【作者】 宋玲；

【导师】 郑行望；

【作者基本信息】 陕西师范大学 ， 分析化学， 2007， 硕士

【摘要】 本论文由综述和研究报告两部分组成。第一部分为综述，对电化学发光现象的发展历史及其反应类型进行了评述，并着重介绍了鲁米诺电化学发光体系在分析化学领域中的广泛应用。第二部分为研究报告，主要对聚鲁米诺与有机物或无机离子形成复合物膜修饰电极在电化学发光中的应用进行了研究。电化学发光分析（electrogenerated chemiluminescence analysis or electrochemilumiescence，ECL），是指直接利用电化学反应形成激发态发光体或通过电解产物之间、电解产物与体系中某组分之间进行化学反应产生发光体，并依据发光体产生的发光辐射信号实现分析物检测的发光分析方法。它是电化学与化学发光分析方法相结合的产物。这使得它不但具有化学发光分析法的许多优点如灵敏度高、线性范围宽及仪器设备简单等特点，还具有其自身优于化学发光分析法的一些特点，如反应的可控性强、发光区域确定便于信号检测以及许多化学发光活性高但不稳定的物质能现场生成并应用于发光分析之中等。鲁米诺电化学发光现象自二十世纪20年代末期被发现以来，在该现象发现的初期，电化学发光分析方法发展缓慢。到了80年代，鲁米诺电化学发光分析方法的发展非常迅速，进入90年代，电化学发光的仪器装置以及电极材料和光信号的传导材料等都进一步的发展，更加拓宽了鲁米诺电化学发光分析方法的研究领域，促进了鲁米诺电化学发光分析方法的实际应用。目前，国内外电化学发光研究的专家学者已经对鲁米诺电化学发光分析方法给予了足够的关注和青睐，该方法已经深入到环境分析、食品分析、免疫分析和药物分析等众多研究科学领域。近年来，鲁米诺电化学发光体系新分析特性的研究及其应用倍受人们的关注，其中，以聚鲁米诺为发光试剂的电化学发光分析方法尤其受到人们的关注。本论文的研究工作旨在利用聚鲁米诺与有机物或无机离子形成复合物膜修饰电极来优化聚鲁米诺电化学发光分析特性。在本论文的具体工作主要包括：1．基于电聚合和配位效应所构建的聚鲁米诺和金属离子复合物膜修饰电极，可极大的提高、优化聚鲁米诺的电化学发光分析特性。在一定条件下，聚鲁米诺—镍（Ⅱ）复合物膜在碱性条件下的弱电化学发光信号可以强烈的、选择性的被尿素所增敏，在最佳条件下，增敏电化学发光信号与尿素的浓度在2.0×10^-9g／mL～1.0×10^-7g／mL范围内呈线性关系，检出限为2×10^-10g／mL。2．在酸性条件下，鲁米诺与硫酸联苯胺可以通过电聚合的方法固定在石墨电极表面，并且，在碱性条件下，该修饰电极弱的电化学发光信号可以被过氧化氢强烈的增敏。据此，我们建立了一种测定过氧化氢的高灵敏度的电化学发光分析新方法。在最佳条件下，增敏电化学发光信号与过氧化氢的浓度在1.0×10^-7 mol／L～2.0×10^-10mol／L范围内呈线性关系，检出限为6×10^-11mol／L。更多还原

【Abstract】 Two parts are included in this thesis. In the first part of this thesis, thedeveloping history of Electrogenerated Chemiluminescent （ECL） and its type ofreaction are reviewed. In addition to these, the wildly analytical application of luminolECL system in the analytical chemistry are also given in this chapter.ECL is the luminescence generated by relaxation of exited state molecules that areproduced during an electrochemically initiated reaction in the near surface of theworking electrode. ECL is an important and powerful detection method in analyticalchemistry in recent years. So, this method not only retains the advantages over moreconventional CL. ECL analysis, compared with CL analysis, offered more alternativepotentials to regulate the ECL reaction for analytical purpose.Since the luminol-based ECL phenomenon was firstly observed by Harvey in 1929,the ECL was paid much attention by the analysts, and a lot of analytes had beendetected with luminal ECL system. ECL proved to be useful for analytical applicationand increasing investigations resulted in highly sensitive and selective detectionmethods. It has been applied successfully in many fields. Such as life science, clinicalmedicine, environment, immunoassays and DNA probe analysis etc.Recent years, the investigation of new analytical performances and analyticalapplication in luminol-based ECL system has been paid much attention by the analysts.In this thesis, we focused our interesting on the optimizing ECL performance of theluminol system by polyluminol compositing films modified electrode. The works areincluded in the followings:1. The Investigation of the Electrochemiluminescence Performances of theCompositing Films of Polyluminol with Metal Ions and its Analytical ApplicationIn this paper, it was found that the compositing films made from polyluminol andsome metal ions (such as Ni²⁺, Fe²⁺ and Co²⁺) can be easily generated on the surface ofthe graphite electrode by electropolymerizing luminol and these metal ions in the acidicmedium. Then, it was further found, compared to other resulting films, the compositingfilms made from polyluminol and Ni²⁺ presented the better electrochemiluminescence （ECL） analytical performance for urea based on its sensing effect for weak ECL signalof electro-oxidation polyluminol. Based on these findings, a novel ECL method for thedetermination of urea in urine samples was developed, and a new idea to improve theECL analytical performances of polyluminol by compositing metal ions was alsoproposed. Under the optimum experimental conditions, the ECL response regressedlinearly to the concentration of urea within the range from 2.0×10^-9 g/mL to1.0×10^-7g/mL with a detecting limit of 1.7×10^-10g/mL.2. the Investigation of the Electrochemiluminescence Performances of theCompositing Films of Polyluminol with Organic Compound and its AnalyticalApplicationBased the electropolymerizing method, the compositing film of polyluminol andorganic compounds, can be fabricated on the graphite electrode surface. Then, it wasfurther found the resulting films can be enhanced by hydrogen peroxide strongly inalkaline solution. Based on these findings, a novel method for the determination ofhydrogen peroxide in rainwater was develop. Under the optimum experimentalconditions, the enhancing ECL intensity was linear with the hydrogen peroxideconcentration in the range of the 1.0×10^-7mol/L to1.0×10^-10mol/L （correlationcoefficient, 0.9970） and the detection limit for H₂O₂ was 6×10¹¹mol/L.更多还原