化妆品中托萘酯、利拉萘酯的高效液相色谱定量及高效液相色谱-串联质谱确证

doi:10.3969/j.issn.2097-2806.2024.02.016

摘要/Abstract

摘要：

建立了化妆品中托萘酯、利拉萘酯的高效液相色谱法（HPLC）和高效液相色谱-串联质谱（HPLC-MS/MS）确证方法。以乙腈为提取溶剂，经涡旋、超声制成样品溶液。在HPLC方法中，采用5 μm粒径的常规C18色谱柱，以乙腈和0.1%甲酸水为流动相，在258和283 nm波长下进行定量测定，同时结合200~400 nm范围光谱进行定性。HPLC-MS/MS方法所用流动相与HPLC法相同，经粒径为1.8 μm的高效C18柱分离，用ESI源在MRM模式下对目标物进行确证。在HPLC方法中，托萘酯和利拉萘酯的线性范围分别为0.1~10.0 mg/L和0.2~20.0 mg/L （R²>0.99），检出限为3.0和6.0 mg/kg，定量限为10和20 mg/kg，加标回收率为93.3%~107.9% （RSD<5%）。在HPLC-MS/MS方法中，托萘酯和利拉萘酯的线性范围均为0.05~5.00 μg/L （R²>0.99），检出限均为0.002 mg/kg，定量限均为0.005 mg/kg，加标回收率为84.0%~112.8% （RSD<5%）。本研究建立的方法简便、快速、专属性强、准确度高，适用于化妆品中托萘酯和利拉萘酯的测定。

关键词: 高效液相色谱, 高效液相色谱-串联质谱, 托萘酯, 利拉萘酯, 化妆品

Abstract:

A method for the determination of tolnaftate and liranaftate in cosmetics by high performance liquid chromatography （HPLC） and verification by high performance liquid chromatography-tandem mass spectrometry （HPLC-MS/MS） was established. Samples （including 5 kinds of matrix: cream, emulsion, liquid, gel, and oil） were extracted with acetonitrile, mixed thoroughly by vortex and ultra-sonication. In HPLC method, the separation was performed by C18 column of 5 μm particle sizes using acetonitrile and 0.1% formic acid water as mobile phases at the wavelength of 258 nm and 283 nm. The HPLC-MS/MS method employed a rapid resolution C18 column of 1.8 μm particle sizes and the same mobile phases as the HPLC method. The target compounds were analyzed by multiple reaction monitoring （MRM） in electro-spray ionization （ESI） mode. Both the HPLC and HPLC-MS/MS methods show good performance in methodology validation. In HPLC method, the linearities of tolnaftate and liranaftate are in the range of 0.1-10.0 mg/L and 0.2-20.0 mg/L, respectively （correlation coefficient, R²>0.99）, the limits of detection （LOD） are 3.0 mg/kg and 6.0 mg/kg, the limits of quantitation （LOQ） are 10 mg/kg and 20 mg/kg, and the spiked recoveries are between 93.3% and 107.9% （relative standard deviation, RSD<5%）. While in HPLC-MS/MS method, the linearities of tolnaftate and liranaftate both are 0.05-5.00 μg/L （R²>0.99）, the LODs are 0.002 mg/kg, the LOQs are 0.005 mg/kg, and the spiked recoveries are between 84.0% and 112.8% （RSD<5%）. The method established in this study is simple, rapid, with strong specificity and high accuracy and is suitable for the determination of tolnaftate and liranaftate in cosmetics.

Key words: HPLC, HPLC-MS/MS, tolnaftate, liranaftate, cosmetics

中图分类号:

TQ658

鲁毅翔, 伍丽婷, 蒋济民, 陈海露, 黄璇. 化妆品中托萘酯、利拉萘酯的高效液相色谱定量及高效液相色谱-串联质谱确证[J]. 日用化学工业（中英文）, 2024, 54(2): 231-238.

Yixiang Lu, Liting Wu, Jimin Jiang, Hailu Chen, Xuan Huang. Determination of tolnaftate and liranaftate in cosmetics by high performance liquid chromatography and verification by high performance liquid chromatography-tandem mass spectrometry[J]. China Surfactant Detergent & Cosmetics, 2024, 54(2): 231-238.

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参考文献 20

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序号	名称	CAS登记号	保留时间/min	前级离子（m/z）	产物离子（m/z）	碰撞电压/eV
1	托萘酯	2398-96-1	1.71	308.1	148^*	19
1	托萘酯	2398-96-1	1.71	308.1	120.1	31
2	利拉萘酯	88678-31-3	2.04	329.1	108^*	21
2	利拉萘酯	88678-31-3	2.04	329.1	188.2	46

序号	色谱柱	内径×柱长/mm	粒径/μm	填料类型	T		n		R
序号	色谱柱	内径×柱长/mm	粒径/μm	填料类型	托萘酯	利拉萘酯	托萘酯	利拉萘酯	托萘酯	利拉萘酯
1	Inertsil ODS-3	4.6×250	5	C18	1.07	1.03	17 978	18 294	5.88	—
2	Capcellpak MGⅡ	4.6×250	5	C18	1.00	0.99	17 369	17 414	5.55	—
3	SunFire^TM C18	4.6×250	5	C18	1.02	1.00	19 172	19 560	6.39	—
4	SymmetryShield RP18	4.6×250	5	RP C18	1.05	1.00	17 839	18 542	3.75	—
5	Synergi Hydro-RP	4.6×250	4	RP C18	1.12	1.15	19 589	20 080	5.85	—
6	ACE Excel 5 C18-PFP	4.6×250	5	C18-PFP	1.02	1.08	20 902	21 198	1.71	—
7	CAPCELL PAK ADME	4.6×250	5	ADME	1.33	1.33	5 963	5 739	2.73	—

序号	流动相		T		n		R
序号	水相	有机相	托萘酯	利拉萘酯	托萘酯	利拉萘酯	托萘酯	利拉萘酯
1	甲酸水溶液（φ（HCOOH）=0.1%）	乙腈	1.02	1.00	19 172	19 560	6.39	—
2	水	乙腈	1.00	1.00	18 445	18 819	6.20	—
3	甲酸铵水溶液（w（HCOONH₄）=0.1%）	乙腈	1.01	1.00	18 966	19 100	6.27	—
4	磷酸水溶液（φ（H₃PO₄）=0.05%）	乙腈	1.08	1.09	20 748	20 976	6.15	—
5	水	甲醇	1.03	1.03	13 173	13 998	6.23	—
6	磷酸二氢钾溶液（w（KH₂PO₄）=0.34%）	甲醇	1.03	1.02	13 366	14 095	6.27	—

名称	HPLC				HPLC-MS/MS
名称	线性范围/ （mg/L）	R²	回归方程	LOD & LOQ/（mg/kg）	线性范围/ （μg/L）	R²	回归方程	LOD & LOQ/（mg/kg）
托萘酯	0.1~10.0	1.000	y=0.56x-0.008 2	3，10	0.05~5.00	1.000	y=1.18×10⁵x-621	0.002，0.005
利拉萘酯	0.2~20.0	1.000	y=0.34x-0.001 0	6，20	0.05~5.00	1.000	y=9.07×10⁴x-100	0.002，0.005

名称	检测方法	ρ/（mg/L or μg/L）^*	RSD/%
			精密度		稳定性
			1 d	3 d	24 h	48 h	72 h
托萘酯	HPLC	0.1	1.9	2.8	2.5	2.3	2.7
	HPLC	10	1.3	1.4	1.5	1.9	3.6
	HPLC-MS/MS	0.05	4.4	4.3	4.4	4.1	4.6
	HPLC-MS/MS	5	1.3	6.3	4.1	3.8	3.9
利拉萘酯	HPLC	0.2	2.7	3.9	2.3	2.7	2.5
	HPLC	20	1.0	1.1	1.1	1.6	3.4
	HPLC-MS/MS	0.05	3.2	3.6	4.9	4.9	6.3
	HPLC-MS/MS	5	1.3	5.4	4.1	5.3	5.6