MOFs功能化三聚氰胺海绵柱结合高效液相色谱法测定化妆品中对羟基苯甲酸酯类防腐剂

doi:10.3969/j.issn.2097-2806.2025.05.002

摘要/Abstract

摘要：

建立了一种利用功能化三聚氰胺海绵（MeS）作为样品前处理材料的高效液相色谱分析方法，用于定量测定化妆品中对羟基苯甲酸酯类（PBs）防腐剂。通过利用聚偏氟乙烯的粘接性能，将金属有机骨架材料—MIL-68（Al）与MeS结合，制备了一种高效吸附材料—MIL-68（Al）/MeS。将MIL-68（Al）/MeS作为固相萃取材料对样品溶液进行提取，结合高效液相色谱，应用于化妆品样品中4种PBs的提取和检测分析。结果显示，该方法的检出限为0.24~0.43 ng/mL，线性范围为5.00~200.00 ng/mL。日内和日间精密度分别为91.8%~98.4%和101.4%~107.9%，相对标准偏差（RSD）<11.6%。该方法无需离心和过滤步骤，在保证高回收率的前提下，简化了样品前处理过程，是一种便捷高效的化妆品中防腐剂含量测定方法，也适合作为大学仪器分析课程的开放创新实验。

关键词: 对羟基苯甲酸酯, 化妆品, 功能化三聚氰胺海绵, 样品前处理, 高效液相色谱法

Abstract:

This study developed a high-performance liquid chromatography （HPLC） method that leverages a functionalized melamine sponge as a sample pre-treatment material for the quantitative determination of paraben preservatives （PBs） in cosmetics. Utilizing the adhesive properties of polyvinylidene fluoride, the metal-organic framework material, MIL-68（Al）, was effectively combined with melamine sponge （MeS） to create an efficient adsorbent, MIL-68（Al）/MeS. This novel material was used as a solid-phase extraction medium to isolate and quantify four types of PBs from various cosmetic samples. The method demonstrates excellent analytical performance, characterized by detection limits ranging from 0.24 to 0.43 ng/mL and a broad linear range of 5.00 to 200.00 ng/mL. The developed method exhibits robust intra-day and inter-day precision with recovery rates between 91.8%-98.4% and 101.4%-107.9%, respectively, and maintained a relative standard deviation （RSD） below 11.6%. Notably, this analytical procedure eliminates the need for centrifugation and filtration steps, significantly simplifying the sample preparation process while ensuring high recovery rates. The MIL-68（Al）/MeS composite is not only effective in adsorbing the target analytes but also enhances the efficiency of the extraction process. By reducing the complexity and time required for sample preparation, this method offers a practical and effective approach to ensuring product safety and compliance with regulatory standards. It also holds potential as an educational tool in analytical chemistry, providing a hands-on experience for undergraduate students through innovative experiments.

Key words: parabens, cosmetics, functionalized melamine sponge, sample pre-treatment, HPLC

中图分类号:

TQ658

马品一, 李靖康, 高德江, 宋大千. MOFs功能化三聚氰胺海绵柱结合高效液相色谱法测定化妆品中对羟基苯甲酸酯类防腐剂[J]. 日用化学工业（中英文）, 2025, 55(5): 548-553.

Pinyi Ma, Jingkang Li, Dejiang Gao, Daqian Song. MOFs-Functionalized melamine sponge columns combined with high-performance liquid chromatography for determination of parabens in cosmetics[J]. China Surfactant Detergent & Cosmetics, 2025, 55(5): 548-553.

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参考文献 17

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分析物	回归方程	线性范围/（ng/mL）	相关系数	基质效应/%	LOD/（ng/mL）
对羟基苯甲酸甲酯	Y=2 476X+143	5.00~200.00	0.999	8.2	0.31
对羟基苯甲酸乙酯	Y=2 401X+75	5.00~200.00	0.997	10.6	0.25
对羟基苯甲酸丙酯	Y=2 362X+107	5.00~200.00	0.998	5.8	0.43
对羟基苯甲酸丁酯	Y=2 395X+93	5.00~200.00	0.996	7.3	0.24

分析物	加标质量浓度/（ng/mL）	日内		日间
分析物	加标质量浓度/（ng/mL）	回收率/%	RSD/%	回收率/%	RSD/%
对羟基苯甲酸甲酯	40.00	96.8	7.9	106.5	6.5
对羟基苯甲酸甲酯	200.00	97.4	2.1	105.3	2.8
对羟基苯甲酸乙酯	40.00	92.5	11.6	105.8	7.1
对羟基苯甲酸乙酯	200.00	91.8	2.5	103.7	3.2
对羟基苯甲酸丙酯	40.00	93.7	10.4	107.2	5.3
对羟基苯甲酸丙酯	200.00	96.3	3.1	107.9	3.9
对羟基苯甲酸丁酯	40.00	94.1	10.2	103.3	8.4
对羟基苯甲酸丁酯	200.00	98.4	3.5	101.4	5.6

样品	加标质量浓度/（ng/mL）	对羟基苯甲酸甲酯		对羟基苯甲酸乙酯		对羟基苯甲酸丙酯		对羟基苯甲酸丁酯
样品	加标质量浓度/（ng/mL）	回收率/%	RSD/%	回收率/%	RSD/%	回收率/%	RSD/%	回收率/%	RSD/%
婴儿牛奶营养霜	0.00	未检出
	40.00	98.4	5.9	97.3	6.5	99.1	4.7	97.8	5.6
	200.00	99.7	2.1	100.1	2.4	101.3	2.0	99.9	3.1
婴儿洁面润肤霜	0.00	未检出
	40.00	95.2	7.3	89.5	8.1	92.4	7.9	94.6	6.4
	200.00	97.9	3.5	96.3	3.9	98	4.2	97.0	4.5
痤疮膏	0.00	未检出
	40.00	96.4	8.7	95.2	7.6	97.6	6.3	98.4	7.1
	200.00	94.0	6.9	93.5	5.5	95.8	4.8	94.2	6.0
润唇膏	0.00	未检出
	40.00	97.1	6.4	96.8	7.0	97.9	6.1	97.4	6.7
	200.00	98.3	3.2	97.7	3.6	99.0	2.8	98.5	3.4
眼霜	0.00	未检出
	40.00	102.1	3.7	103.2	4.0	101.3	3.4	100.4	3.8
	200.00	106.8	6.3	105.9	6.8	107.6	5.9	106.7	6.4
护手霜	0.00	未检出
	40.00	95.0	4.9	94.1	5.3	96.1	4.5	95.4	4.8
	200.00	95.7	7.5	94.8	8.1	96.5	6.9	95.9	7.4
卸妆油	0.00	未检出
	40.00	95.5	8.2	94.6	8.5	96.4	7.8	95.8	8.1
	200.00	96.8	4.8	95.9	5.2	97.6	4.5	96.5	5.0
粉底液	0.00	31.52 ng/mL		未检出		5.59 ng/mL		未检出
	20.00	97.3	6.5	96.5	7.1	98.1	6.2	97.6	6.9
	50.00	98.5	4.3	97.9	3.7	99.2	4.0	98.7	3.4
防晒霜	0.00	71.55 ng/mL		15.02 ng/mL		未检出		21.72 ng/mL
	20.00	105.9	5.6	104.3	6.2	106.2	5.8	105.7	6.5
	50.00	101.7	3.9	100.8	4.3	99.5	3.5	102.3	4.1
化妆水	0.00	未检出		109.50 ng/mL		未检出		未检出
	20.00	96.0	7.1	95.1	7.5	97.3	6.9	96.5	7.2
	50.00	97.2	6.6	96.1	4.9	98.2	7.4	97.4	4.8