烯丙基四苯基乙烯在构建荧光光纤传感器和油田荧光示踪剂中的应用

发布时间：2018-02-26 10:22

本文关键词： 荧光传感聚集诱导发光光纤传感器爆炸物检测油田荧光示踪剂　出处：《中国科学技术大学》2017年硕士论文　论文类型：学位论文

【摘要】：荧光分析传感技术具有设计简单、容易操作、选择性强、灵敏度高等优点在生物和化学物质分析、环境污染物检测等方面发挥着举足轻重的作用。然而,传统的荧光探针在分析检测时往往不可避免地存在着一些缺陷,如当探针浓度改变时通常会出现微小的stocks位移,荧光强度呈非线性改变,浓度过高则会发生聚集,使探针荧光发生聚集诱导荧光淬灭,因此影响了探针的荧光信号,降低了检测的灵敏度。相比其他传统的荧光材料,聚集诱导发光(Aggregation induced emission,AIE)类分子具有较突出的优点,在聚集态时,这类分子能够发出很强的荧光,而在溶液状态下只有很微弱的荧光,甚至没有荧光,这使提高荧光探针的灵敏度成为可能。在具有AIE特性的众多化合物中,因发光性能优良,合成方法简单、容易进行基团修饰等优势四苯基乙烯(Tetraphenylethylene,TPE)及其衍生物近年来受到了很多研究者的关注,并取得了许多成果。因此,本论文基于四苯基乙烯衍生物开展了一些研究,取得的阶段性成果如下:1.合成了四苯基乙烯的衍生物烯丙基四苯基乙烯(ALTPE)。将1,6-己二硫醇,ALTPE与含有八个乙烯基的聚倍半硅氧烷(POSS-V8)以及2,4,6-三甲基苯甲酰基氧化膦(UV819)光引发下,基于巯基-烯的(thiol-ene)"click"点击聚合机理,在乙烯基硅烷修饰的光纤锥表面光镀一层共价交联聚合物荧光多孔膜(PFSF),构建光纤锥荧光传感器。结果表明:PFSF呈现出ALTPE较好的AIE特性发出很强的蓝色荧光,同时具有较好的光热稳定性;POSS-V8的存在不仅可以使薄膜呈多孔性有助于气体的扩散,还能够降低膜的折射率,使更多的薄膜荧光耦合到光纤锥中。构建的光纤锥传感器可以实现对2,4,6-三硝基甲苯(TNT)和2,4-二硝基甲苯(DNT)等硝基芳香族爆炸物气体的检测,且重复使用性好,抗有机挥发类气体的干扰能力强。2.将烯丙基四苯基乙烯与苯乙烯、乙烯基苯磺酸钠通过分散聚合的方法制备了球形度高、粒径分布窄的交联聚合物荧光微球。结果表明:该微球分散到水溶液中具有较好的热稳定性、悬浮稳定性,在分散到水溶液中荧光强度不受pH值变化及金属离子存在的影响,有望应用在油田荧光失踪中,也为开发更多种油田荧光示踪剂提供了新思路。
[Abstract]:Fluorescence sensing technology has the advantages of simple design, easy operation, high selectivity and high sensitivity. It plays an important role in the analysis of biological and chemical substances and the detection of environmental pollutants. Some defects are inevitable in the analysis and detection of traditional fluorescent probe. For example, when the probe concentration changes, there is usually a small stocks shift, the fluorescence intensity is nonlinear, and the concentration is too high. The fluorescence of the probe was induced by fluorescence agglomeration induced fluorescence quenching, which affected the fluorescence signal of the probe and reduced the sensitivity of the detection. Compared with other traditional fluorescent materials, the aggregation induced luminescence induced Mission AIEs have outstanding advantages. In the aggregated state, these molecules emit very strong fluorescence, while in the solution state there is only very weak fluorescence, or even no fluorescence, which makes it possible to improve the sensitivity of the fluorescence probe. Because of its excellent luminescence properties, simple synthesis method and easy group modification, Tetraphenylethyleneine (TPE) and its derivatives have been paid much attention by many researchers in recent years, and many achievements have been made in the synthesis of Tetraphenylethyleneine (TPE) and its derivatives. In this paper, some studies were carried out based on tetraphenyl ethylene derivatives. The results obtained are as follows: 1. Allyl tetraphenyl ethylene derivatives ALTPEPe have been synthesized. Under the photoinitiation of ALTPE and POSS-V8 (containing eight vinyl groups) and UV819, the derivatives of tetraphenyl ethylene were synthesized. Thiol-ene-based thiol-ene) "click" click polymerization mechanism, An optical fiber cone fluorescence sensor was constructed by photoplating a layer of covalent cross-linked polymer fluorescence porous film on the surface of the fiber cone modified by vinyl silane. The results showed that the AIE of ALTPE showed a strong blue fluorescence. At the same time, the existence of POSS-V8 with good photothermal stability can not only make the film porous to help the gas diffusion, but also reduce the refractive index of the film. The optical fiber cone sensor can be used for the detection of nitro aromatic explosive gases, such as 2N 4N 6 trinitrotoluene (TNT) and 2 N 4 dinitrotoluene (DNT), and has good reusability. The ability to resist the interference of organic volatile gases is strong. 2. Allyl tetraphenylethylene, styrene and sodium vinyl benzene sulfonate were prepared by dispersion polymerization. The results showed that the microspheres dispersed into aqueous solution had good thermal stability and suspension stability, and the fluorescence intensity was not affected by the change of pH value and the presence of metal ions. It is expected to be used in oil field fluorescence disappearance, and it also provides a new idea for the development of more oil field fluorescent tracers.
【学位授予单位】：中国科学技术大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TP212;TE39;O657.3

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