基于新型导电聚合物纳米复合材料电化学传感器的制备及应用

发布时间：2018-03-20 21:01

本文选题：导电聚合物　切入点：聚3　出处：《青岛科技大学》2017年博士论文　论文类型：学位论文

【摘要】：导电聚合物因其独特的导电性能和氧化还原特性而成为电化学领域的研究热点。导电聚合物纳米复合材料各成分之间通过协同效应强化了各自的特性,而且赋予了复合材料新的功能,如:催化功能和抗污染功能等。本研究体系以聚(3,4-乙撑二氧噻吩)、聚吡咯和聚苯胺为主体材料,采用电化学方法合成了导电聚合物纳米复合材料。导电聚合物与氧化石墨烯、碳纳米管、金属纳米粒子和抗污染材料等复合,制备了一系列新型导电聚合物纳米复合材料。利用导电聚合物复合材料修饰电极制制了检测致病物(亚硝酸钠)和疾病标志物(葡萄糖、乳腺癌易感基因和MicroRNAs)的传感器。论文的主要内容包括以下五个部分:(1)成功制备一个灵敏度高、稳定性好的无酶葡萄糖传感器。通过循环伏安法将氧化石墨烯(GO)掺杂聚(3,4-乙撑二氧噻吩)(PEDOT)电沉积到电极表面,获得GO/PEDOT纳米复合物;随后,铜纳米颗粒(CuNPs)通过电化学还原方法修饰到其粗糙的表面。修饰电极用于电化学检测葡萄糖。在最佳条件下,表现出超高的灵敏度(909.1μA/mM/cm2),超快的反应速度(小于1秒),较宽线性范围(0.1μM~1.3 mM)和低检测限(47 nM)。这些增强的传感性能归功于铜纳米粒子在氧化石墨烯/聚(3,4-乙撑二氧噻吩)纳米复合物表面高分散度和纳米复合物良好的导电性。实验结果表明CuNPs/GO/PEDOT纳米复合物修饰的电化学传感器极有希望应用于实际样品中葡萄糖检测。(2)在玻碳电极上,发展了一种新型的两步电化学法合成镍纳米颗粒/还原氧化石墨烯/聚(3,4-乙撑二氧噻吩)导电聚合物复合材料的策略。通过循环伏安法,氧化石墨烯掺杂聚(3,4-乙撑二氧噻吩)复合材料电化学共聚合到玻碳电极表面;随后,在-0.9 V恒电压下,镍阳离子电化学还原为镍纳米颗粒。在电化学还原过程中,掺杂在PEDOT/GO复合材料中的氧化石墨烯还原为导电能力更强的还原氧化石墨烯(RGO),同时,镍离子被还原为镍纳米颗粒。纳米复合材料(NiNPs/PEDOT/RGO)修饰电极对葡萄糖表现出超强的电化学催化活性,该修饰电极被成功发展为无酶葡萄糖传感器。在最佳实验条件下,该传感器与一定浓度范围内葡萄糖(1.0μM~5.1 mM)成线性关系,检测限为0.8μM。并且表现出在临床应用方面的潜力。(3)通过两步法成功合成三维纳米结构聚苯胺/碳纳米管复合材料。首先在PDDA和PSS的协助下将多壁碳纳米管自组装到玻碳电极表面形成网格结构;然后导电聚合物聚苯胺纳米线阵列通过电沉积原位修饰到多壁碳纳米管上。由于其独特的微观结构和超强的导电能力,聚苯胺/碳纳米管复合材料在超级电容器和催化亚硝酸盐还原方面表现出优异的电化学性能。实验证明聚苯胺/碳纳米管复合材料能够提供较高的比电容和较强的循环稳定性。作为亚硝酸根电化学传感器表现出超高的灵敏度,较低的检测限(6.08μM)和快速的反应时间(低于5 s)。(4)在诊断学和疾病监控方面,来源于非特异性吸附的生物污染一直是一个突出的挑战;科研工作者非常渴望能够有效减少复杂的生物介质中的非特异性蛋白质吸附。本研究通过将聚乙二醇修饰到聚苯胺纳米线表面得到一种新型的纳米线复合材料,探讨了该复合材料在抗污染电化学生物传感器方面的应用。聚乙二醇修饰的聚苯胺纳米线(PANI/PEG)展现出大的比表面积,保持了导电性能,同时无论对单一蛋白质还是复杂的血清样品都表现出优异的抗污染性能。通过将DNA探针固定到PANI/PEG上,可以轻易获得灵敏的、低污染的乳腺癌易感基因(BRCA1)电化学传感器。此DNA生物传感器表现出对乳腺癌易感基因较高的灵敏度,检测电信号与乳腺癌易感基因浓度在0.01pM到1 nM之间呈现出线性关系,并且该生物传感器在检测DNA错配方面也收到了满意的结果。此外,基于聚乙二醇修饰的聚苯胺纳米线DNA生物传感器支持在复杂人血清中BRCA1的定量检测,说明PANI/PEG纳米材料在生物传感器和生物电子学方面应用潜力。(5)将含巯基的抗污染材料(多肽序列、聚乙二醇、巯基己醇)引入聚苯胺修饰电极表面,成功构建了高选择性的miRNA生物传感器。在这三种抗污染材料中,我们独立设计合成的多肽能有效地抑制蛋白质的非特异性吸附,其抗污染能力可以与聚乙二醇相媲美。在四种miRNA生物传感器中,多肽修饰的聚苯胺修饰电极表现出对单碱基错配、三碱基错配和完全不互补miRNA最大的特异性因子。实验结果表明抗污染材料的加入并没有明显改变传感器的灵敏度。我们设计的多肽序列作为抗污染材料也有潜力应用于其它传感器中。
[Abstract]:Conductive polymer because of its unique electrical conductivity and redox properties has become a hot research field of electrochemistry. Between the components of conductive polymer nanometer composite material strengthened through the synergy of their own characteristics, but also gives the function of the new composite materials such as catalytic function and anti pollution function. This study system based on poly (3,4- two oxygen ethylene thiophene), polypyrrole and polyaniline as main material, conductive polymer nanocomposites were synthesized by electrochemical method. The conductive polymer and graphene oxide, carbon nanotubes, composite metal nanoparticles and anti pollution materials, a series of novel conductive polymer nanometer composite material was prepared. The composite modified electrode was prepared to detect pathogenicity of using conductive polymer (sodium nitrite) and disease markers (glucose, breast cancer susceptibility gene and MicroRNAs) of the main sensor. Including the following five parts: (1) the successful preparation of a high sensitivity, good stability Enzymeless glucose sensor. By cyclic voltammetry, graphene oxide (GO) doped poly (ethylene oxide 3,4- two thiophene) (PEDOT) electrodeposited on the electrode surface, GO/PEDOT nano composite; then (CuNPs), copper nanoparticles by electrochemical reduction method to modify its rough surface. The modified electrode for the electrochemical detection of glucose. Under the optimum conditions, the sensitivity of ultra high performance (909.1 A/mM/cm2), fast response (less than 1 second), wide linear range (0.1 M~1.3 mM) and low detection limit (47 nM). The sensing performance enhancement due to copper nanoparticles on graphene oxide / poly (ethylene oxide 3,4- two thiophene) nanocomposites and good conductivity of high dispersion surface nano composites. The experimental results show that CuNPs/GO/PEDOT nanocomposite modified electric Chemical sensors promising application in glucose detection. In real samples (2) on the glassy carbon electrode, the development of a new two step electrochemical synthesis of nickel nanoparticles / graphene / poly (ethylene oxide 3,4- two thiophene) strategy of conductive polymer composites. By cyclic voltammetry, oxidation graphene doped poly (ethylene oxide 3,4- two thiophene) composite electrochemical polymerization to the glassy carbon electrode surface; then, in the -0.9 V constant voltage, the electrochemical reduction of nickel cations for Ni nanoparticles. The electrochemical reduction process, the reduction of graphene oxide doped composite materials in PEDOT/GO in the reduction of graphene oxide the conductive ability stronger (RGO), at the same time, nickel ions are reduced to nickel nanoparticles. Nano composites (NiNPs/PEDOT/RGO) modified electrode for glucose showed strong electrocatalytic activity, the modified electrode was successfully developed Non enzymatic glucose sensor. Under the optimum conditions, the glucose sensor with a certain range of concentration (1 M~5.1 mM) into a linear relationship, the detection limit is 0.8 M. and exhibited in clinical application potential. (3) through the two step synthesis of 3D nanostructures of Polyaniline / carbon nanotube composite material. In the first PDDA and PSS help multi wall carbon nanotubes self-assembled onto the surface of glassy carbon electrode to form a grid structure; then the conductive polymer polyaniline nanowires modified multiwalled carbon nanotubes by electrodeposition in situ. Due to its unique microstructure and super conductivity, polyaniline / carbon nanotube composites in super the capacitor and the catalytic nitrite reduction showed excellent electrochemical performance. The experimental results show that the polyaniline / carbon nanotube composite material can provide high specific capacitance and good cycle stability As the sensitivity of nitrite electrochemical sensor showed a super high and low detection limit (6.08 M) and fast response time (less than 5 s). (4) in the diagnosis and disease monitoring, source of non-specific adsorption of biological pollution has been a prominent challenge; researchers are eager to can effectively reduce the non-specific protein adsorption complex biological medium. This study of the polyethylene glycol modified into polyaniline composite obtained a nanowire nanowire surface model, the paper discusses the application of the composite materials in electrochemical biosensors and anti pollution aspects. Polyethylene Glycol Modified Polyaniline nanowires (PANI/PEG) exhibits a large the specific surface area, maintain the conductivity, while both the single protein or complex serum samples showed excellent anti pollution performance. By fixing DNA probe to PANI/PEG That can easily obtain sensitive, low pollution susceptibility genes of breast cancer (BRCA1). This DNA electrochemical sensor biosensor showed high sensitivity of susceptibility genes for breast cancer, the detection signal and the breast cancer susceptibility gene concentration presents the line relationship between 0.01pM to 1 nM, and the biosensor detection of DNA mismatch has also received satisfactory results. In addition, polyethylene glycol modified polyaniline nanowire DNA biosensor support in quantitative serum BRCA1 complex detection based on PANI/PEG nano materials used in biosensors and bioelectronics potential. (5) the thiol containing anti pollution materials (peptide sequence, polyethylene glycol 6-mercapto-1-hexanol), introduction of polyaniline modified electrode surface was successfully constructed miRNA biosensor with high selectivity. In these three kinds of anti pollution materials, we designed and synthesized more independent Peptide can effectively inhibit nonspecific protein adsorption, its anti pollution capacity can be comparable with polyethylene glycol. In four kinds of miRNA biosensors, polyaniline modified electrode showed the peptide modified single base mismatch, three base mismatch and non complementary specificity factor miRNA maximum. The experimental results show that the addition of anti pollution the material did not significantly alter the sensitivity of the sensor. The peptide sequence we designed as anti pollution materials have the potential applied to other sensors.

【学位授予单位】：青岛科技大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O657.1

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