化妆品中性激素的检测方法研究进展

doi:10.3969/j.issn.1001-1803.2020.09.009

摘要/Abstract

摘要：

概述了化妆品中性激素的种类、安全风险,介绍目前检测标准和文献所涵盖的性激素种类。综述了高效液相色谱法、超高效液相色谱法、液相色谱-质谱法及凝胶渗透色谱-液相色谱-串联质谱法、超高效合相色谱法、聚合物整体柱微萃取与高效液相色谱联用法、固相萃取-微乳液相色谱法等检测方法在性激素检测上的应用及其优劣。最后对化妆品中性激素检测技术的发展趋势进行了介绍。

关键词: 化妆品, 性激素, 检测技术

Abstract:

The categories and safety risks of sex hormones in cosmetics were presented. The detection standards and the cutting-edge methods reported referring to these categories of sex hormones in cosmetics were also introduced. The advantages and disadvantages of various detection methods were introduced, including HPLC, UPLC, HPLC-MS and other detection methods （GPC-LC-MS/MS, UPC2, PMME-HPLC, and SPE-MELC）. Finally, the development trend of detection methods for sex hormones in cosmetics was mentioned.

Key words: cosmetics, sex hormone, detection technology

中图分类号:

TQ658

胡贝,李丽霞,刘红,黄伟,丁晓萍. 化妆品中性激素的检测方法研究进展[J]. 日用化学工业, 2020, 50(9): 629-637.

HU Bei,LI Li-xia,LIU Hong,HUANG Wei,DING Xiao-ping. Research progress on detection of sex hormones in cosmetics[J]. China Surfactant Detergent & Cosmetics, 2020, 50(9): 629-637.

图/表 5

表 1

表 2

表 3

高效液相色谱法检测性激素"

检测物	提取净化方法	色谱柱	检测器及检测波长	检出限	定量限	回收率/%	文献
雌三醇、雌二醇、睾酮、炔雌醇、己烯雌酚、乙酸甲地孕酮、孕酮、丙酸睾酮	所有形态的样品均以甲醇超声提取,乳膏状样品再经HLB固相萃取柱富集净化	ZORBAX Eclipse XDB-C₁₈（150 mm×4.6 mm, 5 μm）	二极管阵列检测器：196 nm,242 nm,288 nm; 荧光检测器：激发波长为280 nm,发射波长为310 nm	0.1~ 0.5 μg·g^-1	—	90.3~ 102.9	[1]
炔诺孕酮、乙酸甲地孕酮、乙酸氯地孕酮、乙酸甲羟孕酮、丙酸睾丸酮	甲醇超声提取	Kromasil 100-5C₁₈（250 mm×4.6 mm, 5 μm）	二极管阵列检测器：242 nm,290 nm	0.552~ 1.01 mg·kg^-1	1.10~ 5.04 mg·kg^-1	96.2~ 110	[3]
雌三醇、雌二醇、雌酮、己烯雌酚、睾酮、甲睾酮、黄体酮	甲醇超声提取	依利特C₁₈柱（250 mm×4.6 mm, 5 μm）	二极管阵列检测器：204 nm,245 nm	0.12~ 0.56 ng	—	95.0~ 100.8	[12]
炔诺孕酮、醋酸甲地孕酮、醋酸氯地孕酮、醋酸甲羟孕酮、丙酸睾丸酮	V（甲醇）∶ V （水）= 90∶10提取,正己烷除脂	Kromasil 100-5C₁₈（250 mm×4.6 mm, 5 μm）	二极管阵列检测器：242 nm,290 nm	0.550~ 5.040 mg·kg^-1	0.662~ 5.260 mg·kg^-1	88~120	[13]
雌二醇、雌三醇、雌酮、睾酮、甲基睾酮、孕酮、己烯雌酚	V（甲醇）∶V （水）= 90∶10提取,正己烷除脂	XTerra RP₁₈（250 mm×4.6 mm, 5 μm）	二极管阵列检测器：197 nm,240 nm;荧光检测器：激发波长为280 nm,发射波长为310 nm	0.010~ 1.0 mg·L^-1	—	79.5~ 98.4	[14]
雌三醇、雌二醇、己烯雌酚、睾酮、己烷雌酚、醋酸甲地孕酮、甲孕酮、孕酮	甲醇超声提取	ZORBAX Extend-C₁₈（150 mm×4.6 mm, 5 μm）	紫外检测器：230 nm	0.05~ 0.2 mg·L^-1	—	93.3~ 107.2	[15]
雌三醇、睾酮、甲基睾酮、β-雌二醇、雌酮、孕酮、己烯雌酚	乙醇超声提取	Waters XTerra TMRP₁₈（150 mm×4.6 mm, 3.5 μm）	二极管阵列检测器：230 nm	0.01~ 0.06 mg·L^-1	—	84~104	[16]
雌三醇、雌酮、炔雌醇、己烯雌酚	甲醇超声提取	Inertisl ODS-C₁₈（250 mm×4.6 mm, 5 μm）	二极管阵列检测器：279 nm	0.02~ 0.03 mg·kg^-1	—	97.3~ 110.6	[17]
雌二醇、雌三醇、雌酮、睾酮、甲基睾酮、孕酮、己烯雌酚	甲醇超声提取	XTerra RP₁₈（150 mm×4.6 mm, 5 μm）	二极管阵列检测器：197 nm,240 nm	0.15~ 1.0 mg·L^-1	—	92.0~ 95.2	[18]

表 3

表 4

表 5

液相色谱-质谱联用法检测性激素"

检测物	提取净化方法	色谱柱	流动相及流速	质谱模式	检出限	定量限	回收率/%	文献
21种性激素	V（甲醇）∶V（乙腈）= 1∶1涡旋提取,HLB固相萃取柱净化萃取	Waters ACQUITY UPLC BEH C₁₈（50 mm×2.1mm, 1.7 μm）	纯水（含0.5 mmol/L NH₄F）-甲醇和乙腈混合溶液（体积比为1∶1）梯度洗脱,0.3 mL/min	ESI正离子、ESI负离子	—	0.05~ 0.61 mg·kg^-1	74~ 110	[22]
15种雄激素	甲醇超声提取,HLB固相萃取柱净化	ACQUITY UPLC BEH C₁₈（50 mm × 2.1 mm, 1.7 μm）	含0.1%甲酸的甲醇溶液-0.1%甲酸水溶液梯度洗脱,0.3 mL/min	ESI正离子	—	1.0~ 20.0 μg·kg^-1	76.5~ 92.1	[23]
112种禁用药物（含4种性激素）	0.2%甲酸乙腈提取,QuEChERS净化	Agilent ZORBAX Eclipse Plus（RRHd）C₁₈（150 mm×3.0 mm, 1.8 μm）	0.2%甲酸水溶液-0.2%甲酸乙腈溶液梯度洗脱,0.5 mL/min	ESI正离子	—	2.0~ 10.0 μg·kg^-1	82.0~ 108	[24]
5种性激素	甲醇超声提取	ACQUITY UPLC BEN C₁₈（50 mm× 2.1mm,1.7 μm）	V（甲醇）∶V（0.1%的甲酸水溶液）= 60∶40,0.4 mL/min	ESI正离子	0.005~ 0.05 mg·L^-1	0.02~ 0.2 mg·L^-1	79.8~ 115.3	[25]
13种性激素	50%乙腈超声提取	Poroshell 120 EC-C₁₈（100 mm×4.6 mm, 2.7 μm）	水-乙腈梯度洗脱,0.3 mL/min	ESI正离子、ESI负离子	0.001~ 0.026 μg·g^-1	—	80.8~ 116.8	[26]
22种激素（含 15种性激素）	乙腈超声提取后,法一：HLB固相萃取柱净化; 法二：凝胶渗透色谱净化	ZORBAX Eclipse XDB-C₁₈（100 mm×2.1 mm,1.8 μm）	正离子模式：乙腈-0.1%（体积分数）甲酸水溶液梯度洗脱;负离子模式：乙腈-水梯度洗脱,均为0.2 mL/min	ESI正离子、ESI负离子	法一：0.01~ 0.40 mg·kg^-1; 法二：0.1~ 4.0 mg·kg^-1	—	法一：61.5~ 111; 法二：60.8~ 113	[27]
11种性激素	甲醇超声提取,精油样品经BRP固相萃取柱净化	Ultimate XB-C₈ （100 mm×2.1 mm,3 μm）	V（水）∶V（乙腈）=40∶60,0.3 mL/min	ESI正离子、ESI负离子	0.000 5~ 1.5 mg·L^-1	—	73~ 105	[28]
3种性激素	饱和氯化钠溶液分散,乙腈涡旋提取,亚铁氰化钾和醋酸锌沉淀大分子,硅胶固相萃取柱净化	Phenomenex Luna C₁₈（50 mm×2 mm,3 μm）	水-乙腈梯度洗脱,0.2 mL/min	ESI负离子	0.125 ng·g^-1	0. 25 ng·g^-1	87.5~ 100.3	[29]
10种性激素	甲醇超声提取	ACQUITY UPLC BEH C₁₈（50 mm× 2.1 mm,1.7 μm）	乙腈-水梯度洗脱,0.3 mL/min	ESI正离子、ESI负离子	0.002~ 0.2 μg·g^-1	—	51.5~ 137	[30]
7种雌激素	V（乙酸乙酯）∶ V（正己烷）=2∶98 提取,硅胶固相萃取小柱净化	ACQUITY UPLC^TM BEH SHELD RP₁₈（100 mm×2.1 mm,1.7 μm）	水-乙腈梯度洗脱,0.3 mL/min	ESI负离子	0.3~ 7 μg·kg^-1	1~ 20 μg·kg^-1	88.5~ 114.8	[31]
19种激素（含 7种性激素）	甲醇超声提取,HLB固相萃取柱净化	Agilent ZORBAX Eclipse XDB-C₁₈（50 mm×2.1 mm, 1.8 μm）	乙腈-水梯度洗脱,0.3 mL/min	ESI正离子、ESI负离子	0.002~ 0.8 mg·kg^-1	—	72.31~ 97.89	[32]
6种雌激素	甲醇超声提取	Agilent ZORBAX EclipseXDB-C₈ 色谱柱（150 mm× 4.6 mm, 5 μm）	V（水）∶V（乙腈）=45∶55,0.3 mL/min	ESI负离子	0.2~ 12 ng·g^-1	0.7~ 40 ng·g^-1	85.2~ 102.8	[33]
9种禁限用物质（含7种性激素）	甲醇超声提取	CAPCELL PAK MG C₁₈（150 mm×2 mm,5 μm）	10 mmol·L^-1醋酸铵溶液-乙腈梯度洗脱,0.2 mL/min	ESI正离子、ESI负离子	0.001~ 15 μg·g^-1	0.005~ 75 μg·g^-1	80.5~ 109.5	[34]
25种性激素	甲醇或乙腈超声提取,HLB固相萃取柱净化	ACQUITY UPLC^TM BEH SHELD RP₁₈（100 mm×2.1 mm, 1.7 μm）	雌激素：水-乙腈梯度洗脱;雄、孕激素：0.1%甲酸水溶液（A）与含0.1%甲酸的乙腈-甲醇的混合溶液（V∶V=1∶9）（B）梯度洗脱,均为0.3 mL/min	ESI正离子、ESI负离子	油剂：1.0~ 30.5 μg·kg^-1; 乳剂：0.2~ 12.5 μg·kg^-1; 水剂：0.1~ 22.7 μg·kg^-1	油剂：3.3~ 101.8 μg·kg^-1; 乳剂：0.6~ 41.6 μg·kg^-1; 水剂：0.4~ 75.5 μg·kg^-1	油剂：58.6~ 108.1; 乳剂：67.1~ 128.4; 水剂：68.8~ 126.4	[35]

表 5

参考文献 44

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序号	中文名称	英文名称
1012	雌激素类	Oestrogens
1088	孕激素类	Progestogens
1173	具有雄激素效应的物质	Substances with androgenic effect

序号	中文名称	英文名称	CAS号	《化妆品安全技术规范》（2015 年版）	GB/T 34918— 2017	SN/T 2533—2010
1	雌三醇	Estriol	50-27-1	√	√
2	睢酮	Estrone	53-16-7	√	√
3	己烯雌酚	Diethylstilbestrol	56-53-1	√
3	己烯雌酚	Diethylstilbestrol	6898-97-1		√
4	雌二醇	Estradial	50-28-2	√	√
5	睾丸酮	Testosterone	58-22-0	√	√
6	甲基睾丸酮	Methyltestosterone	58-18-4	√	√
7	黄体酮	Progesterone	57-83-0	√	√	√
8	孕三烯酮	Gestrinone	16320-04-0	√
9	炔诺孕酮	Norgestrel	6533-00-2	√
10	醋酸甲地孕酮	Megestrol acetate	595-33-5	√		√
11	醋酸氯地孕酮	Chlormadinone acetate	302-22-7	√		√
12	醋酸甲羟孕酮	Medroxyprogesterone 17-acetate	71-58-9	√		√
13	己酸羟孕酮	Hydroxyprogesterone caproate	630-56-8	√		√
14	炔诺酮	Norethisterone	68-22-4			√
15	甲烯雌醇醋酸酯	Melengestrol acetate	2919-66-6			√
16	左炔诺孕酮	Levonorgestrel	797-63-7			√
17	地屈孕酮	Dydrogesterone	152-62-5			√
18	醋酸羟孕酮	17α-hydroxyprogesterone acetate	302-23-8			√
19	米非司酮	Mifepristone	84371-65-3			√

检测物	提取净化方法	色谱柱	检测器及检测波长	检出限	定量限	回收率/%	文献
己烯雌酚、17-α-雌二醇、17-β-雌二醇、己烷雌酚、17-α-乙炔雌二醇	乙腈提取,亚铁氰化钾和醋酸锌沉淀大分子,HLB固相萃取小柱富集净化	Waters ACQUITY UPLC BEH C₁₈（100 mm×2.1 mm, 1.7 μm）	二极管阵列检测器：200 nm	0.1~ 0.3 mg·L^-1	—	83.1~ 95.4	[19]
雌三醇、雌二醇、睾丸酮、雌酮、甲基睾丸酮、己烯雌酚、黄体酮	溶液状样品：50%乙腈水溶液提取;膏状、乳状样品：饱和氯化钠溶液、硫酸振荡溶解,环己烷除脂,50%乙腈水溶液提取	Waters ACQUITY BEH C₁₈（50 mm×2.1 mm, 1.7 μm）	紫外检测器：230 nm	0.3~2.0 ng	—	100.1~ 104.9	[20]
雌酮、雌二醇、苯甲酸雌二醇、美雌醇、炔雌醇环戊醚	V（乙腈）∶V（水）= 20∶80超声提取,正己烷除脂	LCU C₁₈（20 mm×5.0 mm, 2 μm）	紫外检测器：203 nm	0.016~ 0.042 μg·mL^-1	0.052~ 0.104 μg·mL^-1	85~ 95	[21]