超高效液相色谱法测定液态水基类化妆品中22种性激素

doi:10.3969/j.issn.1001-1803.2021.04.015

摘要/Abstract

摘要：

建立了液态水基类化妆品中22种性激素的超高效液相色谱分析方法。样品经80%乙腈水溶液超声提取,离心后上清液经PRiME HLB固相萃取柱净化。采用CORTECS C₁₈+ （2.1 mm×100 mm,2.7 μm）色谱柱分离,以乙腈-水为流动相进行梯度洗脱,PDA检测器多波长检测,外标法定量。结果表明,22种性激素在各自的质量浓度范围内线性关系良好（相关系数r>0.99）,检出限（LOD）和定量下限（LOQ）分别为0.03~0.1 μg/mL和0.1~0.4 μg/mL。在5,25和50 μg/g 3个加标水平下的回收率为80.3%~99.6%,相对标准偏差（RSD,n=6）为0.3%~7.7%。该方法前处理简单、灵敏度高、准确性好,适用于液态水基类化妆品中性激素的测定。

关键词: 超高效液相色谱法, 通过式固相萃取, 化妆品, 性激素, 测定

Abstract:

An ultra-high performance liquid chromatography method was established for determination of 22 sex hormones in water-based cosmetics. The sample was ultrasonically extracted with 80% acetonitrile solution. After centrifugation, the supernatant was purified by PRiME HLB column. Chromatographic separation was achieved on an CORTECS C₁₈+ （2.1 mm×100 mm, 2.7 μm） column by gradient elution using acetonitrile-water as mobile phases. PDA detector was used to test samples by multiple wavelengths, and external standard method was used for quantification. The results show that there are good linear relationships for 22 sex hormones in the respective concentration range with their correlation coefficients （r） all above 0.99. The limits of detection （LOD） and limits of quantitation （LOQ） for 22 sex hormones are in the range of 0.03-0.1 μg/mL and 0.1-0.4 μg/mL, respectively. Average recoveries at three levels of 5,25,50 μg/g are in the range of 80.3%-99.6%, with relative standard deviations（RSD, n=6） of 0.3%-7.7%. With the advantages of simplicity, sensitivity and accuracy, this method is suitable for the analysis of sex hormones in water-based cosmetics．

Key words: ultra - high performance liquid chromatography, pass - through solid phase extraction, cosmetics, sex hormones, determination

中图分类号:

TQ658

胡贝,李丽霞,吴茜,刘红,黄伟,丁晓萍. 超高效液相色谱法测定液态水基类化妆品中22种性激素[J]. 日用化学工业, 2021, 51(4): 363-369.

HU Bei,LI Li-xia,WU Qian,LIU Hong,HUANG Wei,DING Xiao-ping. Determination of 22 sex hormones in water-based cosmetics by ultra-high performance liquid chromatography[J]. China Surfactant Detergent & Cosmetics, 2021, 51(4): 363-369.

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序号	化合物	ME/%	序号	化合物	ME/%
1	雌三醇	94.0	12	孕酮	88.5
2	肾上腺甾酮	98.2	13	醋酸美伦孕酮	91.2
3	双酚A	88.0	14	美雌醇	85.0
4	诺龙	103.0	15	17-乙酸睾丸激素	90.6
5	17-β-雌二醇	77.7	16	丙酸诺龙	85.9
6	17-α-雌二醇	83.4	17	醋酸氯睾酮	84.9
7	睾酮	101.2	18	丙酸睾酮	85.1
8	雌酮	85.3	19	4-辛基酚	104.5
9	孕二烯酮	92.5	20	苯甲酸雌二醇	74.2
10	甲睾酮	93.0	21	戊酸雌二醇	106.0
11	甲羟孕酮	90.6	22	苯丙酸诺龙	81.9

序号	化合物	线性范围/（μg·mL^-1）	线性方程	相关系数r	检出限/（μg·mL^-1）	定量限/（μg·mL^-1）
1	雌三醇	0.5~19.0	y=4.46×10⁴x+7.62×10³	0.999 2	0.03	0.1
2	肾上腺甾酮	0.5~20.7	y=2.29×10⁴x+4.56×10³	0.999 2	0.03	0.1
3	双酚A	0.5~19.0	y=5.36×10⁴x+6.54×10³	0.999 0	0.03	0.1
4	诺龙	0.5~19.1	y=2.74×10⁴x+1.14×10⁴	0.999 0	0.03	0.1
5	17-β-雌二醇	0.5~21.5	y=3.65×10⁴x+8.60×10³	0.999 0	0.03	0.1
6	17-α-雌二醇	0.5~21.1	y=3.54×10⁴x+1.27×10⁴	0.998 6	0.03	0.1
7	睾酮	0.5~19.5	y=2.43×10⁴x+9.64×10³	0.998 6	0.03	0.1
8	雌酮	0.6~22.5	y=4.03×10⁴x+8.62×10³	0.998 7	0.03	0.1
9	孕二烯酮	0.5~20.0	y=2.33×10⁴x+4.40×10³	0.998 9	0.03	0.1
10	甲睾酮	0.5~18.8	y=2.35×10⁴x+3.74×10³	0.999 2	0.03	0.1
11	甲羟孕酮	0.5~19.5	y=1.91×10⁴x+3.16×10³	0.999 2	0.05	0.2
12	孕酮	0.5~18.5	y=2.06×10⁴x+5.03×10³	0.998 8	0.03	0.1
13	醋酸美伦孕酮	0.5~18.4	y=2.26×10⁴x+5.76×10³	0.998 7	0.03	0.1
14	美雌醇	0.5~20.4	y=4.00×10⁴x+1.25×10⁴	0.998 3	0.03	0.1
15	17-乙酸睾丸激素	0.5~20.5	y=1.89×10⁴x+8.15×10³	0.997 7	0.05	0.2
16	丙酸诺龙	0.5~18.7	y=1.70×10⁴x+8.73×10³	0.998 3	0.03	0.1
17	醋酸氯睾酮	0.5~18.1	y=1.28×10⁴x+3.42×10³	0.997 9	0.05	0.2
18	丙酸睾酮	0.5~20.2	y=1.69×10⁴x+4.18×10³	0.998 3	0.05	0.2
19	4-辛基酚	0.6~24.6	y=1.17×10⁴x+1.51×10³	0.999 2	0.10	0.4
20	苯甲酸雌二醇	0.5~20.7	y=2.63×10⁴x-3.59×10²	0.994 6	0.03	0.1
21	戊酸雌二醇	0.5~21.0	y=2.04×10⁴x+4.48×10³	0.998 4	0.05	0.2
22	苯丙酸诺龙	0.6~22.3	y=1.21×10⁴x+3.58×10³	0.997 7	0.06	0.2

序号	化合物	平均加标回收率/%			相对标准偏差RSD/%
序号	化合物	低水平	中水平	高水平	低水平	中水平	高水平
1	雌三醇	86.7	91.0	93.1	6.0	2.1	2.4
2	肾上腺甾酮	84.0	91.3	91.9	7.5	2.6	2.9
3	双酚A	86.8	90.4	94.1	3.1	1.7	4.9
4	诺龙	99.6	94.5	93.8	6.6	2.6	2.8
5	17-β-雌二醇	92.8	91.5	95.2	1.8	2.0	4.2
6	17-α-雌二醇	87.7	91.2	95.1	7.1	1.5	3.3
7	睾酮	91.0	92.8	93.6	4.3	2.6	2.4
8	雌酮	81.8	91.8	94.5	2.3	1.9	2.4
9	孕二烯酮	80.3	92.4	93.5	7.6	2.4	2.4
10	甲睾酮	80.4	91.7	93.0	7.7	2.5	2.5
11	甲羟孕酮	82.5	90.9	93.6	6.5	3.0	2.5
12	孕酮	83.7	90.7	93.6	6.4	2.4	2.7
13	醋酸美伦孕酮	93.3	92.1	94.5	7.6	2.2	2.5
14	美雌醇	80.8	92.0	94.3	5.1	2.7	2.7
15	17-乙酸睾丸激素	85.1	94.8	96.3	1.6	3.2	3.2
16	丙酸诺龙	83.8	98.1	99.4	4.8	4.0	2.1
17	醋酸氯睾酮	80.3	92.9	95.9	0.3	2.7	2.7
18	丙酸睾酮	80.9	91.5	94.2	0.9	2.8	2.7
19	4-辛基酚	89.6	92.2	91.9	5.5	4.1	3.5
20	苯甲酸雌二醇	82.9	90.1	91.4	6.7	3.4	3.7
21	戊酸雌二醇	88.5	85.7	88.6	6.2	4.7	3.3
22	苯丙酸诺龙	81.9	92.0	93.8	5.5	3.0	3.0