表面印迹ZnO荧光传感器的制备及其选择性检测四环素类抗生素的研究

发布时间：2018-05-27 00:34

本文选题：分子印迹聚合物 + 四环素　；参考：《江苏大学》2017年硕士论文

【摘要】：四环素(TC)是一种具有高浓度灭菌的广谱抑菌剂,由于价格低且抗菌效果明显,已广泛应用于水产养殖和兽药,以促进动物的快速生长和预防动物疾病。但是TC的过量使用会导致其在一些肉类食物和水体中严重超标。超标的食物会直接危害人类健康,而进入水体的TC不仅会危害生态环境,还会通过生态食物链系统进入人体,同样危害人类健康。基于荧光传感器的荧光分析检测方法由于具有样品处理简单、检出限低、灵敏度高、响应时间短、抗干扰能力强、可直接观察等优点,被用于检测各类有毒有害的物质。然而荧光传感器一般并不具备选择性识别能力,而与表面分子印迹技术(SMIT)的结合能赋予荧光传感器专一识别目标分子的能力,并且在不影响荧光传感器光学性能的基础上,提高其物化稳定性。而制备分子印迹聚合物(MIPs)的方法有很多种,例如沉淀聚合、溶胶-凝胶(Sol-gel)聚合和原子转移自由基聚合(ATRP)等。但对不同聚合方法制备的分子印迹荧光传感器的形貌、结构、荧光性能和分析检测性能之间的相互关系,还未有报道。本论文以TC为目标分子,以氧化锌纳米棒(ZnO NRs)为固体基质和荧光传感器,分别通过沉淀聚合、Sol-gel聚合和ATRP制备表面分子印迹ZnO荧光传感器(MIPs-ZnO NRs);利用透射电子显微镜(TEM)、傅立叶变换红外光谱仪(FT-IR)、紫外光谱仪(UV-vis)、X射线衍射仪(XRD)和分子荧光分光光度计等表征仪器研究了MIPs-ZnO NRs的形貌、结构和光学性能;通过对MIPs-ZnO NRs的浓度、稳定性和响应时间等因素的研究,确定了最佳的检测TC的条件。通过选择性识别和定量检测实验,研究了这几种不同聚合方法制备的MIPs-ZnO NRs对水相中TC的荧光识别和检测能力。主要研究成果如下:(1)首先通过水热法制备ZnO NRs,并通过KH570在其表面修饰上乙烯基,将其作为荧光材料和支撑材料;再通过沉淀聚合法制备MIPs-ZnO NRs;最后将其用于选择性检测水环境中TC。(2)将ZnO NRs作为荧光材料和支撑材料、十六烷基三甲基溴化铵(CTAB)作为致孔剂,通过Sol-gel法制备了介孔表面印迹ZnO荧光传感器(PMIPs-ZnO NRs)。洗脱完TC和CTAB的PMIPs-ZnO NRs可以实现对TC的选择性检测。在本实验中,将特殊结构(介孔)引入到MIPs-ZnO NRs,同时也制备了无介孔的MIPs-ZnO NRs(NPMIPs-ZnO NRs),通过对两者选择性检测TC的研究,分析总结介孔在MIPs-ZnO NRs选择性检测TC中的作用。(3)首先,在ZnO NRs修饰上NH_2,在此基础上修饰上溴代烷烃,将其作为荧光材料、支撑材料和引发剂。通过ATRP法制备一种印迹聚合层超薄的MIPs-ZnO NRs,并将其用于选择性检测TC。在本实验中,ATRP法是一种新型的活性自由基聚合法,可以实现聚合层厚度可控,有助于提高选择性检测TC性能。
[Abstract]:Tetracycline (TCC) is a broad-spectrum bacteriostatic agent with high concentration of sterilization. Because of its low cost and obvious antibacterial effect, it has been widely used in aquaculture and veterinary drugs to promote the rapid growth of animals and prevent animal diseases. But the overuse of TC can cause it to exceed the standard in some meat food and water body. Food in excess of the standard will directly harm human health, while TC entering the water body will not only harm the ecological environment, but also enter the human body through the ecological food chain system, which will also endanger human health. Due to the advantages of simple sample processing, low detection limit, high sensitivity, short response time, strong anti-interference ability and direct observation, the fluorescence detection method based on fluorescence sensor is used to detect various toxic and harmful substances. However, fluorescence sensors generally do not have selective recognition ability, and the combination with surface molecular imprinting technology can give fluorescence sensors the ability to specifically recognize target molecules, and on the basis of not affecting the optical properties of fluorescence sensors, The physicochemical stability is improved. There are many methods for preparing molecularly imprinted polymer (MIPs), such as precipitation polymerization, sol-gel polymerization and atom transfer radical polymerization (ATRP). However, the relationship between the morphology, structure, fluorescence properties and analytical properties of molecularly imprinted fluorescent sensors prepared by different polymerization methods has not been reported. In this thesis, TC was used as target molecule, ZnO NRs was used as solid matrix and fluorescence sensor was used. Surface molecularly imprinted ZnO fluorescence sensors MIPs-ZnO NRsO were prepared by precipitation polymerization of sol-gel and ATRP, respectively, using transmission electron microscopy (TEM), Fourier transform infrared spectrometer (FTIR), UV-VIS X-ray diffractometer (XRD) and molecular fluorescence spectroscopy (MFS). The morphology of MIPs-ZnO NRs was studied by means of meter and other characterization instruments. The optimum conditions of TC detection were determined by studying the concentration, stability and response time of MIPs-ZnO NRs. The fluorescence recognition and detection of TC in aqueous phase by MIPs-ZnO NRs prepared by different polymerization methods were studied by selective recognition and quantitative detection experiments. The main research results are as follows: firstly, ZnO NRs were prepared by hydrothermal method, and then modified with vinyl on the surface by KH570, which were used as fluorescent materials and support materials. MIPs-ZnO NRs were prepared by precipitation polymerization, and then used for selective detection of TC.Rs2 in water environment. ZnO NRs was used as fluorescent material and supporting material, and cetyltrimethylammonium bromide (CTAB) was used as pore-forming agent. A mesoporous surface imprinted ZnO fluorescence sensor, PMIPs-ZnO NRsO, was prepared by Sol-gel method. After eluting TC and CTAB PMIPs-ZnO NRs can realize the selective detection of TC. In this experiment, special mesoporous structure (mesoporous) was introduced into MIPs-ZnO NRs, and MIPs-ZnO NRs(NPMIPs-ZnO NRsS without mesoporous was also prepared. The role of mesoporous in MIPs-ZnO NRs selective detection of TC was analyzed and summarized. NH _ 2 was modified by ZnO NRs and then brominated alkanes were modified as fluorescent materials, supporting materials and initiators. A kind of ultra-thin MIPs-ZnO NRs with imprinted polymerization layer was prepared by ATRP method and used for selective detection of MIPs-ZnO. In this experiment, ATRP is a new active radical polymerization method, which can control the thickness of polymerization layer and improve the performance of selective detection of TC.
【学位授予单位】：江苏大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3;X832

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