可调式溶剂分散液一液微萃取在快速检测和分离技术中的应用研究

发布时间：2018-04-09 17:51

本文选题：可调式溶剂分散液—液微萃取　切入点：福美双　出处：《河北大学》2017年硕士论文

【摘要】：分散液—液微萃取技术以优异的绿色化学指标和数百倍的富集倍数等优良性能而备受青睐。它是由萃取剂、分散剂和水溶液组成的三元萃取体系。本文将从萃取剂的视角对分散液—液微萃取技术进行新的诠释,建立了以可调式溶剂为萃取剂的分散液—液微萃取技术的新型预处理结合快速测定和分离技术用于水样、尿样以及油样品中有害物质的检测。本文共分为4章,具体内容如下:第1章:简述分散液—液微萃取的概念、分散液—液微萃取中萃取剂的分类以及本文的研究目的、内容及意义。第2章:本实验首次将一种可调式溶剂分散液—液微萃方法与智能手机三原色法联用测定水样中的福美双。显色反应为福美双在碱性条件下与Cu~(2+)络合生成黄色的疏水性螯合物。间氯苯胺作为碱性萃取剂,可溶于酸,之后通过加入碱调节溶液的pH值使疏水性的有色分析物萃取到不溶于碱溶液的有机相,整个过程不需要分散剂,几秒内便可完成萃取。智能手机测定过程是在一个可折叠的自制暗箱内完成,操作简便,经济快速。在最佳条件下福美双的浓度在0.08μg/mL-1.5μg/mL范围内有很好的线性关系,检出限(LOD,S/N=3)为0.023μg/mL。该方法已应用于实际水样分析,加标回收率在80%-119%之间。该方法成本低廉、测量方便,为野外水体中福美双的现场测定提供了可能性。第3章:为了探究可调式溶剂分散液—液微萃取与毛细管电泳技术联用的适用性,本文提出了以酸碱反应为基础的分散液—液微萃取结合瞬时等速电泳测定尿样中的四种苯胺类化合物。该方法中以碱性溶剂间氯苯胺为萃取剂,将其溶于酸性去离子水中,之后注入碱性样品水溶液中,酸碱反应发生,萃取剂去质子化形成不溶于水的小液滴萃取分析物。离心后,取出萃取剂将其溶于1:1的甲醇/缓冲溶液形成的背景电解质中,此溶液为均相溶液,可直接大体积进毛细管电泳。在最佳的优化条件下,提出的萃取技术得到了较好的分析性能,4种苯胺类的标准曲线分别在0.005μg/mL—1.5μg/mL、0.02μg/mL—8μg/m L、0.02μg/m L—8μg/m L、0.04μg/m L—8μg/m L范围内有良好的线性关系,其相关系数均大于0.999;检出限范围为0.97—3.22 ng/m L;日内精密度RSD%2.16(n=6),日间精密度RSD%2.40(n=4);富集倍数为28-127。本实验很好的解决了疏水性萃取剂与BGE溶液的兼容性问题,成功测定了实际尿样中的苯胺类化合物,为测定ng/m L级别的苯胺类化合物提供了一种非常有潜力的手段。第4章:为了进一步扩展可调式溶剂分散液—液微萃取技术在毛细管电泳大体积直接进样方案的发展,本研究提出了一种新型的“绿色”溶剂低共熔剂(Deep eutectic solvents,DESs)为正相萃取技术,可调式溶剂分散液—液微萃取为反相萃取技术,两步萃取加热过的植物油中的苯胺类化合物。正相萃取阶段,利用氯化胆碱与乙二醇合成的亲水性的DESs从实际油样中萃取极性分析物;反相萃取阶段,利用上述低共熔剂的可溶性,将富含目标分析物的DESs相释放到一定量的碱性去离子水中,再将溶于酸的苯胺类萃取剂打入其中,形成乳浊液,萃取后,将目标分析物萃取到有机相,将有机相取出后溶于背景电解质中,直接进毛细管电泳。在最佳的优化条件下,两步萃取技术得到了较好的分析性能,相关系数R20.999,两种分析物的线性范围分别为0.0025μg/m L—1.0μg/mL和0.01μg/m L—6μg/mL,检出限0.97—3.22 ng/m L和重现性RSD%2.49,n=3。上述提到的萃取技术具有很好的灵敏度和稳定性,为油样中ng/mL级别的极性化合物的测定打开了新思路。
[Abstract]:The dispersion of liquid liquid micro extraction technology with excellent performance and excellent index of green chemistry and the enrichment of hundreds of times. It is favored by the extractant, three element extraction system of dispersant and water solution composition. This paper from the perspective of extractant dispersion - liquid micro extraction technology for the new interpretation a, extraction agent dispersed liquid-liquid microextraction with adjustable solvent for the new pretreatment combined with rapid determination and separation technology for the detection of urine samples, and harmful substances in the oil samples. This paper is divided into 4 chapters, the specific contents are as follows: the first chapter: introduces the concept of dispersion liquid-liquid microextraction the classification, dispersed extractant liquid-liquid microextraction in and the purpose, content and significance. The second chapter: the experiment for the first time a dispersive liquid-liquid micro extraction method and intelligent mobile phone three method combined with the determination of adjustable solvent Thiram. Color reaction for Thiram in alkaline conditions with Cu~ (2+) complex formation of hydrophobic chelate yellow. M-chloroaniline as alkaline extraction agent, acid soluble, after adding alkali by adjusting the pH value of the solution to the analyte extraction colored hydrophobic to alkali insoluble organic solution the phase, the whole process does not need dispersant, a few seconds can be completed. The extraction process is completed by the intelligent mobile phone, in a folding homemade dark box has the advantages of simple operation, rapid economic. Thiram under optimal conditions have a good linear relationship in the range of 0.08 g/mL-1.5 g/mL, the detection limit (LOD 0.023 g/mL., S/N=3) the method has been applied to the actual analysis of water samples, the recoveries were 80%-119%. The method has the advantages of low cost, convenient measurement, provides the possibility for the determination of thiram field water. The third chapter: in order to explore the adjustable solution Dispersant applicability of liquid-liquid microextraction with capillary electrophoresis coupled with the proposed determination of four aniline compounds in urine by acid-base reaction based dispersive liquid-liquid microextraction combined with transient isotachophoresis. Chloroaniline with alkaline solvent between the method for extracting agent, which is soluble in acidic deionized water, after injection of alkaline samples in aqueous solution, acid-base reaction, extraction agent to form small droplets of extraction of protonated water insoluble analyte. After centrifugation, remove the extractant dissolved in methanol / 1:1 buffer solution formed in the background electrolyte, the solution for the homogeneous solution, can be directly large volume injection by capillary electrophoresis. In the optimal condition, the extraction technology was analyzed with good performance, 4 kinds of aniline standard curve respectively in 0.005 g/mL, 1.5 g/mL, 0.02 g/mL, 8 g/m L, 0.02 g/m L 8 g/m L 0.04, g/m L 8 g/m L range has a good linear relationship, the correlation coefficient is greater than 0.999; the detection limit range of 0.97 - 3.22 ng/m L; the within day precision RSD%2.16 (n=6), inter day precision RSD%2.40 (n=4); enrichment factor is 28-127. in this experiment is a good solution to the compatibility the problem with agent BGE solution hydrophobic extraction, successful aniline compounds in urine were determined by the actual, provides a promising method for the determination of aniline compounds ng/m L level. The fourth chapter: in order to further expand the development of adjustable solvent dispersion liquid-liquid microextraction capillary electrophoresis in large volume the sample program, this study proposes a new "green" solvent of low total flux (Deep eutectic solvents, DESs) for normal phase extraction technology, adjustable solvent dispersion liquid-liquid microextraction for reversed phase extraction technology, the two step extraction heating plant Aniline compounds in oil. Positive phase extraction stage, using choline chloride and ethylene glycol synthesis of hydrophilic DESs from the actual oil extraction of polar analytes; reversed phase extraction stage, the low total soluble flux, rich target analyte DESs release to a certain amount of alkaline deionized water. The soluble aniline extraction agent acid into the emulsion formation, after extraction, the target analyte extraction into the organic phase, the organic phase after removing the dissolved in the background electrolyte, directly into the capillary electrophoresis. In the optimal condition, the two step extraction technology has been of good performance, correlation coefficient R20.999, the linear range of two analytes were 0.0025 g/m L 1 g/mL and 0.01 g/m L - 6 g/mL, the detection limit is 0.97 - 3.22 ng/m L and RSD%2.49 n=3. reproducibility, extraction technology mentioned above has good sensitivity And the stability is a new idea for the determination of ng/mL level polar compounds in oil samples.

【学位授予单位】：河北大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O658.2

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