【作者】 马红玉；

【导师】 石志红；

【作者基本信息】 河北大学 ， 分析化学， 2020， 硕士

【摘要】 磁固相萃取（MSPE）将纳米或微米级磁性固体吸附剂分散在样品溶液中,增大了吸附剂与目标物的接触面积;同时因其吸附剂具有磁性可以在外加磁场作用下与溶液快速分离,极大地缩短了样品前处理的时间。此外,MSPE过程仅需要微量有机溶剂。MSEP由于其优异的性能广泛地应用于基质复杂的样品中目标物的富集与提取。本文制备了三种新型磁性固体吸附剂材料,结合高效液相色谱及液质联用技术测定样品中的目标物。全文共分为如下四个部分:第一章:概述了MSPE的操作原理及几种常见的吸附剂材料;总结了MSPE在食品、环境和生物基质样品中的应用。第二章:采用磁性海泡石（Sep-M）作为吸附剂,结合UPLC-MS/MS检测饮料中的两种人工合成色素。首先,通过共沉淀法制备Sep-M,并通过TEM、FT-IR、XRD等进行表征。酸性条件下,表面带正电荷的吸附剂与带负电荷的目标物发生静电相互作用,因此通过改变溶液的酸碱度即可实现萃取和洗脱。优化了样品溶液pH、萃取时间、洗脱剂种类等影响萃取回收率的因素。在最佳条件下,线性范围为0.005¹.0μg/mL,R²大于0.99,加标回收率在91.0¹23.9%之间,RSD（n=6）小于3.6%,LOD在0.033⁰.057ng/mL范围内。最终该方法成功应用于测定11种饮料样品中的合成色素,其中4种样品中检测到目标物。第三章:制备Fe₃O₄@PDA@PA磁性纳米复合材料,并将其作为磁固相萃取的吸附剂,结合HPLC-UV测定口服液中的五种蒽醌类化合物。首先通过溶剂热法制备Fe₃O₄磁性微球,然后多巴胺（DA）通过自聚合作用在Fe₃O₄表面形成聚多巴胺（PDA）层,最后将植酸（PA）涂覆在PDA层表面。纳米复合材料具有较大的比表面积,通过疏水作用和π-π作用将目标物吸附在表面上。利用TEM、FT-IR、XRD等方法对材料进行了表征。研究中对吸附剂种类、离子强度、萃取时间、洗脱剂种类等影响萃取回收率的因素进行了优化。在最佳条件下,该方法具有良好的线性,线性范围为0.025².0μg/mL,R²均大于0.99,加标回收率在70.0¹08.7%之间,RSD（n=6）小于8.6%,检出限（LOD）在4.5⁷.0ng/mL范围内。该方法成功检测出五种口服液中蒽醌类化合物的含量。第四章:制备β-环糊精（β-CD）修饰的Fe₃O₄@CS纳米粒子,结合HPLC-UV测定了减肥茶中蒽醌类化合物的含量。通过水热法一步合成Fe₃O₄@CS纳米粒子,然后用β-CD对Fe₃O₄@CS纳米粒子进行改性。运用TEM、FT-IR、XRD等手段表征材料。实验中考察了材料用量、离子强度、样品溶液pH、洗脱条件等因素对回收率的影响。在最佳条件下,方法的线性范围是0.01².0μg/mL,R²均大于0.99,加标回收率在74.0¹07.3%范围内,RSD（n=5）小于9.9%。最终该方法成功检测出7种减肥茶中蒽醌类化合物的含量。更多还原

【Abstract】 Magnetic solid phase extraction（MSPE）increases the contact area between the adsorbent and the target by dispersing nano-or micro-scale magnetic solid adsorbents in the sample solution.Because of its magnetic properties,it can be quickly separated from the solution under the action of an external magnetic field,greatly reducing sample processing time.In addition,the MSPE process requires only a small amount of organic solution.Due to its excellent properties,MSEP is widely used in the extraction and enrichment of targets in samples with complex matrices.In this paper,three new magnetic solid adsorbent materials were prepared and combined with high performance liquid chromatography and liquid-mass spectrometry to determine the target substances in the samples.The full text is divided into the following four parts:Chapter one:Outlines the operating principle of MSPE and several common adsorbent materials;summarizes the application of MSPE in food,environmental and biological matrix samples.Chapter two:This experiment uses magnetic sepiolite（Sep-M）as the adsorbent for magnetic-solid phase extraction,combined with UPLC-MS/MS to detect two common synthetic pigments.First,Sep-M was prepared by co-precipitation and characterized by TEM,FT-IR,and XRD.The adsorbent has a positive charge on the surface under acidic conditions,and an electrostatic interaction occurs with the target analytes.The extraction and elution were achieved by changing the pH of the solution.Factors affecting extraction recovery such as pH of sample solution,extraction time,and eluent type were optimized.Under the optimal conditions,the method had good linearity in the range of 0.005¹.0μg/mL with the coefficient of determination over than 0.99.The recoveries of the synthetic pigments ranged from 91.0%to 123.9%with relative standard deviations（n=6）less than 3.6%.The limit of detection was 0.033⁰.057 ng/mL.Finally,it was successfully applied to the determination of synthetic pigments in eleven kinds of beverage samples,four of which were contained in samples.Chapter three:Fe₃O₄@PDA@PA magnetic nanocomposites were prepared and used as adsorbents for magnetic solid phase extraction,and five anthraquinones in oral liquid were measured in combination with HPLC-UV.First,Fe₃O₄ magnetic microspheres were prepared by solvothermal method.Then dopamine（DA）formed a polydopamine（PDA）layer through self-polymerization,and finally phytic acid（PA）was coated on the surface of the PDA layer.Nanocomposites have a large specific surface area,and the target is adsorbed on the surface by hydrophobic interaction andπ-πinteraction.The materials were characterized by TEM,FT-IR,and XRD.In the study,factors affecting the extraction recovery,such as the type of adsorbent,ionic strength,extraction time,eluent type were optimized.Under the optimal conditions,the established method had a wide linear range of 0.025².0μg/mL with the coefficient of determination over than 0.99.The spiked recovery was between 70.0¹08.7%,and the RSD（n=6）was less than 8.6%.The limit of detection（LOD）was in the range of4.5⁷.0 ng/mL.The method successfully detected the content of anthraquinones in five oral solutions.Chapter four:β-cyclodextrin（β-CD）modified Fe₃O₄@CS nanoparticles were prepared in this experiment,and the content of anthraquinones in slimming tea was determined by HPLC-UV.Fe₃O₄@CS nanoparticles were synthesized in one step by hydrothermal method,and then Fe₃O₄@CS nanoparticles were modified withβ-CD.TEM,FT-IR,XRD and other means were used to characterize the materials.The effects of the amount of materials,ionic strength,sample solution pH,and elution conditions on the recovery were investigated in the experiment.Under the optimal conditions,the linear range of the method is 0.01².0μg/mL,and R² is greater than 0.99.The recoveries of the four anthraquinones ranged from 74.0%to107.3%with relative standard deviations（n=5）less than 9.9%.In the end,the method was successfully used for the analysis of anthraquinones in seven slimming tea samples.更多还原