咔唑及希夫碱类多孔材料的化学传感研究

发布时间：2018-05-27 01:04

本文选题：多孔有机骨架材料 + 荧光和比色传感　；参考：《山西师范大学》2017年硕士论文

【摘要】：近年来,化学传感器由于使用方便,灵敏度高、选择性好、响应迅速、操作简单等优点,在化学、生物、医学和环境等诸多领域有着潜在的应用价值。多孔有机骨架材料POFs凭借其高的比表面积、高的稳定性和可修饰性等特点在荧光传感领域的应用也受到人们的广泛关注。本论文主要研究了咔唑基多孔材料及希夫碱有机骨架材料在离子传感和生物传感领域的应用,主要分为四部分:第一章首先简要介绍了荧光和化学传感器,然后综述了多孔有机骨架作为荧光传感器的研究进展。最后对本论文的选题意义及研究所取得的进展进行了描述。第二章通过三氯化铁氧化偶联成功合成了具有四面体结构的三维有机骨架材料Cz-TPM及共轭结构的有机骨架材料Cz-BCB。Cz-TPM由于具有大量的富电子咔唑基团和对客体分子的高密度结合位点,我们对其I-和Hg2识别性能进行研究。研究表明Cz-TPM可实现对I-和Hg2+的可视化和荧光识别。I-的加入使Cz-TPM分散液的外观颜色由无色变为黄色,紧接着加入Hg2+使分散液的颜色由黄色恢复到无色。荧光检测表明Cz-TPM对I-具有专一选择性,成功实现了对I-的turn-off光学识别响应(猝灭常数Ksv[I-]:2372M-1),随后在Cz-TPM@I体系中加入Hg2+,实现了对Hg2+专一灵敏的turn-on模式光学响应。更重要的是,Cz-TPM具有优异的溶剂稳定性,通过水洗和离心分离就能使其再生并重复使用。据我们所知,这是首例有关咔唑多孔有机骨架对I-和Hg2+的荧光传感的报道。紧接着我们研究了具有共轭结构的有机骨架材料Cz-BCB对I-和Hg2+的可视化和荧光传感性能,发现由于Cz-BCB中存在大的π-共轭体系使其对I-和Hg2+传感效果更灵敏(猝灭常数Ksv[I-]:4611M-1);同时,Cz-BCB对Fe2+的识别具有高灵敏性和抗干扰性,检测限可达到0.46μM。第三章在溶剂热的条件下通过缩合反应制备了具有酮式结构COF-JLU2。COF-JLU2骨架中特殊的结构,以及良好的化学稳定性和热稳定性,促使我们尝试利用COF-JLU2对金属离子,pH值以及核苷酸碱基进行荧光识别。研究表明COF-JLU2可选择性荧光识别Al3+(turn-on型),Al3+检测限达到0.31μM;此外,pH的变化使COF-JLU2发生质子化与去质子化,荧光强度及外观颜色都会发生改变,因而可实现对pH值的检测;COF-JLU2骨架中的氢键的给体-给体-受体(DDA)部分与胞嘧啶分子中(AAD)部分互补,因而对胞嘧啶具有很好的荧光传感效果。第四章对本论文的主要工作进行了总结并对该课题的研究前景进行展望。
[Abstract]:In recent years, chemical sensors have been widely used in many fields, such as chemistry, biology, medicine and environment, because of their advantages such as convenient use, high sensitivity, good selectivity, quick response and simple operation. Because of its high specific surface area, high stability and modifiability, porous organic skeleton material POFs has been widely used in the field of fluorescence sensing. The applications of carbazolyl porous materials and Schiff base organic skeleton materials in the field of ion sensing and biosensor are mainly studied in this paper. The first chapter briefly introduces the fluorescent and chemical sensors. Then the research progress of porous organic skeleton as fluorescence sensor is reviewed. Finally, the significance of the topic and the progress of the research are described. In chapter 2, the three-dimensional organic skeleton material Cz-TPM with tetrahedron structure and the organic skeleton material Cz-BCB.Cz-TPM with conjugated structure have been successfully synthesized by oxidative coupling of ferric trichloride with a large number of electron-rich carbazole groups and high density binding sites to guest molecules. We study its I-and Hg2 recognition performance. The results show that Cz-TPM can realize the visualization of I- and Hg2 and the addition of fluorescence recognition. I- can change the appearance color of Cz-TPM dispersion from colorless to yellow, and then add Hg2 to restore the color of dispersion from yellow to colorless. Fluorescence detection shows that Cz-TPM is specific to I-, and the turn-off optical recognition response to I- (quenching constant Ksv [I-] 2372M-1) has been successfully realized. Subsequently, Hg2 was added to the Cz-TPM@I system to achieve a specific and sensitive turn-on mode optical response to Hg2. More importantly, Cz-TPM has excellent solvent stability, which can be regenerated and reused by washing and centrifugal separation. To the best of our knowledge, this is the first report on the fluorescence sensing of I-and Hg2 by a carbazole porous organic skeleton. Then we studied the visualization and fluorescence sensing properties of Cz-BCB, an organic skeleton material with conjugated structure, to I- and Hg2. It is found that the large 蟺 -conjugated system in Cz-BCB makes the sensing effect more sensitive to I- and Hg2 (quenching constant Ksv [I-] 4611M-1H, and Cz-BCB has high sensitivity and anti-interference to Fe2, and the detection limit can reach 0.46 渭 M. In chapter 3, the special structure, chemical stability and thermal stability of keto-type COF-JLU2.COF-JLU2 skeleton were prepared by condensation reaction under solvothermal conditions. We try to use COF-JLU2 to recognize pH value and nucleotide base of metal ions. The results showed that the detection limit of Al3 turn-on type Al3 in COF-JLU2 was 0.31 渭 M. in addition, the change of pH value made COF-JLU2 protonation and deprotonation, and the fluorescence intensity and appearance color would change. Therefore, the hydrogen donor-acceptor DDAs in the framework of COF-JLU2 can be detected by pH, which is complementary to the AAD in cytosine molecules, so it has a good fluorescence sensing effect on cytosine. The fourth chapter summarizes the main work of this paper and prospects for the research of this topic.
【学位授予单位】：山西师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB383.4;TP212

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