UPLC-ESI-Q-TOF/MS法测定化妆品中倍他米松及其8种类似物

doi:10.3969/j.issn.1001-1803.2022.02.014

摘要/Abstract

摘要：

建立了同时分析倍他米松及其8种类似物的超高效液相色谱-高分辨质谱联用仪（UPLC-ESI-Q-TOF/MS）的定性、定量检测方法。采用小颗粒色谱柱,梯度洗脱,电喷雾离子源正离子模式（ESI⁺）,利用TOF采集的化合物母离子推测分子组成,子离子推测结构,并借助对照品加以确证,利用质谱一级准分子离子建立含量测定方法。对建立的检测方法进行方法学验证,发现考察范围内线性关系良好,检出浓度为0.05~0.34 mg/kg,回收率为93.1%~103.7%,相对标准偏差普遍小于6%。在对10批化妆品的分析中,有5批检出激素,并首次发现了2种新的激素添加物：倍他米松17-丙酸酯、倍他米松21-丙酸酯。

关键词: 超高效液相色谱-高分辨质谱联用仪, 化妆品, 糖皮质激素

Abstract:

A method of ultra-performance liquid chromatography-high resolution mass spectrometry （UPLC-ESI-Q-TOF/MS） was developed for simultaneous determination of betamethasone and its 8 analogues. The separation was executed on a small particle column, and gradient elution was used. The mass spectrometer was performed in positive ion mode, and the identification was performed by MS² scan with aid of standards, and the determination was carried out in MS scan mode by the external standard method. The analysis method developed was validated. The linear relationship in the linear range was satisfactory, the detection limit was between 0.05 and 0.34 mg/kg. The recovery was 93.1%-103.7%, and the relative standard deviation was less than 6%. In the analysis of 10 batches of cosmetics, glucocorticoids were detected in five batches. Furthermore, two glucocorticoids additives were found for the first time, i.e., betamethasone 17-propionate and betamethasone 21-propionate.

Key words: UPLC-ESI-Q-TOF/MS, cosmetics, glucocorticoid

中图分类号:

TQ658

贾昌平,张斌,张珊珊,郑佳新,郑梅,陈卫. UPLC-ESI-Q-TOF/MS法测定化妆品中倍他米松及其8种类似物[J]. 日用化学工业, 2022, 52(2): 207-213.

Jia Changping,Zhang Bin,Zhang Shanshan,Zheng Jiaxin,Zheng Mei,Chen Wei. Determination of betamethasone and eight analogues in cosmetics by UPLC-ESI-Q-TOF/MS[J]. China Surfactant Detergent & Cosmetics, 2022, 52(2): 207-213.

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参考文献 13

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化合物	分子式	R_t/min	[M+H]⁺	主要子离子
BM	C₂₂H₂₉FO₅	9.362	393.208 1	373.201 1, 355.189 9, 337.180 1, 319.169 6, 279.173 7, 237.127 1, 147.080 2
DXM	C₂₂H₂₉FO₅	9.777	393.208 1	373.201 6, 355.190 6, 337.179 0, 319.167 5, 291.173 8, 237.127 8, 147.079 4
17-DXMP	C₂₅H₃₃FO₆	12.766	449.233 1	429.226 0, 355.189 9, 337.180 0, 319.168 2, 291.174 0, 279.174 2, 153.089 8, 147.080 6
BMA	C₂₄H₃₁FO₆	12.835	435.217 8	415.210 6, 397.200 1, 379.189 6, 355.190 4, 337.179 8, 319.169 9, 309.184 3, 291.174 6, 279.174 6, 147.080 5
DXMA	C₂₄H₃₁FO₆	13.133	435.217 8	415.213 8, 397.201 3, 379.192 5, 355.189 7, 337.180 7, 319.169 3, 309.186 3, 291.174 6, 237.129 2, 147.079 3
17-BMP	C₂₅H₃₃FO₆	13.225	449.233 1	355.190 7, 337.179 5, 319.168 7, 301.156 5, 291.172 8, 279.174 5, 263.143 5, 147.080 4
21-BMP	C₂₅H₃₃FO₆	13.801	449.233 1	429.229 2, 411.215 4, 393.205 6, 373.200 0, 355.189 9, 337.179 3, 319.168 6, 309.184 1, 291.173 1, 279.173 3, 147.081 0, 57.033 7
21-DXMP	C₂₅H₃₃FO₆	14.093	449.233 1	429.228 1, 411.217 4, 393.206 8, 373.200 6, 355.191 0, 337.180 2, 327.195 5, 319.168 7, 309.184 4, 291.174 0, 237.126 9, 147.080 1, 57.034 1
BMDP	C₂₈H₃₇FO₇	15.992	505.261 4	485.251 1, 411.217 2, 393.204 7, 355.189 8, 337.179 8, 319.169 9, 309.184 4, 301.160 1, 291.175 3, 279.175 2, 153.090 3, 57.033 3

化合物	线性范围/（μg/mL）	线性方程	相关系数r	检出限/（mg/kg）	定量限/（mg/kg）
BM	0.2~10	Y=224X+45 843	0.999 4	0.30	0.98
DXM	0.2~10	Y=223X+38 615	0.999 5	0.34	1.12
17-DXMP	0.2~10	Y=321X+79 377	0.997 8	0.06	0.21
BMA	0.2~10	Y=187X+45 046	0.999 2	0.06	0.19
DXMA	0.2~10	Y=185X+36 189	0.999 4	0.09	0.30
17-BMP	0.2~10	Y=247X+36 166	0.999 3	0.06	0.19
21-BMP	0.2~10	Y=208X+48 504	0.999 1	0.06	0.21
21-DXMP	0.2~10	Y=306X+73 529	0.999 1	0.05	0.17
BMDP	0.2~10	Y=250X+20 969	0.999 7	0.07	0.23

化合物	保留时间/min	RSD/%	平均回收率/%	RSD/%
BM	9.337	2.2	96.2	1.7
DXM	9.612	2.0	96.5	0.7
17-DXMP	12.755	0.1	103.7	5.2
BMA	12.823	0.1	97.3	0.5
DXMA	13.059	0.9	98.0	1.6
17-BMP	13.217	0.1	96.5	0.6
21-BMP	13.795	0.1	96.2	0.9
21-DXMP	14.070	0.1	93.1	3.5
BMDP	15.976	0.1	95.3	0.9

化合物	保留时间/min	RSD/%	峰面积	RSD/%
BM	9.244	0.2	1 225 531	0.8
DXM	9.666	0.2	1 207 812	1.2
17-DXMP	12.733	0.1	1 837 828	1.0
BMA	12.798	0.1	1 035 126	1.0
DXMA	13.084	0.1	1 011 937	0.9
17-BMP	13.195	0.1	1 336 494	0.7
21-BMP	13.763	0.1	1 148 433	1.1
21-DXMP	14.043	0.1	1 667 113	1.0
BMDP	15.931	0.1	1 320 455	0.8

序号	样品名称（标示）	剂型	检出物质	含量/ （mg/kg）
1	保湿面膜	面膜	—	—
2	百草藓方	水剂	17-BMP 21-BMP	49.1 15.3
3	蚕丝面膜	面膜	BM	4.6
4	亮肤霜	霜剂	DXM	22.4
5	祛斑精华液	水剂	—	—
5	防晒霜	霜剂	DXM	12.9
6	美颜霜	霜剂	DXM	3.0
7	护肤乳	乳剂	—	—
8	洁面乳	乳剂	—	—
9	修护祛痘膏	霜剂	—	—
10	收敛爽肤水	水剂	—	—