多功能荧光化学传感器、荧光力传感器的设计合成

发布时间：2018-05-02 05:50

  本文选题：多功能荧光传感器 + 2　； 参考：《中国科学技术大学》2017年博士论文

【摘要】：荧光传感器在环境污染监测、生命科学、电子信息等领域扮演着非常重要的角色,并在最近十几年里面取得了长足的发展。作为其中重要的一员,荧光化学传感器由于具有高灵敏度、高选择性、简便易行以及实时检测等优点而备受关注。已有许多类型的荧光化学传感器被设计合成并用于检测阳离子、阴离子及氨基酸等分析物。但是大部分已报道的荧光化学传感器的功能比较单一,只能对一种或两种待分析物进行检测。通常来说制备这些传感器比较繁琐耗时。因此,设计一种能够同时检测多种不同待分析物的荧光化学传感器就显得非常有必要。和广泛报道的荧光化学传感器相比,荧光力传感器(也被称作力致变色材料)的发展还处在相对初级的阶段。作为一种新的智能材料,荧光力传感器因在很多领域具有潜在的应用价值,比如说光学存储、显示、安全通信等,所以最近引起了研究学者的大量关注。目前,文献中报道的这类材料在灵敏度、可回复性、荧光颜色变化的多样性上还存在诸多问题。因此,开发新型的荧光力传感器并赋予其以优异的性能是非常有必要的。本论文的主要内容及研究成果分为以下四个部分:1.通过Suzuki偶联反应,设计、合成了两种含有2,2'-联咪唑单元的线形和支化共轭聚合物,并且研究了它们对金属离子、氨基酸和酸性气体的荧光传感性能。结果发现,这两种聚合物的荧光都能够通过光诱导电子转移过程被Co2+有效地淬灭,表现出"关闭型"荧光响应特性。其检测过程不受Cu2+的干扰。聚合物对Ag+表现出"比率型"荧光变化。由于巯基对Ag+有很强的络合作用,聚合物-Ag+配合物对半胱氨酸也表现出优异的传感性能。半光氨酸的线性检测范围可以通过改变配合物溶液中Ag+的当量来方便的调节。此外,我们还发现当聚合物溶液接触HCl或NH3气体时,溶液的荧光颜色可以在绿色和蓝色之间可逆的变化。相较于线形聚合物,支化聚合物具有更高的检测灵敏度。这些结果说明这种基于2,2'-联咪唑结构单元的共轭聚合物可以用作一种性能优异的多功能荧光化学传感器。2.设计、合成了一种含2,2'-联咪唑、苯并噻二唑及咔唑结构单元的三元共轭聚合物P1。P1能够在水溶液中形成形貌较为规整的球状纳米粒子。由于分子链中咔唑-联咪唑和咔唑-苯并噻二唑单元之间存在非常明显的荧光共振能量转移效应,纳米粒子表现出一定强度的橘黄色荧光(荧光量子产率为9%)。基于电荷转移作用,该纳米粒子能够用于检测缺电子的硝基化合物,并且对缺电子性最强的三硝基苯酚表现出最佳的灵敏度。其检测过程不受各种金属离子的干扰。我们还发现因为纳米粒子的微相富集作用,对含水量高的纳米粒子溶液来说具有更高的检测灵敏度。3.设计、合成了两种芘硼酸环状酯化合物PPB和NPB,并对它们的固态荧光性质进行了研究。含有五元环状硼酸酯的芘衍生物(PPB)表现出可逆的力致变色及气致变色性质,并且在室温下就具有很快地自回复能力(大约5分钟)。而六元环状硼酸酯化合物(NPB)却并没有表现出这一性质。结果证明PPB和NPB的固态荧光性质强烈地依赖于其分子的堆积结构和固态塑性。相对更加柔软的PPB晶体因为存在滑移面,在受到剪切应力的时候能够通过分子滑移形成三明治夹心结构的激基缔合物。由于室温下的回复速度很快,PPB可以用于制作具有自擦除能力的写字板。4.基于罗丹明结构,我们设计、合成了一种新颖的力致变色弹性体。为了使第一重网络分子链呈充分舒展状态以提高力响应的灵敏度,弹性体经过三次溶胀-光聚合反应过程。结果表明最终的三重网络弹性体显示出非常独特的性质。在单轴连续拉伸及卸力期间,弹性体显示出三种荧光颜色之间的变化。通过合理的调节拉伸比例,可以表现出多姿多彩的荧光颜色。这种新合成的力致变色基团开环所形成的两性离子荧光量子产率可以高达67%,这比广泛使用的部花青素结构高出近两个数量级。另外,弹性体对力表现出很高的响应灵敏度,其可检测活化应变值为0.24。因此可以用于侦测手指关节的相关运动。弹性体的合成简单、原料易得并且表现出很好的机械性能。这些因素都使其在实际应用上非常具有优势。
[Abstract]:Fluorescence sensors have played a very important role in environmental pollution monitoring, life science, electronic information and other fields, and have made great progress in the last decade. As one of the important members, fluorescent chemical sensors have attracted much attention because of their advantages of high sensitivity, high selectivity, easy to use and real-time detection. There are many types of fluorescent chemical sensors designed to be synthesized and used to detect cations, anions and amino acids. But most of the reported fluorescent chemical sensors have a single function and can only detect one or two kinds of analytes. Generally, the preparation of these sensors is more time-consuming. Therefore, the design is designed. A fluorescent chemical sensor that can detect a variety of different analytes at the same time is necessary. Compared with the widely reported fluorescent chemical sensors, the development of a fluorescent force sensor (also called a force photochromic material) is still in a relatively primary stage. As a new intelligent material, the fluorescent force sensors are in a lot of collar. The domain has potential application value, such as optical storage, display, safe communication, and so on. So recently, a lot of attention has been paid to the researchers. At present, there are many questions on the variety of sensitivity, recoverability, and color change of the materials reported in the literature. Excellent performance is necessary. The main contents and research results of this paper are divided into four parts: 1. through the coupling reaction of Suzuki, two kinds of linear and branched conjugated polymers containing 2,2'- linimidazole are synthesized and their fluorescence sensing properties for metal ions, amino acids and acid gases are studied. It is found that the fluorescence of the two polymers can be effectively quenched by the photoinduced electron transfer process by Co2+, showing a "closed" fluorescence response characteristic. The detection process is not disturbed by Cu2+. The polymer shows a "ratio type" fluorescence change to Ag+. Because of the strong complexation of the sulfhydryl group to the Ag+, the polymer -Ag+ complex has the cysteamine. Acid also shows excellent sensing properties. The linear detection range of hemiparine can be easily regulated by changing the equivalent of Ag+ in the complex solution. In addition, we also find that when the polymer solution contacts the HCl or NH3 gas, the fluorescence color of the solution can be reversible in the green and blue between the green and the blue. These results show that the conjugated polymer based on the 2,2'- imidazole structural unit can be used as a multifunctional fluorescent chemical sensor.2. with excellent performance. The synthesis of a three element conjugated polymer containing 2,2'- imidazole, benzothiazole two azoles and carbazole junction units can be synthesized. Due to the obvious fluorescence resonance energy transfer effect between carbazole biazoles and carbazole benzothiazole two units in the molecular chain, the nanoparticles show a certain intensity of orange fluorescence (the fluorescence quantum yield is 9%). Based on the charge transfer effect, the nanoparticle is the nanoparticles. It can be used to detect nitro compounds lacking electrons and has the best sensitivity to the most electron deficient three nitrophenol. The detection process is not disturbed by various metal ions. We also found that the microphase enrichment of nanoparticles has a higher detection sensitivity.3. for the nanoparticles with high water content. Two kinds of pyrene borate cyclic ester compounds PPB and NPB were synthesized and their solid-state fluorescence properties were studied. The pyrene derivative (PPB) containing five membered ring borate (PPB) showed reversible photochromic and gas chromic properties, and at room temperature it had a fast self recovery capacity (about 5 minutes) and six membered ring borate ester. The compound (NPB) does not show this property. The results show that the solid-state fluorescence properties of PPB and NPB depend strongly on the stacking structure and solid plasticity of their molecules. The relatively softer PPB crystals can form the radical associates with sandwich sandwich structures at the time of shear stress, because of the existence of sliding surfaces. Because the recovery speed at room temperature is very fast, PPB can be used to make a self erasable writing board.4. based on the Luo Danming structure. We design a novel force photochromic elastomer. In order to make the first heavy network molecular chain fully stretches to improve the sensitivity of the force response, the elastomer passes three times of swelling photopolymerization. The results show that the final three heavy network elastomers show very unique properties. During the uniaxial continuous stretching and unloading, the elastomer shows the changes between the three kinds of fluorescent colors. By reasonable adjustment of the tensile ratio, the colorful fluorescent color can be displayed. This new synthetic force chromotropic group opens the ring. The fluorescence quantum yield of the amphoteric ion can be as high as 67%, which is nearly two orders of magnitude higher than that of the widely used anthocyanin structure. In addition, the elastic body has a high response sensitivity to the force, and it can detect the activation strain of 0.24. so that it can be used to detect the related motion of the finger joints. It also shows good mechanical properties. These factors make it very advantageous in practical applications.

【学位授予单位】：中国科学技术大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O657.3
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本文编号：1832616