作者：罗悦^1,2, 汪隽², 罗茜¹, 付薛衡¹, 许淑霞³, 罗进¹

作者单位：1. 四川省分析测试服务中心，四川 成都 610023;
2. 成都理工大学材料与化学化工学院，四川 成都 610059;
3. 成都理工大学生态环境学院，四川 成都 610059

关键词：超临界流体萃取;高效液相色谱-质谱;化妆品;防腐剂

摘要：

通过将超临界流体萃取与高效液相色谱-质谱联用（HPLC-MS）结合，建立化妆品中4种对羟基苯甲酸酯类防腐剂（对羟基苯甲酸甲酯（MP）、对羟基苯甲酸乙酯（EP）、对羟基苯甲酸丙酯（PP）和对羟基苯甲酸正丁酯（BP））的高效、灵敏的测定方法。化妆品样品用14000 kPa和65 ℃的超临界流体萃取后，进行HPLC-MS外标法测定。对提取压强、提取温度、提取时间和色谱、质谱优化影响萃取和检测的条件进行优化。结果表明，4种对羟基苯甲酸酯类防腐剂线性范围0.01~100 μg/mL（相关系数> 0.9997），检出限（LOD，S/N=3）0.52~0.58 ng/kg。在2.00~800.00 mg/kg加标浓度下，4种对羟基苯甲酸酯类的加标回收率在95.15%~107.69%（n=3）。该方法操作简单、环境友好，可用于化妆品中对羟基苯甲酸酯类防腐剂的灵敏、准确检测。

Supercritical fluid extraction- high performance liquid chromatography-mass spectrometry analysis of paraben preservatives in cosmetics
LUO Yue^1,2, WANG Jun², LUO Xi¹, FU Xueheng¹, XU Shuxia³, LUO Jin¹
1. Analysis Center of Sichuan, Chengdu 610023, China;
2. College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, Chengdu 610059, China;
3. College of Ecological Environment, Chengdu University of Technology, Chengdu 610059, China
Abstract: Four kinds of paraben preservatives including methyl hydroxybenzoate (MP), ethyl p-hydroxybenzoate (EP), propyl p-hydroxybenzoate (PP) and n-butyl p-hydroxybenzoate (BP) in cosmetics was accurately and sensitively determined by supercritical fluid extraction (SFE) coupled with liquid chromatography-mass spectrometry (HPLC-MS) in cosmetics. The cosmetics sample was first extracted by CO₂ supercritical fluid at 14000 kPa and 65 ℃, and then analyzed by HPLC-MS with external standard method. The results showed that within the concentration range of 0.01-100 μg/mL, the four parabens showed a good linear relation with correlation coefficient above 0.9997. The detection of limits (LOD, S/N=3) were from 0.52-0.58 ng/kg_. Within the spiked concentrations of 2.00 to 800.00 mg/kg, the recoveries of the four parabens ranged from 95.15% to 107.69% (n=3). The present method is fast, simple, and environment-friendly, which provides a batch detection method for sensitive and accurate screening of parabens in cosmetics.
Keywords: supercritical fluid extraction;high performance liquid chromatography-mass spectrometry;cosmetics;preservatives
2023, 49(1):75-80  收稿日期: 2020-12-30;收到修改稿日期: 2021-04-21
基金项目: 四川省科技计划项目（2021YFN0019）; 四川省杰出青年基金培育项目（19JCQN0061）
作者简介: 罗悦(1993-),男,四川巴中市人,硕士研究生,专业方向为环境监测
参考文献
[1] HAJKOVA R, SOLICH P, PPOSPISILOVA M, et al. Simultaneous determination of methylparaben, propylparaben, sodium diclofenac and its degradation product in a topical emulgel by reversed-phase liquid chromatography[J]. Analytica Chimica Acta, 2002, 467(1-2): 91-96
[2] SONI M G, CARABIN I G, BURDOCK G A. Safety assessment of esters of p-hydroxybenzoic acid (parabens)[J]. Food and Chemical Toxicology, 2005, 43(7): 985-1015
[3] EE M R, LIN C Y, LI Z G, et al. Simultaneous analysis of antioxidants and preservatives in cosmetics by supercritical fluid extraction combined with liquid chromatography–mass spectrometry[J]. Journal of Chromatography A, 2006, 1120(1-2): 244-251
[4] 高元元, 张建, 程宾. 气相色谱法测定食品中对羟基苯甲酸酯[J]. 食品与发酵科技, 2018, 54(5): 120-124
[5] XU J, YUAN H, ZENG L, et al. Recent progress in Michael addition-based fluorescent probes for sulfur dioxide and its derivatives[J]. Chinese Chemical Letters, 2018, 29(10): 1456-1464
[6] PARK M, SNYDER S A. Sample handling and data processing for fluorescent excitation-emission matrix (EEM) of dissolved organic matter (DOM)[J]. Chemosphere, 2018, 193: 530-537
[7] 王玉田, 张艳, 商凤凯, 等. 三维荧光结合AWRCQLD测量化妆品中三种添加剂[J]. 光谱学与光谱分析, 2020, 40(2): 501-505
[8] CHILBULE A, SINGH R, MANN B, et al. Development and validation of an analytical method for determination of bronopol and kathon preservative in milk[J]. Journal of Food Science and Technology, 2019, 56(6): 3170-3176
[9] 肖作为, 何蔓, 陈贝贝, 等. 基于金属有机骨架材料的磁固相萃取与高效液相色谱-紫外检测法分析饮料和方便面中4种防腐剂[J]. 色谱, 2020, 38(1): 127-136
[10] GEDZIUTE J, MARKSE M, ZEVZIKOVIENE A, et al. Investigation of food supplements with preservative E211 (Sodium benzoate) using thin-layer chromatography[J]. ScienceRise Pharmaceutical Science, 2018, 3(13): 4-7
[11] 赵晶, 张爱琳. 辣萝卜干中苯甲酸、山梨酸和糖精钠的测定分析研究[J]. 安徽农业科学, 2014, 42(20): 6776-6778
[12] ABAD G L, LUCAS S S, GISMERA M J, et al. Determination of paraben-, isothiazolinone-and alcohol-type preservatives in personal care products by HPLC with dual (diode-array and fluorescence) detection[J]. Microchemical Journal, 2020: 105613
[13] 陈静, 毛北萍, 袁晓倩, 等. 高效液相色谱法同时测定化妆品中8种防腐剂[J]. 香料香精化妆品, 2020, 05: 40-45
[14] JESUS F F S, COELHO A G, ASSIS P L, et al. Simple and fast method for simultaneous determination of propionate and sorbate in bread by capillary electrophoresis with UV spectrophotometric detection[J]. Journal of Food Composition and Analysis, 2018, 72: 93-96
[15] 张帅, 高立娣, 梁辉, 等. 高效毛细管电泳法同时分离测定化妆品中7种防腐剂[J]. 分析测试学报, 2020, 39(2): 258-262
[16] ARLA R, KOUMARAVELOU K. Quantitative determination and validation of ethylhexylglycerin using Gas chromatography method[J]. International Journal of Research in Pharmaceutical Sciences, 2018, 9(1): 30-36
[17] 宋洪强. 气相色谱法测定环境水质中10种防腐剂的含量[J]. 广东化工, 2020, 47(17): 176-177
[18] FU C, LIANG Y, XU W, et al. Simultaneous determination of 10 preservatives in 6 different dosage forms of cosmetics by HPLC-MS/MS[J]. Chinese Journal of Pharmaceutical Analysis, 2016, 36(8): 1456-1464
[19] 陈静, 毛北萍, 郑荣, 等. 高效液相色谱-质谱联用法同时测定8种不同基质类型化妆品中的23种防腐剂[J]. 日用化学工业, 2018, 48(12): 717-724
[20] 刘曼, 施敏, 曹学丽. 离子液体双水相萃取-HPLC分析红酒中的痕量氯酚类物质[J]. 食品科学, 2017, 38(12): 260-265
[21] 朱明达, 贺文智, 索全伶, 等. 超临界CO₂萃取技术在天然食品添加剂领域的应用[J]. 中国食品添加剂, 2005(4): 85-88