气相色谱三重四极杆串联质谱法测定化妆品中24种致敏原

doi:10.3969/j.issn.1001-1803.2020.02.010

摘要/Abstract

摘要：

建立了气相色谱三重四极杆质谱法同时测定化妆品中24种致敏原的分析方法。样品经甲醇超声提取,以多重反应监测模式（MRM）进行定性及定量分析。结果表明,24种致敏原在质量浓度0.1~10.0 mg/L范围内线性关系良好,相关系数r ²>0.993,阴性样品在三个质量浓度水平的加标平均回收率为81.8%~106.7%,相对标准偏差为1.3%~8.7%,方法的检出限为1~3 mg/kg,定量限为10 mg/kg。

关键词: 气相色谱三重四极杆质谱法, 化妆品, 过敏原

Abstract:

A simultaneous determination method was developed for the reliable screening, quantification and confirmation of 24 allergens in cosmetics by gas chromatography triple quadrupole mass spectrometry （GC-MS/MS） . The samples were ultrasonic extracted from cosmetics with methanol, and then qualitative and quantitative analysis was performed by GC-MS/MS under multi reaction monitor mode （MRM） . The results show that the 24 allergens have a good linear relationship in the range of 0.1-10.0 mg/L with correlative coefficients （r ²） larger than 0.993, and the average recoveries range from 81.8% to 106.7% at three spiked levels with relative standard deviations of 1.3%-8.7%. The detection limit is 1-3 mg/kg and the quantification limit is 10 mg/kg.

Key words: gas chromatography triple quadrupole mass spectrometry, cosmetics, allergen

中图分类号:

TQ658

黄学泓,张林田,李冠斯. 气相色谱三重四极杆串联质谱法测定化妆品中24种致敏原[J]. 日用化学工业, 2020, 50(2): 129-136.

HUANG Xue-hong,ZHANG Lin-tian,LI Guan-si. Determination of 24 allergens in cosmetics by gas chromatography triple quadrupole mass spectrometry[J]. China Surfactant Detergent & Cosmetics, 2020, 50(2): 129-136.

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参考文献 16

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序号	致敏原	结构
1	苎烯	5989-27-5
2	芳樟醇	78-70-6
3	苯甲醇	100-51-6
4	香茅醇	106-22-9
5	辛炔酸甲酯	111-12-6
6	香叶醇	106-24-1
7	柠檬醛	5392-40-5
8	羧基香茅醛	107-75-5
9	肉桂醛	104-55-2
10	茴香醇	105-13-5
11	肉桂醇	104-54-1
12	丁香酚	97-53-0
13	异甲基紫罗兰酮	127-51-5
14	异丁香酚	97-54-1
15	铃兰醛	80-54-6
16	香豆素	91-64-5
17	金合欢醇	4602-84-0
18	戊基肉桂醛	122-40-7
19	新铃兰醛	31906-04-4
20	戊基肉桂醇	101-85-9
21	己基肉桂醛	101-86-0
22	苯甲酸苄酯	120-51-4
23	水杨酸苄酯	118-58-1
24	肉桂酸苄酯	103-41-3
25	橡苔提取物	90028-68-5
26	树苔提取物	90028-67-4

组别	化合物	定量离子（m/z）			定性离子（m/z）			碰撞能量/V
1	苎烯	136	→	77	121	→	93	35	/	5
2	芳樟醇	121	→	77	121	→	93	25	/	5
2	苯甲醇	108	→	79	108	→	77	15	/	30
3	香茅醇	123	→	81	138	→	95	5	/	5
	辛炔酸甲酯	95	→	67	123	→	55	5	/	10
	香叶醇	123	→	81	136	→	93	5	/	5
4	柠檬醛	69	→	41	123 123	→ →	91 79	5 5	/ /	15 30
4	羟基香茅醛	121	→	93	121 71	→ →	77 41	5 5	/ /	25 10
5	肉桂醛	131	→	77	103	→	77	30	/	10
	茴香醇	138	→	109	138	→	77	5	/	10
	肉桂醇	134	→	92	92	→	65	5	/	30
	丁香酚	164	→	77	164	→	149	35	/	5
6	α-异甲基紫罗兰酮	150	→	135	135	→	91	5	/	10
6	异丁香酚	164	→	77	164	→	149	5	/	35
7	铃兰醛	189	→	91	189	→	131	35	/	5
7	香豆素	146	→	118	146	→	90	10	/	25
8	金合欢醇	93	→	77	107	→	91	10	/	5
8	戊基肉桂醛	202	→	129	145	→	117	5	/	5
9	新铃兰醛	136	→	79	136	→	117	20	/	10
9	戊基肉桂醇	133	→	77	133	→	115	35	/	5
10	己基肉桂醛	145	→	91	216	→	129	10	/	5
11	苯甲酸苄酯	105	→	77	212	→	105	15	/	5
11	水杨酸苄酯	91	→	65	228	→	91	20	/	5
12	肉桂酸苄酯	192	→	191	238	→	193	20	/	5

序号	化合物名称	保留时间/min	线性方程	相关系数（r²）	检出限/（mg·kg^-1）
1	苎烯	5.274	Y=1.399×10³X + 1.410×10³	0.999 2	1
2	芳樟醇	6.875	Y=9.762×10²X + 4.197×10²	0.999 5	1
3	苯甲醇	7.490	Y=1.194×10⁴X + 2.277×10⁴	0.997 9	1
4	香茅醇	9.313	Y=2.727×10³X - 3.627×10³	0.998 7	1
5	辛炔酸甲酯	9.895	Y=1.867×10³X + 1.688×10²	0.999 9	1
6	香叶醇	10.088	Y=0.315×10³X + 0.161×10³	0.994 5	2
7	柠檬醛	10.613	Y=1.094×10⁴X - 3.848×10³	0.998 8	1
8	羧基香茅醛	11.235	Y=1.195×10³X - 1.106×10³	0.999 0	2
9	肉桂醛	12.375	Y=1.478×10⁴X + 2.558×10³	0.999 2	1
10	茴香醇	12.575	Y=4.001×10³X - 4.051×10³	0.999 5	1
11	肉桂醇	12.772	Y=5.451×10³X - 6.638×10³	0.999 1	1
12	丁香酚	12.979	Y=5.024×10³X - 4.958×10³	0.999 7	1
13	异甲基紫罗兰酮	13.723	Y=7.013×10³X - 4.603×10²	0.999 8	1
14	异丁香酚	14.705	Y=2.097×10³X + 0.131×10³	0.999 1	1
15	铃兰醛	15.374	Y=7.864×10³X + 1.086×10²	0.999 4	1
16	香豆素	16.103	Y=1.036×10⁴X + 0.823×10³	0.999 8	1
17	金合欢醇a	16.939	Y=2.671×10³X - 1.982×10³	0.995 0	2
17	金合欢醇b	17.293	Y=1.329×10³X + 1.595×10³	0.997 2	2
18	戊基肉桂醛	17.239	Y=1.663×10³X - 1.901×10³	0.997 8	1
19	新铃兰醛a	17.625	Y=3.140×10³X - 3.354×10²	0.994 5	3
19	新铃兰醛b	17.754	Y=4.121×10³ X - 7.902×10³	0.997 6	3
20	戊基肉桂醇	17.797	Y=2.222×10³X - 5.209×10³	0.996 6	2
21	己基肉桂醛	18.494	Y=2.055×10⁴X + 1.063×10³	0.999 9	1
22	苯甲酸苄酯	19.770	Y=3.396×10⁴X + 6.340×10³	0.999 8	1
23	水杨酸苄酯	20.670	Y=7.226×10³X - 2.653×10³	0.993 1	1
24	肉桂酸苄酯	22.675	Y=8.696×10³X - 1.206×10⁴	0.998 7	1

化合物名称	平均回收率/%			平均RSD/%
化合物名称	10 mg/kg	20 mg/kg	100 mg/kg	10 mg/kg	20 mg/kg	100 mg/kg
苎烯	85.5	89.4	93.1	6.9	5.9	4.1
芳樟醇	95.2	102.5	99.0	5.7	4.2	3.7
苯甲醇	93.0	101.3	97.2	5.5	3.9	2.9
香茅醇	90.1	105.1	98.1	7.3	5.1	4.7
辛炔酸甲酯	91.4	103.7	101.0	5.3	4.3	3.8
香叶醇	89.5	97.4	98.5	7.6	6.1	4.4
柠檬醛	88.5	91.7	93.7	5.9	6.7	4.7
羧基香茅醛	87.0	99.4	99.0	6.8	7.5	5.2
肉桂醛	94.9	105.1	102.4	5.9	4.7	4.1
茴香醇	91.8	90.2	94.9	4.2	3.6	2.7
肉桂醇	86.1	95.6	97.2	6.9	5.6	4.4
丁香酚	92.9	96.3	96.8	5.4	3.1	5.3
α-异甲基紫罗兰酮	96.3	103.6	100.0	4.9	3.9	1.3
异丁香酚	89.0	96.3	97.3	7.3	6.3	3.9
铃兰醛	97.3	104	99.3	4.6	3.5	3.4
香豆素	90.3	106.7	101.9	5.7	4.2	2.9
金合欢醇	81.8	85.9	91.8	8.7	6.8	4.9
戊基肉桂醛	91.2	100.4	97.8	6.1	6.4	4.6
新铃兰醛	86.4	90.1	93.0	5.7	4.9	5.4
戊基肉桂醇	93.6	103.1	97.9	7.9	5.8	5.0
己基肉桂醛	95.7	99.3	100.7	5.3	5.1	2.5
苯甲酸苄酯	90.1	105.5	98.2	6.0	4.3	3.9
水杨酸苄酯	82.7	90.8	92.6	8.6	6.6	6.7
肉桂酸苄酯	84.9	90.1	93.4	5.3	4.9	5.2

致敏原	含量/（mg·kg^-1）
致敏原	沐浴露	润肤霜	洗面奶	唇膏	香水	面部喷雾	面膜
苎烯	2 467		1 020		306		155
芳樟醇	1 265		224		1 179		291
苯甲醇
香茅醇	377		141	379	523	78
2-辛炔酸甲酯
香叶醇	418						238
柠檬醛	651
羟基香茅醛					1 373	96
肉桂醛
茴香醇
肉桂醇					108	23
丁香酚				198
α-异甲基紫罗兰酮						149
异丁香酚
铃兰醛	420	91
香豆素		67
金合欢醇		172
戊基肉桂醛
新铃兰醛	139	87
戊基肉桂醇
己基肉桂醛			868		569	197
苯甲酸苄酯			1 514				1 896
水杨酸苄酯		383		101	3 271
肉桂酸苄酯