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

Abstract

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

CLC Number:

TQ658

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.

Figures/Tables 14

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References 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

Determination of tolnaftate and liranaftate in cosmetics by high performance liquid chromatography and verification by high performance liquid chromatography-tandem mass spectrometry

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HPLC			HPLC-MS/MS
t/min	φ（A）/%	φ（B）/%	t/min	φ（A）/%	φ（B）/%
0	15	85	0	15	85
7	15	85	3	15	85
8	5	95	3.5	5	95
11	5	95	6.5	5	95
12	15	85	7	15	85
16	15	85	10	15	85

名称	加标浓度/ （mg/kg）	膏霜		乳液		水		凝胶		油
名称	加标浓度/ （mg/kg）	回收率/%	RSD/%	回收率/%	RSD/%	回收率/%	RSD/%	回收率/%	RSD/%	回收率/%	RSD/%
托萘酯	10	102.8	1.4	99.0	1.4	103.2	1.3	103.3	1.1	97.1	4.4
	20	102.9	1.2	100.4	3.2	99.5	1.6	100.7	0.5	95.4	1.8
	100	102.9	0.7	103.3	0.7	105.7	3.1	100.6	1.0	101.1	0.2
	1 000	97.3	0.2	98.1	0.2	98.8	1.0	96.1	0.6	98.5	1.9
利拉萘酯	20	105.1	2.3	97.5	1.5	96.0	4.6	97.0	2.4	107.9	3.8
	40	98.0	2.6	93.3	4.4	96.6	1.3	98.6	0.8	95.4	2.3
	200	103.0	0.9	103.0	0.8	101.4	0.9	100.5	1.1	101.4	1.2
	2 000	97.5	0.4	97.3	0.6	99.0	0.6	97.9	0.3	99.2	1.1

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