【作者】 丁红春；

【导师】 章竹君；

【作者基本信息】 陕西师范大学 ， 分析化学， 2003， 硕士

【摘要】 本论文分为综述和研究报告两部分。综述部分包括电化学发，光（ECL）的基本原理、特点、发展历史极其在分析化学中的应用和发展。研究报告部分主要对一些金属离子配合物的电化学发光法的特性进行了详细的研究。 电化学发光或电致化学发光（Electrochemiluminescence或Electrogenerated Chimiluminescence, ECL）是指直接利用电化学反应形成激发态发光体而发光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光辐射而实现分析物测定的发光分析技术。它不但具有化学发光分析的许多优点如灵敏度高、线性范围宽和仪器简单等优点之外，还具有自身优于化学发光的一些特点，如电发光反应过程控制性强、许多反应活性高但不稳定（如自由基和反应中间体等）的物质可以应用于电化学发光分析之中，而开拓出新的发光分析特性。 1929年，N. Harvey在碱性水溶液中电解鲁米诺时，发现了在阴阳两极上的发光现象，揭开了电化学发光现象和研究的序幕。到了八十年代，电化学发光进入实际应用中，在这一时期电化学发光技术得到了发展和深化。 进入九十年代后，电化学发光的仪器装置和电极材料有了进一步的发展并与其他技术结合，更加拓宽了电化学发光分析法的应用领域。目前，电化学发光分析技术已经在微流控分析系统，微阵列光化学传感器，纳米粒子的性质表征和分析特性的开发以及生物芯片分析等研究领域展现出诱人的发展前景。 本论文的研究工作分为两大部分：一、金属配合物的电化学发光分析特性的研究。目前用于电化学发光反应的分子识别体系较少，特别是一些电活性低的物质，如有毒重金属离子对电化学发光信号的增敏作用还未见报道。本论文的研究工作发现虽然Pb（Ⅱ）、Cd（Ⅱ）、Fe（Ⅲ）对鲁米诺的弱电化学发光增敏很弱或基本无增敏，但当这些离子和配位剂形成配合物时，其增敏作用得到大大增强。据此，我们建立了一种电化学发光测定这类金属离子的新方法。此方法快速、灵敏、简单。利用铁（Ⅲ）和邻菲啰啉形成的配合物(Fe（o-Phen）₃³⁺)对碱性介质中鲁米诺在印刷电极上的电还原发光信号有强的增敏作用，在最佳实验条件下，测定Fe（Ⅲ）的线性范围为4.0×10^-7～4.0×10^-6mol/L，检出限为1.8×10^-7mol/L。基于镉的7-碘-8-羟基喹啉-5-磺酸（铁试剂）络合物和铅的7-碘-8-羟基喹啉-5-磺酸（铁试剂）络合物对鲁米诺电化学发光体系的电化学发光信号的增敏作用，建立了一种 测定锅和铅的流动注射电化学发光新方法。在最佳的实验条件下，该方法的测定 褥（11）的线性范围为 1＊xlo”’－l＊x10“g／mL，检出限为3．6xlo”’g／mL，铅（11） 的线性范围为 2．oxlo”7叶刀xlo“g／mL，检出限为 6，Zxlo”sg／mL。相对标准偏差均小 于5％。 二、电化学发光芯片的研究。我们研制出一种纳升级进样器并把它和电化学发 光芯片检测器偶合完成样品分析，以过氧化氢－鲁米诺电化学发光体系为代表验证了 该体系的分析特性。从实验结果可以看出该进样器性能稳定，重现性好。更多还原

【Abstract】 Two parts are included in this thesis. In the first part of this thesis, the basic principle, the new progress and the advantages in Electrochemiluminescent (ECL) assay etc., are reviewed. In addition to these, the ECL reaction mechanisms of some useful ECL systems, the main problems and the future prospect on the ECL analysis were also given in this part. In the second part of this thesis, we mainly concentrated on the study of the highly sensitive luminol ECL methods for some metal ions based on their complexes compound form.Electrochemiluminescence method is one of the most interesting subjects in analytical chemistry field. This technique not only retains the advantage of the conventional chemiluminescence (CL) analysis, but also offers some advantages over more conventional CL. Firstly, the ECL reaction can be easily regulated and manipulated by the applied potential. Firstly, the ECL reaction can be easily regulated and manipulated by the applied potential. Secondly, the ECL emission is concentrated close to the vicinity of the electrode, which can be shaped and accurately positioned in relation to the optical measurement system for maximum sensitivity. Thirdly, the analyte can be in-situ modified electrochemically to form the corresponding CL active specie without the chemical contamination due to the addition of the necessary reactants in the corresponding CL reactions. Thus, ECL analysis, compared to CL analysis, offered the more alternative potentials to regulate the ECL reaction for analytical purpose.Since the luminol-based ECL phenomena was firstly observed by Harvey in 1929, the ECL was paid much attention by the analysts, and a lots of analytes had been detected with ECL analytical technique during the 1980s and 1990s. This approach has many obvious advantages over other analytical methods, and it has been applied successfully to many fields, such as life science, clinical medicine, environment, immunoassays and DNA probe analysis etc. Nowadays, analysts are working on biological chip and exploiting ECL substance etc.Our research works are divided into two parts. Firstly, although the enhancing effect of Pb(II), Cd(II) and Fe(III) for the weak ECL signal of electro-oxidation Luminol were observed, they are weak. However, we further found that, when these ion become their ions complexes compounds, such as, Fe(o-Phen)33+, Cd-T-I-H2QS and Pb-7-I-H2QS, they could greatly enhance the weak ECL signal arising from the electro-oxidated or electro-reducing Luminol in alkaline medium. Based on these observations and the optimum experimental conditions developed, the relative ECL intensity was linear with increasing Fe(III) concentration in the range 4.0+10-7 to 4.0+10-6 mol/L and a 1.8+10-7 mol/L detection limit for Fe(III) could be achieved; The linear range of Cd(II) was from l.0+10-7 to 1.0+10-4 g/mL and with 3.6+10-8 g/mL detecting limit; The linear range of Pb(II) was from 2.0+10-7 to 1.0+10-4g/mL and with a detecting limit of 6.2+10-8 g/mL.In addition to these, a novel sampling device with the nL in volume was designed. Then, based on the combination of this device with an ECL-based micro-detector, we successfully determinate H2O2 by ECL-based microfluidic system. Our results further prove that the ECL detector owned the great potential in this research field.更多还原