基于荧光猝灭原理的溶解氧传感膜制备新技术的研究

发布时间：2018-03-09 16:08

本文选题：溶解氧传感膜　切入点：荧光猝灭原理　出处：《浙江工业大学》2015年硕士论文　论文类型：学位论文

【摘要】：溶解氧浓度检测对于环境监测、工业生产、临床医学以及水产养殖等领域均有十分重要的意义。传统的溶解氧检测方法是Clark电极法。然而,Clark电极容易被样品中的其它组分污染(如H2S、蛋白质等),并且在检测过程中消耗氧气,破坏检测样本。因此,近年来基于荧光猝灭原理的溶解氧传感器以其灵敏度高、检测速度快并能在线检测等优势受到越来越多研究者的关注。作为光学溶解氧传感器的核心组件,溶解氧传感膜的性能尤为重要,它通常由氧敏荧光指示剂和支撑基质组成。目前,随着工业的发展,溶解氧传感膜在长期稳定性、灵敏度等方面仍需进一步的提升。本文通过氟化有机改性溶胶-凝胶法制备高性能的基于荧光猝灭原理的溶解氧传感膜,并采用可逆加成/断裂链转移(RAFT)细乳液界面聚合法制备包埋荧光指示剂的纳米聚合物粒子,以探索提高溶解氧传感膜性能的新方法。以四乙氧基硅烷(TEOS)和3,3,3-三氟丙基三甲氧基硅烷(TFP-TMOS)为前驱体,以三(4,7-联苯-1,10-邻菲Up啉)二氯化钌为氧敏荧光指示剂,采用氟化有机改性溶胶-凝胶法制备溶解氧传感膜。通过单因素实验,对溶解氧传感膜的性能进行了优化,并且对优化后传感膜的表面形态进行分析,同时结合溶解氧传感器对传感膜在灵敏度、响应速度以及长期稳定性等性能进行检测。结果表明,氟化有机改性溶胶-凝胶法制备的溶解氧传感膜具有灵敏度高、响应速度快、长期稳定性好等优点。以甲基丙烯酸甲酯(MMA)为反应单体,石蜡和三(4,7-联苯-1,10-邻菲Up啉)二氯化钌的混合液为核心材料,自制双亲性大分子RAFT试剂充当乳化剂和RAFT试剂,以偶氮异丁腈(AIBN)为引发剂,采用RAFT(可逆加成/断裂链转移)细乳液界面聚合法成功制备了包含荧光指示剂的纳米聚合物粒子。主要研究了AIBN的用量对聚合反应的转化率和粒子形态的影响以及RAFT试剂对粒子粒径的调节规律。结果表明:荧光指示剂被成功包裹到纳米聚合物粒子内部,聚合物粒子呈规整的球形结构,且粒径分布均匀;粒子的粒径随RAFT试剂用量增大而减小。此外,进一步探索了将所制备的包含荧光指示剂的纳米聚合物粒子分散到优化后的氟化有机改性溶胶-凝胶基质中以制备溶解氧传感膜。
[Abstract]:Determination of dissolved oxygen concentration for environmental monitoring, industrial production, Clinical medicine and aquaculture are of great significance. The traditional method for detection of dissolved oxygen is the Clark electrode. However, the Clark electrode is liable to be contaminated by other components of the sample (such as H2S, protein, etc.). Consuming oxygen in the process, Therefore, in recent years, the dissolved oxygen sensor based on the principle of fluorescence quenching has high sensitivity. More and more researchers pay attention to the advantages of high detection speed and on-line detection. As the core component of optical dissolved oxygen sensor, the performance of dissolved oxygen sensing film is particularly important. It usually consists of oxygen sensitive fluorescent indicators and supporting substrates. At present, with the development of industry, the dissolved oxygen sensing membrane is stable in the long run. In this paper, the fluorinated organic modified sol-gel method is used to prepare the high performance dissolved oxygen sensing film based on the principle of fluorescence quenching. The nano polymer particles embedded with fluorescent indicator were prepared by reversible addition / chain break transfer (RAFT) fine emulsion interfacial polymerization. In order to explore a new method to improve the performance of dissolved oxygen sensing film, using tetraethoxy silane (TEOS) and 3H 3fluoropropyl trimethoxy silane (TFP-TMOS) as the precursors, the oxygen sensitive fluorescence indicator of ruthenium dichloride (Ru _ 2O _ 2) was used as the indicator of oxygen-sensitive fluorescence, using trisodioxy-7- biphenyl -10- (o-phenanthroline) as fluorescent indicator, and trifluoropropyltrimethoxysilane (TFP-TMOS) as the precursor. The dissolved oxygen sensing membrane was prepared by fluorinated organic modified sol-gel method. The performance of the dissolved oxygen sensing film was optimized by single factor experiment, and the surface morphology of the optimized film was analyzed. At the same time, the sensitivity, response speed and long-term stability of the sensing film were tested by the dissolved oxygen sensor. The results show that the dissolved oxygen sensing film prepared by fluorinated organic sol-gel method has high sensitivity and fast response speed. Using methyl methacrylate (MMA) as reaction monomer, paraffin and Ru _ 2 as core materials, amphiphilic macromolecule RAFT reagent was used as emulsifier and RAFT reagent. Using azo-iso-butyronitrile (AIBN) as initiator, Nanosized polymer particles containing fluorescent indicators were successfully prepared by RAFT (reversible addition / chain break transfer) fine emulsion interfacial polymerization. The effects of the amount of AIBN on the conversion and particle morphology of the polymerization were studied. The results showed that the fluorescent indicator was successfully encapsulated into the inner of nano-polymer particles. The polymer particles have a regular spherical structure, and the particle size distribution is uniform, and the particle size decreases with the increase of the amount of RAFT reagent. In order to prepare the dissolved oxygen sensing film, the nanoparticles containing fluorescent indicator were dispersed into the fluorinated organic modified sol-gel matrix.
【学位授予单位】：浙江工业大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：O631;TB383.2

【相似文献】