UHPLC-MS/MS法测定网络销售婴幼儿湿疹类产品中43种糖皮质激素类药物

doi:10.3969/j.issn.1001-1803.2020.12.012

摘要/Abstract

摘要：

建立了快速、准确测定网络销售婴幼儿湿疹类产品中43种糖皮质激素类药物的超高效液相色谱-串联三重四级杆质谱（UHPLC-MS/MS）检测方法。对样品前处理条件、色谱和质谱条件进行了优化,最终样品以乙腈超声提取,提取液稀释后直接进样,采用UHPLC-MS/MS在多重反应监测（MRM）模式下进行定性筛查。对筛查结果疑似阳性的样品,根据保留时间和特征离子对的相对丰度比定性,并采用定量离子对进行外标法定量。采用该方法对网络销售的41批湿疹相关“妆”字号产品和“消”字号产品进行检测,其中有6批产品中检出糖皮质激素,两类产品的检出率分别为5.9%和57.1%。该方法操作简便、准确可靠,可用于实际样品检测的需要,为化妆品安全监管提供技术支撑。

关键词: 超高效液相色谱-串联质谱, 糖皮质激素, 婴幼儿, 湿疹, 化妆品

Abstract:

A fast and accurate method for the determination of 43 kinds of glucocorticoids in infant eczema products by UHPLC-MS/MS was established. The samples were extracted with acetonitrile ultrasonically. The supernatant was diluted and injected directly. After optimizing the sample pretreatment and chromatography conditions, as well as mass spectrometry parameters, UHPLC-MS /MS analysis method was performed for qualitative screening in MRM mode. The samples with suspected positive screening results were further confirmed. Qualitative analysis was conducted according to retention time and relative abundance ratio of characteristic ion pairs. Quantitative ion pairs were used for quantitative measurement by external standard method. This method was used for detecting 41 batches of eczema-related cosmetic products and disinfection products sold online. Glucocorticoids were detected in 6 batches of products, and the detection rates of the two types of products were 5.9% and 57.1%, respectively. The method is simple, accurate and reliable, which can be used for the actual sample detection and provide technical support for cosmetic safety supervision.

Key words: UHPLC-MS/MS, glucocorticoids, infant, eczema, cosmetics

中图分类号:

TQ658

董亚蕾,刘钊,王海燕,孙磊. UHPLC-MS/MS法测定网络销售婴幼儿湿疹类产品中43种糖皮质激素类药物[J]. 日用化学工业, 2020, 50(12): 885-891.

DONG Ya-lei,LIU Zhao,WANG Hai-yan,SUN Lei. Determination of 43 glucocorticoids in infant eczema products by UHPLC-MS/MS[J]. China Surfactant Detergent & Cosmetics, 2020, 50(12): 885-891.

图/表 6

表 1

43种糖皮质激素化合物的质谱参数"

编号	物质名称	英文名称	母离子（m/z）	子离子（m/z）	CE/V
编号	物质名称	英文名称	母离子（m/z）	子离子（m/z）	CE/V
1	曲安西龙	Triamcinolone	395.2	*357.1, 225.1	20, 27
2	泼尼松龙	Prednisolone	361.2	*343.1, 147.4	14, 38
3	氢化可的松	Hydrocortisone	363.2	*121.0, 105.1	33, 67
4	泼尼松	Prednisone	359.2	*341.1, 147.0	14, 35
5	可的松	Cortisone	361.2	*163.1, 121.0	30, 40
6	甲基泼尼松龙	Methylprednisolone	375.2	*357.1, 161.1	15, 29
7	倍他米松	Betamethasone	393.2	*355.0, 146.8	18, 37
8	地塞米松	Dexamethasone	393.2	*355.0, 146.8	17, 40
9	氟米松	Flumethasone	411.2	*253.0, 121.1	25, 47
10	倍氯米松	Beclomethasone	409.2	*279.1, 147.1	28, 32
11	曲安奈德	Triamcinolone acetonide	435.2	*338.9, 396.9	20, 15
12	氟氢缩松	Fludroxycortide	437.2	*361.0, 285.2	26, 30
13	曲安西龙双醋酸酯	Triamcinolone diacetate	479.2	*440.9, 321.0	14, 22
14	泼尼松龙醋酸酯	Prednisolone 21-acetate	403.2	*147.0, 307.1	32, 17
15	氟米龙	Fluoromethalone	377.2	*278.9, 320.9	20, 16
16	氢化可的松醋酸酯	Hydrocortisone 21-acetate	405.2	*309.1, 120.8	24, 44
17	地夫可特	Deflazacort	442.2	*141.9, 123.9	40, 40
18	氟氢可的松醋酸酯	Fludrocortisone 21-acetate	423.2	*238.9, 120.9	39, 41
19	泼尼松醋酸酯	Prednisone 21-acetate	401.2	*295.0, 146.8	23, 39
20	可的松醋酸酯	Cortisone 21-acetate	403.2	*162.8, 343.0	37, 26
21	甲基泼尼松龙醋酸酯	Methylprednisolone 21-acetate	417.2	*399.2, 253.2	12, 25
22	倍他米松醋酸酯	Betamethasone 21-acetate	435.21	*309.0, 337.0	22, 16
23	布地奈德	Budesonide	431.2	*413.1, 146.9	15, 31
24	氢化可的松丁酸酯	Hydrocortisone 17-butyrate	433.2	*345.0, 120.8	19, 31
25	地塞米松醋酸酯	Dexamethasone 21-acetate	435.2	*309.0, 337.0	20, 19
26	氟米龙醋酸酯	Fluorometholone 17-acetate	419.2	*279.0, 321.0	26, 21
27	氢化可的松戊酸酯	Hydrocortisone 17-valerate	447.3	*345.2, 120.8	21, 31
28	曲安奈德醋酸酯	Triamcinolone acetonide acetate	477.2	*338.9, 320.8	22, 25
29	氟轻松醋酸酯	Fluocinonide	495.2	*120.8, 337.0	52, 25
30	二氟拉松双醋酸酯	Diflorasone diacetate	495.2	*316.8, 278.8	23, 27
31	倍他米松戊酸酯	Betamethasone 17-valerate	477.3	*354.9, 278.8	14, 28
32	泼尼卡酯	Prednicarbate	489.2	*380.9, 114.8	13, 25
33	哈西奈德	Halcinonide	455.2	*104.9, 121.0	63, 38
34	阿氯米松双丙酸酯	Alclomethasone dipropionate	521.2	*301.0, 279.0	25, 24
35	安西奈德	Amcinonide	503.2	*338.9, 321.0	22, 23
36	氯倍他索丙酸酯	Clobetasol 17-propionate	467.2	*372.9, 354.9	17, 20
37	氟替卡松丙酸酯	Fluticasone propionate	501.2	*312.9, 292.9	19, 21
38	莫米他松糠酸酯	Mometasone furoate	521.1	*503.0, 263.0	13, 38
39	倍他米松双丙酸酯	Betamethasone dipropionate	505.2	*318.9, 278.9	20, 35
40	倍氯米松双丙酸酯	Beclmetasone dipropionate	521.2	*503.0, 319.0	14, 20
41	氯倍他松丁酸酯	Clobetasone 17-butyrate	479.2	*342.8, 278.9	24, 24
42	氟轻松	Fluocinolone acetonide	453.2	*121.0, 337.2	40, 20
43	地索奈德	Desonide	417.2	*323.3, 225.1	17, 30

表 1

表 2

表 3

表 4

图 1

图 2

参考文献 15

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化合物	线性范围/ （μg·L^-1）	线性方程	相关系数（r）	回收率/%	RSD/% （n=6）
氯倍他索丙酸酯	2~80	y=1 419.4x+235.4	0.999 8	83.7~102.3	3.6~8.8
地塞米松	2~80	y=1 005.2x+442	0.999 9	87.6~ 95.4	2.1~6.5
地塞米松醋酸酯	2~80	y=1 108.7x+1 729.4	0.999 4	95.1~100.3	3.4~7.6
倍他米松	2~40	y=863x-437	0.999 6	91.6~105.8	1.4~7.1
倍他米松醋酸酯	2~40	y=557.9x+166.5	0.999 9	89.2~ 96.5	2.0~3.7
地索奈德	2~40	y=11 043x-2 184	0.999 7	96.7~103.9	1.3~5.3

样品编号	样品名称	样品类型	检出激素	含量/（mg·kg^-1）
1	保湿霜	妆	氯倍他索丙酸酯	131.3
2	护理霜	妆	地索奈德	1 084.3
3	抑菌剂	消	氯倍他索丙酸酯	522.1
4	抑菌膏	消	氯倍他索丙酸酯	277.3
5	百草膏	消	地塞米松	8.1
5	百草膏	消	地塞米松醋酸酯	353.8
6	清X霜	消	倍他米松	115.4
6	清X霜	消	倍他米松醋酸酯	5.0