表面分子印迹石墨烯复合材料的制备及应用

发布时间：2018-01-11 19:44

本文关键词：表面分子印迹石墨烯复合材料的制备及应用　出处：《江南大学》2015年硕士论文　论文类型：学位论文

【摘要】：表面分子印迹技术是将分子识别位点设计在载体表面或接近表面的地方,制得的表面分子印迹聚合物与传统的分子印迹聚合物相比,具有目标分子更易接近印迹位点、吸附动力学更快、吸附容量更高等优点。表面分子印迹聚合物近年来已在手性分离、固相萃取以及化学仿生传感器等领域展现出良好的应用前景,引起了研究者们的广泛关注。石墨烯具有大的比表面积,优异的电、热、机械性能,是制备表面印迹材料很好的载体。本论文对石墨烯进行修饰,成功制备出一系列表面分子印迹石墨烯复合材料,并应用于电化学传感器和糖蛋白的特异性识别和分离。本论文具体研究内容如下:(1)通过非共价键修饰法获得了乙烯基功能化的石墨烯(GR/NVC),以其为载体,以对硝基苯酚(4-NP)为模板分子、甲基丙烯酸为单体、乙二醇二甲基丙烯酸酯为交联剂、AIBN为引发剂,制备石墨烯表面印迹复合材料(GR/MIPs)。探究了制备条件的影响,如N-乙烯基咔唑(NVC)和模板分子的浓度、溶液的p H值、孵化时间等。将石墨烯表面印迹复合材料应用于电化学传感器的制备,制备的GR/MIPs传感器能特异性识别和检测4-NP,对4-NP的DPV电流响应是GR/NIPs传感器的12倍,与传统的MIP传感器相比,GR/MIPs传感器吸附动力学更快、电流响应值更高。GR/MIPs传感器对4-NP的线性检测范围是0.01~100μM和200~1000μM,检测下限是5 n M。与绝大多数4-NP电化学传感器相比,GR/MIPs传感器检测范围更宽,检测下限更低,具有良好的选择性、稳定性和再现性,可以检测湖水和自来水样品中4-NP。(2)室温下利用溶胶-凝胶技术,一锅法水相合成氧化石墨烯分子印迹复合材料(GO/MIPs)。以氧化石墨烯(GO)为载体,扑热息痛(PR)为模板分子,苯基三乙氧基硅烷和四甲氧基硅烷为单体,结合表面印迹技术和溶胶-凝胶法,在氧化石墨烯表面制备对PR具有特异性识别作用的分子印迹聚合物(GO/MIPs)。将GO/MIPs应用于电化学传感器检测PR,并探究了单体和模板分子的量及孵化时间等因素的影响。GO/MIP传感器对PR有特异性识别能力,对PR的线性检测范围是0.1~80μM,检测下限为0.02μM。与其它大多数PR电化学传感器相比,有较宽的线性检测范围和较低的检测下限。GO/MIP传感器还具有良好的稳定性,检测药片和人尿液中的PR的结果也令人满意。(3)结合表面分子印迹、硼亲和作用和溶胶-凝胶技术制备一种新型的硼酸修饰氧化石墨烯蛋白印迹复合材料(GO/APBA/MIPs),用于特异性识别和分离卵清蛋白(OVA)。探讨了硅氧烷、3-氨基苯硼酸和模板蛋白的量,反应时间,缓冲溶液的p H值对复合材料识别性能的影响。通过吸附实验发现,GO/APBA/MIPs具有吸附动力学快(60min达到吸附平衡)、吸附容量大(359.7 mg g-1)、对OVA有特异性识别能力等优点。由于引入硼酸基团,利用其对糖蛋白的硼亲和作用,使得GO/APBA/MIPs比GO/MIPs在印迹作用的基础上,对OVA的吸附能力、特异性识别能力均得到进一步提高,可用于分离OVA。
[Abstract]:The surface molecular imprinting technique to design molecular recognition sites on the surface of the carrier or near the surface, compared to molecular imprinted polymer surface molecular imprinted polymers were prepared with the traditional, more accessible with target molecular imprinting sites, faster adsorption kinetics, adsorption capacity of more high. Surface molecular imprinted polymers in recent years has been in chiral separation. The field of solid phase extraction and chemical bionic sensor show a good application prospect, has aroused widespread concern of researchers. Graphene has a large surface area, excellent mechanical properties, electrical, thermal, carrier preparation of surface imprinted material is very good. The modification of graphene was successfully prepared a series of surface molecular imprinting graphene composites, identification and isolation of specific and applied to the electrochemical sensor and glycoproteins. The major contents in this dissertation are as follows: (1). A non covalent modification of graphene obtained vinyl functionalized (GR/NVC), with its carrier, with p-nitrophenol (4-NP) as the template molecule, methacrylic acid as monomer, ethylene glycol two methyl acrylate as crosslinking agent, AIBN as initiator, the preparation of graphene surface imprinted composite material (GR/MIPs). To explore the influence of preparation conditions, such as N- vinylcarbazole (NVC) and the concentration of the template molecule, the solution p value of H, incubation time. The application of graphene surface imprinted composite materials in electrochemical sensor preparation, GR/MIPs sensor prepared specific recognition and detection of 4-NP, DPV the current response for 4-NP is 12 times of the GR/NIPs sensor, compared with the traditional MIP sensor, faster kinetics of adsorption of GR/MIPs sensor,.GR/MIPs sensor with high current linear response to 4-NP detection range is 0.01~100 M and 200~1000 M, the detection limit is 5 N M. and the Compared to most of the 4-NP electrochemical sensor, GR/MIPs sensor to detect a wider range, lower detection limit, good selectivity, stability and reproducibility, can detect 4-NP. lake water and tap water samples (2) by sol-gel method at room temperature, one pot of water phase synthesis of graphene oxide molecular imprinting composite (GO/MIPs). The oxidation graphene (GO) as the carrier, paracetamol (PR) as the template molecule, phenyltriethoxysilane and tetramethoxysilane as monomer, combined with surface imprinting technique and sol-gel method, molecular imprinted polymer in graphene oxide surface preparation with specific recognition of PR (GO/MIPs). The application of GO/MIPs in electrochemical sensor for the detection of PR, and to explore the influence of the.GO/MIP sensor monomer and template molecule weight and incubation time and other factors have specific recognition ability of PR, the linear detection range of PR is 0.1~80 M, a detection limit of 0.02 M. compared with most other PR electrochemical sensor, a wide linear detection range and lower detection limit of.GO/MIP sensor has good stability, the results of urine pills and people in PR are satisfactory. (3) combined with the surface molecular imprinting, boron affinity and the sol-gel method to prepare a boronic acid modified graphene oxide blot new composite materials (GO/APBA/MIPs), for the specific recognition and separation of ovalbumin (OVA). To investigate the siloxane, 3- amino phenylboronic acid and template protein amount, reaction time, buffer solution p the effect of H on the recognition performance of composite materials. The adsorption experiments found that GO/APBA/MIPs has a faster adsorption kinetics (60min adsorption equilibrium), adsorption capacity (359.7 mg g-1), the advantages of the OVA specific recognition ability. Because of the introduction of boric acid group, use the The boron affinity of glycoprotein made GO/APBA/MIPs more capable of adsorbing OVA and specific recognition ability than GO/MIPs on the basis of imprinting, and it could be used to separate OVA..

【学位授予单位】：江南大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB33

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