發(fā)布時(shí)間：2018-07-25 18:17

【摘要】：第一章緒論毛細(xì)管電泳以其分離效能高、樣品用量少等優(yōu)點(diǎn),成為繼液相色譜技術(shù)后應(yīng)用最廣泛的新型分離分析技術(shù)之一,在生物分析、食品分析、藥物分析等領(lǐng)域得到日益廣泛的應(yīng)用。本章主要介紹了毛細(xì)管電泳的原理和裝置、樣品衍生技術(shù)的原理及其應(yīng)用以及碳納米材料在毛細(xì)管電泳中的研究進(jìn)展。本論文基于前人研究基礎(chǔ),采用小型化電泳分析系統(tǒng),深入探討了提高安培檢測靈敏度的改進(jìn)方法:一方面,基于電化學(xué)衍生機(jī)理,利用強(qiáng)電活性的2-硫代巴比妥酸與弱電活性的N-乙酰神經(jīng)氨酸進(jìn)行衍生反應(yīng),并輔以移動(dòng)化學(xué)反應(yīng)界面在線富集技術(shù),實(shí)現(xiàn)了唾液中N-乙酰神經(jīng)氨酸的電化學(xué)檢測;另一方面,從電極改進(jìn)的角度出發(fā),通過制備石墨烯-金納米復(fù)合電極,實(shí)現(xiàn)了小分子胺類化合物的電化學(xué)靈敏檢測。第二章基于移動(dòng)化學(xué)反應(yīng)界面在線富集/小型化毛細(xì)管電泳-安培檢測法測定唾液中N-乙酰神經(jīng)氨酸的方法研究唾液酸作為多種疾病的廣普性標(biāo)志物,它的分析對臨床研究具有重要意義,其中N-乙酰神經(jīng)氨酸(NANA)是人體中唾液酸的主要存在形式。在本研究工作中,基于電化學(xué)衍生機(jī)理,采用小型化毛細(xì)管電泳-安培檢測聯(lián)用系統(tǒng)(mini-CE-AD)實(shí)現(xiàn)了 NANA的測定。NANA首先在酸性條件下被高碘酸氧化,然后氧化產(chǎn)物β-甲酰丙酮酸與具有電活性的2-硫代巴比妥酸(TBA)發(fā)生衍生反應(yīng),生成帶有電活性的NANA-TBA加合物,經(jīng)NaOH溶液稀釋后,可由mini-CE-AD直接進(jìn)樣檢測�；谝苿�(dòng)化學(xué)反應(yīng)邊界在線富集方法,NANA-TBA的檢測限可達(dá)到0.50μg/mL(1.6 μ,S/N=3)。該方法已成功用于人體唾液中NANA含量的檢測,回收率在91.8-109%范圍,相對標(biāo)準(zhǔn)偏差1.8-3.9%。由于其設(shè)計(jì)制作簡單、成本低、便攜等特點(diǎn),該裝置作為傳統(tǒng)和微芯片CE的有益補(bǔ)充將在更多領(lǐng)域發(fā)揮實(shí)用性價(jià)值。第三章基于小型化毛細(xì)管電泳-石墨烯/金納米復(fù)合電極安培檢測法測定胺類化合物的方法研究本研究工作通過原位化學(xué)反應(yīng),以檸檬酸鈉為還原劑制備石墨烯-金納米復(fù)合材料,并通過將該材料與液態(tài)石蠟混合后填入熔融石英毛細(xì)管的一端,制備成復(fù)合電極,實(shí)現(xiàn)了胺類化合物的靈敏檢測。石墨烯-金納米復(fù)合材料的形貌和結(jié)構(gòu)通過掃描電子顯微鏡、X射線衍射和傅里葉變換紅外光譜進(jìn)行表征,結(jié)果表明,本方法成功將平均粒徑12.8 nm的金納米顆粒復(fù)合在石墨烯上,并與之形成相互關(guān)聯(lián)的網(wǎng)狀結(jié)構(gòu)。石墨烯-金納米復(fù)合電極結(jié)合mini-CE-AD聯(lián)用系統(tǒng),嘗試用于2種生物胺的分離檢測,進(jìn)一步驗(yàn)證了其分析性能。石墨烯-金納米復(fù)合電極依靠其靈敏度高、穩(wěn)定性好、表面可再生等優(yōu)勢,有望應(yīng)用于更多的領(lǐng)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.
【學(xué)位授予單位】：華東師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O658.9;O657.1
，

本文編號(hào)：2144639