基于纳米材料的固相萃取与高效液相色谱联用检测痕量有机物

发布时间：2018-01-12 03:12

本文关键词：基于纳米材料的固相萃取与高效液相色谱联用检测痕量有机物　出处：《辽宁大学》2016年硕士论文　论文类型：学位论文

【摘要】：近年来,纳米材料由于具有比表面积大,吸附能力强,吸附快速等优点而受到广泛关注。本硕士论文采用磁性多壁碳纳米管,纳米氧化铝,中空多孔碳球三种纳米材料作为固相萃取剂,结合高效液相色谱(HPLC)分别检测富马酸替诺福韦酯,两种色素添加剂(柠檬黄和日落黄)以及九种双酚类物质。本论文基本研究工作如下：1、成功合成了磁性可分离的铁氧镍/多壁碳纳米管(NiFe2O4/MWCNTs)复合材料做固相萃取剂,通过扫描电镜(SEM),傅里叶变换红外光谱(FT-IR),N2吸附/脱附等温线和振动样品磁强计(VSM)等技术对其进行了一系列表征。吸附动力学和吸附热力学研究表明所合成的NiFe2O4/MWCNTs对富马酸替诺福韦酯(TDF)展示了较高吸附容量和快速的吸附能力,吸附率可达到95%以上。在洗脱实验中,本文采用了C8离子液体([C8mim][PF6])作为洗脱液,洗脱率达92%,避免了使用对环境有害有毒的有机溶剂。本方法在最优条件下,得到了好的线性范围(4.0-400.0 ng mL-1),低的检测限(LOD,0.67 ng mL-1)和定量限(LOQ,2.2 ng mL-1)以及良好的精密度(RSD of6.7%, n= 5),本方法被成功应用于实际样中TDF的检测,加标回收率在91.4%到99.6%之间,证明本方法在实际应用中有具有较好的竞争力。2、发展了nano-Al2O3/滤膜微固相萃取(nano-Al2O3/Filter membrane-μ-SPE)技术,结合HPLC分析方法,同时检测食品中色素添加剂-柠檬黄(TA)和日落黄(SY)。预先将nano-Al2O3负载在滤膜上,构筑新型Filter membrane-μ-SPE的装置,富集两种色素,本方法集分离与浓缩于一步完成,吸附在滤膜上的色素很容易被定量沈脱,直接进入HPLC检测。优化一系列试验参数,包括萃取剂的种类,nano-Al2O3在滤膜上的负载量,溶液pH值,离子强度以及洗脱条件。在最优条件下,本方法具有好的线性范围1.0-200.0 ng mL-1,相关系数r2均大于0.9982,检测限在0.10-0.20 ngmL-1之『白J,平均回收率在86.9%-124.0%范围内。采用本方法应用于不同的食品样品中TA和SY的检测,结果表明,nano-Al2O3/ Filter membrane-μ-SPE法,操作简单方便,富集-洗脱一步完成。无需额外的样品处理过程,该方法同时检测实际样中痕量的TA和SY取得满意的测试结果。3、采用拓展的一步Stober方法合成了核壳结构的中空多孔碳小球。以Si02为核体,使间苯二酚和甲醛围绕SiO2核表面发生聚合反应,形成以SiO2为中心核体酚醛树脂聚合物为外壳体的复合材料,经过碳化和去除模板后,合成中空多孔碳球(HPCSs). HPCSs的结构通过SEM,TEM和N2吸附/脱附等温线进行表征。结果表明：通过可控合成反应,成功地制备出比表面积大、粒径均一中空多孔结构的碳微球。HPCSs对9种双酚类物质(BPs)展现了较高萃取效能和吸附容量。以HPCSs作为固相萃取剂结合HPLC法建立了同时检测自来水、环境水以及软饮料中的九种BPs的新方法。优化富集/洗脱条件及色谱检测参数,通过加标回收方法验证该方法的可行性,取得满意实验结果。在最优条件下,方法加标回收率在83.5%-129.9%之间,相对标准偏差小于5.6%,定量限在0.183-2.351 ngmL-1之间。
[Abstract]:In recent years, nanomaterials have large surface area, strong adsorption capacity, fast adsorption has attracted widespread attention. This dissertation adopts magnetic multi walled carbon nanotubes, nano alumina, porous hollow carbon spheres of three kinds of nano materials as solid-phase extractant, combined with high performance liquid chromatography (HPLC) were used to detect the fumaric acid tenofovir ester, two kinds of pigment additives (tartrazine and sunset yellow) and nine kinds of bisphenol. In this paper the basic research work is as follows: 1. The synthesis of nickel ferrite magnetic separation / multi walled carbon nanotubes (NiFe2O4/MWCNTs) composite solid phase extraction agent, by scanning electron microscopy (SEM), Fourier transform infrared the spectrum (FT-IR), N2 adsorption / desorption isotherms and vibrating sample magnetometer (VSM) techniques were characterized. The adsorption kinetics and adsorption thermodynamics study indicated that the synthesis of NiFe2O4/MWCNTs of fumaric acid Tenofovir (TDF) showed high adsorption capacity and fast adsorption capacity, adsorption rate can reach more than 95%. In the elution experiment, this paper uses C8 ionic liquids ([C8mim][PF6]) as the eluent, elution rate of 92%, to avoid the use of toxic organic solvents harmful to the environment. This method under optimal conditions the linear range, good (4.0-400.0 ng mL-1), low detection limit (LOD, 0.67 ng mL-1) and the limit of quantitation (LOQ, 2.2 ng mL-1) and good precision (RSD of6.7%, n= 5), this method has been successfully applied to the detection of actual sample in TDF, the recovery was 91.4% 99.6% standard addition, proved that this method has good.2 competence in the practical application, the development of the nano-Al2O3/ membrane solid phase microextraction (nano-Al2O3/Filter membrane- -SPE) technology, with HPLC analysis method, and the detection of food additives - lemon yellow pigment (TA) and sunset yellow (S Y). Pre nano-Al2O3 load in the membrane, the construction of the new Filter membrane- device -SPE, enrichment of two kinds of pigment, this method in separation and concentration in one step, adsorption in the membrane of pigment is easy to be quantitative Shen off, directly into the HPLC test. A series of optimizing test parameters, including the type of extractant the amount of nano-Al2O3 in the membrane, the solution pH value, ionic strength and elution conditions. Under the optimum conditions, the method has a good linear range of 1.0-200.0 ng mL-1, the correlation coefficient of R2 was greater than 0.9982, the detection limit of J 0.10-0.20 ngmL-1 in white ", the average rate of recovery in the range of 86.9%-124.0%. The results show that the detection by this method, applied to TA and SY in different food samples, nano-Al2O3/ Filter membrane- -SPE method, simple and convenient operation, enriched elution step. No need to sample additional processing, and the detection method In the actual trace TA and SY to obtain satisfactory test results of.3 hollow carbon spheres with core-shell structure was synthesized by one-step Stober method development. With Si02 as the core, polymerization of resorcinol and formaldehyde on SiO2 nuclear surface, forming composite material of SiO2 center core phenolic resin polymer as shell the body, after carbonization and template removal, synthesis of hollow porous carbon spheres (HPCSs). The structure of HPCSs by SEM, TEM and N2 adsorption / desorption isotherms were characterized. The results show that the controllable synthesis reaction, successfully prepared a large specific surface area, uniform particle size of hollow porous carbon microspheres.HPCSs 9 kinds of bisphenol (BPs) show a higher extraction efficiency and adsorption capacity. Tap water was developed for the determination of HPCSs as solid phase extraction with HPLC method, a new method of nine kinds of BPs in environmental water and soft drinks in the optimization. The enrichment / elution conditions and chromatographic detection parameters were verified by the standard recovery method. Satisfactory results were obtained. Under the optimal conditions, the recovery rate of the method was between 83.5%-129.9%, the relative standard deviation was less than 5.6%, and the quantitation limit was between 0.183-2.351 ngmL-1.

【学位授予单位】：辽宁大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O657.72;O658.2

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