导电聚合物多孔纳米材料的电化学制备及其催化与传感性能研究
发布时间：2018-12-10 06:05
【摘要】：近几年来,多孔纳米导电聚合物由于具有可调的氧化还原性能、极大的比表面积和出色的环境稳定性,在传感领域中展现出广阔的应用前景。本论文基于多孔纳米导电聚合物负载金属纳米颗粒,构建了新型化学和生物传感器,用于高灵敏检测疾病标志物,为疾病的早期诊断与治疗奠定基础。(1)利用硬模板法电化学制备了多孔聚3,4-乙烯二氧噻吩(PEDOT)纳米材料,并通过电沉积进一步在多孔PEDOT基底上负载铜纳米颗粒(CuNPs)。拥有大比表面积的三维(3D)纳米多孔FEDOT具有超高的导电性和稳定性,为负载大量CuNPs提供了合适的基底。所制备的多孔CuNPs/PEDOT纳米复合材料对葡萄糖的氧化展现出优异的电催化活性,这是由于其与众不同的多孔纳米结构,可以负载更多的CuNPs从而提供许多活性位点用于葡萄糖的氧化,除此之外,上述3D孔状结构还可以促进葡萄糖分子的扩散从而加快电子间的传递。在最佳优化条件下,多孔纳米复合修饰电极对葡萄糖的检测具有线性范围宽、灵敏度高等优点,其线性范围为0.1-482.1μM,检出限为52 nM。所构建的葡萄糖传感器(多孔CuNPs/PEDOT修饰电极)的灵敏度为329.6μA/mM/cm2,是平面PEDOT负载CuNPs修饰电极灵敏度的8倍之高。研究表明,3D纳米多孔结构对传感器各方面的性能均有显著的增强效应。(2)利用硬模板法电化学制备了多孔聚苯胺(PANI)掺杂聚苯乙烯磺酸钠(PSS)三维多孔纳米材料,由于其具有大的比表面积、高的导电性和较多的功能基团,因此可作为固定甲胎蛋白(AFP)抗体的优异基底,基于此我们构建了新型特异性检测AFP的电化学生物传感器。通过利用多孔PANI纳米材料自身固有的氧化还原信号变化这一优势,所构建的AFP免疫传感器无需外加氧化还原试剂,且对于目标物AFP的检测展现出优异的传感性能。在最佳条件下,免疫传感器对AFP的检测呈现出较宽的线性范围,即0.01-1,000 pg/m L,检出限为5.3 fg/m L(S/N=3)。此外,该传感器的响应灵敏度约为平面PANI修饰电极的两倍,这说明3D多孔结构有利于增强传感器的灵敏度。(3)利用硬模板法电化学制备了3D多孔结构的聚3,4-乙烯二氧噻吩(PEDOT)掺杂聚苯乙烯磺酸钠(PSS)纳米复合材料,并在多孔基底表面进一步电沉积AuNPs,得到AuNPs/PEDOT修饰电极。由于3D多孔纳米结构的PEDOT拥有大的比表面积,因此可以负载大量的AuNPs。然后将巯基修饰的捕获探针(P1)通过Au-S键作用固定在金颗粒表面,最终得到乳腺癌易感基因(BRCA1)特异性的电化学生物传感器。在最优条件下,基于纳米多孔PEDOT材料的DNA生物传感器对BRCA1的检测展现出较高的灵敏度,其中线性范围为1.0 fM-0.1 nM,检出限为0.67 fM(S/N=3)。基于上述研究,所构建的电化学传感器在生物传感领域具有广阔的应用前景。
[Abstract]:In recent years, porous nano-conductive polymers have shown a broad application prospect in the field of sensing due to their adjustable redox properties, great specific surface area and excellent environmental stability. In this paper, a novel chemical and biological sensor was constructed based on porous nano-conductive polymer loaded metal nanoparticles, which can be used to detect disease markers with high sensitivity. It lays a foundation for the early diagnosis and treatment of the disease. (1) porous poly34-ethylenedioxythiophene (PEDOT) nanomaterials were electrochemical prepared by hard template method, and copper nanoparticles (CuNPs). Were further loaded on porous PEDOT substrate by electrodeposition. Three-dimensional (3D) nano-porous FEDOT with large specific surface area has high electrical conductivity and stability, which provides a suitable substrate for loading a large amount of CuNPs. The porous CuNPs/PEDOT nanocomposites exhibit excellent electrocatalytic activity for glucose oxidation due to their unique porous nanostructures. More CuNPs can be loaded to provide many active sites for glucose oxidation. In addition, the 3D pore structure can promote the diffusion of glucose molecules and accelerate the electron transfer. Under the optimum conditions, the porous nano-composite modified electrode has the advantages of wide linear range and high sensitivity for glucose detection. The linear range is 0.1-482.1 渭 m and the detection limit is 52 nM.. The sensitivity of the glucose sensor (porous CuNPs/PEDOT modified electrode) is 329.6 渭 A / mm / cm ~ (2), which is 8 times higher than that of the planar PEDOT loaded CuNPs modified electrode. The results show that 3D nano-porous structure has a significant enhancement effect on all aspects of sensor performance. (2) porous Polyaniline (PANI) doped polystyrenesulfonate (PSS) three-dimensional porous nanomaterials were prepared by using hard template method. Because of its large specific surface area, high conductivity and more functional groups, it can be used as an excellent substrate for fixing alpha-fetoprotein (AFP) antibodies. Based on this, we have constructed a novel electrochemical biosensor for the specific detection of AFP. By taking advantage of the inherent redox signal variation of porous PANI nanomaterials, the proposed AFP immunosensor does not require the addition of redox reagents and exhibits excellent sensing performance for the detection of the target AFP. Under the optimum conditions, the detection of AFP by immunosensor showed a wide linear range, i.e. 0.01-1000 pg/m / L, and the detection limit was 5.3 fg/m L (S/N=3). In addition, the sensitivity of the sensor is about twice as high as that of the planar PANI modified electrode. The results show that 3D porous structure is beneficial to enhance the sensitivity of the sensor. (3) 3D porous (PSS) nanocomposites doped with polystyrenesulfonate (PSS) were prepared by hard template method. The AuNPs/PEDOT modified electrode was prepared by electrodeposition of AuNPs, on the porous substrate surface. Due to the large specific surface area of 3D porous nanostructures, PEDOT can be loaded with a large amount of AuNPs.. Then the sulfhydryl modified capture probe (P1) was immobilized on the surface of gold particles by Au-S bond, and a specific electrochemical biosensor of breast cancer susceptibility gene (BRCA1) was obtained. Under the optimal conditions, DNA biosensors based on nano-porous PEDOT materials show high sensitivity to BRCA1 detection, and the linear range is 1.0 fM-0.1 nM, detection limit of 0.67 fM (S/N=3). Based on the above research, the electrochemical sensor has a broad application prospect in the field of biosensor.
【学位授予单位】：青岛科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB383.1;O657.1
本文编号：2370085
[Abstract]:In recent years, porous nano-conductive polymers have shown a broad application prospect in the field of sensing due to their adjustable redox properties, great specific surface area and excellent environmental stability. In this paper, a novel chemical and biological sensor was constructed based on porous nano-conductive polymer loaded metal nanoparticles, which can be used to detect disease markers with high sensitivity. It lays a foundation for the early diagnosis and treatment of the disease. (1) porous poly34-ethylenedioxythiophene (PEDOT) nanomaterials were electrochemical prepared by hard template method, and copper nanoparticles (CuNPs). Were further loaded on porous PEDOT substrate by electrodeposition. Three-dimensional (3D) nano-porous FEDOT with large specific surface area has high electrical conductivity and stability, which provides a suitable substrate for loading a large amount of CuNPs. The porous CuNPs/PEDOT nanocomposites exhibit excellent electrocatalytic activity for glucose oxidation due to their unique porous nanostructures. More CuNPs can be loaded to provide many active sites for glucose oxidation. In addition, the 3D pore structure can promote the diffusion of glucose molecules and accelerate the electron transfer. Under the optimum conditions, the porous nano-composite modified electrode has the advantages of wide linear range and high sensitivity for glucose detection. The linear range is 0.1-482.1 渭 m and the detection limit is 52 nM.. The sensitivity of the glucose sensor (porous CuNPs/PEDOT modified electrode) is 329.6 渭 A / mm / cm ~ (2), which is 8 times higher than that of the planar PEDOT loaded CuNPs modified electrode. The results show that 3D nano-porous structure has a significant enhancement effect on all aspects of sensor performance. (2) porous Polyaniline (PANI) doped polystyrenesulfonate (PSS) three-dimensional porous nanomaterials were prepared by using hard template method. Because of its large specific surface area, high conductivity and more functional groups, it can be used as an excellent substrate for fixing alpha-fetoprotein (AFP) antibodies. Based on this, we have constructed a novel electrochemical biosensor for the specific detection of AFP. By taking advantage of the inherent redox signal variation of porous PANI nanomaterials, the proposed AFP immunosensor does not require the addition of redox reagents and exhibits excellent sensing performance for the detection of the target AFP. Under the optimum conditions, the detection of AFP by immunosensor showed a wide linear range, i.e. 0.01-1000 pg/m / L, and the detection limit was 5.3 fg/m L (S/N=3). In addition, the sensitivity of the sensor is about twice as high as that of the planar PANI modified electrode. The results show that 3D porous structure is beneficial to enhance the sensitivity of the sensor. (3) 3D porous (PSS) nanocomposites doped with polystyrenesulfonate (PSS) were prepared by hard template method. The AuNPs/PEDOT modified electrode was prepared by electrodeposition of AuNPs, on the porous substrate surface. Due to the large specific surface area of 3D porous nanostructures, PEDOT can be loaded with a large amount of AuNPs.. Then the sulfhydryl modified capture probe (P1) was immobilized on the surface of gold particles by Au-S bond, and a specific electrochemical biosensor of breast cancer susceptibility gene (BRCA1) was obtained. Under the optimal conditions, DNA biosensors based on nano-porous PEDOT materials show high sensitivity to BRCA1 detection, and the linear range is 1.0 fM-0.1 nM, detection limit of 0.67 fM (S/N=3). Based on the above research, the electrochemical sensor has a broad application prospect in the field of biosensor.
【学位授予单位】：青岛科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB383.1;O657.1
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