HPLC-MS/MS法测定3种不同基质化妆品中10种斯汀类禁用药物

doi:10.3969/j.issn.1001-1803.2023.04.016

摘要/Abstract

摘要：

建立了高效液相色谱-质谱联用法（HPLC-MS/MS）测定3种不同基质类型化妆品中10种斯汀类禁用药物的分析方法。样品经0.1%甲酸-乙腈超声提取后，采用Agilent Eclipse plus C₈ （2.1 mm×100 mm，1.8 μm）色谱柱，以甲醇-5 mmol/L甲酸铵0.1%甲酸水溶液作为流动相梯度洗脱。使用三重四极杆质谱多反应监测模式（MRM）检测，标准曲线外标法定量。结果表明，盐酸倍他司汀、咪唑斯汀、盐酸依匹斯汀、富马酸依美斯汀在1~16 μg/L质量浓度范围，其余六种斯汀类在0.1~1.6 μg/L质量浓度范围内线性良好，相关系数（r²）>0.99，检出限（LOD）和定量下限（LOQ）分别为0.003~0.12 μg/L和0.011~0.39 μg/L。3个不同质量浓度添加水平下，水剂、乳液类和膏霜类样品回收率分别为88.0%~107.8%，87.1%~106.5%和87.1%~107.7%，相对标准偏差（RSD）<10%。该方法前处理简单、高效、方法回收率高重复性好，适用于水剂、乳液和膏霜类化妆品中10种斯汀类禁用药物的同时测定。

关键词: 高效液相色谱-串联质谱, 化妆品, 禁用药物, 抗组胺药物, 斯汀类

Abstract:

A high performance liquid chromatography-tandem mass spectrometry （HPLC-MS/MS） method has been established for the simultaneous determination of 10 banned stines drugs in 3 different matrixes of cosmetics. The sample was ultrasonically extracted with 0.1% formic acid-acetonitrile and performed on an Agilent Eclipse plus C₈ column （2.1 mm×100 mm, 1.8 μm） with gradient elution using methanol and 5 mmol/L ammonium formate-0.1% formic acid aqueous solution as the mobile phase. The determination was performed by MS/MS in multiple reaction detection （MRM） mode, and the external standard method was used for quantification. Betahistine dihydrochlorride, mizolastine, epinastine hydrochloride, and emedastine difumarate have good linearity in the range of 1-16 μg/L, while the other six stines have good linearity in the range of 0.1-1.6 μg/L, with the correlation coefficient （r²）>0.99. The limits of detection （LODs） and the limits of quantification （LOQs） are in the range of 0.003-0.12 μg/L and 0.011-0.39 μg/L, respectively. At three different levels of addition, the recoveries of water aqua, lotion and cream samples are 88.0%-107.8%, 87.1%-106.5%, and 87.1%-107.7%, respectively. And the relative standard deviation （RSD） is less than 10%. The method is accurate, high-efficiency, simple pre-treatment, and high recovery rate. It is suitable for the simultaneous determination of 10 stines in cosmetics.

Key words: high performance liquid chromatography-tandem mass spectrometry, cosmetic, prohibited drug, antihistamines, stines

中图分类号:

TQ658

吴鸳鸯, 张丽媛, 王任, 何婷婷. HPLC-MS/MS法测定3种不同基质化妆品中10种斯汀类禁用药物[J]. 日用化学工业（中英文）, 2023, 53(4): 481-486.

Wu Yuanyang, Zhang Liyuan, Wang Ren, He Tingting. Determination of 10 prohibited stines in 3 different matrixes of cosmetics by HPLC-MS/MS[J]. China Surfactant Detergent & Cosmetics, 2023, 53(4): 481-486.

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参考文献 15

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No.	Compound	Retention time/min	Precursorion（m/z）	Product ions （m/z）	Fragmentor/eV	CE/eV
1	Ebastine	8.393	470.4	167.0*，203.0	135	25，30
2	Betahistine dihydrochloride	2.042	137.2	94.0*，106.0	100	8，10
3	Acrivastine	6.638	349.2	278.0*，260.0	135	10，25
4	Azelastine hydrochloride	7.377	382.2	112.0*， 58.1	135	25，50
5	Mizolastine	7.871	433.3	108.9*，308.0	135	45，20
6	Epinastine hydrochloride	6.088	250.2	193.0*， 91.0	135	35，35
7	Setastine hydrochloride	8.003	358.2	215.0*，136.9	135	10，40
8	Emedastine difumarate	5.250	303.2	246.1*， 71.9	135	20，30
9	Clemastine fumarate	8.027	344.2	215.0*，130.0	100	15， 8
10	Bepotastine besylate	6.807	389.2	167.0*，201.9	135	50，20

No.	Compound	Linear equation	Linear range/（μg/L）	LOD/（μg/L）	LOQ/（μg/L）
1	Ebastine	y=13 515.28x+1 615.27	0.1~1.6	0.003	0.011
2	Betahistine dihydrochloride	y=964.30x-98.62	1~16	0.12	0.39
3	Acrivastine	y=7 123.00x+433.91	0.1~1.6	0.008	0.026
4	Azelastine hydrochloride	y=8 836.62x+74.87	0.1~1.6	0.013	0.043
5	Mizolastine	y=4 668.40x-1 433.94	1~16	0.030	0.10
6	Epinastine hydrochloride	y=961.00x-167.34	1~16	0.037	0.12
7	Setastine hydrochloride	y=10 380.71x-155.78	0.1~1.6	0.021	0.070
8	Emedastine difumarate	y=1 491.56x-764.85	1~16	0.076	0.25
9	Clemastine fumarate	y=5 679.22x+240.55	0.1~1.6	0.008	0.025
10	Bepotastine besylate	y=3 245.71x+12.93	0.1~1.6	0.009	0.029

No.	Compound	Spiked level/（mg/kg）	Average recoveries （RSDs）/%
No.	Compound	Spiked level/（mg/kg）	Water aqua	Lotion	Cream
1	Ebastine	0.2	89.8（2.77）	88.1（2.83）	88.9（3.78）
		0.4	103.2（1.39）	93.9（4.72）	92.2（3.38）
		1.0	106.0（2.24）	92.0（0.44）	87.8（1.52）
2	Betahistine dihydrochloride	2	99.0（4.87）	95.2（3.99）	88.8（1.96）
		4	90.2（0.32）	90.1（1.73）	88.8（1.79）
		10	91.9（1.69）	97.6（2.76）	87.1（0.78）
3	Acrivastine	0.2	101.9（1.61）	97.4（4.29）	94.5（4.48）
		0.4	100.2（4.55）	99.4（2.85）	101.5（4.62）
		1.0	107.8（1.61）	104.3（2.14）	103.3（3.96）
4	Azelastine hydrochloride	0.2	92.2（4.92）	87.1（0.76）	101.9（4.52）
		0.4	91.5（2.78）	90.6（1.49）	95.5（4.46）
		1.0	89.4（3.96）	89.1（1.22）	98.9（3.72）
5	Mizolastine	2	93.1（2.03）	93.6（1.78）	104.2（0.61）
		4	90.9（1.33）	90.9（1.81）	92.0（1.75）
		10	88.0（0.52）	90.6（2.16）	90.6（2.73）
6	Epinastine hydrochloride	2	104.4（2.36）	103.8（4.95）	106.8（1.33）
		4	104.6（1.69）	104.2（2.03）	105.0（1.21）
		10	103.4（2.91）	104.1（0.61）	106.0（0.52）
7	Setastine hydrochloride	0.2	104.0（2.51）	91.3（1.31）	100.0（2.73）
		0.4	92.9（3.88）	90.7（1.61）	89.9（3.52）
		1.0	91.4（1.43）	91.0（1.98）	90.1（4.75）
8	Emedastine difumarate	2	102.0（4.60）	106.5（0.83）	107.7（0.87）
		4	90.0（1.85）	95.9（3.26）	96.4（4.41）
		10	88.4（2.58）	99.8（1.07）	97.6（2.23）
9	Clemastine fumarate	0.2	99.1（4.02）	88.3（2.55）	88.3（1.15）
		0.4	94.0（2.74）	91.1（4.65）	92.2（2.64）
		1.0	98.4（1.49）	90.1（3.68）	91.7（4.79）
10	Bepotastine besylate	0.2	95.9（4.58）	90.7（0.21）	97.2（1.89）
		0.4	94.9（2.94）	91.9（3.85）	102.7（3.01）
		1.0	88.5（2.52）	88.7（2.79）	88.9（2.07）