导电聚合物纳米粒子的制备及其分析应用研究

【作者】 贾丽娟；

【导师】 张成孝；

【作者基本信息】 陕西师范大学 ， 材料物理与化学， 2010， 硕士

【摘要】 导电聚合物是一种性能优良的新型功能材料。它除具有良好的柔韧性、可塑性等聚合物特性和易于加工成型等金属特性外,还具有独特的光、电、磁、热等性能,在电磁屏蔽、金属防腐和隐身材料以及传感器和分子器件组装中有着广泛的应用前景。纳米材料是指在三维空间中至少有一维处在纳米尺度范围(1-100 nm)或由它们作为基本单元构成的材料。纳米材料是一种具有全新结构的材料,随着材料尺寸的降低,其表面的电子结构和晶体结构发生变化,产生了一些宏观物质所不具有的特殊效应：小尺寸效应、表面效应、量子尺寸效应和宏观隧穿效应等,从而具有传统材料所不具有的物理化学性质。导电聚合物纳米粒子具有规整的形貌,较大的比表面积,在催化、分离、药物释放和传感器等领域均具有潜在的用途。而聚吡咯纳米粒子良好的环境稳定性和生物相容性使其与其它导电聚合物相比,在化学和生物传感器材料上具有更为广阔的应用前景。因而将功能化聚吡咯、聚吡咯复合物的膜或者纳米粒子等,用于负载或者固定生物物质,有望用于电化学生物传感器的研究也成为近来研究的热点之一。电化学发光分析法具有灵敏度高、选择性好、线性范围宽、设备简单、分析速度快、应用广泛,同时获得多种信息,有利于研究快速发光反应和发光反应机理等特点。本论文旨在制备出具有导电性,且带有功能基团可负载大量电化学发光信号物质和生物识别物质的导电聚合物纳米粒子,并将其作信号物和探针载体,应用于电化学发光传感器。同时结合生物识别亲合力高、特异性强、目标范围广的特点,应用于相应生物分子或小分子的检测中。本论文由四章组成。第一章为前言,介绍了导电聚合物及其纳米结构的合成与特点,评述了导电聚合物的研究进展,简要介绍了导电聚合物纳米材料在电化学传感器中的应用,以及本论文的研究目的、意义及主要研究内容。论文第二章为吡咯/N-(2-羧乙基)吡咯纳米粒子制备的研究。首先合成了N-(2-羧乙基)吡咯单体,以此单体为功能化试剂,采用微乳液聚合法和化学氧化法,使吡咯单体与N-(2-羧乙基)吡咯单体共聚,成功制备了吡咯/N-(2-羧乙基)吡咯纳米粒子(简称PPy/PPa NPs)。通过环境扫描电子显微镜和透射电子显微镜观察,该纳米粒子具有较规整的形貌,粒径在40-50nm；通过傅里叶变换红外光谱确定了纳米粒子表面功能化羧基的存在。第三章为PPy/PPa NPs负载钌联吡啶衍生物的电化学发光研究。利用PPy/PPa NPs上的羧基共价连接氨基钌联吡啶衍生物,以此复合纳米粒子(简称Rul-PPy/PPa NPs)修饰电极,制作出一种新的电化学发光化学传感器。结果表明该传感器具有很好的电化学和电化学发光特性,测定TPA的线性范围为1.0x10-7mol/L-1.0x10-5 mol/L,检出限为3×10-8mol/L(S/N=3)。第四章为PPy/PPa NPs负载电化学发光适体探针夹心法测定凝血酶的研究。以吡咯/N-(2-羧乙基)吡咯纳米粒子为信号负载物,结合凝血酶的两段适体构建高灵敏度的电化学发光适体传感器。将一端有氨基修饰的凝血酶适体Ⅰ共价键合在修饰有对氨基苯磺酸的石墨电极表面,形成生物识别层,特异性捕捉目标蛋白质凝血酶,再结合负载凝血酶适体Ⅱ的Rul-PPy/PPaNPs,建立一种夹心式电化学发光法测定凝血酶的新方法,测定凝血酶的线性范围为1.0×10-15-1.0×10-12mol/L。更多还原

【Abstract】 Conductive polymers are excellent new functional materials. They have obvious polymer characteristics, such as good flexibility, plasticity and are easy to mold. They also have unique optical, electrical, magnetic, thermal and other properties. So conductive polymers have been used in sensors and molecular devices, electromagnetic shielding, metal corrosion, electrochemical, bio-technology and other fields.Nano-material is one kind of a material which size is nanometer scale range (1-100 nm) at least in one dimension of three-dimensions. In recent years, conducting polymer nanoparticles with regular morphology and large surface area have been received much attention duo to their widely applications in catalysis, separation, drug delivery and sensors. Compared to other conductive polymer nanoparticles, polypyrrole nanoparticles have excellent environmental stability and biocompatibility as chemical and biological sensors materials in a more broad application potential. Thus the use of the functional polypyrrole, polypyrrole complex films or nanoparticles, for a load or a fixed biological material in the electrochemical biosensor has become a hot topic in recent research.The electrogenerated chemiluminescence (ECL) sensors and biosensors have been received much attention duo to their high sensitivity, good selectivity, fastness and simplicity.This thesis aims to synthesize novel conductive polymer nanoparticles and to develop a ECL biosensor using synthesize conductive polymer. This thesis consists of four chapters. The first chapter is introduction, in which the synthesis, the structure and characteristics of conductive polymers are described, and the application of them, and especially includes the conductive polymer nanometer material’s application in the electrochemical sensors are reviewed.The second chapter is the research of synthesis poly (pyrrole-co-pyrrole propylic acid) nanoparticles. Poly (pyrrole-co-pyrrole propylic acid) nanoparticles (PPy/PPa NPs) were synthesized by using an oil/water micro-emulsion method. The PPy/PPa NPs synthesized were characterized by fourier transform infrared absorption spectroscopy (FTIR), transmission electron microscope (TEM) and scanning electron microscope (SEM). The nanoparticles have a more regular morphology, and particle size at 40-50 nm. And the presence of the carboxylic acid (-COOH) functionality in nanoparticles was confirmed using the FTIR.In the third chapter, an ECL sensor for the determination of tri-propylamine (TPA) was designed and fabricated by coating Rul complex-PPy/PPa NPs on the surface of a paraffin-impregnated graphite electrode (PIGE). It was found that ECL intensity of the sensor fabricated was linear with the concentration of TPA in the range from 1.0×10-7 to 1.0×10-5 mol/L, with a detection limit of 3×10-8 mol/L TPA(S/N=3). The ECL sensor also showed good reproducibility and stability.In the forth chapter, an ultrasensitive ECL detection method of thrombin based on PPy/PPa NPs carrying a large number of ruthenium complex tags was developed. The probe single thrombin aptamer II and ruthenium complex were loaded on PPy/PPa NPs which was taken as an ECL probe. When the capture thrombin aptamer I with an amine group was covalently immobilized onto the surface of the PIGE, and then recognition of the target thrombin and further captured with the ECL probe to form DNA sandwich conjugate, a strong ECL response was electrochemically generated. The ECL intensity was linearly related to the concentration of thrombin in the range from 1.0×10-15 to 1.0×10-12mol/L(S/N=3).更多还原