【作者】 江俊；

【导师】 汪新； 冯燕；

【作者基本信息】 安徽大学 ， 有机化学， 2017， 硕士

【摘要】 化学传感器对于许多领域和学科有着巨大的应用,高灵敏度和易操作性是传感器开发的两个主要问题,可以通过荧光技术实现这些要求,因此荧光传感器表现为化学传感器中最有前景的。荧光传感材料的发展越来越吸引科学家的注意,因为其实现真正的感觉系统是最直观的。共轭聚合物已经成为其中最重要的一类传导材料,由于它们容易将化学信号转换成容易测量的光学信号,而且由于分子导线效应使信号放大、荧光信号调节等优点,这引起诸多科研工作者的兴趣。通过调研文献、查阅资料,本篇论文设计合成了两种双取代聚炔的共轭聚合物荧光探针,并通过核磁共振氢谱、碳谱,质谱,红外吸收光谱等系列手段对所合成的化合物进行结构表征。然后我们进一步探索研究了所设计、合成化合物的光学性质和检测能力,并做了一些实际水样的检测实验,和制成试纸做为检测平台,取得了 一定的成果。本篇论文主要分为三个部分,首先对荧光探针的设计、工作原理做简单介绍,再衍生到共轭聚合物荧光探针的简介。第二部分是设计合成一系列双取代共轭聚合物荧光探针P1-P4。通过调研文献可以获知Pd²⁺能够与N、S原子配位,我们通过改变聚炔悬垂集团中N、S原子的种类和个数从而调节荧光探针对Pd²⁺的专一性检测。对比实验可以得出化合物P3对于Pd²⁺的检测选择性更好、灵敏度更高。众所周知,大多数农药含有N、P、S等元素,所以我们设想用某种农药分子从P3/Pd²⁺的配合物上将Pd²⁺夺下来,从而达到检测农药分子的效果。通过实验可得到P3/Pd²⁺配合物能够专一性检测甲基托布津,且检测限达到12.1 nM。接着我们尝试着将探针做些实际的应用,在实际水样检测的实验中探针P3能很好的检测Pd²⁺,然后我们将P3用试纸负载也能实现对Pd²⁺的检测。第三部分是设计合成另一种双取代共轭聚合物荧光探针P5。通过后功能化的方式将氮三唑接入双取代聚炔支链上,由于氮原子能很好的与Cu²⁺配位,通过能量转移的方式,当加入Cu²⁺离子后P5的荧光会发生萃灭,然后用荧光仪记录这一变化从而达到检测Cu²⁺的效果。草甘膦是一种含N、P等元素的农药,目前被广泛使用中。根据文献可以了解到草甘膦能与Cu²⁺以1:1的形式形成配合物,因此我们尝试用P5/Cu²⁺的配合物来检测草甘膦分子。实验结果显示P5/Cu²⁺的配合物能很好的检测草甘膦分子,且选择性良好,灵敏度较高。更多还原

【Abstract】 Application of chemical sensors for many areas and disciplines with a huge,high sensitivity and ease of operation are two of main problems of the sensor,fluorescence can easily meet those requirements,based on fluorescent sensors for chemical sensing is one of the most promising candidates.The development of fluorescent materials attracted the attention of scientists,because it is implemented as a true sensory systems are the most intuitive.Conjugated polymers have become one of the most important class of conductive material,because they are easier to chemical signals into optical signal,and because of the effect of molecular wires make signal amplification,cause the interest of many researchers.In this paper,two disubstituted polyacetylene fluorescent probes were designed and synthesized,and their structures were characterized by 1H NMR,13C NMR,MS,and IR spectra.Then,we further studied the optical properties and the detection ability of the designed and synthesized compounds,and made some practical water samples detection experiments,and made the test paper as the testing platform,certain results have been achieved.This thesis is divided into three parts.Firstly,the design and working principle of the fluorescent sensor are introduced briefly,and then the conjugated polymer fluorescent probe is introduced.The second part is the design and synthesis of a series of disubstituted polyacetylene fluorescent probes P1-P4.By investigating the literature we can know that,Pd²⁺ can coordinate with N,S atoms,and we adjust the specificity of Pd²⁺fluorescence sensors by changing the type and number of N,S atoms in polyacetylene pendant groups.Comparable experiments show that compound P3 has better selectivity and sensitivity for detection of Pd²⁺.As we all know,most pesticides contain N,P,S and other elements,so we envisage a kind of pesticide molecules from the P3/Pd²⁺complex will be won on the Pd²⁺,so as to achieve the effect of detection of pesticide molecules.The experimental results showed that P3/Pd²⁺ complexes could specifically detect thiophanate-methyl and the detection limit was 12.1 nM.Then we try to do some practical application of the sensor,in the actual water sample detection sensor P3 can be a good test of Pd²⁺,and then we make P3 with a test paper load can also achieve the detection of Pd²⁺.The third part is the design and synthesis of another disubstituted polyacetylene fluorescent sensor P5.After nitrogen-triazole is attached to the branched-polyacetylene branch,the nitrogen atom can coordinate with Cu²⁺.By the energy transfer,when the Cu²⁺ ion is added,the fluorescence of P5 will be turn off,this change was then recorded using a fluorometer to measure the effect of Cu²⁺.Glyphosate is a pesticide which containing N,P and other elements,is currently widely used.Glyphosate can form complexes with Cu²⁺ in the form of 1:1,so we try to use P5/Cu²⁺ complex to detect glyphosate molecules.The results showed that the complex of P5/Cu²⁺ could be used to detect glyphosate,and the selectivity was good and the sensitivity was high.更多还原