高效液相色谱-串联质谱法测定婴幼儿化妆品中微量丙烯酰胺

doi:10.3969/j.issn.1001-1803.2022.01.014

摘要/Abstract

摘要：

建立液液萃取法-HPLC-MS/MS法测定不同化妆品基质中丙烯酰胺的残留量。以ACE EXCEL 3 C18-AR（100×4.6 mm,3 μm）为固定相,以乙腈-0.1%甲酸水为流动相,等度洗脱,样品采用二氯甲烷-0.1%甲酸水溶液进行液液萃取,取上清液进行HPLC-MS/MS测定,ESI正离子扫描,MRM监测,以保留时间及相对丰度比定性,内标法测定丙烯酰胺的残留量。结果表明,在三类不同基质的化妆品中丙烯酰胺质量浓度在2.5~2 500 μg/L范围内均具有良好的线性关系,相关系数（r）均大于0.995,不同质量浓度水平下的回收率为86.9%~113.5%,精密度为0.6%~10.4%,定量限均为0.025 mg/kg,油状和乳状基质中检出限为0.005 mg/kg,膏霜类基质中为0.008 mg/kg。该方法准确可靠,适用于不同基质化妆品中丙烯酰胺残留量的测定。

关键词: 液液萃取法, 高效液相色谱-串联质谱法, 丙烯酰胺

Abstract:

To establish a liquid-liquid extraction HPLC-MS/MS method for the identification and quantification of acrylamide in three cosmetics matrixes. The cosmetics were dissolved in dichloromethane and the acrylamide was extracted with 0.1% formic acid. The extracted solution was separated on an ACE EXCEL 3 C18-AR （100×4.6 mm, 3 μm） chromatographic column with a mixture of 0.1% formic acid and acetonitrile as mobile phase for isocratic elution and detected with a triple quadrupole mass analyzer using ESI with positive ionization. Ions was monitored in the multiple reaction mode. The acrylamide was identified with relative retention time and ion abundance ratio, and quantified by internal standard method. The established method showed a good linearity in the mass concentration range of 2.5-2 500 μg/L with a LOQ of 0.025 mg/kg for acrylamide in three kinds of cosmetics matrix. The LOD of oil and emulsion matrix were 0.005 mg/kg, and the LOD of cream-like matrix was 0.008 mg/kg. The extraction recovery and precision were 86.9%-113.5% and 0.6%-10.4%, respectively. The established liquid-liquid extraction HPLC-MS/MS method is proved to be accurate and sensitive, and can be applied to determine acrylamide in different cosmetic products.

Key words: liquid-liquid extraction method, HPLC-MS/MS, acrylamide

中图分类号:

TQ658

邵方娴,李耕,陈民辉. 高效液相色谱-串联质谱法测定婴幼儿化妆品中微量丙烯酰胺[J]. 日用化学工业, 2022, 52(1): 91-97.

Shao Fangxian,Li Geng,Chen Minhui. Determination of acrylamide residue in baby cosmetics by HPLC-MS/MS[J]. China Surfactant Detergent & Cosmetics, 2022, 52(1): 91-97.

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参考文献 15

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基质类型	方法号	方法一		方法二		方法三
基质类型	化合物	丙烯酰胺	内标	丙烯酰胺	内标	丙烯酰胺	内标
油状	基质效应/% ^*	100.8	100.4	93.0	93.4	95.4	90.8
	RSD/%	3.2	1.1	11.3	14.7	2.5	2.0
	内标校正的基质效应/% ^**	100.3		100.0		105.0
	RSD/%	3.9		3.8		2.3
乳状	基质效应/% ^*	27.8	28.9	56.4	57.7	77.7	80.6
	RSD/%	5.7	3.2	9.0	6.3	6.1	4.9
	内标校正的基质效应/% ^**	96.0		97.7		96.7
	RSD/%	2.5		2.9		2.5
膏霜类	基质效应/% ^*	48.8	55.2	119.9	125.9	72.0	77.5
	RSD/%	14.7	3.4	15.4	14.0	5.6	7.0
	内标校正的基质效应/% ^**	88.2		95.1		92.1
	RSD/%	12.7		1.5		2.7

基质类型	方法号	方法一		方法二		方法三
基质类型	化合物	丙烯酰胺	内标	丙烯酰胺	内标	丙烯酰胺	内标
油状	绝对提取回收率/%^*	103.6	99.3	79.6	81.2	90.8	93.9
	RSD/%	0.7	1.5	4.5	5.1	2.5	2.0
	提取回收率/%^**	104.3		97.5		96.7
	RSD/%	1.5		1.2		5.3
乳状	绝对提取回收率/%^*	102.0	95.3	82.0	82.3	80.0	85.6
	RSD/%	9.8	11.2	0.3	1.8	5.4	6.2
	提取回收率/%^**	107.1		99.6		93.4
	RSD/%	2.2		2.1		4.1
膏霜类	绝对提取回收率/%^*	91.3	85.9	50.0	54.3	82.4	92.2
	RSD/%	8.8	8.7	7.3	13.7	5.8	0.2
	提取回收率/%^**	106.5		92.6		88.4
	RSD/%	6.9		6.0		2.4

化合物	油状				乳状				膏霜类
化合物	基质效应/ %	RSD/ %	内标校正基质效应/%	RSD/ %	基质效应/ %	RSD/ %	内标校正基质效应/%	RSD/ %	基质效应/ %	RSD/ %	内标校正基质效应/%	RSD/ %
丙烯酰胺	90.3	8.2	99.8	5.4	85.4	10.8	99.7	6.6	79.0	9.7	97.8	6.9
内标	90.5	6.9			85.6	8.2			80.5	4.1

基质类型	标准曲线	相关系数r	检出限/（mg/kg）	定量限/（mg/kg）
油状	Y=0.409 7 X+0.016 06	r=0.999 8	0.005（SN=13）	0.025（SN=53）
乳状	Y=0.393 6 X-0.024 57	r=0.999 7	0.005（SN=7）	0.025（SN=18）
膏霜类	Y=0.351 2 X+0.020 97	r=0.999 5	0.008（SN=3）	0.025（SN=10）

基质类型	加入质量浓度/（µg/L）	测得质量浓度/（µg/L）	提取回收率/%	平均提取回收率/%	精密度/%
油状基质	4.954	4.969	100.3	101.3	1.7
		5.117	103.3
		4.969	100.3
	24.77	24.10	97.3	98.5	1.7
		24.23	97.8
		24.87	100.4
	123.8	126.0	101.8	99.0	2.6
		119.7	96.7
		122.1	98.6
乳状基质	4.954	4.473	90.3	88.3	2.0
		4.325	87.3
		4.325	87.3
	24.77	26.49	107.0	108.2	4.4
		28.11	113.5
		25.81	104.2
	123.8	137.8	111.3	110.6	0.6
		136.1	109.9
		137.0	110.7
膏霜类基质	4.954	4.647	93.8	89.6	4.1
		4.369	88.2
		4.305	86.9
	24.77	25.75	103.9	98.7	4.6
		23.91	96.54
		23.69	95.62
	123.8	116.7	94.3	97.4	10.4
		110.3	89.1
		134.6	108.7