小型化电泳-电化学检测灵敏度改进方法研究
发布时间：2018-07-25 18:17
【摘要】：第一章绪论毛细管电泳以其分离效能高、样品用量少等优点,成为继液相色谱技术后应用最广泛的新型分离分析技术之一,在生物分析、食品分析、药物分析等领域得到日益广泛的应用。本章主要介绍了毛细管电泳的原理和装置、样品衍生技术的原理及其应用以及碳纳米材料在毛细管电泳中的研究进展。本论文基于前人研究基础,采用小型化电泳分析系统,深入探讨了提高安培检测灵敏度的改进方法:一方面,基于电化学衍生机理,利用强电活性的2-硫代巴比妥酸与弱电活性的N-乙酰神经氨酸进行衍生反应,并辅以移动化学反应界面在线富集技术,实现了唾液中N-乙酰神经氨酸的电化学检测;另一方面,从电极改进的角度出发,通过制备石墨烯-金纳米复合电极,实现了小分子胺类化合物的电化学灵敏检测。第二章基于移动化学反应界面在线富集/小型化毛细管电泳-安培检测法测定唾液中N-乙酰神经氨酸的方法研究唾液酸作为多种疾病的广普性标志物,它的分析对临床研究具有重要意义,其中N-乙酰神经氨酸(NANA)是人体中唾液酸的主要存在形式。在本研究工作中,基于电化学衍生机理,采用小型化毛细管电泳-安培检测联用系统(mini-CE-AD)实现了 NANA的测定。NANA首先在酸性条件下被高碘酸氧化,然后氧化产物β-甲酰丙酮酸与具有电活性的2-硫代巴比妥酸(TBA)发生衍生反应,生成带有电活性的NANA-TBA加合物,经NaOH溶液稀释后,可由mini-CE-AD直接进样检测。基于移动化学反应边界在线富集方法,NANA-TBA的检测限可达到0.50μg/mL(1.6 μ,S/N=3)。该方法已成功用于人体唾液中NANA含量的检测,回收率在91.8-109%范围,相对标准偏差1.8-3.9%。由于其设计制作简单、成本低、便携等特点,该装置作为传统和微芯片CE的有益补充将在更多领域发挥实用性价值。第三章基于小型化毛细管电泳-石墨烯/金纳米复合电极安培检测法测定胺类化合物的方法研究本研究工作通过原位化学反应,以柠檬酸钠为还原剂制备石墨烯-金纳米复合材料,并通过将该材料与液态石蜡混合后填入熔融石英毛细管的一端,制备成复合电极,实现了胺类化合物的灵敏检测。石墨烯-金纳米复合材料的形貌和结构通过扫描电子显微镜、X射线衍射和傅里叶变换红外光谱进行表征,结果表明,本方法成功将平均粒径12.8 nm的金纳米颗粒复合在石墨烯上,并与之形成相互关联的网状结构。石墨烯-金纳米复合电极结合mini-CE-AD联用系统,尝试用于2种生物胺的分离检测,进一步验证了其分析性能。石墨烯-金纳米复合电极依靠其灵敏度高、稳定性好、表面可再生等优势,有望应用于更多的领域。
[Abstract]:The first chapter introduces that capillary electrophoresis (CE) has become one of the most widely used separation and analysis techniques after liquid chromatography because of its high separation efficiency and low sample consumption. It is used in biological analysis, food analysis, and so on. Drug analysis and other fields are increasingly widely used. In this chapter, the principle and apparatus of capillary electrophoresis, the principle and application of sample derivation and the research progress of carbon nano-materials in capillary electrophoresis are introduced. On the basis of previous studies, the improved method to improve the sensitivity of amperometric detection was discussed by using a miniaturized electrophoretic analysis system. On the one hand, the mechanism of electrochemical derivation was used to improve the sensitivity of amperometric detection. The electrochemical detection of N-acetylneuraminic acid in saliva was achieved by derivatization reaction of strongly active 2-thiobarbituric acid and weakly active N-acetyl neuraminic acid, and on-line enrichment of moving chemical reaction interface, on the other hand, the electrochemical detection of N-acetylneuraminic acid in saliva was achieved. From the point of view of electrode improvement, electrochemical sensitive detection of small molecular amines was realized by preparing graphene gold nanocomposite electrode. The second chapter studies sialic acid as a common marker of many diseases based on the mobile chemical reaction interface on-line enrichment / miniaturization capillary electrophoresis-amperometric method for the determination of N-acetyl neuraminic acid in saliva. N- acetyl neuraminic acid (NANA) is the main form of sialic acid in human body. In this work, based on the mechanism of electrochemical derivation, a miniaturized capillary electrophoresis / amperometric detection system (mini-CE-AD) was used to realize the determination of NANA. NANA was first oxidized by periodate under acidic conditions. Then the oxidation product 尾 -formylpyruvate reacted with 2-thiobarbituric acid (TBA), an electroactive 2-thiobarbituric acid (2-thiobarbituric acid), to form an electroactive NANA-TBA adduct, which was diluted by NaOH solution and detected by mini-CE-AD directly. The detection limit of NANA-TBA based on moving chemical reaction boundary method can reach 0.50 渭 g/mL (1.6 渭 s / n ~ (3). The method has been successfully applied to the determination of NANA in human saliva. The recovery is in the range of 91.8-109%, and the relative standard deviation is 1.8-3.9%. Because of its simple design, low cost and portability, the device will play a practical role in more fields as a useful supplement to the traditional and microchip CE. In chapter 3, amperometric determination of amines based on miniaturized capillary electrophoresis and graphene / gold nanocomposite electrode was studied by in situ chemical reaction. The graphene gold nanocomposites were prepared with sodium citrate as reducing agent. The composite electrode was prepared by mixing the material with liquid paraffin and filling one end of the fused quartz capillary to achieve the sensitive detection of amines. The morphology and structure of graphene gold nanocomposites were characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The results showed that the gold nanoparticles with average diameter of 12.8 nm were successfully synthesized on graphene by this method. And form a network structure that is related to it. The graphene gold nanocomposite electrode combined with mini-CE-AD system was applied to the separation and detection of two biogenic amines and its analytical properties were further verified. Graphene-gold nanocomposite electrode is expected to be used in many fields due to its high sensitivity, good stability, surface regeneration and other advantages.
【学位授予单位】：华东师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O658.9;O657.1
，
本文编号：2144639
[Abstract]:The first chapter introduces that capillary electrophoresis (CE) has become one of the most widely used separation and analysis techniques after liquid chromatography because of its high separation efficiency and low sample consumption. It is used in biological analysis, food analysis, and so on. Drug analysis and other fields are increasingly widely used. In this chapter, the principle and apparatus of capillary electrophoresis, the principle and application of sample derivation and the research progress of carbon nano-materials in capillary electrophoresis are introduced. On the basis of previous studies, the improved method to improve the sensitivity of amperometric detection was discussed by using a miniaturized electrophoretic analysis system. On the one hand, the mechanism of electrochemical derivation was used to improve the sensitivity of amperometric detection. The electrochemical detection of N-acetylneuraminic acid in saliva was achieved by derivatization reaction of strongly active 2-thiobarbituric acid and weakly active N-acetyl neuraminic acid, and on-line enrichment of moving chemical reaction interface, on the other hand, the electrochemical detection of N-acetylneuraminic acid in saliva was achieved. From the point of view of electrode improvement, electrochemical sensitive detection of small molecular amines was realized by preparing graphene gold nanocomposite electrode. The second chapter studies sialic acid as a common marker of many diseases based on the mobile chemical reaction interface on-line enrichment / miniaturization capillary electrophoresis-amperometric method for the determination of N-acetyl neuraminic acid in saliva. N- acetyl neuraminic acid (NANA) is the main form of sialic acid in human body. In this work, based on the mechanism of electrochemical derivation, a miniaturized capillary electrophoresis / amperometric detection system (mini-CE-AD) was used to realize the determination of NANA. NANA was first oxidized by periodate under acidic conditions. Then the oxidation product 尾 -formylpyruvate reacted with 2-thiobarbituric acid (TBA), an electroactive 2-thiobarbituric acid (2-thiobarbituric acid), to form an electroactive NANA-TBA adduct, which was diluted by NaOH solution and detected by mini-CE-AD directly. The detection limit of NANA-TBA based on moving chemical reaction boundary method can reach 0.50 渭 g/mL (1.6 渭 s / n ~ (3). The method has been successfully applied to the determination of NANA in human saliva. The recovery is in the range of 91.8-109%, and the relative standard deviation is 1.8-3.9%. Because of its simple design, low cost and portability, the device will play a practical role in more fields as a useful supplement to the traditional and microchip CE. In chapter 3, amperometric determination of amines based on miniaturized capillary electrophoresis and graphene / gold nanocomposite electrode was studied by in situ chemical reaction. The graphene gold nanocomposites were prepared with sodium citrate as reducing agent. The composite electrode was prepared by mixing the material with liquid paraffin and filling one end of the fused quartz capillary to achieve the sensitive detection of amines. The morphology and structure of graphene gold nanocomposites were characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The results showed that the gold nanoparticles with average diameter of 12.8 nm were successfully synthesized on graphene by this method. And form a network structure that is related to it. The graphene gold nanocomposite electrode combined with mini-CE-AD system was applied to the separation and detection of two biogenic amines and its analytical properties were further verified. Graphene-gold nanocomposite electrode is expected to be used in many fields due to its high sensitivity, good stability, surface regeneration and other advantages.
【学位授予单位】：华东师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O658.9;O657.1
，
本文编号：2144639
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