衍生化-磁固相萃取高效液相色谱荧光检测内分泌干扰物  

Determination of Endocrine Disruptors by High Performance Liquid Chromatography-Fluorescence Detection Using Magnetic Dispersive Solid Phase Extraction

作　　者：孙怡琳 亢洋 郑龙芳 张琬茹 马爱新 赵建 王晓 赵先恩 SUN Yi-Lin;KANG Yang;ZHENG Long-Fang;ZHANG Wan-Ru;MA Ai-Xin;ZHAO Jian;WANG Xiao;ZHAO Xian-En(Shandong Provincial Key Laboratory of Life-organic Analysis, Key Laboratory of Pharmaceutical Intermediates and Analysis of Natural Medicine, College of Chemistry and Chemical Engineering,Qufu Normal University,Qufu 273165,China;Shandong Key Laboratory of TCM Quality Control Technology,Shandong Analysis and Test Center, Qilu University of Technology(Shandong Academy of Sciences),Jinan 250014,China)

机构地区：[1]曲阜师范大学化学与化工学院山东省绿色天然产物与医药中间体高校重点实验室,曲阜273165 [2]齐鲁工业大学(山东省科学院)山东省分析测试中心山东省中药质量控制技术重点实验室,济南250014

出　　处：《分析化学》2019年第1期86-92,共7页Chinese Journal of Analytical Chemistry

基　　金：国家自然科学基金项目(Nos.21775088;81303179)资助~~

摘　　要：食品与环境中的极微量内分泌干扰物即可严重干扰人体的内分泌功能,对人类健康构成巨大威胁。本研究通过荧光衍生化和磁固相萃取(MDSPE)样品前处理技术,建立了高效液相色谱荧光检测(HPLC-FLD)三氯生(TCS)、β-雌二醇(E2)、壬基酚(NP)和4-辛基酚(OP)的分析方法。以2'-甲酰氯罗丹明(RHB-Cl)为柱前衍生试剂,考察并优化了衍生化和MDSPE实验条件。结果表明,最优的衍生化条件为在室温(20℃)、p H 9.5的Na_2CO_3-NaHCO_3缓冲液条件下,衍生反应5 min得到衍生产物。磁性氧化石墨烯作为MDSPE吸附剂,用量15 mg,萃取时间15 min,洗脱剂为甲醇-乙酸(9∶1,V/V)、洗脱时间3 min,能够实现4种内分泌干扰物衍生物的富集与净化。在优化的色谱条件下,12 min内实现了4种衍生物的分离。荧光激发和发射波长分别为554和570 nm,方法检出限为1.1～1.9 ng/L,定量限为4.0～7.5 ng/L,线性、精密度和回收率良好。与已报道的方法相比,本方法具有简便、快速、灵敏度高等优势,可用于牛奶、牙膏、生活废水中TCS、E2、NP和OP的测定,为食品和饮用水安全监督提供了一种新方法。A new high performance liquid chromatography-fluorescence detection(HPLC-FLD)method was developed by fluorescence derivatization and magnetic dispersive solid phase extraction(MDSPE)technology for the determination of triclosan(TCS),β-estradiol(E2),nonylphenol(NP),and 4-octylphenol(OP).With 2′-carbonyl chloride rosamine(RHB-Cl)as precolumn derivatization reagent,the derivatization and MDSPE conditions were investigated.The results showed that the maximum derivatives were obtained after derivatizationin for 5 min in Na 2CO 3-NaHCO 3 buffer solution at pH 9.5 at room temperature(20℃).Under the optimized conditions including using magnetic graphene oxide as MDSPE adsorbent(15 mg),extraction for 5 min,methanol/acetic acid(9∶1,V/V)as elution agent,and elution for 3 min,four endocrine disruptor compound derivatives were enriched and purified.Under optimized chromatographic conditions,the four derivatives were separated within 12 min.The fluorescence excitation and emission wavelengths were set at 554 nm and 570 nm,respectively,achieving highest detection sensitivity for four endocrine disruptor compounds derivatives.The limits of detection(LODs)were in the range of 1.1-1.9 ng/L,and the limits of quantification(LOQs)were in the range of 4.0-7.5 ng/L.This method had good linearity,precision and recovery results,and also showed obvious advantages such as simplicity,rapidity and high sensitivity comparing to the reported methods.It was a convenient and validated method for the routine analysis of endocrine disruptor compounds in milk,toothpaste and waste water,and could provide a new method for food,drinking and water safety supervision.

关 键 词：磁性氧化石墨烯 分散固相萃取 衍生化 高效液相色谱 内分泌干扰物 牛奶 环境水样 

分 类 号：O657.3[理学—分析化学]