高效液相色谱-串联质谱法测定美白类化妆品中5种荧光增白剂

doi:10.3969/j.issn.1001-1803.2020.06.012

摘要/Abstract

摘要：

建立了高效液相色谱-串联质谱法（HPLC-MS/MS）测定美白类化妆品中5种荧光增白剂（FWAs）的分析方法。在样品中加入10 mL 50%甲醇溶液,超声提取30 min,经WAX固相萃取小柱净化后,采用CAPCELL PAK-C₁₈ （2.0 mm×150 mm,3 μm）色谱柱,以甲醇-5 mmol/L 乙酸铵溶液为流动相进行梯度洗脱,采用电喷雾离子源（ESI）,在负离子、多反应监测（MRM）模式下扫描,外标法定量。结果表明,5种荧光增白剂在各自范围内线性关系良好,相关系数均大于0.99,检出限为0.1~1.01 mg/L,定量限为0.33~2.03 mg/L;在3个添加水平下的平均回收率为90.6%~113.2%,相对标准偏差为2.2%~14.1%。

关键词: 高效液相色谱-串联质谱, 荧光增白剂, 固相萃取, 化妆品

Abstract:

A method for the determination of five fluorescent whitening agents （FWAs） in cosmetics by high performance liquid chromatography-tandem mass spectrometry （HPLC-MS/MS） was developed. The samples were extracted with 50% methanol by ultrasonic extraction for 30 min, purified by WAX SPE column, and analyzed by HPLC-MS/MS on a CAPCELL PAK-C₁₈ column （2.0 mm×150 mm, 3 μm）, employing methanol-5 mmol/L ammonium acetate as mobile phase in a gradient elution mode. Electrospray ionization （ESI） source was operated in the negative mode using multiple reaction monitoring （MRM） scanning mode. The results were quantified by external standard method. The results indicated that the method had good linear relationships with correlation coefficients （r） greater than 0.99. The limits of detection（LODs） are 0.1-1.01 mg/L and the limits of quantification （LOQs） are 0.33-2.03 mg/L. The average recoveries at three spiked levels are in the range of 90.6%-113.2%, and the relative standard deviations （RSDs） are in the range of 2.2%-14.1%.

Key words: HPLC-MS/MS, fluorescent whitening agents, solid phase extraction, cosmetics

中图分类号:

TQ658

窦月,田金强,王乾蕾,王永凤,潘柯伊. 高效液相色谱-串联质谱法测定美白类化妆品中5种荧光增白剂[J]. 日用化学工业, 2020, 50(6): 427-432.

DOU Yue,TIAN Jin-qiang,WANG Qian-lei,WANG Yong-feng,PAN Ke-yi. Determination of five fluorescent whitening agents in cosmetics by high performance liquid chromatography-tandem mass spectrometry[J]. China Surfactant Detergent & Cosmetics, 2020, 50(6): 427-432.

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参考文献 15

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化合物	化学文摘号	母离子（m/z）	子离子（m/z）	锥孔电压/eV	碰撞能/eV
FWA220	4193-55-9	537.3	309.2*	-90	-45
FWA220	4193-55-9	537.3	197	-90	-60
FWA357	41098-56-0	585.5	545.6*	-85	-35
FWA357	41098-56-0	585.5	505.4	-85	-40
FWA85	12224-06-5	827.3	623*	-130	-60
FWA85	12224-06-5	827.3	543.4	-130	-75
FWA113	12768-92-2	915.2	587.3*	-145	-85
FWA113	12768-92-2	915.2	667.1	-145	-70
FWA71	16090-02-1	879.2	569.3*	-150	-80
FWA71	16090-02-1	879.2	649.2	-150	-70

化合物	回收率/%
化合物	WAX	HLB	NH₂	MAX	CN
FWA85	83.3	56.3	75.9	0	0
FWA220	101.1	65.3	86.0	0	0
FWA357	86.7	77.0	94.7	0	0
FWA71	102.3	65.6	66.3	0	0
FWA113	102.4	63.7	63.2	0	0

剂型	化合物	线性范围/（mg·L^-1）	线性方程	相关系数	检出限/（mg·L^-1）	定量限/（mg·L^-1）
水剂	FWA220	0.10~10.20	y = 1 180x-298	0.998 6	0.14	0.49
	FWA357	0.11~11.15	y = 407x-308	0.992 7	1.01	2.03
	FWA85	0.12~12.26	y = 958x+31	0.997 4	0.10	0.36
	FWA113	0.12~12.18	y = 1 160x-577	0.997 5	0.10	0.35
	FWA71	0.10~10.44	y = 1 310x-192	0.993 4	0.10	0.33
乳剂	FWA220	0.10~10.20	y = 882x-128	0.998 9	0.14	0.49
	FWA357	0.11~11.15	y = 286x-174	0.997 8	1.01	2.03
	FWA85	0.12~12.26	y = 443x+129	0.998 2	0.10	0.36
	FWA113	0.12~12.18	y = 778x+50	0.997 3	0.10	0.35
	FWA71	0.10~10.44	y = 684x-274	0.997 1	0.10	0.33
清洁剂	FWA220	0.10~10.20	y = 1 090x-446	0.996 9	0.14	0.49
	FWA357	0.11~11.15	y = 355x-255	0.994 6	1.01	2.03
	FWA85	0.12~12.26	y = 701x-139	0.998 8	0.10	0.36
	FWA113	0.12~12.18	y = 832x-455	0.996 6	0.10	0.35
	FWA71	0.10~10.44	y = 840x-18.1	0.999 5	0.10	0.33

化合物	加入量/（mg·L^-1）	水剂		乳剂		清洁剂
化合物	加入量/（mg·L^-1）	平均回收率/%	相对标准偏差/%	平均回收率/%	相对标准偏差/%	平均回收率/%	相对标准偏差/%
FWA85	1	96.9	11.6	90.6	6.6	98.4	6.8
	5	96.3	9.5	102.7	7.7	101.2	5.0
	10	102.2	7.3	107.5	2.2	96.6	3.0
FWA220	1	96.4	8.0	98.8	6.5	102.3	4.8
	5	94.1	5.0	91.5	5.4	93.1	5.7
	10	104.2	3.3	103.4	4.1	92.1	3.6
FWA357	1	93.8	13.5	101.9	7.4	99.8	9.7
	5	92.9	5.8	94.7	7.1	86.8	9.1
	10	111.6	6.5	103.0	3.6	93.0	6.4
FWA71	1	108.2	8.2	97.6	14.1	111.9	10.0
	5	100.4	9.5	102.1	10.1	111.3	13.1
	10	97.3	6.2	98.9	8.5	113.2	8.0
FWA113	1	95.4	10.4	98.0	12.5	105.1	10.2
	5	92.1	7.2	93.2	6.0	94.0	8.7
	10	97.7	4.6	92.7	4.3	110.1	7.9