UPLC-MS/MS法测定精油类化妆品中13种双酚类及烷基酚类环境激素

doi:10.3969/j.issn.2097-2806.2023.07.013

摘要/Abstract

摘要：

建立了一种超高效液相色谱-串联质谱（UPLC-MS/MS）方法测定精油类化妆品中13种双酚类及烷基酚类环境激素。精油类化妆品以10%的氨水-乙腈溶液超声提取，氮吹浓缩后，以甲醇和水流动相梯度洗脱，经Agilent Poroshell EC-C18（3.0×150 mm，2.7 μm）色谱柱分离，电喷雾离子源负离子模式（ESI^-）扫描，多反应监测模式（MRM）定量分析。结果表明，13种双酚类及烷基酚类环境激素在0.25~200 ng/mL中一定质量浓度范围内呈现良好线性关系，线性相关系数均大于0.99，各物质检出浓度（LOD）为0.000 375~0.007 5 µg/g，定量浓度（LOQ）为0.001 25~0.025 µg/g；在0.025，0.05及0.25 µg/g三种不同加标浓度水平下，各物质平均回收率范围为81.8%~113.4%，日内精密度（n=6）为1.1%~8.5%，日间精密度（n=18）为3.5%~11.5%，方法前处理过程简单、回收率好、稳定性高，实现了13种目标物质的有效色谱分离，适用于精油类化妆品中13种双酚类及烷基酚类环境激素的同时定量定性分析。

关键词: 超高效液相色谱-串联质谱（UPLC-MS/MS）法, 精油类化妆品, 双酚类, 烷基酚类, 环境激素

Abstract:

Environmental hormone is a kind of substance that can disturb biological endocrine, among which bisphenols and alkylphenols have great potential harm because they are widely used in the manufacture of plastics. At present, there are many researches on the related detection technologies in the fields of environment and food, but there are few reports on high-throughput simultaneous detection of bisphenols and alkylphenols in cosmetics. In order to analyze the migration amount of bisphenols and alkylphenols environmental hormones in cosmetics, an ultra-high performance liquid chromatography-tandem mass spectrometry （UPLC-MS/MS） method was developed for the determination of 13 environmental hormones including 9 bisphenols and 4 alkylphenols in essential oil cosmetics. The chromatographic conditions, extraction reagent, dosage and ultrasonic time were optimized, then actual samples were measured with this established method. The essential oil cosmetics were extracted by ultrasonic extraction with 10% ammonium-acetonitrile solution, concentrated by nitrogen blowing, and eluted by gradient elution of methanol and water on an Agilent Poroshell EC-C18 column （3.0 mm×150 mm, 2.7 μm）. The 13 analytes were scanned by electrospray ion source negative ion mode （ESI^-）, and analyzed with multiple response monitoring model （MRM）. The results show that there is a good linear relationship for 13 kinds of bisphenols and alkylphenols environmental hormones in the certain mass concentration range of 0.25-200 ng/mL, with the linear correlation coefficients greater than 0.99. The limits of detection （LOD） and the limits of quantitation （LOQ） of each substance are 0.000 375-0.007 5 µg/g and 0.001 25-0.025 µg/g, respectively. The average recoveries at three spiked levels of 0.025, 0.05 and 0.25 µg/g range from 81.8% to 113.4% with the intra-day precision （n=6） of 1.1% to 8.5%, and the inter-day precision （n=18） of 3.5% to 11.5%. The method is established with simple pretreatment, good recovery and high stability, which has achieved effective chromatographic separation of 13 target substances. It is suitable for simultaneous quantitative and qualitative analysis of 13 bisphenols and alkylphenols environmental hormones in essential oil cosmetics.

Key words: UPLC-MS/MS, essential oil cosmetics, bisphenols, alkylphenols, environmental hormones

中图分类号:

TQ658

刘真, 王玉梅, 杨军丽, 孙小杰. UPLC-MS/MS法测定精油类化妆品中13种双酚类及烷基酚类环境激素[J]. 日用化学工业（中英文）, 2023, 53(7): 826-832.

Liu Zhen, Wang Yumei, Yang Junli, Sun Xiaojie. Determination of 13 bisphenols and alkylphenols environmental hormones in essential oil cosmetics by UPLC-MS/MS method[J]. China Surfactant Detergent & Cosmetics, 2023, 53(7): 826-832.

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参考文献 12

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序号	化合物（缩写）	保留时间/min	母离子（m/z）	子离子（m/z）	裂解电压/V	碰撞能/eV
1	双酚S（BPS）	3.291	249.0	108.0*，92.0	130	21，28
2	双酚F（BPF）	3.935	199.1	77.0*，197.0	130	41，30
3	双酚E（BPE）	4.199	213.1	198.1*，197.0	130	15，24
4	双酚A（BPA）	4.464	227.0	212.0*，133.0	145	24，36
5	双酚B（BPB）	4.843	241.1	212.1*，211.1	125	15，28
6	双酚AF（BPAF）	4.974	335.0	265.0*，68.9	140	10，42
7	双酚C（BPC）	5.129	255.1	240.1*，147.1	125	16，40
8	双酚Z（BPZ）	5.334	267.1	173.1*，145.0	125	35，41
9	双酚P（BPP）	6.114	345.1	315.1*，133.0	140	36，44
10	辛基酚（OP）	6.348	205.0	133.0*，117.0	80	28，80
11	壬基酚（NP）	6.694	219.0	133.0*，147.0	80	40，40
12	4-正辛基酚（4-n-OP）	6.779	205.0	106.0*，119.0	80	28，54
13	4-正壬基酚（4-n-NP）	7.023	219.0	106.0*，119.0	80	30，45

序号	基质效应	序号	基质效应
1	0.76	8	0.74
2	0.70	9	0.53
3	0.75	10	0.57
4	0.76	11	0.20
5	0.83	12	0.16
6	0.81	13	0.16
7	0.79

序号	线性方程	线性范围/ （ng/mL）	相关系数	检出浓度/ （μg/g）	检出限/ （ng/mL）	定量浓度/ （μg/g）	定量限/ （ng/mL）
1	y=17 464.54x-1 886.21	0.25~50	0.998 8	0.000 375	0.075	0.001 25	0.25
2	y=586.96x-721.58	5.0~200	0.998 7	0.007 5	1.5	0.025	5.0
3	y=6 412.50x-3 547.29	2.5~200	0.997 5	0.003 75	0.75	0.012 5	2.5
4	y=3 762.23x-19.59	2.5~200	0.997 4	0.003 75	0.75	0.012 5	2.5
5	y=9 034.37x-6 177.68	2.5~200	0.997 9	0.003 75	0.75	0.012 5	2.5
6	y=14 800.71x+5 009.43	0.25~50	0.998 5	0.000 375	0.075	0.001 25	0.25
7	y=3 148.51x-2 723.54	2.5~200	0.998 3	0.003 75	0.75	0.012 5	2.5
8	y=5 303.02x-2 717.85	2.5~200	0.998 0	0.003 75	0.75	0.012 5	2.5
9	y=2 645.32x-595.29	2.5~200	0.998 4	0.003 75	0.75	0.012 5	2.5
10	y=2 000.33x-3 943.13	5.0~200	0.999 7	0.007 5	1.5	0.025	5.0
11	y=4 003.16x+13 568.09	2.5~200	0.994 1	0.003 75	0.75	0.012 5	2.5
12	y=2 264.59x+4 504.78	5.0~200	0.999 4	0.007 5	1.5	0.025	5.0
13	y=1 365.40x+2 228.90	5.0~200	0.999 8	0.007 5	1.5	0.025	5.0

浓度添加水平/（μg/g）	序号	平均回收率/%	日内精密度/%（n=6）	日间精密度/%（n=6）	序号	平均回收率/%	日内精密度/%（n=6）	日间精密度/%（n=6）
0.025		87.5	2.9	4.9		91.3	5.9	5.9
0.05	1	86.3	2.1	7.1	8	86.9	3.6	9.6
0.25		103.8	3.3	5.2		94.3	2.6	7.5
0.025		90.3	4.8	4.8		87.2	3.9	7.5
0.05	2	91.1	5.3	7.3	9	84.7	3.4	7.4
0.25		96.3	2.8	3.5		92.6	1.8	6.0
0.025		92.6	4.6	7.6		101.6	4.5	5.9
0.05	3	99.5	3.5	8.5	10	105.4	4.6	9.2
0.25		90.2	2.2	5.2		82.0	3.5	6.0
0.025		83.6	4.7	7.7		106.1	5.5	6.5
0.05	4	101.9	3.9	7.9	11	110.4	3.8	9.8
0.25		87.7	2.7	6.7		98.9	2.0	5.8
0.025		113.2	4.7	5.7		82.1	3.1	6.1
0.05	5	113.4	3.0	9.0	12	87.4	5.9	8.0
0.25		98.5	2.1	5.1		90.9	2.8	7.2
0.025		103.9	2.9	3.9		85.2	8.5	11.5
0.05	6	99.2	2.4	7.4	13	92.7	7.2	9.4
0.25		98.1	1.1	6.6		81.8	3.6	6.6
0.025		102.2	7.5	10.5
0.05	7	100.5	5.0	8.1
0.25		94.2	2.6	7.6

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