HPLC-MS/MS法测定染发剂中32种染料中间体及其稳定性分析

doi:10.3969/j.issn.1001-1803.2021.12.015

摘要/Abstract

摘要：

建立了高效液相色谱-串联质谱测定染发剂中32种染料中间体的检测方法,并对染料中间体进行稳定性分析。样品采用甲醇-2 g/L亚硫酸氢钠水溶液（体积比为2∶8）的混合溶液提取,以10 mmol/L甲酸铵水溶液（pH=8）和乙腈-甲醇溶液（体积比为1∶1）为流动相,Atlantis T3色谱柱梯度洗脱分离,采用电喷雾正负离子（ESI⁺、ESI^-）源多反应监测模式进行检测。32种化合物在0.005~50 mg/kg范围内线性关系良好,相关系数r>0.995。样品基质效应为4.1%~44.6%。在0.2、2、10 mg/kg 3个加标水平下,平均回收率为80.2%~109.6%;在0.5、2和5 mg/kg 3个加标水平下,相对标准偏差（RSD）为0.8%~9.8%。方法检出限为0.005 2~2.4 mg/kg,定量限为0.018~7.9 mg/kg。正离子检测模式下染料中间体在10 h峰面积平均增加了30.3%,负离子检测模式下染料中间体在20 h峰面积平均减小了29.6%。该方法简便、快速、灵敏,可为染发剂中染料中间体的检测提供技术支持,同时染料中间体的不稳定性可为定量分析和质量控制提供理论依据。

关键词: 染料中间体, HPLC-MS/MS, 稳定性

Abstract:

A method was developed for the determination of 32 kinds of component in hair dyes using high performance liquid chromatography-tandem mass spectrometry, and the stability analysis of dye intermediates. The samples were extracted with mixed solution with methyl alcohol and 2 g/L sodium bisulfite aqueous solution （V/V=2∶8）. The analytes were separated on a Atlantis T3 column with 10 mmol/L ammonium formate aqueous solution （pH=8） and mixed solution with methyl alcohol and acetonitrile （V/V=1∶1） as mobile phases, and finally analyzed using electrospray ionization in positive and negative ion mode （ESI⁺, ESI^-） with multilpe reaction monitoring （MRM）. The linear ranges of the 32 dyes are from 0.005-50 mg/kg with correlation coefficients （r） more than 0.995. The matrix effects range from 4.1% to 44.6% in samples. The average recoveries are 80.2%-109.6% at the spiked levels of 0.2, 2 and 10 mg/kg. The average relative standard deviations is 0.8%-9.8% at the spiked levels of 0.5, 2 and 5 mg/kg. The limits of detection and the limits of quantification are 0.005 2-2.4 mg/kg and 0.018-7.9 mg/kg for the 32 dyes. The peak area of dyes increases by an average of 30.3% at 10 h in positive ion detection mode. The peak area of dyes decreases by an average of 29.6% at 20 h in negative ion detection mode. The method is simple, rapid and sensitive, and can provide technical support for dye detection in hair dyes. The instability of dyes can provide theoretical basis for quantitative analysis and quality control. The instability of dye intermediates can provide theoretical basis for quantitative analysis.

Key words: dye intermediates, HPLC-MS/MS, stability

中图分类号:

TQ658

李若绮,武悦,孙莺,李广宁. HPLC-MS/MS法测定染发剂中32种染料中间体及其稳定性分析[J]. 日用化学工业, 2021, 51(12): 1269-1277.

Li Ruoqi,Wu Yue,Sun Ying,Li Guangning. Determination of 32 kinds of component in hair dyes by HPLC-MS/MS and stability analysis of dye intermediates[J]. China Surfactant Detergent & Cosmetics, 2021, 51(12): 1269-1277.

图/表 7

图 1

图 2

表 1

32种染料中间体的主要质谱参数和保留时间"

序号	化合物名称	母离子（m/z）（ESI模式）	子离子（m/z）	保留时间/min	DP/V	CE/V	CXP/V
1	p-苯二胺	109.2 （+）	92.1^* 65.2	1.52	60 60	21 31	8 8
2	p-氨基苯酚	110.0 （+）	93.0^* 65.1	1.80	62 62	22 28	9 9
3	N,N-双（2-羟乙基）-p-苯二胺硫酸盐	197.1 （+）	121.1^* 152.2	2.65	60 60	22 36	10 10
4	m-氨基苯酚	109.9 （+）	65.1^* 92.9	2.30	60 60	22 28	7 7
5	4-氨基-2-羟基甲苯	124.0 （+）	109.0^* 77.0	3.23	70 70	26 35	8 8
6	4-氨基-m-甲酚	124.0 （+）	109.2^* 77.2	2.55	61 61	26 35	8 8
7	甲苯-2,5-二氨硫酸盐	123.0 （+）	108.2^* 77.0	2.45	68 68	24 40	7 7
8	苯基甲基吡唑啉酮	175.2 （+）	133.0^* 65.1	2.82	78 78	25 42	9 9
9	2-氨基-3-羟基吡啶	111.1 （+）	94.0^* 66.2	1.24	61 61	25 30	9 9
10	2,4-二氨基苯氧基乙醇HCl	169.1 （+）	124.1^* 108.1	2.45	49 49	25 27	7 7
11	2,6-二氨基吡啶	110.0 （+）	93.0^* 66.1	2.29	52 52	33 30	7 7
12	2-氯-p-苯二胺硫酸盐	143.1 （+）	108.1^* 80.1	2.80	55 55	25 36	10 10
13	2-硝基-p-苯二胺	154.0 （+）	119.1^* 92.1	2.88	44 44	22 33	10 10
14	6-氨基-m-甲酚	124.1 （+）	106.0^* 77.1	3.47	50 50	22 36	7 7
15	p-甲基氨基苯酚硫酸盐	124.0 （+）	109.1^* 80.1	2.84	52 52	43 24	10 10
16	m-苯二胺	109.0 （+）	92.1^* 65.2	2.22	50 50	31 22	15 15
17	o-苯二胺	109.0 （+）	92.0^* 65.2	2.68	65 65	33 22	15 17
18	N-苯基-p-苯二胺	185.1 （+）	108.1^* 93.1	5.08	70 70	29 31	7 7
19	N,N-二乙基-p-苯二胺硫酸盐	165.1 （+）	121.0^* 136.2	4.40	46 46	21 34	9 9
20	N,N-二乙基甲苯-2,5-二胺HCl	179.1 （+）	150.1^* 135.0	4.77	50 50	23 36	10 10
21	甲苯-3,4-二胺	123.0 （+）	106.0^* 77.1	3.33	60 60	37 22	7 7
22	4-硝基-o-苯二胺	154.0 （+）	137.0^* 107.0	3.25	60 60	19 28	10 10
23	6-羟基吲哚	134.0 （+）	107.1^* 77.1	3.78	60 60	28 42	8 8
24	o-氨基苯酚	110.0 （+）	92.1^* 65.1	2.78	65 65	30 22	7 7
25	2,7-萘二酚	159.0 （-）	130.0^* 102.0	4.06	-50 -50	-33 -33	-10 -10
26	1,5-萘二酚	159.0 （-）	115.0^* 131.0	3.91	-75 -75	-25 -27	-10 -10
27	4-氨基-3-硝基苯酚	153.0 （-）	123.0^* 122.0	3.25	-68 -68	-14 -25	-10 -10
28	1-萘酚	143.0 （-）	115.0^* 41.1	5.46	-90 -90	-34 -49	-7 -7
29	4-氯-m-苯二酚	143.0 （-）	79.0^* 107.0	3.64	-90 -90	-19 -16	-4 -4
30	2-甲基-m-苯二酚	123.0 （-）	55^* 79	2.86	-55 -55	-34 -17	-14 -13
31	p-苯二酚	109.0 （-）	109.0^* 108.0	2.19	-65 -65	-10 -21	-5 -5
32	m-苯二酚	109.0 （-）	65^* 67	2.68	-63 -63	-17 -19	-4 -4

表 1

表 2

样品中32种染料中间体的线性方程、线性范围、相关系数、检出限、定量限、基质效应（n=3）"

序号	化合物名称	线性范围/ （mg·kg^-1）	线性方程	相关系数	检出浓度/ （mg·kg^-1）	定量浓度/ （mg·kg^-1）	基质效应/ %
1	p-苯二胺	0.25~500	Y=2.5×10⁵X-2.68×10³	0.999 4	0.1	0.29	29.4
2	p-氨基苯酚	1~500	Y=5.1×10⁴X-1.69×10³	0.999 3	0.4	1.2	26.0
3	N,N-双（2-羟乙基）-p-苯二胺硫酸盐	0.05~500	Y=3.3×10⁶X+4.15×10³	0.998 6	0.005	0.018	28.2
4	m-氨基苯酚	0.25~1 000	Y=2.4×10⁴X+9.77×10³	0.997 9	0.02	0.081	32.6
5	4-氨基-2-羟基甲苯	0.25~2 500	Y=1.5×10⁵X+8.17×10⁴	0.997 9	0.1	0.25	39.0
6	4-氨基-m-甲酚	0.25~1 000	Y=2.2×10⁵X+6.73×10⁴	0.995 5	0.1	0.31	33.9
7	甲苯-2,5-二氨硫酸盐	0.25~500	Y=3.7×10⁵X+8.01×10³	0.996 0	0.02	0.078	24.0
8	苯基甲基吡唑啉酮	0.05~500	Y=9.2×10⁵X+9.56×10⁴	0.998 2	0.02	0.071	35.9
9	2-氨基-3-羟基吡啶	0.05~500	Y=8.2×10⁵X+4.80×10⁴	0.997 5	0.02	0.068	40.6
10	2,4-二氨基苯氧基乙醇HCl	0.05~500	Y=3.7×10⁵X+5.61×10⁴	0.995 2	0.02	0.084	30.5
11	2,6-二氨基吡啶	0.05~500	Y=2.8×10⁶X+9.24×10⁴	0.996 5	0.01	0.045	42.0
12	2-氯-p-苯二胺硫酸盐	0.25~1 000	Y=9.1×10⁴X+1.64×10³	0.996 7	0.1	0.41	39.7
13	2-硝基-p-苯二胺	0.05~500	Y=3.8×10⁵X+3.38×10⁴	0.996 0	0.005	0.019	37.2
14	6-氨基-m-甲酚	0.25~500	Y=3.8×10⁵X+1.88×10⁴	0.999 0	0.1	0.44	37.0
15	p-甲基氨基苯酚硫酸盐	0.05~500	Y=2.2×10⁶X+4.30×10⁴	0.997 6	0.02	0.078	36.7
16	m-苯二胺	0.1~1 000	Y=2.1×10⁵X+2.46×10⁴	0.998 7	0.04	0.16	34.8
17	o-苯二胺	0.25~2 500	Y=7.1×10⁴X-3.52×10³	0.999 8	0.1	0.35	44.6
18	N-苯基-p-苯二胺	0.05~500	Y=1.1×10⁶X-1.53×10⁵	0.995 3	0.02	0.073	31.2
19	N,N-二乙基-p-苯二胺硫酸盐	0.05~500	Y=4.5×10⁶X-9.86×10⁴	0.998 7	0.02	0.081	32.8
20	N,N-二乙基甲苯-2,5-二胺HCl	0.05~500	Y=7.3×10⁶X-8.47×10⁴	0.999 0	0.02	0.076	27.0
21	甲苯-3,4-二胺	0.25~500	Y=3.5×10⁵X-3.31×10³	0.998 1	0.1	0.47	40.7
22	4-硝基-o-苯二胺	0.05~500	Y=6.1×10⁵X+2.37×10⁴	0.996 1	0.02	0.078	21.9
23	6-羟基吲哚	1~2 500	Y=2.1×10⁴X-3.98×10³	0.999 6	0.4	1.5	33.8
24	o-氨基苯酚	1~2 500	Y=9.8×10⁴X-4.14×10⁴	0.995 3	0.4	1.4	44.1
25	2,7-萘二酚	0.1~2 500	Y=6.0×10⁴X+61.5	0.998 1	0.04	0.17	6.8
26	1,5-萘二酚	0.05~2 500	Y=2.3×10⁵X+5.86×10²	0.996 1	0.02	0.078	7.2
27	4-氨基-3-硝基苯酚	0.25~2 500	Y=6.0×10⁴X+4.16×10⁴	0.998 2	0.1	0.37	4.1
28	1-萘酚	0.25~2 500	Y=4.9×10⁴X+62.0	0.999 5	1	4.1	5.7
29	4-氯-m-苯二酚	0.5~2 500	Y=1.0×10⁴X+26.4	0.998 4	0.2	0.79	8.0
30	2-甲基-m-苯二酚	5~2 500	Y=1.1×10³X-49.2	0.995 7	2	7.2	12.4
31	p-苯二酚	5~2 500	Y=5.0×10³X+1.01×10³	0.999 4	2	7.0	6.2
32	m-苯二酚	5~2 500	Y=3.4×10³X-5.40×10³	0.998 6	2	7.9	19.5

表 2

表 3

图 3

图 4

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