银纳米材料的制备及其在电化学传感器中的应用研究

发布时间：2018-06-29 23:11

本文选题：电化学传感器 + 银纳米材料　；参考：《浙江大学》2015年硕士论文

【摘要】：电化学生物传感器具有准确、快速、简便、灵敏等特点,在食品检测、药物分析及临床应用等相关领域具有重要应用前景。随着纳米材料的飞速发展,纳米材料在生物传感器中的应用已成为研究的热点,而具有优良导电能力的银纳米材料更是受到越来越广泛的关注。本论文主要围绕几类银纳米材料的制备,研究考察了所构筑电极在葡萄糖、手性氨基酸、过氧化氢等检测分析中的应用。 1.制备不同形貌的纳米材料：金-银纳米管、银纳米方块、银纳米颗粒、氧化铜纳米线。金-银纳米管、银纳米方块、银纳米颗粒均采用多元醇还原法得到,形貌均一且其直径均在100nm左右。氧化铜纳米线通过湿化学法制备,制备简单、形貌均一且直径为100nm.。通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X-射线粉末衍射(XRD)表征了纳米材料的形貌结构。 2.构筑了基于银纳米方块的辣根过氧化物酶／葡萄糖氧化酶的葡萄糖双酶传感器,采用原子力显微镜和循环伏安法表征了电极的构筑过程,循环伏安法表征验证了双酶体系修饰电极对葡萄糖的检测机理,银纳米方块和HRP起到了双重放大信号的作用。在优化条件下,采用安培计时电流法在-0.2V的工作电位下测定葡萄糖,线性范围为10μmol L-1～1.5mmol L-1,检测限为0.698μmol L-1,且具有较高的灵敏性和良好的稳定性,可用于血清样品中葡萄糖的检测。 3.构筑了基于银纳米线的电化学手性传感器,实现了对苯丙氨酸的手性识别。透射电子显微镜表征了β-CD-S-AgNWs的形貌,差分脉冲伏安法表征验证了复合纳米材料β-CD-S-AgNWs修饰电极对L-苯丙氨酸的检测机理。通过优化银纳米线与p-CD的质量比、反应时间等条件,构筑电极可实现对L-苯丙氨酸的分析测定,其线性范围为0.5-12mmolL-1,检测限为0.024μmol L-1。 4.将制备的银纳米材料、银合金纳米材料及其他金属纳米材料与壳聚糖混合,构筑纳米材料-壳聚糖复合膜修饰的H202无酶传感器,并初步探索了不同形貌纳米材料的电催化活性和导电性的差异。通过循环伏安法表征了修饰电极的电化学特性,考察了工作电位、检测体系pH值及纳米材料滴涂量对修饰电极灵敏度的影响。在优化条件下,以上构筑电极可以对过氧化氢进行快速、灵敏的检测。其中,基于Au-AgNTs-CS修饰电极对H202的检测范围为0.008～1.3mmol L-1,检测限为3.18μmol L-1;基于AgNPs-CS修饰电极对H202的检测范围为0.008～1.75mmol L-1,检测限为0.066μmol L-1;基于CuONWs-CS修饰电极对H202的检测范围为0.008～0.654mmol L-1,检测限为7.42μmol L-1。根据上述检测结果可以得出：银纳米材料较银合金及氧化铜纳米材料导电能力更强；同种银纳米材料相比,颗粒越小,导电能力越强,检测限越低,检测范围越宽。
[Abstract]:Electrochemical biosensor has the characteristics of accuracy, rapidity, simplicity and sensitivity. It has important application prospect in food detection, drug analysis and clinical application. With the rapid development of nanomaterials, the application of nanomaterials in biosensors has become a hot topic, and silver nanomaterials with excellent conductivity have been paid more and more attention. In this paper, the preparation of several kinds of silver nanomaterials was studied and the application of the electrodes in the detection and analysis of glucose, chiral amino acids and hydrogen peroxide was investigated. 1. Gold-silver nanotubes, silver nanometers, silver nanoparticles, copper oxide nanowires were prepared. Au-Ag nanotubes, silver nanometers and silver nanoparticles were obtained by polyol reduction method with uniform morphology and diameter of 100nm. Copper oxide nanowires were prepared by wet chemical method. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray powder diffraction (XRD) were used to characterize the morphology and structure of the nanocrystalline materials. A glucose double enzyme sensor of horseradish peroxidase / glucose oxidase based on silver nanobox was constructed. Atomic force microscopy (AFM) and cyclic voltammetry (CV) were used to characterize the process of electrode construction. Cyclic voltammetry confirmed the mechanism of glucose detection at the electrode modified by double enzyme system. Silver nanometers and HRP played a double amplification role. Under the optimized conditions, the ammeter time current method was used for the determination of glucose at a working potential of -0.2 V. The linear range was 10 渭 mol / L ~ (-1) and the detection limit was 0.698 渭 mol / L ~ (-1). The method had high sensitivity and good stability, and the linear range was 10 渭 mol / L ~ (-1) and the detection limit was 0.698 渭 mol / L ~ (-1). It can be used for the determination of glucose in serum samples. An electrochemical chiral sensor based on silver nanowires was constructed to realize chiral recognition of phenylalanine. The morphology of 尾 -CD-S-AgNWs was characterized by transmission electron microscope (TEM), and the detection mechanism of L- phenylalanine by 尾 -CD-S-AgNWs modified electrode was verified by differential pulse voltammetry. By optimizing the mass ratio of silver nanowires to p-CD and reaction time, the determination of L- phenylalanine can be achieved by using the constructed electrode. The linear range is 0.5-12 mmol / L ~ (-1) and the detection limit is 0.024 渭 mol / L ~ (1.4). The prepared silver nanomaterials, silver alloy nanomaterials and other metal nanomaterials were mixed with chitosan to construct an enzymatic sensor modified by nano-materials and chitosan composite films. The difference of electrocatalytic activity and conductivity of nano-materials with different morphologies was preliminarily explored. The electrochemical characteristics of the modified electrode were characterized by cyclic voltammetry. The effects of working potential, pH value of the system and the amount of nano-material on the sensitivity of the modified electrode were investigated. Under the optimized conditions, the above constructed electrodes can be used for rapid and sensitive detection of hydrogen peroxide. Of which, The detection range of H202 based on Au-AgNTs-CS modified electrode is 0.008~1.3mmol L-1, the detection limit is 3.18 渭 mol L-1, the detection limit of H202 based on AgNPs-CS modified electrode is 0.008~1.75mmol L-1, the detection limit is 0.066 渭 mol L-1, and the detection limit of H202 based on CuONWs-CS modified electrode is 0.008~0.654mmol L-1 with detection limit of 7.42 渭 mol L-1. According to the above results, it can be concluded that silver nanomaterials have stronger conductivity than silver alloys and copper oxide nanomaterials, and the smaller the particles, the stronger the conductivity, the lower the detection limit and the wider the detection range.
【学位授予单位】：浙江大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TP212.2;TB383.1

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