【作者】 王爽；

【导师】 杨国程；

【作者基本信息】 长春工业大学 ， 分析化学， 2015， 硕士

【摘要】 化学修饰电极(Chemically modified electrode,CME)是电化学和电分析化学的前沿领域之一。它的应用非常广泛,主要分布在环境分析、食品分析、生物分析和药物分析中。本文进一步探究CME在电分析化学中的应用价值,对分子单层膜修饰电极传感生物小分子的性能进行比较。本论文共分为五章,第一章为绪论部分,主要针对化学修饰电极的起源,发展现状,应用以及研究意义进行阐述；第二章中采用原位电化学还原法和电化学氧化法制备修饰电极,其中4-羧基苯基、4-磺酸基苯基、4-脲嘧啶基、4-安替比林基、4-吡啶基利用原位电化学还原法共价修饰到玻碳电极(Glassy carbon electrode, GCE)上,联毗啶和邻菲罗啉则利用电化学氧化法实现了电极表面的修饰,各种表征说明CMEs较裸电极优越,重用性好,其中联吡啶、邻菲罗啉、4-脲嘧啶基和4-吡啶基修饰的GCE电极检测性能比较好；第三章通过高压静电纺丝将聚乙烯醇(Polyvinyl alcohol, PVA)、PVA和醋酸钴的混合物分别纺丝到掺氟的氧化锡玻璃片(FTO)上,然后经过高温煅烧形成的纳米级的金属氧化物/碳纤维电极对抗坏血酸(Ascorbic acid, AA)进行检测,实验表明碳纤维/金属氧化物复合电极传感AA时的电化学信号有所增强；第四章继续对第三章中出现的信号增强进行研究,利用静电纺丝将聚乙烯吡咯烷酮(Polyvinyl pyrrolidone,PVP),PVP/醋酸钴以及PVP/柠檬酸铁铵分别纺到FTO电极上,结果表明高温煅烧后的产物对多巴胺(Dopamine, DA)有双信号电化学响应,这表明此复合电极检测DA时不仅实现了信号增强还出现了协同效应；第五章通过在氮掺杂的类金刚石碳膜(nitrogen-doped diamond like carbon,N:DLC)电极上交替修饰铂纳米粒子(Platinum nanoparticals, PtNPs)和对氨基苯甲酸(4-Aminobenzioc acid,4-ABA)来检测硫酸肼(hydrazine sulfate),以此来研究结构与传感性能之间的关系,结果表明传感硫酸肼的性能可以通过改变电极结构来提升。研究结果表明单纯的共价化学修饰电极在同时传感生物小分子时存在一定的局限性；我们可以通过在纳米纤维中掺杂金属实现对目标分子的协同检测；交替修饰也可以提高电极的检测性能。更多还原

【Abstract】 Chemically modified electrode (CME) is one of the most active research areas in the field of the electroanalytical and electrocatalytical chemistry. It is very widely applied in food, environmental, biological and pharmaceutical analysis. This thesis aims at further application of CMEs in electroanalytical area, monolayer modified electrodes were prepared and used to detect small biological molecule.This thesis is divided into five chapters. The origin, development, application and significance of the CMEs were reviewed in chapter one; In chapter two, in-situ electrochemical reduction method and electrochemical oxidation method were applied for the design of the electrode surface. Among them, the 4-carboxyphenyl,4-sulfophenyl, 4-2,6-dihydroxypyrimidyl, antipyryl,4-pyridyl was covalently successfully modified on GCE via in-situ electrochemical reduction method, meanwhile, the midification of the pyridyl and phenanthrolyl on GCE was achieved by electrochemical oxidation method. The various characterization results showed that the CMEs were superior to the original bulk electrode due its advantage of predominant reusability, wherein pyridyl, phenanthrolyl, 4-2,6-dihydroxypyrimidyl and 4-pyridyl-modified GCE have better performance comparatively. In chapter three, electrospun cobalt acetate and polyvinyl alcohol (PVA) nanofibers were collected on a FTO electrode and then calcined at a high temperature of 600℃. Then the product of metallic oxide nanoparticles and carbon fiber were used to sense ascorbic acid (AA), experimental results showed that metallic oxide and carbon fiber produced enhanced electrochemical signal toward detecting AA. The chapter four further investigate the enhanced effect mentioned in chapter three. In chapter four, electrospun polyvinyl pyrrolidone (PVP), PVP and cobalt acetate, PVP and ammonium ferric citrate on FTO, respectively. The consequence declared that the electrode annealed at high temperature owned a double-singal electrochemical response toward sensing dopamine (DA), the results manifested that the composite modified electrode not only realized enhanced electrochemical signal for sensing DA, but also produced synergy effect. In the last chapter, platinum nanoparticles (PtNPs) and 4-aminobenzioc acid (4-ABA) were applied to alternately modify nitrogen-doped diamond like carbon (N:DLC) film electrode toward sensing hydrazine sulfate to study the relationship between interface structure and electrochemical sensing properties. Results manifested that the optimization of sensing hydrazine sulfate can realize via the modification of the electrodes structure.This study results show that the covalent CME have a limitation in sensing biological small molecules simultaneously; we can use nanofibers mixed with metal to achieve collaborative detection of target molecules;alternate modification also can improve the detection performance of the electrode.更多还原