glucocorticoid in cosmetics sold on wechat moments and research on safety supervision policy of online cosmetics sales in China[J]. Flavour Fragrance Cosmetics, 2018 (3) : 43-49.
[2]	Liu Mieyun, Dong Qing, Li Zhu, et al. Analysis of the results of cosmetics sampling and testing in various provinces, municipalities and autonomous regions in China from 2017 to 2019[J]. Guangdong Chemical Industry, 2021, 48(2) : 71-73.
[3]	Yang Zehua, Wang Xiangbo. Analysis and advices of the problems in the supervision and sampling of Chinese cosmetics[J]. Detergent & Cosmetics, 2020, 43(9) : 17-21.
[4]	Ruan Haolan, Chen Qi, Luo Zhuoya. The situation and harm of glucocorticoid abuse in cosmetic masks[J]. Pharmacy Today, 2018, 28(10) : 717-720.
[5]	Hu Bei, Li Lixia, Liu Hong, et al. Research progress on detection of sex hormones in cosmetics[J]. China Surfactant Detergent & Cosmetics, 2020, 50(9) : 629-637.
[6]	Yan Qianru, Wu Weikui. Application of ultra performance liquid chromatography in the analysis of prohibited substances, restricted substances and functional ingredients in cosmetics[J]. Chinese Pharmaceutical Affairs, 2017, 31(1) : 74-78.
[7]	Pang Daobiao, Xu Li, Ji Shaofan, et al. Study on quick determination of six kinds of sex hormones in cosmetics by ultra performance convergence chromatography[J]. Flavour Fragrance Cosmetics, 2017 (3) : 29-32.
[8]	Lin Zhihui, Zhao Yan, Xing Yuanna, et al. Simultaneous determination of 21 sexual hormones in cosmetics by ultra high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Analysis Laboratory, 2017, 36(4) : 441-447.
[9]	Chen Xi, Zhang Xiaolin, Liu Ying, et al. LC-MS/MS determination of 22 hormones in cosmetics[J]. Physical Testing and Chemical Analysis Part B: Chemical Analysis, 2013, 49(4) : 468-472, 476.
[10]	Wen Yi, Wang Ying, Zhou Bingsheng, et al. Determination of sexual hormones in liquid cosmetics by polymer monolith microextraction coupled with high performance liquid chromatography[J]. Chinese Journal of Analytical Chemistry, 2007, 35(5) : 681-684. doi: 10.1016/S1872-2040(07)60052-8
[11]	Li Ning, Hou Xuanzhu, Wang Jinxuan, et al. Simultaneous determination of 8 hormones in cosmetics by solid phase extraction with microemulsion liquid chromatography[J]. Journal of Instrumental Analysis, 2010, 29(2) : 115-119.
[12]	Luo Taihui, Huang Xiaolan, Wu Huiqin, et al. High throughput screening of 86 kinds of glucocorticoids in cosmetics using QuEChERS and isotope dilution-liquid chromatography copuled to high resolution time-of-flight mass spectrometry[J]. Chinese Journal of Analytical Chemistry, 2017, 45(9) : 1381-1388.
[13]	Cui Han, Shen Baozhen, Chen Xi, et al. Simultaneous determination of 15 kinds of glucocorticoid and sex hormone in cosmetics by GPC-LC-MS/MS[J]. China Surfactant Detergent & Cosmetics, 2014, 44(5) : 295-298.
[14]	Dong Yalei, Liu Zhao, Wang Haiyan, et al. Determination of 43 glucocorticoids in infant eczema products by UHPLC-MS/MS[J]. China Surfactant Detergent & Cosmetics, 2020, 50(12) : 885-891, 895.
[15]	Liu Hong, Yang Piaopiao, Li Lixia. Detection of 73 glucocorticoids in cosmetics by ultra performance liquid chromatography-tandem mass spectrometry with pass-through column purification[J]. Journal of Instrumental Analysis, 2020, 39(9) : 1112-1119.
[16]	Li Hongying, Liu Yun, Wang Wei, et al. Study on detection of glucocorticoids in cosmetics by LC-MS/MS and UPLC-LTQ/Orbitrap MS[J]. Chinese Journal of Analysis Laboratory, 2020, 39(12) : 1443-1449.
[17]	Zhang Yanshu, Lin Zhenhua, Hu Yuling, et al. Advance on pretreatment methods for cosmetic samples analysis[J]. Journal of Instrumental Analysis, 2016, 35(2) : 127-136.
[18]	Li Xiaodong, Zhao Ying, Du Shanshan, et al. Determination of 17 kinds of carbamate pesticide residues in vegetables by UPLC-MS/MS[J]. Chemical Analysis and Meterage, 2018, 27(1) : 13-17.