功能化碳量子点的制备及其电化学发光免疫分析应用

发布时间：2018-06-01 13:15

本文选题：碳量子点 + 石墨烯　；参考：《聊城大学》2016年硕士论文

【摘要】：电致化学发光(ECL)是由电化学反应产生的化学发光,由于其不需要外加激发光源,而且背景信号低,线性范围宽,设备简单,现已成为一种应用广泛的具有高灵敏度和高选择性的检测方法。ECL免疫传感器是将电致化学发光技术和免疫技术的优点相结合而发展的产物。免疫分析信号增强技术一直是免疫分析领域研究的一个重要课题,而将抗体与抗原固定在传感器表面是一个非常重要的步骤,这对于提高传感器的灵敏度至关重要。近年来,新型纳米材料、信号增强技术和蛋白质固定化技术在电化学免疫传感器检测肿瘤标志物中的应用研究颇受关注。纳米技术与免疫分析方法的结合为免疫分析的研究与发展提供了新的思路,特别是复合纳米材料具有独特的性质,对发展高灵敏的免疫传感器起了非常重要的作用。近年来,新型碳纳米材料如碳纳米管(CNTs)、石墨烯(Graphene)、碳量子点(CQDs)等由于其独特的性质而被广泛应用于很多领域。石墨稀因具有大的比表面积、机械强度高、化学稳定性高、导热性突出等优点而广泛应用于能量储存和转换、催化、医学、生物传感器等方面。碳量子点因具有稳定的化学组成、低毒性、发光性能优良、制备成本低和生物相容性等特点,在生物成像、光电催化、氧化还原、药物识别等领域具有良好的应用前景。本文主要以功能化碳量子点的制备及其在电化学生物传感器中的应用为主旨,具体开展了以下研究工作:1.碳量子点及含杂碳量子点的制备与表征成功制备了碳量子点(CQDs)及含杂碳量子点,用TEM对其外貌形态进行了表征,用紫外吸收光谱和荧光光谱对其光学行为进行了研究,同时还研究了其电化学发光行为。结果显示,制备的CQDs及含杂CQDs,其颗粒均一,具有可控发光性,而且电化学发光信号稳定。另外,还利用CQDs的还原性,成功制备了具有多面体结构的纳米金颗粒(AuNPs),这与传统方法制备的AuNPs是不同的。2.一种基于CQDs的测量癌胚抗原(CEA)的电化学发光夹心免疫传感器成功制备了一种基于CQDs测量CEA的电化学发光夹心免疫传感器。用聚多巴胺和银纳米颗粒的聚合物(PDA-AgNPs)作为平台固定一抗(Ab1),同时也能够提高电子传导速率。CQDs通过氨基固定在聚乙烯亚胺(PEI)功能化的石墨烯氧化物(GO)上,然后将AuNPs固定在CQDs-PEI-GO上后再与二抗(Ab2)键合。通过CEA与Ab1和Ab2的结合,CQDs能够固定在电极表面而产生电化学发光信号。在最佳实验条件下,该传感器ECL强度与CEA浓度的对数呈线性关系,线性方程为IECL=3380.3+1138.4 lg cCEA/ng mL-1,相关系数为R=0.9989,CEA的最低检出限为1.67 pg mL-1(S/N=3)。该传感器还成功应用于实际样品中CEA的检测。该传感器具有良好的灵敏度、稳定性、特异性和重现性,有望应用于疾病诊断中。3.一种基于CQDs与联吡啶钌(Ru(bpy)32+)共反应检测双酚A(BPA)的电化学发光传感器成功制备了一种基于CQDs与Ru(bpy)32+共反应测定BPA的ECL传感器。将CQDs固定在聚吡咯功能化的石墨烯氧化物(PPy-GO)上制备了复合物PPy-GO-CQDs并修饰在电极表面,PPy-GO不仅能够负载大量CQDs而且能够加快电极与溶液之间的电子传输,进而提高检测的灵敏度。然后用修饰好的电极在含有Ru(bpy)32+的溶液中,利用BPA对Ru(bpy)32+/CQDs发光体系的ECL的猝灭作用来检测BPA。在最佳实验条件下,该传感器对BPA检测的线性范围为5-1000 nmol mL-1,检出限为2 nmol mL-1。实验证明该传感器具有良好的稳定性,较高的灵敏度和更低的检出限和更宽的线性范围。4.基于碳量子点(CQDs)做联吡啶钌(Ru(bpy)32+)电化学发光的共反应剂对癌胚抗原(CEA)的高灵敏检测成功制备了一种基于CQDs与Ru(bpy)32+共反应测定CEA的夹心免疫ECL传感器。将CQDs固定在PEI-GO上,然后选用CQDs-PEI-GO复合物来固定一抗Ab1。用介孔硅(MSN)负载Ru(bpy)32+和固定AuNPs,其中AuNPs能够增加电子的传导进而增大ECL信号。同时,将二抗Ab2固定在MSN上。这里,CQDs作为Ru(bpy)32+发光的共反应剂。在最佳实验条件下,该传感器的线性范围为1 pg·mL-1-1000ng·mL-1,检出限是0.33 pg mL-1(S/N=3)。该传感器具有良好的特异性、稳定性和重现性。
[Abstract]:Electrochemiluminescence (ECL) is an electrochemiluminescence (chemiluminescence) produced by electrochemical reaction. Because it does not need an excited light source, and the background signal is low, the linear range is wide and the equipment is simple, it has become a widely used detection method with high sensitivity and high selectivity,.ECL immune sensor is the Electrochemiluminescence and immunization technology. The immunoassay signal enhancement technology has been an important subject in the field of immunization analysis, and it is a very important step to immobilized the antibody and antigen on the surface of the sensor, which is very important to improve the sensitivity of the sensor. In recent years, the new nano materials, signal enhancement technology and The application of protein immobilization technology in the detection of tumor markers by electrochemical immunosensor has attracted much attention. The combination of nanotechnology and immunoassay method provides a new idea for the research and development of immunoassay, especially the unique properties of the composite nanomaterials, which are very important for the development of highly sensitive immune sensors. In recent years, new carbon nanomaterials, such as carbon nanotubes (CNTs), graphene (Graphene) and carbon quantum dots (CQDs), have been widely used in many fields because of their unique properties. Graphite thinning has been widely used in energy storage and energy storage because of its large specific surface area, high mechanical strength, high chemical stability, high thermal conductivity and so on. Carbon quantum dots have good application prospects in the fields of bioimaging, photoelectrocatalysis, oxidation-reduction, and drug recognition because of their stable chemical composition, low toxicity, good luminescence, low preparation cost and biocompatibility. This paper mainly focuses on the preparation of functional carbon quantum dots. And its application in electrochemical biosensor is the main purpose. The following research work has been carried out: the preparation and characterization of 1. carbon quantum dots and hetero carbon quantum dots (QDs) have successfully prepared carbon quantum dots (CQDs) and heterocarbon quantum dots. The morphology of them was characterized by TEM, and the optical behavior of them was carried out by UV absorption and fluorescence spectra. At the same time, the electrochemical luminescence behavior was also studied. The results showed that the prepared CQDs and heterozygous CQDs were homogeneous, with controllable luminescence, and the electrochemiluminescence signal was stable. In addition, the polyhedral structure of nangolden particles (AuNPs) was successfully prepared by the reducibility of CQDs, which was not with the traditional method of AuNPs. .2. a CQDs based electrochemiluminescence sandwich immunosensor for the measurement of carcinoembryonic antigen (CEA), an electrochemiluminescence sandwich immunosensor based on CQDs for the measurement of CEA is successfully prepared. The polymer (PDA-AgNPs) of polydopamine and silver nanoparticles (PDA-AgNPs) is used as a platform to immobilizing an antibody (Ab1), and it can also improve the electron conduction rate.CQD. S is immobilized on the polyethyleneimine (PEI) functionalized graphene oxide (GO) through the amino group, then AuNPs is immobilized on CQDs-PEI-GO and then bonded to the two anti (Ab2). By combining CEA with Ab1 and Ab2, CQDs can be fixed on the surface of the electrode to produce electrochemiluminescence signals. Under optimal experimental conditions, the ECL intensity and CEA concentration of the sensor are in the best experimental condition. The linear equation is linear, the linear equation is IECL=3380.3+1138.4 LG cCEA/ng mL-1, the correlation coefficient is R=0.9989, the minimum detection limit of CEA is 1.67 PG mL-1 (S/N=3). The sensor is also successfully applied to the detection of CEA in the actual sample. The sensor has good sensitivity, stability, specificity and reproducibility, and is expected to be applied to.3 in the diagnosis of disease. An electrochemiluminescence sensor based on the co reaction of CQDs and Ru (bpy) 32+ for the detection of bisphenol A (BPA) was used to prepare a ECL sensor based on CQDs and Ru (bpy) 32+ co reaction assay BPA. -GO can not only load a large number of CQDs but also accelerate the electronic transmission between the electrode and the solution, and then improve the sensitivity of the detection. Then, the modified electrode is used in the solution containing Ru (bpy) 32+ to detect the BPA. on the ECL of the ECL of the Ru (bpy) 32+/CQDs luminescence system by BPA. The sensor is used to detect BPA. The linear range of 5-1000 nmol mL-1, the detection limit of 2 nmol mL-1. experiments proved that the sensor has good stability, high sensitivity and lower detection limit and wider linear range.4. based on carbon quantum dots (CQDs) as a co reactants of the Ru (Ru (bpy) 32+) electrochemical luminescence (Ru (bpy) 32+) for the high sensitivity detection of carcinoembryonic antigen (CEA) A sandwich immune ECL sensor based on the co reaction of CQDs and Ru (bpy) 32+ was prepared. CQDs was immobilized on PEI-GO, and the CQDs-PEI-GO complex was used to fix an anti Ab1. mesoporous silicon (MSN) load Ru. On N. Here, CQDs is a co reactant of Ru (bpy) 32+. Under the best experimental conditions, the linear range of the sensor is 1 pg. ML-1-1000ng. ML-1, and the detection limit is 0.33 PG mL-1 (S/N=3). The sensor has good specificity, stability and reproducibility.
【学位授予单位】：聊城大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O657.3

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