摘要
本文主要包括绪论、Ru(bipy_3~(2+)掺杂SiO_2纳米粒子-漆酚复合物修饰电极的制备、Ru(bipy_3~(2+)掺杂SiO_2纳米粒子-漆酚复合物修饰电极的电化学发光行为及分析应用研究，此外，建立了流动注射-化学发光测定香草醛的体系。
第一章分别对电化学发光、化学修饰电极、Ru(bipy_3~(2+)的电化学发光特点及固定化方法、固定化Ru(bipy_3~(2+)修饰电极在药品检测中的应用、以及流动注射技术和漆酚成膜特性的研究现状进行了评述。
第二章实验研究了Ru(bipy_3~(2+)掺杂SiO_2纳米粒子-漆酚复合物制备条件及复合物修饰玻碳电极的方法，用扫描电镜对Ru(bipy_3~(2+)掺杂SiO_2纳米粒子-漆酚复合物聚合膜进行了初步表征，比较了修饰玻碳电极与裸玻碳电极的电化学发光行为，探讨了影响修饰电极ECL的影响因素。结果表明，复合物聚合膜呈立体孔状结构，能将Ru(bipy_3~(2+)有效固定于玻碳电极表面，SiO_2的存在有利于电荷传输，在磷酸盐缓冲溶液介质中，用Ru(bipy_3~(2+)掺杂SiO_2纳米粒子-漆酚复合物修饰电极制备的ECL传感器具有良好的ECL性能和稳定性。
第三章分别以Ru(bipy_3~(2+)-三丙胺和Ru(bipy_3~(2+)-抗坏血酸经典发光体系考察检验了Ru(bipy_3~(2+)掺杂SiO_2纳米粒子-漆酚复合物修饰电极ECL传感器用于分析检测的可行性。结果表明，三丙胺和抗坏血酸在Ru(bipy_3~(2+)掺杂SiO_2纳米粒子-漆酚复合物修饰电极上的ECL行为与裸电极在液相Ru(bipy_3~(2+)中的ECL行为类似，三丙胺和抗坏血酸对固定化Ru(bipy_3~(2+)ECL强度的增强作用与液相Ru(bipy_3~(2+)的ECL相似，且ECL强度与三丙胺和抗坏血酸的浓度均呈线性关系，其检出限分别达到2.1×10~(-7)mol/L和2.5×10~(-8)g/mL，且具有良好的重现性。说明实验研制的Ru(bipy_3~(2+)掺杂SiO_2纳米粒子-漆酚复合物修饰电极ECL传感器是可以用于实际样品分析检测的。
第四章实验研究发现，厚朴酚对Ru(bipy_3~(2+)掺杂SiO_2纳米粒子-漆酚复合物修饰电极的ECL强度有明显的增强作用，据此建立了Ru(bipy_3~(2+)掺杂SiO_2纳米粒子-漆酚复合物修饰电极ECL传感器测定厚朴酚含量的检测体系。在实验选定的优化条件下，在8×10~(-7)~8×10~(-5)mg/mL浓度范围内，ECL强度与厚朴酚浓度成线性关系，检出限为3.7×10~(-8)mg/mL。对浓度为8×10~(-6)mg/mL厚朴酚进行8次平行测定的RSD为3.5%。
第五章实验研究发现，在酸性条件下，香草醛对Ru(phen_3~(2+)-Ce（Ⅳ）反应体系化学发光有显著的减弱作用，据此建立了流动注射-化学发光检测香草醛的新体系。对影响流动注射化学发光的各因素进行了实验研究，优化了反应条件和各项测定参数。结果表明，优化条件下，在质量浓度为4.00×10~(-7)～8.25×10~(-6)g/mL的范围内，相对发光强度与其质量浓度呈对数线性关系，检出限（3σ）为2.90×10~(-7)g/mL，对质量浓度为3.0×10~(-6)g/mL的香草醛进行11次平行测定，相对标准偏差（RSD）为2.6%。对合成样品中香草醛测定的回收率在98.3%~102.8%之间。采样频率120次/h。
This thesis includes the introduction, the composite film prepared using urushioland Ru (bipy_3~(2+)doped silica nanoparticles as a novel adhesive for modified electrode,and the researches of electrogenerated chemiluminescence analysis (ECL) behavior ofthe modified electrode with the composite film using urushiol and Ru (bipy_3~(2+)dopedsilica nanoparticles as a novel adhesive, the researches of flow injection-electrogenerated chemiluminescence analysis behavior.
Chapter1is a summarization, which includes the introduction of ECL, theprinciple of flow injection method, the developing status, current status and theapplication of chemically modified electrode, the modified electrodes with Ru (bipy)32+and its application in pharmaceutical analysis, and research progress of Chineselacquer.
Chapter2, the researches of ECL behavior of the modified electrode with thecomposite film using urushiol and Ru(bipy_3~(2+)doped silica nanoparticles as a noveladhesive.The modified electrode were prepared using the composite film of urushioland Ru(bipy_3~(2+)doped silica nanoparticles as a novel adhesive. Moreover, thedifferences in the analysis of the modified electrode and the bare glassy carbonelectrode were compared in order to its effective application in the electrochemistryanalysis.
Chapter3, the ECL behavior of the chemiluminescence sensor prepared usingmodified electrode with the composite film of urushiol and Ru(bipy_3~(2+)doped silicananoparticles as a novel adhesive with coreaction reagion of tripropylamine andascorbic acid, the limit of detections of tripropylamine and ascorbic acid are2.1×10~(-7)mol/L and2.5×10~(-8)g/mL, respectively. The sensitivity is higer than that ofliterature reports. It shows that with the method of new type of modifed electrodematerials studied in the experiment, Ru (bipy_3~(2+)can be fixed on the electrode surface.In this way, we can prepare an effective and good charge-transfer function of sensor,which can be used to determination of drug samples.
Chapter4, the determination of trace magnolol using the chemiluminescencesensor prepared using modified electrode with the composite film of urushiol and Ru(bipy_3~(2+)doped silica nanoparticles as a novel adhesive. The each parameters ofchemiluminescence system were optimized. Under optimal conditions, the signalstrength of the system reached the maximum in order to improve the sensitivity. ECLintensity is proportional to the concentration of magnolol in the range of 8×10~(-7)~8×10~(-5)mg/mL. The linear regression equation is I=1.97×10~6c(mg/mL)+96.91,correlation coefficient r=0.9915, the limit of detection is3.7×10~(-8)mg/mL, and therelative standard deviation (RSD) of eight determinations of magnolol atconcentration of8×10~(-6)mg/ml was3.5%.
Chapter5, the determination of vanillin with FIA-CL method. Under acidicconditions, vanillin have significantly weakened on the chemiluminescence ofRu(phen_3~(2+)-Ce(Ⅳ) reaction system, whereby a new system determination ofvanillin with the flow injection-chemiluminescence was developed. Various factorsthat affect the flow injection chemiluminescence experimental were studied tooptimize the reaction conditions and the determination of the parameters. The resultsshowed that under the optimized condition, in the mass concentration range of4.00×10~(-7)~8.25×10~(-6)g/mL, the relative luminous intensity and concentration was alinear relationship in logarithm, the detection limit (3σ) was2.90×10~(-7)g/mL. The RSDof11determinations of Vanillin at mass concentration of3.0×10~(-6)g/mL was2.6%, andthe recoveries of determination of vanillin in synthetic samples were between98.3%and102.8%under sampling frequency of120times/h.
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