新型3D色谱固定相结合气相色谱-质谱法测定染发剂中多种限用和禁用成分

doi:10.3724/SP.J.1123.2023.11018

摘要/Abstract

摘要：

染发剂(hair dyes, HDs)主要成分为多种苯系物、胺类和酚类化合物,具有致敏性、致畸变性和致癌性等危害,近年来受到广泛关注。目前传统的分析检测方法和商品化色谱柱大多存在定性难度大或定量不准确等问题,亟需开发分析检测新技术和新型固定相。同时,染发剂成分复杂、基质干扰较大,需要合适的样品前处理方法。本研究基于3D非极性刚性结构单元三蝶烯(TP),结合极性柔性链聚乙二醇(PEG),设计、合成了蝶烯衍生物TP-PEG,作为色谱柱固定相。采用气相色谱-质谱法(GC-MS)定量分析了22种染发剂成分,并对4种实际样品进行了检测分析。该固定相由非极性3D刚性结构和柔性链状极性结构两部分构成,具有“刚柔并济”的结构特点,扩大了对非极性和极性分析物的选择范围。实验结果表明,不同极性的分析物在该固定相上均展现了尖锐、对称的峰形,且22种分析物在该色谱柱上都达到了基线分离,为染发剂各成分的检测分析提供了保障。结果表明,22种染发剂成分在各自范围内线性关系良好,相关系数均≥0.9985。各染发剂成分在3个添加水平下的平均回收率为89.2%~103.2%, RSD均小于5%。与传统方法相比,该方法效率高,准确性好,验证了新型固定相优异的分离性能以及建立的GC-MS检测方法的有效性。

关键词: 气相色谱-质谱法, 3D固定相, 三蝶烯, 染发剂

Abstract:

Hair dyes (HDs) are mainly composed of various benzene series, amines, and phenolic compounds. These ingredients are well known to have allergenic, teratogenic, and carcinogenic properties. As such, the presence of these ingredients in HDs has received increased attention in recent years. At present, the applications of traditional analytical and detection methods and commercial chromatographic columns are limited by problems such as poor qualitative analysis and inaccurate quantification. Thus, the development of new analytical and detection technologies and stationary phases is an urgent endeavor. Moreover, HDs contain complex compounds and exhibit significant matrix interference. Hence, appropriate sample pretreatment methods are necessary to analyze HDs. In this study, the 3D nonpolar rigid structure of triptycene (TP) was combined with the polar flexible chains of polyethylene glycol (PEG) to design and synthesize a TP derivative, TP-PEG, as a stationary phase for chromatographic columns. The stationary phase enabled the expansion of the selection range for polar and nonpolar analytes. Subsequently, gas chromatography-mass spectrometry (GC-MS) was used to quantitatively analyze 22 ingredients in HDs. The experimental results demonstrated that analytes with different polarities exhibited sharp and symmetrical peak shapes on the stationary phase, and all 22 analytes achieved baseline separation on the chromatographic column. The 22 ingredients in HDs showed good linear relationships within their respective ranges, with correlation coefficients greater than 0.9985. The average recovery rates at three spiked levels were in the range of 89.2%-103.2%, and RSDs were less than 5%. Compared with traditional methods, the proposed method has higher efficiency and better accuracy, thus verifying the excellent separation performance of the new stationary phase and the effectiveness of the established GC-MS detection method. The findings indicated the applicability of the developed method to the detection and analysis of various compounds in HDs.

Key words: gas chromatography-mass spectrometry (GC-MS), 3D stationary phase, triptycene (TP), hair dyes

中图分类号:

O658

张鹏, 李宽, 周进, 韩玮娜, 和永瑞. 新型3D色谱固定相结合气相色谱-质谱法测定染发剂中多种限用和禁用成分[J]. 色谱, 2024, 42(10): 990-995.

ZHANG Peng, LI Kuan, ZHOU Jin, HAN Weina, HE Yongrui. Determination of multiple restricted and prohibited ingredients in hair dyes using a novel 3D stationary phase coupled with gas chromatography-mass spectrometry[J]. Chinese Journal of Chromatography, 2024, 42(10): 990-995.

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No.	Compound	Retention time/min	Primary ion (m/z)	Secondary ions (m/z)
1	phenol (苯酚)	6.41	94.46	66.05^*, 39.42
2	N,N-diethyl p-diphenylamine (N,N-二乙基对二苯胺)	6.61	164.31	149.21^*, 120.42
3	o-phenylene-diamine (邻苯二胺)	11.32	108.09	80.01, 53.13^*
4	3,4-diaminotoluene (3,4-二氨基甲苯)	16.23	122.14	106.42^*, 94.12
5	p-phenylene-diamine (对苯二胺)	17.21	108.72	80.21^*, 53.02
6	2,5-diaminotoluene (2,5-二氨基甲苯)	19.16	122.07	106.51, 94.05^*
7	2,6-diaminopyridine (2,6-二氨基吡啶)	19.61	109.19	81.43^*, 53.11
8	2,4,5-trichlorophenol (2,4,5-trichlorophenol)	20.61	109.46	81.02^*, 53.15
9	2-aminophenol (邻氨基苯酚)	21.83	195.13	124.45, 133.21^*
10	4-methylaminophenol (4-甲氨基苯酚)	23.25	123.45	108.63^*, 94.22
11	p-aminophenol (对氨基苯酚)	23.41	109.06	81.03^*, 53.25
12	4-amino-m-cresol (4-氨基-间甲酚)	25.63	123.17	77.04, 95.21^*
13	5-amino-o-cresol (5-氨基-邻甲酚)	26.61	123.34	78.08, 106.15^*
14	m-aminophenol (间氨基苯酚)	26.68	109.02	81.12^*, 53.03
15	2-amino-3-hydroxypyridine (2-氨基-3-羟基吡啶)	27.33	110.31	55.23^*, 81, 03
16	4-nitro-o-phenylenediamine (4-硝基-邻苯二胺)	27.66	153.04	107.52^*, 95.14
17	p-dihydroxybenzene (对苯二酚)	28.39	110.72	81.07^*, 53.19
18	m-dihydroxybenzene (间苯二酚)	28.65	110.11	81.41^*, 53.52
19	1,5-naphthalenediol (1,5-萘二酚)	32.12	160.05	131.21^*, 103.12
20	2,7-naphthalenediol (2,7-萘二酚)	37.31	160.07	131.51^*, 103.04
21	1-naphthol (1-萘酚)	37.75	144.11	116.23^*, 89.02
22	2-naphthol (2-萘酚)	40.35	144.23	116.01^*, 89.11

No.	Compound	Retention time/min	Primary ion (m/z)	Secondary ions (m/z)
1	phenol (苯酚)	6.41	94.46	66.05^*, 39.42
2	N,N-diethyl p-diphenylamine (N,N-二乙基对二苯胺)	6.61	164.31	149.21^*, 120.42
3	o-phenylene-diamine (邻苯二胺)	11.32	108.09	80.01, 53.13^*
4	3,4-diaminotoluene (3,4-二氨基甲苯)	16.23	122.14	106.42^*, 94.12
5	p-phenylene-diamine (对苯二胺)	17.21	108.72	80.21^*, 53.02
6	2,5-diaminotoluene (2,5-二氨基甲苯)	19.16	122.07	106.51, 94.05^*
7	2,6-diaminopyridine (2,6-二氨基吡啶)	19.61	109.19	81.43^*, 53.11
8	2,4,5-trichlorophenol (2,4,5-trichlorophenol)	20.61	109.46	81.02^*, 53.15
9	2-aminophenol (邻氨基苯酚)	21.83	195.13	124.45, 133.21^*
10	4-methylaminophenol (4-甲氨基苯酚)	23.25	123.45	108.63^*, 94.22
11	p-aminophenol (对氨基苯酚)	23.41	109.06	81.03^*, 53.25
12	4-amino-m-cresol (4-氨基-间甲酚)	25.63	123.17	77.04, 95.21^*
13	5-amino-o-cresol (5-氨基-邻甲酚)	26.61	123.34	78.08, 106.15^*
14	m-aminophenol (间氨基苯酚)	26.68	109.02	81.12^*, 53.03
15	2-amino-3-hydroxypyridine (2-氨基-3-羟基吡啶)	27.33	110.31	55.23^*, 81, 03
16	4-nitro-o-phenylenediamine (4-硝基-邻苯二胺)	27.66	153.04	107.52^*, 95.14
17	p-dihydroxybenzene (对苯二酚)	28.39	110.72	81.07^*, 53.19
18	m-dihydroxybenzene (间苯二酚)	28.65	110.11	81.41^*, 53.52
19	1,5-naphthalenediol (1,5-萘二酚)	32.12	160.05	131.21^*, 103.12
20	2,7-naphthalenediol (2,7-萘二酚)	37.31	160.07	131.51^*, 103.04
21	1-naphthol (1-萘酚)	37.75	144.11	116.23^*, 89.02
22	2-naphthol (2-萘酚)	40.35	144.23	116.01^*, 89.11

Compound	Linear equation	Linear range/(mg/L)	r	LOD/(μg/g)	LOQ/(μg/g)
Phenol	Y=40682X-91414	5-500	0.9989	15	53
N,N-Diethyl p-diphenylamine	Y=4693X-2192	5-500	0.9985	15	59
o-Phenylenediamine	Y=34032X-10404	5-500	0.9999	25	83
3,4-Diaminotoluene	Y=2756X+17.31	5-500	0.9999	20	64
p-Phenylenediamine	Y=3407X-60.29	5-500	0.9985	17	57
2,5-Diaminotoluene	Y=32467X-5902	5-500	0.9999	25	86
2,6-Diaminopyridine	Y=6873X-3593	5-500	0.9994	20	75
2,4,5-Trichlorophenol	Y=11870X-1564	5-500	0.9999	19	69
2-Aminophenol	Y=19379X-4868	5-500	0.9999	16	52
4-Methylamino-phenol	Y=12179X+4961	5-500	0.9993	15	57
p-Aminophenol	Y=8069X+517	5-500	0.9993	19	73
4-Amino-m-cresol	Y=16990X-3721	5-500	0.9999	25	87
5-Amino-o-cresol	Y=7918X-324	5-500	0.9996	35	115
m-Aminophenol	Y=9460X-1634	5-500	0.9999	30	101
2-Amino-3-hydroxypyridine	Y=19450X-15482	5-500	0.9992	25	79
4-Nitro-o-phenylenediamine	Y=12972X-3149	5-500	0.9999	19	61
p-Dihydroxybenzene	Y=9065X+688	5-500	0.9991	25	82
m-Dihydroxybenzene	Y=22318X-2107	5-500	0.9992	20	63
1,5-Naphthalenediol	Y=15165X-1369	5-500	0.9995	20	69
2,7-Naphthalenediol	Y=8431X-33012	5-500	0.9987	25	91
1-Naphthol	Y=10631X-39136	5-500	0.9989	15	47
2-Naphthol	Y=2661X-9289	5-500	0.9989	20	65

Compound	Linear equation	Linear range/(mg/L)	r	LOD/(μg/g)	LOQ/(μg/g)
Phenol	Y=40682X-91414	5-500	0.9989	15	53
N,N-Diethyl p-diphenylamine	Y=4693X-2192	5-500	0.9985	15	59
o-Phenylenediamine	Y=34032X-10404	5-500	0.9999	25	83
3,4-Diaminotoluene	Y=2756X+17.31	5-500	0.9999	20	64
p-Phenylenediamine	Y=3407X-60.29	5-500	0.9985	17	57
2,5-Diaminotoluene	Y=32467X-5902	5-500	0.9999	25	86
2,6-Diaminopyridine	Y=6873X-3593	5-500	0.9994	20	75
2,4,5-Trichlorophenol	Y=11870X-1564	5-500	0.9999	19	69
2-Aminophenol	Y=19379X-4868	5-500	0.9999	16	52
4-Methylamino-phenol	Y=12179X+4961	5-500	0.9993	15	57
p-Aminophenol	Y=8069X+517	5-500	0.9993	19	73
4-Amino-m-cresol	Y=16990X-3721	5-500	0.9999	25	87
5-Amino-o-cresol	Y=7918X-324	5-500	0.9996	35	115
m-Aminophenol	Y=9460X-1634	5-500	0.9999	30	101
2-Amino-3-hydroxypyridine	Y=19450X-15482	5-500	0.9992	25	79
4-Nitro-o-phenylenediamine	Y=12972X-3149	5-500	0.9999	19	61
p-Dihydroxybenzene	Y=9065X+688	5-500	0.9991	25	82
m-Dihydroxybenzene	Y=22318X-2107	5-500	0.9992	20	63
1,5-Naphthalenediol	Y=15165X-1369	5-500	0.9995	20	69
2,7-Naphthalenediol	Y=8431X-33012	5-500	0.9987	25	91
1-Naphthol	Y=10631X-39136	5-500	0.9989	15	47
2-Naphthol	Y=2661X-9289	5-500	0.9989	20	65

Compound	Contents/(mg/kg)
Compound	No. 1 (black)	No. 2 (brown)	No. 3 (coffee)	No. 4 (red)
Phenol	-	15	-	-
o-Phenylene-diamine	-	310	-	-
p-Phenylene-diamine	720	2120	627	890
2-Aminophenol	-	380	160	-
p-Aminophenol	453	1231	194	56
m-Aminophenol	324	534	617	436
p-Dihydroxybenzene	-	170	-	-
m-Dihydroxybenzene	120	310	-	-

新型3D色谱固定相结合气相色谱-质谱法测定染发剂中多种限用和禁用成分

Determination of multiple restricted and prohibited ingredients in hair dyes using a novel 3D stationary phase coupled with gas chromatography-mass spectrometry

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