UPLC-MS/MS法测定化妆品中5种美白剂

doi:10.3969/j.issn.2097-2806.2024.07.016

摘要/Abstract

摘要：

建立了超高效液相色谱-串联质谱法（UPLC-MS/MS）测定化妆品中5种美白剂的方法。样品采用甲醇-水（70∶30）溶液作为提取溶剂，超声提取30 min，采用ZORBAX RR StableBond Aq（Agilent）色谱柱进行液相分离，梯度洗脱，采用电喷雾离子源负离子模式扫描和多反应监测模式采集。结果表明，在最优条件下，5种美白成分实现有效分离，以水乳、霜膏、粉饼化妆品为基质的标准工作曲线均在1.0~200.0 ng/mL范围内线性良好，相关系数R²≥0.996，方法检出限为0.01~0.1 mg/kg，定量限为0.03~0.3 mg/kg。3种不同基质的化妆品样品在1倍、2倍、10倍定量限浓度加标的平均回收率为82.6%~104.8%，相对标准偏差为2.1%~8.6%（n=6）。该方法操作简便，准确性良好，适用于不同基质化妆品中脱氧熊果苷、α-熊果苷、β-熊果苷、对苯二酚和熊果酸5种美白剂的测定。

关键词: 超高效液相色谱-四极杆串联质谱法, 美白剂, 化妆品

Abstract:

A method was established for quantitative determination of five whitening agents in cosmetics using ultra-high performance liquid chromatography-tandem mass spectrometry （UPLC-MS/MS）. The samples were extracted with methanol-water solution （70∶30）, ultrasonic extraction for 30 minutes and then separated by Agilent column （ZORBAX RR StableBond Aq） followed by gradient elution. An electrospray ionization （ESI） source in negative ion mode was utilized for multiple reaction monitoring （MRM） scanning. The results show that under optimal conditions no obvious matrix effect exists in 3 different cosmetic matrices. Among the three cosmetics with different types of matrices, good linearity is obtained for five whitening agents in the range of 1.0-200.0 ng/mL, and the correlation coefficients （R²） are more than 0.996. The limit of detection （LOD） and limit of quantitation （LOQ） are 0.01-0.1 mg/kg and 0.03-0.3 mg/kg, respectively. Spike recovery is performed on three cosmetics at three different spike levels （1, 2, and 10 times of the LOQ）, and the average recovery range is 82.6%-104.8% with a relative standard deviation of 2.1%-8.6% （n=6）. This method is easy to implement, efficient and accurate. It is suitable for quantitative analysis of five whitening agents, including deoxyarbutin, α-arbutin, β-arbutin, hydroquinone, and ursolic acid in common cosmetics, providing technical support for the regulation and risk monitoring of the cosmetics industry.

Key words: UPLC-MS/MS, whitening agents, cosmetics

中图分类号:

TQ658

王昌钊, 李子豪, 王一欣, 杨玥. UPLC-MS/MS法测定化妆品中5种美白剂[J]. 日用化学工业（中英文）, 2024, 54(7): 873-878.

Changzhao Wang, Zihao Li, Yixin Wang, Yue Yang. Determination of 5 whitening agents in cosmetics using UPLC-MS/MS[J]. China Surfactant Detergent & Cosmetics, 2024, 54(7): 873-878.

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参考文献 16

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步骤	时间/min	流速/（mL/min）	流动相体积分数/%
步骤	时间/min	流速/（mL/min）	A	B
1	0.00	0.3	10	90
2	2.50	0.3	90	10
3	4.00	0.3	90	10
4	4.50	0.3	10	90
5	6.00	0.3	10	90

化合物名称	保留时间/min	母离子（m/z）	子离子（m/z）	去簇电压/ V	碰撞能量/eV
脱氧熊果苷	4.20	193.1	108.1^*	-35	-21
脱氧熊果苷	4.20	193.1	193.1	-35	-5
α-熊果苷	2.72	271.2	108.2^*	-90	-34
α-熊果苷	2.72	271.2	151.2	-90	-16
β-熊果苷	1.86	271.2	108.2^*	-90	-32
β-熊果苷	1.86	271.2	151.2	-90	-17
对苯二酚	3.05	109.1	108.1^*	-75	-21
对苯二酚	3.05	109.1	81.1	-75	-17
熊果酸	4.54	455.6	455.6^*	-16	-10
熊果酸	4.54	455.6	455.6	-16	-10

化合物名称	基质名称	回归方程	线性范围/（ng/mL）	相关系数R²	方法检出限/（mg/kg）	方法定量限/（mg/kg）
脱氧熊果苷	水乳	Y=1.68×10⁵X+8.78×10³	1.0~200.0	0.996 1	0.01	0.03
	膏霜	Y=1.41×10⁵X-6.76×10⁴	1.0~200.0	0.998 2	0.01	0.03
	粉饼	Y=1.50×10⁵X+6.25×10⁴	1.0~200.0	0.997 4	0.01	0.03
α-熊果苷	水乳	Y=1.44×10⁵X-1.10×10⁵	1.0~200.0	0.998 2	0.02	0.06
	膏霜	Y=1.01×10⁵X+5.46×10⁴	1.0~200.0	0.997 1	0.02	0.06
	粉饼	Y=1.211×10⁵X-1.02×10⁵	1.0~200.0	0.997 5	0.02	0.06
β-熊果苷	水乳	Y=1.34×10⁵X+3.46×10⁵	1.0~200.0	0.998 8	0.05	0.15
	膏霜	Y=1.51×10⁴X+1.53×10⁴	1.0~200.0	0.997 6	0.05	0.15
	粉饼	Y=1.01×10⁴X-1.33×10⁴	1.0~200.0	0.998 4	0.05	0.15
对苯二酚	水乳	Y=8.37×10⁴X-2.27×10⁴	1.0~200.0	0.998 6	0.05	0.15
	膏霜	Y=9.87×10⁴X+8.35×10³	1.0~200.0	0.999 1	0.05	0.15
	粉饼	Y=7.00×10⁴X+6.00×10³	1.0~200.0	0.997 6	0.05	0.15
熊果酸	水乳	Y=6.02×10⁴X+5.26×10³	1.0~200.0	0.999 2	0.1	0.3
	膏霜	Y=5.22×10⁴X-1.56×10³	1.0~200.0	0.998 5	0.1	0.3
	粉饼	Y=4.13×10⁴X+2.12×10³	1.0~200.0	0.999 0	0.1	0.3

样品名称	添加水平/ （mg/kg）	水乳		膏霜		粉饼
样品名称	添加水平/ （mg/kg）	回收率/%	RSD/%	回收率/%	RSD/%	回收率/%	RSD/%
脱氧熊果苷	0.03	91.8	4.2	87.6	6.8	84.5	7.6
	0.06	92.4	4.6	93.0	4.5	85.8	6.7
	0.30	95.0	3.1	100.4	3.4	90.3	5.5
α-熊果苷	0.06	90.6	6.5	92.1	6.8	88.5	8.6
	0.12	97.0	5.1	90.5	5.4	87.0	5.5
	0.60	92.8	2.5	98.6	5.2	89.9	4.4
β-熊果苷	0.15	88.3	5.6	88.7	7.5	82.6	5.0
	0.30	88.9	4.2	93.4	4.4	85.6	4.7
	1.50	90.4	3.2	99.6	2.1	90.5	3.6
对苯二酚	0.15	89.9	6.5	93.2	5.4	84.6	5.7
	0.30	91.7	4.4	90.8	3.4	88.9	4.8
	1.50	92.3	3.3	104.8	2.0	87.5	3.0
熊果酸	0.3	95.2	5.6	86.9	4.5	91.0	5.5
	0.6	91.3	4.2	89.5	4.0	91.1	3.4
	3.0	97.8	2.9	99.5	2.7	92.4	3.1