气相色谱-串联质谱法测定化妆品中24种致敏芳香化合物

doi:10.3969/j.issn.1001-1803.2020.10.012

Abstract

Abstract:

A gas chromatography-tandem mass spectrometry （GC-MS/MS） method was developed for the simultaneous determination of 24 fragrance allergens in cosmetics. After ultrasonically extracted by methanol and dehydrated by adding anhydrous sodium sulfate, the cosmetics samples were centrifuged, filtered and analyzed by GC-MS/MS with external standard method. The limits of detection of 24 fragrance allergens range from 1 to 28 μg/L, and the correlation coefficients in the linear range were all greater than 0.995. Three types of cosmetics, including perfume, moisturizing water and cleansing cream, were selected to verify the accuracy of the method. The average spiked recoveries range from 70.1% to 119.6%, and the relative standard deviations （RSD） varies from 0.8% to 7.0% （n=6）. The method is simple, rapid, accurate and sensitive, and suitable for the determination of 24 fragrance allergens in cosmetics.

Key words: gas chromatography-tandem mass spectrometry, fragrance allergens, cosmetics

CLC Number:

TQ658

LONG Pei,ZHENG Lin,GAO Jia-nan,WU Yi-xin,XU Jia-ming,REN Fei,XIAO Dao-qing. Determination of 24 fragrance allergens in cosmetics by gas chromatography-tandem mass spectrometry[J].China Surfactant Detergent & Cosmetics, 2020, 50(10): 725-730.

Figures/Tables 5

Fig. 1

Tab. 1

Gas chromatography and mass spectrometry parameters for determination of 24 fragrance allergens"

编号	化合物	CAS					保留时间/ min	特征离子（m/z）					定量离子对（碰撞能）/eV				定性离子对（碰撞能）/eV
1	苧烯（Limonene）	5989	-	27	-	5	4.553	68	,	93	,	67	93	>	77	（15）	68	>	53	（10）
2	芳樟醇（Linalool）	78	-	70	-	6	6.845	71	,	93	,	43	93	>	77	（15）	71	>	43	（10）
3	苄醇（Benzyl alcohol）	100	-	51	-	6	7.797	108	,	79	,	107	108	>	79	（16）	108	>	77	（30）
4	香茅醇（Citronellol）	106	-	22	-	9	11.369	81	,	69	,	41	69	>	41	（10）	81	>	83	（15）
5	2-辛炔酸甲酯（Methyl-2-octynoate）	111	-	12	-	6	12.617	123	,	95	,	67	95	>	67	（10）	123	>	67	（10）
6	香叶醇（Geraniol）	106	-	24	-	1	13.007	93	,	69	,	41	69	>	41	（10）	93	>	77	（15）
7	柠檬醛（Citral）	5392	-	40	-	5	13.364	94	,	69	,	41	69	>	41	（10）	94	>	79	（10）
7	柠檬醛（Citral）	5392	-	40	-	5	14.700	94	,	69	,	41	69	>	41	（10）	94	>	79	（10）
8	羟基香茅醛（Hydroxycitronellal）	107	-	75	-	5	15.759	71	,	43	,	95	71	>	43	（ 5）	95	>	67	（10）
9	肉桂醛（Cinnamic aldehyde）	104	-	55	-	2	18.049	131	,	103	,	132	103	>	77	（15）	131	>	77	（30）
10	4-甲氧基苄醇（Anisyl alcohol）	105	-	13	-	5	18.565	109	,	77	,	138	109	>	77	（16）	109	>	94	（10）
11	肉桂醇（Cinnamic alcohol）	104	-	54	-	1	19.042	134	,	92	,	105	134	>	92	（10）	134	>	105	（20）
12	丁香酚（Eugenol）	97	-	53	-	0	19.567	164	,	104	,	149	164	>	149	（10）	164	>	104	（14）
13	α-异甲基紫罗兰酮（α-Isomethyl ionone）	127	-	51	-	5	21.405	105	,	135	,	107	107	>	91	（10）	105	>	135	（ 5）
14	异丁香酚（Isoeugenol）	97	-	54	-	1	23.860	164	,	149	,	121	164	>	149	（10）	149	>	121	（ 5）
15	丁苯基甲基丙醛（Lilial）	80	-	54	-	6	25.643	204	,	189	,	131	189	>	131	（10）	204	>	189	（10）
16	香豆素（Coumarine）	91	-	64	-	5	26.983	146	,	118	,	90	146	>	118	（10）	118	>	90	（10）
17	合金欢醇（Farnesol）	4602	-	84	-	0	29.885	93	,	81	,	77	81	>	41	（15）	93	>	77	（15）
17	合金欢醇（Farnesol）	4602	-	84	-	0	34.383	93	,	81	,	77	81	>	41	（15）	93	>	77	（15）
18	α-戊基肉桂醛（Amyl cinnamal）	122	-	40	-	7	30.393	202	,	145	,	129	202	>	129	（10）	202	>	145	（25）
19	新铃兰醛（Lyral）	31906	-	04	-	4	31.731	192	,	136	,	149	136	>	79	（25）	192	>	149	（ 5）
20	α-戊基肉桂醇（Amylcinnamic alcohol）	101	-	85	-	9	31.875	133	,	115	,	55	133	>	55	（10）	133	>	115	（10）
21	己基肉桂醛（Jasmonal）	101	-	86	-	0	33.686	216	,	117	,	129	145	>	117	（10）	216	>	129	（10）
22	苯甲酸卞酯（Benzyl benzoate）	120	-	51	-	4	37.220	194	,	105	,	77	105	>	77	（15）	194	>	165	（30）
23	水杨酸卞酯（Benzyl salicylate）	118	-	58	-	1	40.254	228	,	91	,	65	91	>	65	（20）	228	>	65	（10）
24	肉桂酸卞酯（Benzyl cinnamate）	103	-	41	-	3	48.304	131	,	103	,	77	131	>	103	（12）	131	>	77	（28）

Tab. 1

Tab. 2

Tab. 3

Tab. 4

References 18

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化合物	线性范围/（μg·L^-1）	R²	检出限/（μg·L^-1）	化合物	线性范围/（μg·L^-1）	R²	检出限/（μg·L^-1）
苧烯	13.5~1 348	0. 997 2	3	α-异甲基紫罗兰酮	9.9~ 990	0. 997 7	2
芳樟醇	11.2~1 115	0. 996 6	11	异丁香酚	22.4~1 120	0. 996 1	22
苄醇	15.6~1 556	0. 997 5	8	丁苯基甲基丙醛	10.0~ 996	0. 996 7	2
香茅醇	28.0~1 402	0. 996 6	28	香豆素	10.9~1 088	0. 997 2	1
2-辛炔酸甲酯	18.6~1 864	0. 999 0	9	合金欢醇	12.2~1 223	0. 999 0	12
香叶醇	9.9~ 994	0. 996 0	27	合金欢醇	12.2~1 223	0. 995 5	12
柠檬醛	10.2~1 020	0. 999 0	10	α-戊基肉桂醛	17.0~1 702	0. 998 7	17
柠檬醛	10.2~1 020	0. 995 7	10	新铃兰醛	10.6~1 056	0. 998 2	11
羟基香茅醛	11.0~1 102	0. 997 3	11	α-戊基肉桂醇	10.2~1 024	0. 999 4	10
肉桂醛	12.2~1 222	0. 997 9	3	己基肉桂醛	14.6~1 458	0. 996 9	15
4-甲氧基苄醇	11.3~1 130	0. 997 9	11	苯甲酸卞酯	16.7~1 674	0. 997 2	2
肉桂醇	16.5~1 652	0. 996 1	16	水杨酸卞酯	12.6~1 262	0. 996 3	13
丁香酚	12.1~1 214	0. 995 5	6	肉桂酸卞酯	12.2~1 220	0. 997 4	6

化合物	香水		保湿水		洁面膏
化合物	回收率/%	RSD/%	回收率/%	RSD/%	回收率/%	RSD/%
苧烯	84.9	1.1	72.4	2.2	96.6	6.8
芳樟醇	110.9	2.3	112.2	1.4	81.5	4.6
苄醇	95.4	2.4	93.6	1.8	87.7	3.6
香茅醇	81.2	1.2	101.3	0.9	88.7	3.4
2-辛炔酸甲酯	97.8	2.5	94.3	0.8	91.1	4.8
香叶醇	85.0	1.6	98.1	1.4	89.6	3.7
柠檬醛	80.2	2.5	76.5	2.8	85.7	4.7
柠檬醛	88.1	1.8	89.0	1.2	89.3	7.0
羟基香茅醛	91.1	2.3	102.6	2.5	79.9	4.2
肉桂醛	88.2	4.7	95.9	0.9	90.4	4.2
4-甲氧基苄醇	82.1	2.1	92.0	1.5	86.2	6.5
肉桂醇	86.9	3.7	99.3	0.8	94.4	3.9
丁香酚	77.8	2.1	103.9	3.3	82.5	4.1
α-异甲基紫罗兰酮	84.9	2.2	97.8	1.0	87.0	4.8
异丁香酚	73.4	2.3	96.4	4.1	97.4	4.1
丁苯基甲基丙醛	91.0	1.0	84.7	1.8	79.3	4.0
香豆素	75.5	1.5	88.4	2.3	88.8	5.0
合金欢醇	104.2	2.1	106.7	1.7	106.0	5.2
合金欢醇	102.7	3.3	108.2	1.3	90.8	3.9
α-戊基肉桂醛	85.3	2.8	80.9	1.5	108.0	3.8
新铃兰醛	112.3	1.8	116.2	1.5	88.2	5.0
α-戊基肉桂醇	91.7	2.8	94.1	1.1	96.8	3.6
己基肉桂醛	87.6	2.1	83.3	3.0	94.5	2.4
苯甲酸卞酯	84.3	0.9	81.0	0.9	108.1	2.5
水杨酸卞酯	72.0	1.9	80.5	3.0	106.9	5.2
肉桂酸卞酯	71.1	1.6	70.1	2.2	119.6	5.3

化合物	检出率1/%	检出率2/%	化合物	检出率1/%	检出率2/%
苧烯	32.5	15.0	α-异甲基紫罗兰酮	20.0	20.0
芳樟醇	57.5	50.0	异丁香酚	12.5	20.0
苄醇	17.5	15.0	丁苯基甲基丙醛	27.5	30.0
香茅醇	35.0	30.0	香豆素	17.5	15.0
2-辛炔酸甲酯	0	0	合金欢醇	20.0	25.0
香叶醇	42.5	40.0	α-戊基肉桂醛	0	0
柠檬醛	7.5	5.0	新铃兰醛	12.5	10.0
羟基香茅醛	30.0	25.0	α-戊基肉桂醇	0	0
肉桂醛	5.0	10.0	己基肉桂醛	32.5	25.0
4-甲氧基苄醇	0	0	苯甲酸卞酯	7.5	5.0
肉桂醇	2.5	0	水杨酸卞酯	20.0	25.0
丁香酚	7.5	10.0	肉桂酸卞酯	0	0

Determination of 24 fragrance allergens in cosmetics by gas chromatography-tandem mass spectrometry

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