ELECTROCHEMILUMINESCENCE STUDIES OF SOME AMINE COMPOUNDS AND ALKALOIDS

电致化学发光(ECL)是近二十年发展起来的一种新型检测方法，可方便的用作液相色谱和毛细管电泳检测器。由于它的连续可测性、灵敏度高、稳定、方法简单，被广泛应用于分子生物学、药学、化学和环保等领域。本论文工作以ECL为研究目标，通过Ru(bpy)32＋ECL的猝灭检测了苯胺和联苯胺；与HPLC联用成功分离检测了四种苦参类生物碱并讨论了生物碱和胺类化合物结构对其ECL强度的影响；同时还尝试了用溶胶-凝胶方法将Ru(bpy)32＋固定在了玻碳电极表面制备修饰电极以测定兴奋剂类生物碱，显示了ECL作为新型检测器的巨大生命力。 本论文共四章。 第一章，文献综述，主要介绍ECL的发展概况、基本原理及联吡...Electrogenerated chemiluminescence (ECL) is a new kind of detection method, which is developed quickly in the recent twenty years. It was widely used in biological, pharmic, chemical and environmental applications due to its continuance,sensitivity,reproducibility and relative easiness to be automatically controlled. In this dissertation, the study was focused on the ECL detection of aniline and b...学位：理学硕士院系专业：化学化工学院化学系_分析化学学号：20012506

Progress in Electrochemiluminescence Based on Ru(bpy)_3 ~(2+) Immobilization

将可电化学再生的电致化学发光 (ECL)试剂固定于电极表面 ,由此获得ECL传感器 ,从而减少分析过程中试剂的消耗和简化实验装置。本文综述了联吡啶钌及其衍生物的固相ECL近年来的研究进展 ,并简要介绍了各种固定方法及其相关的应用情况。Electrochemiluminescence based on Ru(bpy) 3 2+ immobilized modified electrode has attracted extensive attention in basic science and application studies. This review covers the principles, methods and applications of Ru(bpy) 3 2+ immobilization. Detail for some research work that encompasses the most recent developments has also be presented.国家自然科学基金项目 ( 2 0 3 75 0 3 3 )资助课

Electrochemical Behaviors of Ru(bpy)_3~(2+) Modified Electrode Immobilized in Organic-modified Sol-Gel

采用有机改性溶胶_凝胶制备技术 ,以四甲氧基硅烷 (TMOS)和二甲基二甲氧基硅烷 (DiMe_DiMOS)为共先驱体包埋聚苯乙烯磺酸钠 (PSS) ,通过离子交换成功地将联吡啶钌固定在玻碳电极表面。电化学研究结果表明 ,被固定的联吡啶钌保持了良好的电化学活性 ,同时该方法制备的修饰电极对甲基安非他明有灵敏的电化学响应。In this paper, organic modified sol-gel preparation technique was applied to embed poly-sodium 4-styrenesulfonate (PSS), using TMOS and DiMe-DiMOS as co-precursors and then it was successfully immobilized Ru(bpy) 3 2+ on the surface of glass carbon electrode via ion-exchange. The data from electrochemistry experiments showed that the immobilized Ru(bpy) 3 2+ maintained its electrochemistry behaviors very well and the modified glass carbon electrode prepared in this method presents high sensitivity to methamphetamine.国家自然科学基金资助项目 (2 0 375 0 33

Effect of Substituents of Amines on Electrochemiluminescence of Tri(2,2′-bipyridine)ruthenium with Some Amines

研究了苦豆子中主要生物碱槐定碱、苦参碱 ,以及神经兴奋药物甲基安非他命、安非他命等化合物 ,在碱性联吡啶钌 [Ru(bpy) 3 2 + ]水溶液 (pH 9 0 )中的电致化学发光 (ECL)行为 .在玻碳电极上 ,生物碱中的氨基氮于 +1 30V(vs .Ag/AgCl)左右被氧化为氮正自由基离子 ,该自由基离子与Ru(bpy) 3 2 + 反应生成激发态的Ru(bpy) 3 2 + 而发光 .研究比较了取代基性质、氨基氮周围的三维空间结构对各生物碱ECL的影响 ,并结合生物碱氨基氮的电离势和键角的计算 ,对这些影响进行了解释 .Electrochemiluminescences (ECLs) based on tris(2,2′-bipyridine)ruthenium (Ⅱ) [Ru(bpy) 3 2+] and some alkaloids or amines such as sophoridine, matrine, methamphetamine and amphatamine in phosphate buffer solution (pH 9.0) are studied. The light emission is mainly caused by the electro-oxidation reaction between amino group on the alkaloid compounds and Ru(bpy) 3 2+ in a thin layer flow cell equipped with a glassy carbon disc electrode (22.1 mm 2) at about the potential of +1.30 V (vs. Ag/AgCl). The luminescence wavelength of 610 nm confirms that ECL is caused by Ru(bpy) 3 2+* back to its ground state. The effects of the nature and three-dimensional conformation of the substituents of these alkaloids on the ECL intensities are discussed. Ionization potentials and angle of C-N-C bond taken from calculation data further confirm the experimental results.国家自然科学基金 (No .2 98770 2 2 )资助项

Effect of substituents of amines on electrochemiluminescence of tri(2,2 '-bipyridine) ruthenium with some amines

Electrochemiluminescences (ECLs) based on tris(2,2'-bipyridine) ruthenium (II) [Ru(bpy)(3)(2+)] and some alkaloids or amines such as sophoridine, matrine, methamphetamine and amphatamine in phosphate buffer solution (pH 9.0) are studied. The light emission is mainly caused by the electro-oxidation reaction between amino group on the alkaloid compounds and Ru(bpy)(3)(2+) in a thin layer flow cell equipped with a glassy carbon disc electrode (22.1 mm(2)) at about the potential of + 1.30 V ( vs. Ag/AgCl). The luminescence wavelength of 610 nm confirms that ECL is caused by Ru(bpy)(3)(2+*) back to its ground state. The effects of the nature and three-dimensional conformation of the substituents of these alkaloids on the ECL intensities are discussed. Ionization potentials and angle of C-N-C bond taken from calculation data further confirm the experimental results

Determination of Aniline and Benzidine by Using Electrochemiluminescent Quenching of Ru(bpy)_3~(2+)-C_2O-4~(2-) System

利用苯胺和联苯胺对联吡啶钌 草酸体系电致化学发光的强猝灭作用 ,建立了电致化学发光猝灭的流动注射检测苯胺和联苯胺的方法。该方法具有良好的重现性和稳定性。在所选定的实验条件下 ,苯胺和联苯胺的检出限分别为 5 .0× 10 -7mol/L和 2 .0× 10 -7mol/L。对 1.0× 10 -5mol/L的苯胺和联苯胺 ,测定的标准偏差分别为 3%和 2 .5 % (n =6 )。对苯胺和联苯胺对联吡啶钌 草酸体系电致化学发光的猝灭机理进行了初步的探讨。Aniline and benzidine were found to quench strongly the electrochemiluminescence (ECL) of the Ru(bpy) 2+ 3 C 2O 2- 4 system when a working glassy carbon electrode was maintained at 1.50 V( vs . Ag/AgCl) in pH 6.2 phosphate buffer. A flow injection procedure with electrochemiluminescent quenching detection has been developed for determination of aniline and benzidine.The method exhibits a good reproducibility and stability with a detection limit of 5.0×10 -7 mol/L for aniline and 2.0×10 -7 mol/L for benzidine, respectively . The relative standard deviations ( n =6) were 3% and 2.5% for determination of 1.0×10 -5 mol/L aniline and benzidine, respectively. The mechanism of the inhibition effects was proposed in the preliminary way.国家自然科学基金资助项目 (No .2 0 3 75 0 3 3

Separation of Aromatic Amines by High Performance Capillary Zone Electrophoresis Using a Voltage Gradient

建立了分离 8种环境污染物芳香胺的高效毛细管区带电泳法。以磷酸盐为缓冲溶液 ,考察了pH值、缓冲溶液浓度、各种添加剂 (环糊精、尿素 )和有机试剂对分离的影响 ,在此基础上采用了电压梯度法 ,使 8种芳香胺得到了较好的分离A method to separate eight aromatic amines by high performance capillary zone electrophoresis is discussed. The samples were introduced into the capillary employing 50 mmol/L phosphate at pH 2.41 with 20% isopropanol, 3 mol/L urea and 20 mmol/L β cyclodextrin as buffer solution. The capillary used was 75 μm in I.D. and 26.5 cm in effective length. Ultraviolet detection was set at 214 nm and 250 nm. By using a voltage gradient program, the eight aromatic amines were all separated well.国家自然科学基金资助项目 (No .2 98770 2 2

Study of the Electrochemiluminescence Based on Tris(2,2′-bipyridyl)ruthenium Ⅱand Some Nervous Amine Compounds Using Flow Injection Analysis

利用联吡啶钌 [Ru(bpy) 3Cl2 ]对几种胺类神经药物的电致化学发光 (ECL)流动注射分析进行了研究。使用改进的流动电解池 ,建立了原位在线的ECL方法 ,提高了检测的灵敏度。在浓度为 0 .0 5mol L的磷酸盐缓冲溶液 (pH =9.0 )中 ,甲基安非它明 (METH)的ECL最强。发光强度与浓度在 6.8× 1 0 - 1 1 ～ 6.8× 1 0 - 3mol L范围内具有良好的线性 ,检出限达 2× 1 0 - 1 6 mol/L ,优越于一般的检测方法 ;比较了METH与安非它明 (APM)的电致化学发光 ;研究了可待因、可卡因、吗啡和咖啡因等毒品的ECL行为 ,并利用循环伏安法对它们不同的发光强度进行了分析。实验结果表明 :该系统简单、方便 ,测定灵敏度高 ,尤其是不需要过氧化物 ,能更方便应用于流动分析体系 ,并为刑侦破案提供了一定的依据。A new electrochemiluminescence (ECL) method for the detection of methamphetamine (METH) and some nervous amine compounds is described. The pH of mobile phase and applied potential on glassy carbon electrode obviously influance the intensity of the ECL of METH. The mobile phase was selected as 0.1 mmpl/L Ru(bpy) 3Cl 2 in 0.05 mol/L NaH 2PO 4 NaOH (pH 9.0) buffer. The studies of the effect of applied potential and flow rate on ECL showed that METH gives the brightest light emission at the potential of +1.55 V and at the flow rate of 0.4 mL/min. A linear relationship was obtained from 6.84×10 -11 ～6.84×10 -3 mol/L with a correlation coefficient of R 2=0.9906 and the detection limit was 2×10 -1 mol/L under the experimental condition. The effect of surfactants on ECL was studied. The work also included the study of ECL of related compounds such as codeine, cocaine, morphine and so on. Cyclic voltammetry showed that their different oxidation currents might lead to their different ECL intensity. The method was simple, economical, sensitive, useful and provided some evidences for scout cases.国家自然科学基金 (No .2 9870 2 2 );; 教育部高等学校骨干教师计划资助项

Study of the electrochemiluminescence based on tris(2,2 '-bipyridyl)ruthenium(II) and some nervous amine compounds using flow injection analysis

A new electrochemiluminescence (ECL) method for the detection of methamphetamine (METH) and some nervous amine compounds is described. The pH of mobile phase and applied potential on glassy carbon electrode obviously influance the intensity of the ECL of METH. The mobile phase was selected as 0.1 mmpl/L Ru (bpy)(3)Cl-2 in 0.05 mol/L NaH2PO4-NaOH (pH 9.0) buffer. The studies of the effect of applied potential and flow rate on ECL showed that METH gives the brightest light emission at the potential of + 1.55 V and at the flow rate of 0.4 mL/min. A linear relationship was obtained from 6.84 x 10(-11) similar to 6.84 x 10(-3) mol/L with a correlation coefficient of R-2 = 0.9906 and the detection limit was 2 x 10(-1) mol/L under the experimental condition. We effect of surfactants on ECL was studied. The work also included the study of ECL of related compounds such as codeine, cocaine, morphine and so on. Cyclic voltammetry showed that their different oxidation currents might lead to their different ECL intensity. The method was simple, economical, sensitive, useful and provided some evidences for scout cases