极端酸碱和剪切力诱导变色分子的合成及机理研究

发布时间：2018-09-19 17:32

【摘要】：环境敏感型材料一直是材料届的热门课题。由于环境敏感性能随着环境产生特异性以及可控性的变化,所以被广泛地应用在包括信息,储能领域。常见的环境敏感类型有酸碱,光,热和力等。其中酸碱敏感和力学敏感是本论文讨论的两个类型。酸碱敏感材料虽然发展时间较长,有关于极酸极碱,特别是一个荧光团上同时具有极酸极碱的敏感材料鲜有报道。力学敏感材料也就是压敏材料,在这几年受到了较大的关注,但是由于发展时间短,仍然需要相关的研究和探索。本文第二章探讨的极酸极碱刺激下变色的螺吡喃类探针,该螺吡喃探针与之前报道过的螺吡喃探针不同,仅仅在极酸的刺激下才会开环诱导变色。并且在极碱范围,它又能离子化诱导一个很明显的红移变色。为了验证机理,我们又合成了类似取代基的总共4个螺吡喃探针。首先是对酸性机理研究设计合成了两个螺吡喃结构,分别是去掉一个吲哚环上的吸电子基团羧基和N-位的大位阻基团苯羧基的螺吡喃探针。然后在碱性区域我们同样设计了两个结构,分别是去掉三个酸性官能团和去掉一个酚羟基的螺吡喃探针。我们对其光谱和核磁做了对比。最后我们将该探针用于细菌的不同pH下的标记实验中,探针不仅进入到了细胞,而且还得到了和溶液状态下相同的极酸极碱响应效果。本文第三章探讨的是超分子体系诱导的具有化学弱键类荧光小分子的力致变色行为。本章第一次提出使用环糊精诱导一些小分子更容易断键变色。我们首先合成了具有弱化学键的两个小分子罗丹明Rh和螺吡喃SP。然后我们将这2个小分子于环糊精进行了包结,并用了相关表征验证了包结物的成功合成。接下来对小分子和包结物体系做了力致变色的性能对比,并通过模拟和实验表征探索和分析了相关机理。我们发现氢键在这个体系里有着至关重要的作用,氢键主要在这两个方面发挥相关作用：首先,氢键抓住染料弱键的两端并且牢牢地抓住环糊精内的染料分子；第二,氢键促进了包结物的聚集成规整的大规整结构,加强了分子之间的作用力。这样,染料分子的弱化学键就能集中更多的外力,从而更容易力致变色。这个方法为力致变色和超分子体系的结合提供了一个很好的途径。
[Abstract]:Environmental sensitive materials have always been a hot topic in the field of materials. Environmental sensitivity is widely used in the fields of information and energy storage because it can produce specific and controllable changes with the environment. Common environmental sensitive types are acid and alkali, light, heat and force. Among them, acid-base sensitivity and mechanical sensitivity are two types discussed in this paper. Although acid-base sensitive materials have been developed for a long time, there are few reports on the polar acid-base sensitive materials, especially on a fluorescent group. The mechanical sensitive material, that is, the pressure sensitive material, has been paid more attention in recent years, but because of the short development time, it still needs the related research and exploration. In the second chapter, the discolored spiropyran probe, which is stimulated by polar acid and alkaloids, is different from the previously reported spiropyran probe, and only under the stimulation of polar acid can it open a ring to induce color change. And in the range of polar alkali, it can ionize to induce a very obvious red shift color change. In order to verify the mechanism, we have synthesized a total of 4 spiropyran probes similar to substituents. Firstly, two spiropyran probes were designed and synthesized by studying the acidic mechanism. The two spiropyran probes were designed and synthesized, respectively, which removed the electron-absorbing group carboxyl group from an indole-ring and the N-site large steric resistance group benzene carboxyl group. Then we have also designed two structures in the basic region, one is to remove three acidic functional groups and the other is to remove one phenolic hydroxyl from the spiropyran probe. We compared the spectra with the nuclear magnetic field. Finally, we used the probe to label bacteria under different pH conditions. The probe not only entered the cells, but also got the same response effect as the solution. In the third chapter, we discuss the mechanochromic behavior induced by supramolecular system with chemically weakly bonded fluorescent small molecules. This chapter is the first to suggest that cyclodextrin can induce some small molecules to discolor more easily. We first synthesized two small molecules, Rhodamine Rh and spiropyran SP., which have weak chemical bonds. Then the two small molecules were coated with cyclodextrin, and the successful synthesis of the inclusion compounds was verified by correlation characterization. Then, the mechanical chromotropic properties of small molecule and inclusion system were compared, and the related mechanism was explored and analyzed by simulation and experimental characterization. We find that hydrogen bonds play an important role in this system, and hydrogen bonds play an important role in these two aspects: first, the hydrogen bonds hold the two ends of the weak bonds of the dyes and firmly hold the dye molecules in cyclodextrin. The hydrogen bond promotes the aggregation of the inclusion compounds into a regular structure and strengthens the interaction between molecules. In this way, the weak chemical bonds of dye molecules can concentrate more external forces, thus making it easier to force discoloration. This method provides a good way for the combination of force chromotropic and supramolecular systems.
【学位授予单位】：北京化工大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB34

【相似文献】