高效液相色谱法用于氧化型染发产品中42种限用染发剂的筛查和定量分析

doi:10.3969/j.issn.2097-2806.2024.04.016

Abstract

Abstract:

A method for qualitative screening and quantitative analysis of 42 restricted hair dyes in oxidative hair color products by high performance liquid chromatography （HPLC） was established. The sample was ultrasonically extracted in mixed solvent of aqueous sodium bisulfite solution and ethanol. Firstly, the liquid chromatography condition for qualitative screening of 42 dyes and for quantitative analysis of 35 of them was established, which was as follows: The mobile phase was the mixed solvent of aqueous solution of 0.02 mol/L ammonium acetate and acetonitrile; gradient elution was carried out on a TechMate AQUA-STIII column; the detection wavelengths were 235 nm and 280 nm. If the other seven dyes including 2,6-dimethoxy-3,5-pyridinediamine·HCl, 2-methyl-5-hydroxyethylaminophenol, 3-nitro-p-hydroxyethylaminophenol, pyrazolone methyl pyrazolone, hydroxypropyl bis（N-hydroxyethyl-p-phenylenediamine）·HCl, 4-chlororesorcinol and 6-hydroxyindole were detected in the products, another liquid chromatography condition was required for their quantitative analysis, which was as follows: The mobile phase was the mixed solvent of aqueous solution of 0.02 mol/L ammonium acetate and acetonitrile; isocratic elution was carried out on a Waters Symmetry C₁₈column; the detection wavelength was 235 nm. The results showed that the limits of detection （LODs） of the 42 dyes were from 10 µg/g to 101 µg/g, while the limits of quantification （LOQs） were from 33 µg/g to 337 µg/g. The 42 dyes all had good linearities in their respective range, with correlation coefficients （r） higher than 0.999 8. The average spiked recoveries of 42 dyes at four levels were from 81.3% to 119.6%, with RSDs no more than 5%.

Key words: high performance liquid chromatography （HPLC）, oxidative hair color product, restricted hair dye

CLC Number:

TQ658

Xue Zuo, Zheng Di, Yajing Wang, Ling Yang, Huajun Zhang, Qing Liu. Qualitative screening and quantitative analysis of 42 restricted hair dyes in oxidative hair color products by high performance liquid chromatography[J].China Surfactant Detergent & Cosmetics, 2024, 54(4): 490-498.

Figures/Tables 4

Tab. 1

Information of the reference standards for 42 hair dyes"

序号	组分名称（组分编号）	标准物质来源	标准物质纯度/%
1	1-羟乙基-4,5-二氨基吡唑硫酸盐（C1）	Ark Pharm, Inc.（美国）	97
2	四氨基嘧啶硫酸盐（C2）	北京百灵威科技有限公司	98.9
3	2-氨基-3-羟基吡啶（C3）	北京曼哈格生物科技有限公司	99.9
4	对苯二胺（C4）	Dr. Ehrenstorfer GmbH（德国）	99.90
5	羟乙基对苯二胺硫酸盐（C5）	Ark Pharm, Inc.（美国）	95
6	对氨基苯酚（C6）	Dr. Ehrenstorfer GmbH（德国）	98.59
7	2,6-二氨基吡啶（C7）	Dr. Ehrenstorfer GmbH（德国）	99.4
8	甲苯-2,5-二胺硫酸盐（C8）	北京曼哈格生物科技有限公司	98.25
9	2,4-二氨基苯氧基乙醇盐酸盐（C9）	北京曼哈格生物科技有限公司	98.3
10	间氨基苯酚（C10）	北京曼哈格生物科技有限公司	99.64
11	4-氨基间甲酚（C11）	北京曼哈格生物科技有限公司	99.0
12	间苯二酚（C12）	Dr. Ehrenstorfer GmbH（德国）	99.83
13	N,N-双（2-羟乙基）-对苯二胺硫酸盐（C13）	北京曼哈格生物科技有限公司	99.9
14	对甲基氨基苯酚硫酸盐（C14）	北京曼哈格生物科技有限公司	99.5
15	2-甲基间苯二酚（C15）	北京曼哈格生物科技有限公司	99.7
16	2-氨基-6-氯-4-硝基苯酚（C16）	Sinco Pharmachem（美国）	97.47
17	羟苯并吗啉（C17）	Ark Pharm, Inc.（美国）	95
18	2-氨基-4-羟乙氨基茴香醚硫酸盐（C18）	Toronto research chemicals（加拿大）	99.12
19	4-氨基-2-羟基甲苯（C19）	北京曼哈格生物科技有限公司	99.1
20	6-甲氧基-2-甲氨基-3-氨基吡啶盐酸盐（C20）	Toronto research chemicals（加拿大）	96
21	4-硝基邻苯二胺（C21）	北京曼哈格生物科技有限公司	98.3
22	4-氨基-3-硝基苯酚（C22）	北京曼哈格生物科技有限公司	99.8
23	6-氨基间甲酚（C23）	北京曼哈格生物科技有限公司	99.7
24	2,6-二羟乙基氨甲苯（C24）	Sinco Pharmachem（美国）	95.58
25	2,6-二甲氧基-3,5-吡啶二胺盐酸盐（C25）	Toronto research chemicals（加拿大）	97
26	2-甲基-5-羟乙氨基苯酚（C26）	Toronto research chemicals（加拿大）	98.97
27	3-硝基对羟乙氨基酚（C27）	Sinco Pharmachem（美国）	99.47
28	苯基甲基吡唑啉酮（C28）	北京曼哈格生物科技有限公司	99.9
29	羟丙基双（N-羟乙基对苯二胺）盐酸盐（C29）	Toronto research chemicals（加拿大）	95
30	羟乙基-3,4-亚甲二氧基苯胺盐酸盐（C30）	Ark Pharm, Inc.（美国）	95
31	4-氯间苯二酚（C31）	北京曼哈格生物科技有限公司	99.0
32	6-羟基吲哚（C32）	北京曼哈格生物科技有限公司	99.2
33	5-氨基-6-氯-邻甲酚（C33）	Sinco Pharmachem（美国）	96.79
34	1,3-双-（2,4-二氨基苯氧基）丙烷盐酸盐（C34）	Sinco Pharmachem（美国）	96.68
35	4-羟丙氨基-3-硝基苯酚（C35）	Toronto research chemicals（加拿大）	99.70
36	1,5-萘二酚（C36）	北京曼哈格生物科技有限公司	99.5
37	2,7-萘二酚（C37）	北京曼哈格生物科技有限公司	99.3
38	HC黄2号（C38）	Sinco Pharmachem（美国）	99.9
39	5-氨基-4-氯邻甲酚（C39）	Sinco Pharmachem（美国）	96.9
40	羟乙基-2-硝基对甲苯胺（C40）	Sinco Pharmachem（美国）	97.6
41	N-苯基-对苯二胺（C41）	北京曼哈格生物科技有限公司	97.0
42	1-萘酚（C42）	Dr. Ehrenstorfer GmbH（德国）	99.6

Tab. 1

Fig. 1

Fig. 2

Tab. 2

Regression equations, linear range, LODs, LOQs and spiked recoveries for the 42 dyes （n=6）"

序号^（1）	保留时间^（2）/min	线性方程	线性范围/（mg/L）	检出限/ （mg/g）	定量限/ （μg/g）	曲线最低点浓度水平		1 250 μg		2 500 μg		5 000 μg
序号^（1）	保留时间^（2）/min	线性方程	线性范围/（mg/L）	检出限/ （mg/g）	定量限/ （μg/g）	平均回收率/%	RSD/ %	平均回收率/%	RSD/ %	平均回收率/%	RSD/ %	平均回收率/%	RSD/ %
1	3.442	A=4.708 ρ-2.327	2.008~401.6	25	83	109.8	2.7	94.9	0.4	95.1	0.6	95.8	0.6
2	3.664	A=10.21 ρ-5.959	2.016~403.2	10	33	116.2	3.1	92.1	2.8	103.3	2.7	92.5	1.7
3	5.012	A=8.167 ρ+3.532	2.006~300.9	25	83	98.2	4.4	106.5	1.5	106.2	1.0	104.8	2.3
4	5.454	A=21.86 ρ-1.469	2.018~302.7	10	33	99.7	3.0	100.4	2.1	99.9	1.2	99.2	2.5
5	6.201	A=9.095 ρ+0.4296	1.969~295.3	25	83	91.1	4.4	101.3	1.9	100.3	1.3	98.6	3.0
6	7.018	A=18.22 ρ+3.414	2.004~400.8	10	33	91.6	1.0	101.1	1.8	103.5	1.4	95.4	4.1
7	8.301	A=18.13 ρ-8.501	5.000~400.0	10	33	108.4	1.4	104.3	0.7	100.0	1.3	101.5	2.0
8	9.771	A=9.844 ρ-1.464	2.016~403.2	25	83	104.1	1.4	90.5	2.9	96.5	2.6	95.5	2.6
9	10.973	A=9.914 ρ+0.9675	2.012~402.4	25	83	96.5	3.5	101.5	0.1	102.8	0.4	101.4	0.5
10	11.608	A=17.70 ρ-6.344	2.018~403.6	10	33	118.1	0.4	103.3	1.0	99.6	1.2	101.0	2.0
11	13.278	A=14.98 ρ-4.017	1.988~397.5	25	83	102.9	2.1	97.2	2.3	96.1	0.9	91.3	4.2
12	16.886	A=4.261 ρ-2.054	5.005~400.4	25	83	110.7	2.2	102.8	1.3	99.0	1.2	100.4	2.1
13	19.427	A=4.929 ρ-3.726	5.060~404.8	101	337	92.7	2.8	104.6	3.8	109.0	1.3	107.8	3.0
14	20.363	A=13.47 ρ-7.523	1.996~399.1	25	83	113.7	2.9	90.1	3.2	100.1	1.6	84.9	1.6
15	21.776	A=3.785 ρ-1.454	5.045~403.6	101	337	107.0	2.5	99.0	1.9	97.7	1.4	99.8	2.3
16	27.298	A=15.01 ρ-6.787	1.988~198.8	25	83	98.3	2.0	105.9	2.6	107.3	0.3	109.7	2.2
17	30.650	A=9.351 ρ-2.929	1.954~390.8	24	80	116.5	1.9	96.2	4.0	99.1	1.5	97.5	3.8
18	31.847	A=7.305 ρ-3.776	2.032~406.4	25	83	119.6	0.6	109.7	1.5	113.1	1.4	112.7	1.6
19	32.752	A=16.10 ρ-8.250	5.015~401.2	25	83	110.3	2.5	103.7	4.4	100.3	0.7	100.6	2.7
20	33.975	A=6.425 ρ-0.6760	4.810~384.8	48	160	87.1	3.1	90.8	2.3	98.7	1.4	91.7	3.0
21	34.871	A=13.93 ρ-0.3016	2.006~401.2	25	83	95.8	2.2	97.9	2.4	96.5	2.0	97.6	2.3
22	35.596	A=29.85 ρ-7.754	2.020~404.0	25	83	107.6	2.1	95.5	2.6	96.3	1.7	98.4	2.4
23	36.609	A=14.61 ρ-4.333	2.002~400.4	25	83	109.0	1.5	92.7	1.9	98.7	1.6	94.7	4.5
24	40.004	A=27.46 ρ-3.112	1.927~385.4	10	33	107.0	1.2	105.0	0.7	101.1	1.1	102.4	2.0
25	42.853 （15.334）	A=7.895 ρ+8.340	4.941~395.3	25	83	81.3	1.1	87.2	4.3	89.3	2.7	85.6	4.9
26	43.267 （14.475）	A=13.46 ρ+2.952	2.012~402.4	10	33	92.4	4.1	92.9	4.9	99.7	0.5	108.6	1.9
27	43.542 （11.484）	A=28.13 ρ+6.119	2.026~405.2	10	33	90.0	2.9	93.3	3.7	99.8	0.9	107.2	1.4
28	44.379 （17.221）	A=17.29 ρ+3.545	2.026~405.2	25	83	82.3	2.2	83.5	3.2	89.1	2.2	89.0	3.3
29	45.914 （8.787）	A=4.934 ρ-7.659	5.060 ~404.8	51	170	88.6	2.3	93.9	4.9	84.5	2.0	99.3	5.0
30	46.226	A=6.131 ρ-2.231	4.807~384.6	48	160	111.2	3.2	105.5	1.1	99.5	1.0	101.4	2.0
31	48.062 （22.545）	A=7.341 ρ+1.299	2.010~402.0	25	83	96.7	4.3	93.2	1.8	100.1	0.6	106.2	2.4
32	48.498 （23.515）	A=8.158 ρ+1.267	2.006~401.2	25	83	98.3	4.7	95.1	2.1	98.1	0.7	105.0	1.8
33	50.742	A=14.38 ρ-7.266	4.902~392.2	25	83	106.4	2.7	97.0	2.1	97.2	1.7	95.1	0.8
34	53.257	A=9.231 ρ-3.854	1.954~390.8	49	163	111.8	1.2	104.1	2.2	105.6	1.2	105.2	2.8
35	54.054	A=27.17 ρ+3.961	2.018~403.6	25	83	92.1	2.5	94.3	1.5	95.3	1.8	98.8	2.1
36	55.820	A=28.98 ρ+0.2450	2.008~301.2	10	33	95.9	2.6	84.7	3.8	90.1	2.8	86.7	3.6
37	59.815	A=5.796 ρ-0.7417	2.014~402.8	25	83	100.7	3.1	90.6	3.5	93.3	1.8	105.9	1.3
38	61.180	A=7.039 ρ+2.978	2.056~411.2	10	33	84.2	3.3	101.9	2.0	99.1	1.5	103.8	1.7
39	61.613	A=2.366 ρ+0.5020	4.900~392.0	25	83	96.0	2.9	97.2	2.3	100.5	1.7	103.1	3.5
40	62.649	A=6.781 ρ-0.1798	1.993~299.0	10	33	103.1	2.9	101.3	2.5	96.6	1.2	98.9	2.5
41	63.062	A=24.97 ρ-4.950	1.993~299.0	10	33	109.9	3.8	97.4	3.2	93.2	2.9	95.7	2.2
42	63.549	A=7.120 ρ-2.532	2.010~402.0	25	83	105.4	4.2	86.5	1.4	88.5	3.3	89.3	3.8

Tab. 2

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Qualitative screening and quantitative analysis of 42 restricted hair dyes in oxidative hair color products by high performance liquid chromatography

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