氮掺杂碳纳米管增强中空纤维液相微萃取-高效液相色谱法测定生物样本中溴系阻燃剂  

Determination of Brominated Flame Retardants in Biological Sam⁃ples by Nitrogen Doped Carbon Nanotubes Reinforced Hollow Fi⁃bers Liquid-phase Microextraction Coupled with High Performance Liquid Chromatography

作　　者：马琳琳 张泽霖 清江 孟桃于 焦叶 陈茂龙 文李[1] 程云辉[1] 丁利 MA Lin-lin;ZHANG Ze-lin;QING Jiang;MENG Tao-yu;JIAO Ye;CHEN Mao-long;WEN Li;CHENG Yun-hui;DING Li(School of Food Science and Bioengineering,Changsha University of Science&Technology,Changsha 410114,China;Shanghai Customs Industrial Products and Raw Materials Testing Center,Shanghai 200135,China;Changsha Harmony Health Medical Laboratory Co.,Ltd,Changsha 410000,China)

机构地区：[1]长沙理工大学食品科学与生物工程学院,湖南长沙410114 [2]上海海关工业品与原材料检测中心,上海200135 [3]长沙和合医学实验室有限公司,湖南长沙410000

出　　处：《分析测试学报》2023年第9期1104-1111,共8页Journal of Instrumental Analysis

基　　金：国家重点研发计划项目(2019YFC0810900,2020YFC0811100);天津市科技支撑重点项目(20YFZCSN00630)。

摘　　要：该文建立了氮掺杂碳纳米管(N-CNTs)增强中空纤维液相微萃取(HF-LPME)结合高效液相色谱(HPLC)同时检测生物样品中四溴双酚A(TBBPA)和十溴二苯醚(BDE209)的分析方法。分别以15μL甲苯-正辛醇(1∶1,体积比)和甲苯-乙酸乙酯(1∶1,体积比)有机溶剂对血清和尿样在常温下萃取10 min,在萃取过程中,中空纤维膜排阻样品中蛋白质,避免了大分子物质的干扰。目标化合物经Kjnetex EVO C_(18)(2.1 mm×150 mm,5μm)色谱柱分离,以水和乙腈为流动相进行梯度洗脱。考察了不同萃取溶剂、提取时间、氮掺杂碳纳米管用量、样品pH值、搅拌速率、NaCl浓度和解吸溶剂种类对目标化合物萃取效率的影响。结果表明,在最佳条件下,TBBPA和BDE209分别在2~200 ng/mL和10~200 ng/mL范围内具有良好的线性关系,相关系数(r^(2))不小于0.995,检出限分别为0.375 ng/mL和2.8 ng/mL,定量下限分别为9.4 ng/mL和1.25 ng/mL。在3个加标水平下,目标分析物的回收率为84.5%~114%,相对标准偏差为1.4%~7.5%。该方法在富集TBBPA和BDE209的同时可去除生物样品中的蛋白质,方法简单、快速、灵敏度高、重复性好、绿色环保,适用于复杂基质中TBBPA和BDE209的检测。A nitrogen-doped carbon nanotubes(N-CNTs)reinforced hollow fiber liquid-phase micro⁃extraction(HF-LPME)combined with high performance liquid chromatography(HPLC)was estab⁃lished for the simultaneous determination of tetrabromobisphenol A(TBBPA)and decabromodiphenyl oxide(BDE209)in biological samples.The serum and urine samples were extracted with 15μL tolu⁃ene-n-octanol(1∶1,by volume)and toluene-ethyl acetate(1∶1,by volume)at room temperature for 10 min,respectively.During the extraction process,the hollow fiber membrane blocked the in⁃terference of macromolecules in the sample,which played a role in purification.The target com⁃pounds were separated on a Kjnetex EVO C_(18)(2.1 mm×150 mm,5μm)column by gradient elution,using water and acetonitrile as mobile phases at a flow rate of 0.3 mL/min and a column temperature of 30℃.The effects of different extraction solvent type,extraction time,nitrogen-doped carbon nanotubes amount,sample pH value,stirring rate,NaCl concentration and desorption solvent type on extraction efficiencies of the target compound were investigated.External standard method was used for the quantitative analysis.The results showed that under the optimum conditions,the calibra⁃tion curves were linear in the range of 2-200 ng/mL for TBBPA,and 10-200 ng/mL for BDE209.The correlation coefficients(r^(2))were not less than 0.995,the detection limits(LODs)and the quanti⁃tation limits(LOQs)of the method were in the ranges of 0.375-2.8 ng/mL and 1.25-9.4 ng/mL,re⁃spectively.The average recoveries for the two target analytes at three spiked levels ranged from 84.5%to 114%,with relative standard deviations(RSDs)of 1.4%-7.5%.This method could not on⁃ly enrich TBBPA and BDE209,but also remove protein from biological samples at the same time.The method was sensitive,reproducible,green and environmentally friendly,and was suitable for the detection of TBBPA and BDE209 in complex matrices.

关 键 词：氮掺杂碳纳米管(N-CNTs) 中空纤维液相微萃取(HF-LPME) 溴系阻燃剂 高效液相色谱法(HPLC) 

分 类 号：O657.72[理学—分析化学] O235[理学—化学]