固相萃取-超高效液相色谱串联质谱法测定化妆品中国标方法以外的42种糖皮质激素

doi:10.3969/j.issn.2097-2806.2023.07.016

Abstract

Abstract:

A solid phase extraction （SPE）-ultra performance liquid chromatography-tandem mass spectrometry （UPLC-MS/MS） method was developed for the determination of 42 glucocorticoids in cosmetics, in addition to the existing standard of 50 glucocorticoids. After the samples were dispersed, extracted and purified, 42 glucocorticoids were determined by using UPLC Shim-pack XR-ODSIII C₁₈（2.0 mm×150 mm, 2.2 μm） chromatographic column, 0.1% （V/V） acetic acid acetonitrile solution and 0.1% （V/V） acetic acid aqueous solution as the mobile phase at the mode of electrospray ionization （ESI） and multiple reaction monitoring （MRM）. A total of 42 hormones have good linearity, and the correlation coefficients are above 0.99. For water, emulsion and cream substrates, the limit of detection （LOD） is 0.03 μg/g and the limit of quantification （LOQ） is 0.1 μg/g. The average recoveries of three levels and six parallel tests range from 67.6%-112.5% for water, emulsion and cream substrates. At present, two positive samples with these 42 glucocorticoid components have been screened, which provides a more comprehensive method for monitoring the illegal addition of glucocorticoids in cosmetics.

Key words: a solid phase extraction (SPE)-liquid chromatography-tandem mass spectrometry (LC-MS/MS) method, cosmetic, multiple glucocorticoid detection

CLC Number:

TQ658

Ma Liangbo, Sun Yu, Zhu Guifang, Lu Jiayi, Xu Yan, Liu Tao. Determination of 42 glucocorticoids beyond the national standard method in cosmetics by solid phase extraction-liquid chromatography tandem mass spectrometry[J].China Surfactant Detergent & Cosmetics, 2023, 53(7): 849-856.

Figures/Tables 3

Tab. 1

MS parameters of 42 glucocorticoids"

序号	名称	CAS号	t_R/min	母离子m/z	子离子m/z（碰撞能量E/ev）
1	16α-羟基泼尼龙	13951-70-7	2.501	377.20	*147.00（28），173.10（22）
2	6α-氟-异氟泼尼龙	806-29-1	3.576	397.20	*253.10（17），121.00（26）
3	氟轻可的松	127-31-1	3.628	381.20	*239.10（26），181.10（31）
4	16α-羟基泼尼松龙醋酸酯	86401-80-1	3.872	419.20	*323.20（15），147.00（31）
5	双氟拉松	2557-49-5	4.094	411.20	*253.10（16），121.00（35）
6	帕拉米松	53-33-8	4.124	393.20	*337.20（12），171.10（29）
7	甲泼尼松	1247-42-3	4.165	373.20	*171.00（31），159.00（30）
8	氢化可的松琥珀酸酯	2203-97-6	4.249	463.20	*327.20（17），309.10（18）
9	氯泼尼醇	5251-34-3	4.308	393.20	*205.00（24），271.10（19）
10	异氟泼尼龙醋酸酯	338-98-7	4.604	421.20	*305.10（16），147.00（30）
11	甲基泼尼松龙琥珀酸酯	2921-57-5	4.579	475.10	*457.15（12），161.10（30）
12	去羟米松	382-67-2	4.705	377.20	*147.00（24），171.00（20）
13	氟可龙	152-97-6	4.706	377.20	*147.00（28），121.00（31）
14	帕拉米松乙酸酯	1597-82-6	5.285	435.20	*319.10（13），171.10（21）
15	倍他米松丙酸酯	5534-13-4	5.371	449.25	*355.15（12），279.15（16）
16	地塞米松异烟酸酯	2265-64-7	5.420	498.20	*124.00（27），106.00（37）
17	卤倍他索	98651-66-2	5.507	429.20	*253.10（19），121.00（35）
18	甲泼尼松醋酸酯	1106-03-2	5.514	415.20	*309.10（15），337.10（13）
19	氯倍他索	25122-41-2	5.602	411.15	*373.15（14），171.10（22）
20	倍氯米松-21-丙酸酯	69224-79-9	6.014	465.20	*237.15（25），147.05（25）
21	倍氯米松-17-丙酸酯	5534-18-9	5.737	465.20	*279.15（21），337.20（14）
22	倍他米松丁酸酯	5534-14-5	5.942	463.20	*279.20（18），355.20（13）
23	地塞米松戊酸酯	33755-46-3	6.206	477.30	*355.20（12），279.10（20）
24	地索奈德-21-醋酸	25092-25-5	6.237	459.20	*305.15（17），225.05（27）
25	醋丙氢可的松	74050-20-7	6.338	461.25	*309.15（18），121.05（26）
26	甲羟松	2668-66-8	6.419	345.25	*327.25（15），135.15（20）
27	双氟泼尼酯	23674-86-4	6.444	509.20	*303.10（16），279.10（18）
28	倍他米松苯甲酸酯	22298-29-9	6.598	497.25	*355.15（13），279.15（17）
29	泼尼松龙特戊酸酯	1107-99-9	6.616	445.30	*147.15（25），171.15（29）
30	甲基泼尼松龙醋丙酸酯	86401-95-8	6.722	473.30	*381.20（13），161.00（27）
31	17-α-羟基醋酸去氧皮质酮	302-23-8	6.911	373.20	*313.20（15），271.20（19）
32	醋酸去氧皮质酮	56-47-3	7.098	373.10	*109.00（27）， 97.00（21）
33	氟米松特戊酸酯	2002-29-1	7.162	495.25	*477.25（12），253.15（20）
34	替可的松特戊酸酯	55560-96-8	7.217	463.20	*343.20（21），361.20（18）
35	泼尼松龙醋酸戊酸酯	72064-79-0	7.341	487.25	*289.15（16），147.05（28）
36	地塞米松特戊酸酯	1926-94-9	7.385	477.30	*355.20（17），439.20（13）
37	瑞美松龙	49697-38-3	7.714	371.30	*121.10（30），173.10（22）
38	倍他米松丁酸丙酸酯	5534-02-1	7.986	519.25	*279.15（18），147.05（40）
39	氟可龙戊酸酯	29205-06-9	8.079	461.25	*341.15（12），303.15（15）
40	氢化可的松环戊丙酸酯	508-99-6	8.394	487.30	*327.20（19），309.10（20）
41	氯可托龙特戊酸酯	34097-16-0	8.400	495.25	*477.20（13），457.15（11）
42	己曲安奈德	5611-51-8	8.641	533.30	*415.15（16），397.20（15）

Tab. 1

Tab. 2

Linear equations, correlation coefficients（r2）, LODs, and LOQs of 42 glucocorticoids"

序号	名称	线性范围/（μg/L）	线性方程	相关系数	检出限/（μg/g）	定量限/（μg/g）
1	16α-羟基泼尼龙	5~80	y=16 088.3x+22 475.4	0.999 6	0.03	0.1
2	6α-氟-异氟泼尼龙	5~80	y=24 013.7x+69 600.4	0.993 9	0.03	0.1
3	氟轻可的松	5~80	y=16 156.0x+35 299.1	0.996 0	0.03	0.1
4	16α-羟基泼尼松龙醋酸酯	5~80	y=9 746.50x+15 323.9	0.999 6	0.03	0.1
5	双氟拉松	5~80	y=6 726.65x+31 592.3	0.994 9	0.03	0.1
6	帕拉米松	5~80	y=18 214.3x+81 965.8	0.995 6	0.03	0.1
7	甲泼尼松	5~80	y=41 107.1x+139 932	0.997 5	0.03	0.1
8	氢化可的松琥珀酸酯	5~80	y=28 361.1x+66 198.6	0.998 6	0.03	0.1
9	氯泼尼醇	5~80	y=50 459.5x+172 777	0.996 6	0.03	0.1
10	异氟泼尼龙醋酸酯	5~80	y=10 610.2x+23 824.9	0.999 5	0.03	0.1
11	甲基泼尼松龙琥珀酸酯	5~80	y=28 422.2x+72 211.3	0.999 1	0.03	0.1
12	去羟米松	5~80	y=29 517.2x+125 170	0.995 4	0.03	0.1
13	氟可龙	5~80	y=28 284.0x+124 475	0.994 5	0.03	0.1
14	帕拉米松乙酸酯	5~80	y=15 754.2x+38 480.5	0.998 1	0.03	0.1
15	倍他米松丙酸酯	5~80	y=80 019.8x+376 162	0.991 5	0.03	0.1
16	地塞米松异烟酸酯	5~80	y=70 938.8x+218 609	0.997 9	0.03	0.1
17	卤倍他索	5~80	y=12 305.7x+46 546.5	0.993 6	0.03	0.1
18	甲泼尼松醋酸酯	5~80	y=49 319.2x+76 856.6	0.999 2	0.03	0.1
19	氯倍他索	5~80	y=17 624.1x+59 508.7	0.998 8	0.03	0.1
20	倍氯米松-21-丙酸酯	5~80	y=5 174.89x+13 471.7	0.996 9	0.03	0.1
21	倍氯米松-17-丙酸酯	5~80	y=14 671.6x+52 266.1	0.999 6	0.03	0.1
22	倍他米松丁酸酯	5~80	y=28 428.3x+76 524.6	0.998 3	0.03	0.1
23	地塞米松戊酸酯	5~80	y=23 665.3x+84 358.2	0.998 0	0.03	0.1
24	地索奈德-21-醋酸	5~80	y=23 040.7x+90 995.3	0.996 0	0.03	0.1
25	醋丙氢可的松	5~80	y=29 243.5x+77 392.0	0.998 2	0.03	0.1
26	甲羟松	5~80	y=58 431.8x+175 898	0.998 1	0.03	0.1
27	双氟泼尼酯	5~80	y=23 398.5x+97 915.7	0.995 7	0.03	0.1
28	倍他米松苯甲酸酯	5~80	y=29 462.0x+128 886	0.991 9	0.03	0.1
29	泼尼松龙特戊酸酯	5~80	y=14 495.9x+59 059.0	0.997 5	0.03	0.1
30	甲基泼尼松龙醋丙酸酯	5~80	y=51 364.4x+217 218	0.995 2	0.03	0.1
31	17-α-羟基醋酸去氧皮质酮	5~80	y=97 292.0x+467 253	0.992 8	0.03	0.1
32	醋酸去氧皮质酮	5~80	y=86 019.4x+149 527	0.999 1	0.03	0.1
33	氟米松特戊酸酯	5~80	y=7 627.26x+14 744.9	0.998 4	0.03	0.1
34	替可的松特戊酸酯	5~80	y=42 040.8x+132 973	0.997 6	0.03	0.1
35	泼尼松龙醋酸戊酸酯	5~80	y=28 801.5x+137 142	0.994 0	0.03	0.1
36	地塞米松特戊酸酯	5~80	y=19 723.4x+61 962.6	0.997 8	0.03	0.1
37	瑞美松龙	5~80	y=26 832.0x+80 147.8	0.998 4	0.03	0.1
38	倍他米松丁酸丙酸酯	5~80	y=23 273.4x+95 019.6	0.999 1	0.03	0.1
39	氟可龙戊酸酯	5~80	y=12 905.2x+39 843.7	0.998 5	0.03	0.1
40	氢化可的松环戊丙酸酯	5~80	y=24 830.0x+103 554	0.997 1	0.03	0.1
41	氯可托龙特戊酸酯	5~80	y=11 254.1x+48 004.3	0.997 1	0.03	0.1
42	己曲安奈德	5~80	y=51 638.6x+170 332	0.998 6	0.03	0.1

Tab. 2

Tab. 3

The average recoveries and RSDs of 42 glucocorticoids at three spiked levels in three matrices"

序号	名称	水剂		乳液		面霜
序号	名称	Rec./%	RSD/%	Rec./%	RSD/%	Rec./%	RSD/%
1	16α-羟基泼尼龙	100.5	8.62	88.3	8.54	86.2	8.81
2	6α-氟-异氟泼尼龙	88.2	7.05	85.1	5.67	73.6	5.85
3	氟轻可的松	96.1	6.81	87.2	5.25	77.3	8.62
4	16α-羟基泼尼松龙醋酸酯	87.7	5.90	73.0	6.56	88.0	3.61
5	双氟拉松	87.0	6.94	79.6	7.68	73.9	8.37
6	帕拉米松	83.4	7.42	80.2	14.43	86.8	5.94
7	甲泼尼松	95.2	5.88	90.5	5.94	80.7	6.85
8	氢化可的松琥珀酸酯	97.3	2.46	87.6	8.48	90.2	7.91
9	氯泼尼醇	99.0	7.35	88.4	8.55	78.8	7.14
10	异氟泼尼龙醋酸酯	100.3	6.49	86.8	8.76	77.5	7.80
11	甲基泼尼松龙琥珀酸酯	91.3	5.73	79.6	9.40	67.6	6.79
12	去羟米松	99.6	8.31	93.5	8.73	87.5	5.50
13	氟可龙	101.4	5.50	90.4	8.04	83.6	6.45
14	帕拉米松乙酸酯	90.4	2.12	91.2	6.86	82.4	7.26
15	倍他米松丙酸酯	100.8	7.62	87.3	7.55	87.5	4.94
16	地塞米松异烟酸酯	95.6	6.87	89.7	6.54	80.4	8.43
17	卤倍他索	100.8	7.89	85.4	7.44	78.2	5.39
18	甲泼尼松醋酸酯	89.8	6.30	90.6	6.90	88.2	7.58
19	氯倍他索	101.3	8.01	92.1	6.61	86.7	8.04
20	倍氯米松-21-丙酸酯	95.1	6.94	92.6	7.91	84.1	7.37
21	倍氯米松-17-丙酸酯	102.2	7.35	88.9	8.15	81.4	7.85
22	倍他米松丁酸酯	95.9	8.36	103.4	7.48	87.3	5.87
23	地塞米松戊酸酯	97.4	8.96	98.7	6.93	89.3	7.43
24	地索奈德-21-醋酸	104.3	4.90	89.3	7.15	81.1	6.69
25	醋丙氢可的松	98.9	6.35	85.0	5.83	88.5	6.30
26	甲羟松	92.5	8.48	87.8	6.15	87.9	7.36
27	双氟泼尼酯	95.6	6.95	91.2	7.67	86.2	6.42
28	倍他米松苯甲酸酯	88.3	6.77	94.7	7.85	112.5	15.78
29	泼尼松龙特戊酸酯	92.9	7.24	90.9	6.48	87.7	8.89
30	甲基泼尼松龙醋丙酸酯	91.4	6.65	84.3	6.60	84.9	8.71
31	17-α-羟基醋酸去氧皮质酮	102.1	8.39	83.6	7.48	82.3	7.93
32	醋酸去氧皮质酮	102.4	8.70	93.5	7.31	85.5	9.16
33	氟米松特戊酸酯	104.8	6.52	93.3	5.47	85.1	8.84
34	替可的松特戊酸酯	93.6	7.06	104.7	5.83	86.9	7.62
35	泼尼松龙醋酸戊酸酯	95.8	6.49	87.5	6.32	80.9	8.35
36	地塞米松特戊酸酯	89.0	9.06	87.6	7.01	79.8	9.40
37	瑞美松龙	88.8	8.82	91.3	5.67	84.2	8.46
38	倍他米松丁酸丙酸酯	87.2	6.94	86.5	7.45	86.3	9.39
39	氟可龙戊酸酯	89.3	7.70	86.9	6.74	83.7	9.44
40	氢化可的松环戊丙酸酯	103.8	4.53	89.6	6.86	84.8	8.73
41	氯可托龙特戊酸酯	92.2	6.81	86.6	7.60	79.8	6.75
42	己曲安奈德	106.7	6.38	92.7	8.43	87.2	8.50

Tab. 3

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Determination of 42 glucocorticoids beyond the national standard method in cosmetics by solid phase extraction-liquid chromatography tandem mass spectrometry

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