化妆品中13种防腐剂的高效液相色谱分析及质谱确证

doi:10.3969/j.issn.2097-2806.2024.12.016

Abstract

Abstract:

A method using high performance liquid chromatography （HPLC） was developed for the simultaneous determination of 13 preservatives （levulinic acid, p-hydroxyacetophenone, raspberry ketone, p-anisic acid, caprylhydroxamic acid, hydroxyethoxyphenyl butanone, methylisothiazolinone, phenoxyethanol, benzoic acid, methylparaben, chlorphenesin, dehydroacetic acid, and 5-bromo-5-nitro-1,3-dioxane） in cosmetics. Different types of samples were ultrasonically extracted by methanol, then the separation of 13 preservatives was carried out on a column of Agilent ZORBAX Eclipse XDB-C18 （250 mm×4.6 mm, 5 μm） by gradient elution at a flow rate of 1.0 mL/min, using 0.1% phosphoric acid solution and acetonitrile as mobile phases. The column temperature was 30 ℃, and the detection was completed by a diode array detector with the wavelengths at 275, 230 and 210 nm. Suspected positive samples were further confirmed by liquid chromatography-tandem mass spectrometry or gas chromatography-mass spectrometry. The linear regression analysis data shows good linearity for 13 preservatives in the respective mass concentration range, with their correlation coefficients （r） greater than 0.999 8. The limits of detection （LODs） and limits of quantitation （LOQs） of the method are in the ranges of 0.4-100.0 mg/kg and 1.2-250.0 mg/kg, respectively. At three spiked levels, the average recoveries for 13 target compounds in three kinds of matrix samples are within 84.0%-115.4%, and the relative standard deviations （RSD） are within 0.5%-4.8% （n = 6）. This method is convenient, efficient, and precise, which can be used for qualitative and quantitative analysis of common preservatives in daily cosmetics.

Key words: preservatives, cosmetics, high performance liquid chromatography, mass spectrometry

CLC Number:

TQ658

Po Zou, Wei Xu, Xueyan Li, Changyu Li, Yan Chen, Qinqin Chen. Determination of 13 preservatives in cosmetics by high performance liquid chromatography and verification by mass spectrometry[J].China Surfactant Detergent & Cosmetics, 2024, 54(12): 1532-1540.

Figures/Tables 12

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References 22

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序号	组分名称	ρ（系列混合标准溶液）/（μg/mL）
1	甲基异噻唑啉酮	0.12	0.30	1.20	3.00	12.00	30.00
2	乙酰丙酸	25.0	62.5	250.0	625.0	2 500.0	6 250.0
3	对羟基苯乙酮	0.12	0.30	1.20	3.00	12.00	30.00
4	苯氧乙醇	2.0	5.0	20.0	50.0	200.0	500.0
5	覆盆子酮	0.6	1.5	6.0	15.0	60.0	150.0
6	苯甲酸	0.30	0.75	3.00	7.50	30.00	75.00
7	4-羟基苯甲酸甲酯	0.2	0.5	2.0	5.0	20.0	50.0
8	对茴香酸	0.30	0.75	3.00	7.50	30.00	75.00
9	氯苯甘醚	0.2	0.5	2.0	5.0	20.0	50.0
10	脱氢乙酸	0.30	0.75	3.00	7.50	30.00	75.00
11	5-溴-5-硝基-1,3-二噁烷	2.50	6.25	25.00	62.50	250.00	625.00
12	辛酰羟肟酸	2.0	5.0	20.0	50.0	200.0	500.0
13	羟基乙氧基苯基丁酮	0.6	1.5	6.0	15.0	60.0	150.0

时间/min	φ（流动相A）/%	φ（流动相B）/%
0.0	95	5
4.0	95	5
4.1	80	20
25.0	70	30
25.1	65	35
27.0	65	35
27.1	95	5
30.0	95	5

序号	组分名称	ESI+/ESI-	母离子/（m/z）	子离子/（m/z）	去簇电压/V	碰撞电压/V
1	甲基异噻唑啉酮	+	116.0	71.1/101.1	70	28/30
2	乙酰丙酸	-	115.0	71.1/97.0	60	15/13
3	对羟基苯乙酮	-	135.1	92.0/93.0	80	31/25
4	覆盆子酮	-	163.1	57.0/163.1	40	24/8
5	苯甲酸	-	121.0	77.0/121.0	130	15/10
6	4-羟基苯甲酸甲酯	-	150.7	92.0/135.8	75	24/18
7	对茴香酸	-	151.1	107.1/92.0	60	16/35
8	脱氢乙酸	-	167.0	83.0/123.1	40	22/14
9	辛酰羟肟酸	-	158.1	58.0/110.2	90	17/17
10	羟基乙氧基苯基丁酮	-	206.8	57.0/179.1	60	31/14

序号	组分名称	线性方程	相关系数r	检出限/（mg/kg）	定量限/（mg/kg）
1	甲基异噻唑啉酮	y = 19.003 4 x+0.207 8	0.999 9	0.4	1.2
2	乙酰丙酸	y = 0.093 5 x+0.327 5	0.999 9	100.0	250.0
3	对羟基苯乙酮	y = 31.853 1 x+0.439 1	0.999 9	0.4	1.2
4	苯氧乙醇	y = 2.458 3 x+0.806 6	0.999 9	6.0	20.0
5	覆盆子酮	y = 7.587 5 x+0.788 7	0.999 9	2.0	6.0
6	苯甲酸	y = 27.268 7 x+2.104 0	0.999 9	1.0	3.0
7	4-羟基苯甲酸甲酯	y = 12.770 2 x+0.385 9	0.999 9	0.8	2.0
8	对茴香酸	y = 12.891 1 x+0.670 3	0.999 9	1.0	3.0
9	氯苯甘醚	y = 15.571 8 x+0.241 9	0.999 9	0.6	2.0
10	脱氢乙酸	y = 15.415 7 x-1.730 2	0.999 9	1.0	3.0
11	5-溴-5-硝基-1,3-二噁烷	y = 1.479 2 x+0.566 9	0.999 9	8.0	25.0
12	辛酰羟肟酸	y = 2.972 1 x-1.230 5	0.999 9	7.5	20.0
13	羟基乙氧基苯基丁酮	y = 3.442 5 x+0.277 2	0.999 9	2.0	6.0

组分名称	水剂		乳液		蜡基
组分名称	回收率/%	RSD/%	回收率/%	RSD/%	回收率/%	RSD/%
甲基异噻唑啉酮	88.6~101.7	1.3~1.7	86.5~102.8	1.4~1.7	95.8~110.5	0.9~3.7
乙酰丙酸	97.3~ 99.5	1.6~4.7	94.1~ 99.2	1.1~4.8	92.6~107.3	1.5~3.4
对羟基苯乙酮	87.6~101.1	1.2~1.9	88.2~105.7	1.0~3.2	97.4~111.5	1.8~2.7
苯氧乙醇	88.4~101.0	1.1~2.6	86.9~103.5	0.8~1.5	95.5~110.1	2.0~2.4
覆盆子酮	87.1~100.7	0.5~1.7	88.4~103.9	0.9~1.7	100.2~110.5	1.5~2.4
苯甲酸	86.0~102.5	0.8~1.7	91.2~104.7	1.0~3.4	96.9~107.2	2.0~2.7
4-羟基苯甲酸甲酯	87.7~100.4	1.5~3.0	90.1~103.7	0.9~4.1	96.6~115.4	1.8~2.8
对茴香酸	87.6~ 99.8	1.2~1.7	87.6~103.5	0.8~2.4	94.5~108.5	2.2~2.5
氯苯甘醚	88.3~100.6	1.2~1.6	88.6~103.7	0.9~2.4	93.5~110.3	1.8~2.6
脱氢乙酸	88.3~107.2	1.1~1.9	86.5~102.3	1.1~2.2	95.8~107.2	1.3~2.5
5-溴-5-硝基-1,3-二噁烷	87.4~100.0	1.2~3.0	84.1~102.2	1.0~1.3	84.0~109.5	1.7~2.7
辛酰羟肟酸	91.6~100.2	1.3~2.0	85.8~102.1	1.3~3.0	94.5~108.3	1.2~2.8
羟基乙氧基苯基丁酮	92.0~101.2	1.5~3.3	90.4~104.2	1.1~2.6	96.7~110.6	1.7~3.2

Determination of 13 preservatives in cosmetics by high performance liquid chromatography and verification by mass spectrometry

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