新型多孔有机聚合物材料的合成、表征及生物免疫传感器的设计

发布时间：2018-08-26 18:12

【摘要】：多孔材料发展至今,从无机到有机,从单体小分子到聚合物,从单一材料到复合材料,多孔材料的足迹已经遍布整个材料化学领域。多孔有机聚合物材料作为多孔材料家族中新兴而年轻的一员,在科研人员的广泛关注和研究下,在气体吸附与分离、非均相催化、生物化学传感以及光电材料等领域得到了迅猛发展。在众多多孔有机聚合物材料中,共价有机骨架材料(COFs)兼备有序的孔结构和良好的结晶性。无定形的共价有机聚合物材料(COPs)具有高比表面积、易修饰的孔结构、超强的热稳定性和化学稳定性,引起了广泛的研究热潮。而对于制备生物传感器的材料来讲,关于多孔有机聚合物材料的应用极少。鉴于这两点,本论文设计及合成了一种新型的共价有机聚合物材料(FePor-TFPA-COP)和一种新型的共价有机框架材料(D-T-COF),并且对它们的结构进行了表征,对其性质进行了系统研究,并设计了两种类型的生物免疫传感器,将其用于甲胎蛋白的定量检测。论文具体论述了两个方面的工作:1.通过吡咯和三(4-甲酰基苯基)胺(TFPA)之间芳香取代反应合成了基于铁卟啉的共价有机聚合物,FePor-TFPA-COP。构筑单元的三角锥形结构使FePor-TFPA-COP形成三维结构,因而具有更大的表面积和丰富的表面催化活性位点。FePor-TFPA-COP在H2O2存在下表现出对于经典的过氧化物酶底物3,3',5,5'-四甲基联苯胺(TMB)的强的内在过氧化物酶活性。与辣根过氧化物酶(HRP)相比,FePor-TFPA-COP具有易储存、高灵敏度,以及在恶劣条件下显著的化学和催化稳定性,这保证了测量的准确性和可靠性。首先建立了基于FePor-TFPA-COP的比色免疫传感器,用于甲胎蛋白(AFP)的检测,其线性响应范围为5 pg/mL至100ng/mL,检测限为1pg/mL。同时对实际血清样本中的AFP进行了检测,得到了比较理想的结果,表明该传感器的特异性、灵敏度、实验重复性和稳定性良好。2.以DHNDA和TAPB作为基本结构单元,通过席夫碱反应,以溶剂热法合成了具有高比表面积的新型共价有机框架材料,命名为D-T-COF。同时,通过一系列表征手段证明了材料的有序结构和组成成分,并观察其形貌。通过原位生长策略,让D-T-COF材料直接生长在ITO衬底上,研究了其光电性质。凭借出色的光电流信号,我们设计了一种简单的无标记的PEC免疫传感器检测AFP抗原浓度。在5 ng/mL到50 ng/mL的浓度范围内,该PEC免疫传感器显示出良好的线性特征。此外,该传感器也具有良好的特异性和稳定性。
[Abstract]:Since the development of porous materials, from inorganic to organic, from monomers to polymers, from single materials to composite materials, the footprints of porous materials have spread all over the field of material chemistry. As a new and young member of the porous material family, porous organic polymer materials are widely concerned and studied by researchers, in gas adsorption and separation, heterogeneous catalysis. Biochemistry sensing and optoelectronic materials have been developed rapidly. Among many porous organic polymer materials, the covalent organic skeleton material (COFs) has both ordered pore structure and good crystallinity. Amorphous covalent organic polymer (COPs) with high specific surface area, easy to modify pore structure, super thermal stability and chemical stability, has caused a wide range of research. However, there are few applications of porous organic polymer materials for the preparation of biosensors. In view of these two points, a new covalent organic polymer material (FePor-TFPA-COP) and a new covalent organic frame material (D-T-COF) were designed and synthesized in this paper, and their structures were characterized and their properties were systematically studied. Two types of biosensors were designed for quantitative detection of alpha-fetoprotein. The paper specifically discusses two aspects of work: 1. FePor-TFPA-COP, a covalent organic polymer based on iron porphyrin, was synthesized by aromatic substitution reaction between pyrrole and tris (4-formylphenyl) amine (TFPA). The triangular conical structure of the building unit causes the FePor-TFPA-COP to form a three-dimensional structure. In the presence of H2O2, FePor-TFPA-cop showed a strong intrinsic peroxidase activity to the classical peroxidase substrate (3O3O3O5O5O5, TMB), and thus had a larger surface area and a rich surface catalytic activity site, I. e., FePor-TFPA-cop showed strong intrinsic peroxidase activity in the presence of H2O2. Compared with horseradish peroxidase (HRP), FePor-TFPA-cop has the advantages of easy storage, high sensitivity, and remarkable chemical and catalytic stability under harsh conditions, which ensures the accuracy and reliability of the measurement. Firstly, a colorimetric immunosensor based on FePor-TFPA-COP was established for the detection of alpha-fetoprotein (AFP). The linear response range was from 5 pg/mL to 100 ng / mL, and the detection limit was 1 PG / mL. At the same time, the AFP in the actual serum samples was detected, and the satisfactory results were obtained, indicating the specificity, sensitivity, experimental repeatability and stability of the sensor. 2. A novel covalent organic frame material with high specific surface area was synthesized by Schiff base reaction with DHNDA and TAPB as the basic structure unit and named D-T-COF. At the same time, the ordered structure and composition of the material were proved by a series of characterization methods, and its morphology was observed. The optoelectronic properties of D-T-COF materials grown on ITO substrates were investigated by in situ growth strategy. With excellent photocurrent signal, we designed a simple unlabeled PEC immunosensor to detect AFP antigen concentration. In the range of 5 ng/mL to 50 ng/mL, the PEC immunosensor showed good linear characteristics. In addition, the sensor also has good specificity and stability.
【学位授予单位】：山东大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ317;TP212.3

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