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

Abstract

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

CLC Number:

TQ658

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.

Figures/Tables 7

Fig. 1

Fig. 2

Tab. 1

MS parameters and retention times for the analysis of the 32 dyes"

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

Tab. 1

Tab. 2

Linear equations, linear ranges, correlation coefficients, LODs, LOQs, and matrix effects of the 32 dyes in the sample （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

Tab. 2

Tab. 3

Recoveries and precisions （RSDs） for the 32 dye intermediates in the sample （n=6）"

序号	化合物名称	回收率/%			精密度/%
序号	化合物名称	0.2 mg·kg^-1	2 mg·kg^-1	10 mg·kg^-1	0.5 mg·kg^-1	2 mg·kg^-1	5 mg·kg^-1
1	p-苯二胺	90.1	94.7	101.4	6.8	3.4	4.7
2	p-氨基苯酚	80.2	88.9	91.3	7.6	4.9	4.8
3	N,N-双（2-羟乙基）-p-苯二胺硫酸盐	88.1	87.3	103.8	7.4	3.5	3.8
4	m-氨基苯酚	83.4	83.8	91.2	9.8	5.0	5.0
5	4-氨基-2-羟基甲苯	81.6	84.3	88.1	3.3	1.9	3.6
6	4-氨基-m-甲酚	85.8	89.1	85.3	6.7	3.0	3.4
7	甲苯-2,5-二氨硫酸盐	84.3	83.5	109.3	9.1	6.1	7.4
8	苯基甲基吡唑啉酮	88.4	98.8	90.7	4.7	3.4	2.7
9	2-氨基-3-羟基吡啶	90.4	90.4	93.8	6.9	6.9	8.7
10	2,4-二氨基苯氧基乙醇HCl	86.1	88.7	86.5	5.5	6.2	5.4
11	2,6-二氨基吡啶	89.5	92.2	91.2	5.6	6.2	4.1
12	2-氯-p-苯二胺硫酸盐	82.6	86.5	88.5	9.8	2.4	2.5
13	2-硝基-p-苯二胺	85.4	91.1	93.6	6.5	4.0	6.6
14	6-氨基-m-甲酚	83.8	88.5	88.8	3.9	3.3	3.7
15	p-甲基氨基苯酚硫酸盐	86.4	86.1	94.0	5.0	9.7	3.6
16	m-苯二胺	85.5	92.0	98.3	4.5	4.2	5.3
17	o-苯二胺	82.7	82.3	89.8	9.3	5.3	7.0
18	N-苯基-p-苯二胺	89.3	99.1	98.7	7.1	2.5	1.5
19	N,N-二乙基-p-苯二胺硫酸盐	85.5	94.1	99.3	6.3	2.8	2.7
20	N,N-二乙基甲苯-2,5-二胺HCl	93.6	98.3	92.0	8.5	2.2	1.4
21	甲苯-3,4-二胺	89.4	90.2	98.0	6.2	3.2	5.1
22	4-硝基-o-苯二胺	82.5	85.5	87.5	4.7	9.7	2.9
23	6-羟基吲哚	84.7	88.4	96.7	8.2	8.0	6.9
24	o-氨基苯酚	80.3	88.6	83.3	6.5	3.0	5.2
25	2,7-萘二酚	103.3	98.0	102.4	4.8	3.4	2.3
26	1,5-萘二酚	93.2	92.6	103.6	2.2	1.9	0.8
27	4-氨基-3-硝基苯酚	109.6	91.0	97.2	3.8	1.4	2.3
28	1-萘酚	100.1	90.9	100.4	5.2	4.2	1.4
29	4-氯-m-苯二酚	91.4	98.1	104.3	6.5	2.2	2.1
30	2-甲基-m-苯二酚	104.4	105.5	96.9	3.0	3.9	3.9
31	p-苯二酚	100.5	90.8	106.2	4.1	3.9	3.6
32	m-苯二酚	92.4	100.3	96.1	8.5	7.3	6.3

Tab. 3

Fig. 3

Fig. 4

References 18

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Determination of 32 kinds of component in hair dyes by HPLC-MS/MS and stability analysis of dye intermediates

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