【摘要】：近幾年來,多孔納米導電聚合物由于具有可調的氧化還原性能、極大的比表面積和出色的環(huán)境穩(wěn)定性,在傳感領域中展現出廣闊的應用前景。本論文基于多孔納米導電聚合物負載金屬納米顆粒,構建了新型化學和生物傳感器,用于高靈敏檢測疾病標志物,為疾病的早期診斷與治療奠定基礎。(1)利用硬模板法電化學制備了多孔聚3,4-乙烯二氧噻吩(PEDOT)納米材料,并通過電沉積進一步在多孔PEDOT基底上負載銅納米顆粒(CuNPs)。擁有大比表面積的三維(3D)納米多孔FEDOT具有超高的導電性和穩(wěn)定性,為負載大量CuNPs提供了合適的基底。所制備的多孔CuNPs/PEDOT納米復合材料對葡萄糖的氧化展現出優(yōu)異的電催化活性,這是由于其與眾不同的多孔納米結構,可以負載更多的CuNPs從而提供許多活性位點用于葡萄糖的氧化,除此之外,上述3D孔狀結構還可以促進葡萄糖分子的擴散從而加快電子間的傳遞。在最佳優(yōu)化條件下,多孔納米復合修飾電極對葡萄糖的檢測具有線性范圍寬、靈敏度高等優(yōu)點,其線性范圍為0.1-482.1μM,檢出限為52 nM。所構建的葡萄糖傳感器(多孔CuNPs/PEDOT修飾電極)的靈敏度為329.6μA/mM/cm2,是平面PEDOT負載CuNPs修飾電極靈敏度的8倍之高。研究表明,3D納米多孔結構對傳感器各方面的性能均有顯著的增強效應。(2)利用硬模板法電化學制備了多孔聚苯胺(PANI)摻雜聚苯乙烯磺酸鈉(PSS)三維多孔納米材料,由于其具有大的比表面積、高的導電性和較多的功能基團,因此可作為固定甲胎蛋白(AFP)抗體的優(yōu)異基底,基于此我們構建了新型特異性檢測AFP的電化學生物傳感器。通過利用多孔PANI納米材料自身固有的氧化還原信號變化這一優(yōu)勢,所構建的AFP免疫傳感器無需外加氧化還原試劑,且對于目標物AFP的檢測展現出優(yōu)異的傳感性能。在最佳條件下,免疫傳感器對AFP的檢測呈現出較寬的線性范圍,即0.01-1,000 pg/m L,檢出限為5.3 fg/m L(S/N=3)。此外,該傳感器的響應靈敏度約為平面PANI修飾電極的兩倍,這說明3D多孔結構有利于增強傳感器的靈敏度。(3)利用硬模板法電化學制備了3D多孔結構的聚3,4-乙烯二氧噻吩(PEDOT)摻雜聚苯乙烯磺酸鈉(PSS)納米復合材料,并在多孔基底表面進一步電沉積AuNPs,得到AuNPs/PEDOT修飾電極。由于3D多孔納米結構的PEDOT擁有大的比表面積,因此可以負載大量的AuNPs。然后將巰基修飾的捕獲探針(P1)通過Au-S鍵作用固定在金顆粒表面,最終得到乳腺癌易感基因(BRCA1)特異性的電化學生物傳感器。在最優(yōu)條件下,基于納米多孔PEDOT材料的DNA生物傳感器對BRCA1的檢測展現出較高的靈敏度,其中線性范圍為1.0 fM-0.1 nM,檢出限為0.67 fM(S/N=3)�；谏鲜鲅芯�,所構建的電化學傳感器在生物傳感領域具有廣闊的應用前景。
[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.
【學位授予單位】：青島科技大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TB383.1;O657.1

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