超高效液相色谱-串联质谱法同时测定化妆品中23种抗生素

doi:10.3969/j.issn.1001-1803.2021.12.013

摘要/Abstract

摘要：

建立了超高效液相色谱-串联质谱法同时测定化妆品中23种抗生素的检测方法。样品采用乙腈超声提取,经色谱柱分离,以0.1%甲酸溶液和0.1%甲酸-乙腈梯度洗脱,采用电喷雾离子源正离子模式（ESI⁺）,利用Q-TOF获得的母离子建立含量测定方法,保留时间和二级质谱碎片用于进一步定性确证。结果表明,23种抗生素在线性范围内线性关系良好,相关系数均大于0.995;检出限为0.05~1.36 μg/g,平均回收率为74.1%~125.5%,RSD为2.3%~13.2%。应用该方法对22批次样品进行筛查,首次检出了甲氧苄啶。该方法操作简便,具有良好的选择性、灵敏度及准确度,能够用于化妆品中抗生素类成分的测定。

关键词: UPLC-ESI-Q-TOF/MS, 化妆品, 抗生素

Abstract:

The aim of the study is to develop an ultra high performance liquid chromatography-tandem mass spectrometry method for the identification and determination of 23 antibiotics in cosmetics. The samples were extracted by ultrasonic machine with acetonitrile, and the separation was executed on a column using a mobile phase consisting of 0.1% formic acid （A）, and 0.1% formic acid- acetonitrile （B）. The mass spectrometer was operated in positive ion mode, the determination was conducted in MS scan mode by the external standard method, and confirmatory analysis for target compounds was performed with the retention time and MS² scan. The result show that the linear relationship of the 23 antibiotics in the linear range is good, and the correlation coefficient is greater than 0.995. The detection limit are between 0.05-1.36 μg/g, and the average recovery rate is in the range of 74.1%-125.5%, with RSD within 2.3%-13.2%. One batch of positive sample is detected in 22 batches of the samples. Trimethoprim is detected in cosmetics for the first time. The established method is simple, selective, sensitive and accurate, and can be used for determination of antibiotics in cosmetics.

Key words: UPLC-ESI- Q-TOF/MS, cosmetics, antibiotics

中图分类号:

TQ658

郑佳新,贾昌平. 超高效液相色谱-串联质谱法同时测定化妆品中23种抗生素[J]. 日用化学工业, 2021, 51(12): 1250-1258.

Zheng Jiaxin,Jia Changping. Determination of 23 illegally added antibiotics by UPLC-ESI-Q-TOF/MS in cosmetics[J]. China Surfactant Detergent & Cosmetics, 2021, 51(12): 1250-1258.

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参考文献 10

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编号	物质名称	[M+H]⁺	碰撞能量/V	二级质谱主要碎片
1	磺胺胍	215.059 7	15	156.011 4, 92.049 6, 60.056 0
2	磺胺	173.037 9	25	108.044 4, 93.057 3, 75.022 5
3	甲硝唑	172.071 7	15	128.045 5, 82.052 5
4	美满霉素	458.192 2	25	441.165 4, 352.117 4
5	磺胺醋酰	215.048 5	15	156.011 5, 108.045 1
6	磺胺嘧啶	251.059 7	15	156.011 8, 92.049 8
7	甲氧苄啶	291.145 8	25	230.116 6, 123.066 5
8	土霉素	461.155 5	15	426.119 1
9	磺胺吡啶	250.064 5	25	156.011 5, 92.049 7
10	四环素	445.160 5	35	410.123 1, 269.081 0, 154.049 7, 98.059 9
11	磺胺甲基嘧啶	265.075 4	25	199.096 8, 156.011 3, 92.049 6
12	磺胺二甲噁唑	268.075 0	15	156.011 2, 113.070 7
13	磺胺二甲嘧啶	279.091 0	25	213.113 4, 186.033 1, 156.011 5, 124.087 1
14	磺胺甲噻二唑	271.031 8	15	156.011 3, 108.044 3
15	磺胺甲氧哒嗪	281.070 3	25	186.033 6, 156.011 4, 92.049 8
16	金霉素	479.121 6	25	444.083 8, 371.030 7, 154.049 9
17	多西环素	445.160 5	35	428.134 3, 321.075 4, 201.054 7, 154.049 9
18	磺胺氯哒嗪	285.020 8	15	156.011 4, 92.049 5
19	磺胺多辛	311.080 9	25	245.102 1, 108.044 2
20	磺胺甲噁唑	254.059 4	15	188.082 1, 156.011 3, 108.044 5
21	磺胺异噁唑	268.074 6	15	156.011 3
22	氯霉素	323.019 6	15	274.998 5, 241.005 5, 165.065 4
23	磺胺硝苯	336.064 9	15	294.053 7, 198.021 9

编号	物质名称	线性范围/（μg·mL^-1）	线性方程	相关系数r	检出限/（μg·g^-1）	定量限/（μg·g^-1）
1	磺胺胍	0.19~19.36	Y=158 137X+15 424	0.999 9	0.57	1.89
2	磺胺	0.20~20.14	Y=49 981X+5 900	0.999 9	0.74	2.47
3	甲硝唑	0.21~20.56	Y=388 625X+12 048	0.998 9	0.48	1.60
4	美满霉素	0.16~15.95	Y=50 528X-7 105	0.999 7	0.80	2.67
5	磺胺醋酰	0.24~24.28	Y=50 849X+8 918	0.999 8	0.78	2.62
6	磺胺嘧啶	0.21~21.41	Y=96 527X+25 441	0.999 5	0.75	2.51
7	甲氧苄啶	0.20~10.13	Y=828 286X+59 352	0.999 6	0.11	0.36
8	土霉素	0.22~22.21	Y=149 376X-12 458	1.000 0	0.65	2.15
9	磺胺吡啶	0.27~27.30	Y=233 158X+35 969	0.999 8	0.21	0.70
10	四环素	0.20~20.33	Y=256 691X-32 621	0.999 9	0.59	1.98
11	磺胺甲基嘧啶	0.22~21.61	Y=176 029X+24 705	0.999 8	0.52	1.72
12	磺胺二甲噁唑	0.20~19.78	Y=247 467X-3 688	1.000 0	0.28	0.93
13	磺胺二甲嘧啶	0.23~22.95	Y=259 115X+6 825	1.000 0	0.28	0.94
14	磺胺甲噻二唑	0.24~23.72	Y=124 596X+37 177	0.999 2	0.05	0.16
15	磺胺甲氧哒嗪	0.21~21.08	Y=219 166X+9 053	1.000 0	0.32	1.08
16	金霉素	0.21~20.91	Y=133 418X-9 930	1.000 0	0.52	1.73
17	多西环素	0.19~18.58	Y=211 829X-19 334	0.999 9	0.43	1.42
18	磺胺氯哒嗪	0.23~22.55	Y=95 198X+6 777	0.999 9	0.81	2.69
19	磺胺多辛	0.19~19.15	Y=254 141X+3 148	1.000 0	0.27	0.90
20	磺胺甲噁唑	0.22~21.62	Y=183 315X+6 569	1.000 0	0.06	0.19
21	磺胺异噁唑	0.24~23.90	Y=214 277X+3 289	1.000 0	0.23	0.77
22	氯霉素	0.93~18.65	Y=4 292X+3 697	0.995 6	1.36	4.53
23	磺胺硝苯	0.26~26.43	Y=22 256X+1 044	0.999 2	0.46	1.52

编号	物质名称	膏霜		水剂
编号	物质名称	回收率/%	RSD/%	回收率/%	RSD/%
1	磺胺胍	94.4	7.2	83.9	9.8
2	磺胺	94.5	5.2	89.7	8.0
3	甲硝唑	79.0	2.7	79.4	3.6
4	美满霉素	125.5	5.1	113.9	12.3
5	磺胺醋酰	105.4	2.4	94.8	4.2
6	磺胺嘧啶	119.6	5.6	89.3	13.2
7	甲氧苄啶	91.1	9.3	90.0	2.3
8	土霉素	100.3	5.3	89.3	4.1
9	磺胺吡啶	105.4	3.1	88.7	5.0
10	四环素	106.1	6.1	94.9	3.0
11	磺胺甲基嘧啶	90.6	3.3	84.8	6.1
12	磺胺二甲噁唑	81.5	4.4	87.5	7.2
13	磺胺二甲嘧啶	74.1	4.9	107.4	6.7
14	磺胺甲噻二唑	83.3	7.4	91.1	6.0
15	磺胺甲氧哒嗪	76.8	10.5	83.7	7.7
16	金霉素	77.1	7.2	100.5	9.7
17	多西环素	80.8	10.6	104.8	5.6
18	磺胺氯哒嗪	86.9	3.9	93.6	6.4
19	磺胺多辛	81.3	4.2	76.7	4.4
20	磺胺甲噁唑	91.0	5.1	94.3	4.0
21	磺胺异噁唑	97.6	3.7	103.3	6.0
22	氯霉素	92.0	7.5	102.6	6.2
23	磺胺硝苯	98.5	5.2	92.3	8.9

编号	物质名称	保留时间/min	RSD/%	峰面积	RSD/%
1	磺胺胍	1.393	0.4	148 608	1.2
2	磺胺	1.695	0.4	49 043	2.6
3	甲硝唑	2.176	0.1	427 131	0.9
4	美满霉素	2.391	0.2	33 979	2.1
5	磺胺醋酰	2.477	0.2	60 447	1.4
6	磺胺嘧啶	2.592	0.2	110 351	1.2
7	甲氧苄啶	2.606	0.1	801 911	1.4
8	土霉素	2.716	0.2	142 269	1.3
9	磺胺吡啶	2.762	0.1	308 163	0.5
10	四环素	2.912	0.1	213 916	0.6
11	磺胺甲基嘧啶	2.927	0.1	182 606	0.6
12	磺胺二甲噁唑	3.017	0.2	214 948	0.9
13	磺胺二甲嘧啶	3.178	0.1	264 606	1.0
14	磺胺甲噻二唑	3.235	0.1	152 138	1.1
15	磺胺甲氧哒嗪	3.249	0.1	205 757	1.5
16	金霉素	3.466	0.1	119 654	1.1
17	多西环素	3.588	0.1	168 755	0.8
18	磺胺氯哒嗪	3.752	0.1	100 528	1.3
19	磺胺多辛	3.858	0.2	219 005	0.5
20	磺胺甲噁唑	3.960	0.1	178 397	1.1
21	磺胺异噁唑	4.109	0.1	234 427	1.2
22	氯霉素	4.141	0.2	9 740	2.3
23	磺胺硝苯	5.038	0.1	28 805	2.1

编号	样品名称	检出成分	含量/（μg·g^-1）
1	劲爽控油清痘洁面膏	未检出	—
2	控油抗痘矿物炭洁面泥	未检出	—
3	茶树精油祛痘面膜	未检出	—
4	控油清痘洁面膏	未检出	—
5	深控油抗痘洁面泥	未检出	—
6	清痘舒缓洁面泡沫	未检出	—
7	清痘净肤收敛爽肤水	未检出	—
8	清痘调理精华乳	未检出	—
9	清痘净肤细致精华乳	未检出	—
10	清痘净肤水油平衡乳液	未检出	—
11	草本祛痘膏	磺胺甲噁唑甲氧苄啶	84 736 94 011
12	清痘冰感水凝露	未检出	—
13	平衡洁面抗痘冻	未检出	—
14	清痘平衡露	未检出	—
15	控油祛痘洁面膏	未检出	—
16	控油抗痘洁面乳	未检出	—
17	祛痘柔滑洁面乳	未检出	—
18	清颜控痘洁面乳	未检出	—
19	水杨酸控油净痘精华乳	未检出	—
20	睡眠修护祛痘膏	未检出	—
21	粉色祛痘修复液	未检出	—
22	茶树祛痘凝胶	未检出	—