香豆素和黄酮类荧光探针的合成与识别性质研究
发布时间：2018-12-27 08:37
【摘要】：小分子荧光化合物作为探针在生物、环境等领域中已经逐渐成为一种方便有效的检测手段,因此小分子探针的研究和开发显得越来越重要。本论文着眼于当前一些具有重要检测意义的物质,采用简便、高效的合成方法目标性的合成了香豆素和黄酮类两类荧光化合物作为探针。分别研究了化合物对特定物质检测的光物理性质,分析了相应的识别效果并探究了相应的识别机制。(1)香豆素酰胺类化合物1-6(2)黄酮类化合物7-13香豆素体系中,合成了六个香豆素酰胺类化合物,即化合物1-6。在此类荧光探针的设计、合成、表征以及研究的过程中,不仅得到了六个可以特异性识别氰离子的新型探针还得到了两个化合物的晶体结构(化合物4和6)。实验发现,六个化合物均可以在乙腈中实现对氰离子的识别,这不仅表现在化合物的吸收光谱以及荧光光谱会随着氰离子加入发生明显的变化,还表现在化合物加入氰离子前后溶液颜色以及荧光的变化可以通过肉眼观察到。例如,化合物3、4和6的溶液颜色都可以随着氰离子的加入变为无色,此外化合物3和6的溶液的荧光会由于氰离子的加入发生猝灭,而化合物4溶液的荧光会随着氰离子的加入变得更强。黄酮体系中,合成了七个黄酮衍生物,即化合物7-13。通过对此类化合物进行不同的修饰后,发现此类化合物在不同的条件下可以实现对不同物质的检测。实验发现化合物7-9在乙腈中不仅可以实现对氰离子的选择性识别还可以实现对铜离子的检测识别,而且识别现象不仅可以通过紫外吸收和荧光光谱的变化得以实现还可以通过肉眼观察加入相应离子前后相应的溶液颜色以及荧光的变化来实现。对于化合物10和11的研究中发现这两个化合物可以实现在缓冲溶液中对特定金属离子的识别。化合物10可以同时识别铜离子和锌离子,铜离子可以使化合物本身的荧光发生猝灭而锌离子的加入可以使化合物的荧光发生明显的增强。相应的颜色和荧光的变化同样是肉眼可见的。化合物11可以单一性的识别铜离子,并且对铜离子具有特别低的吸收和荧光检测限。化合物12和13的设计与合成是为了实现对特定氨基酸的识别。实验发现化合物12加入镍离子后吸收在发生明显变化的同时荧光也发生了猝灭,在此基础上加入半胱氨酸(Cys)或同型半胱氨酸后(Hcy)后吸收和荧光都会发生明显的恢复现象。对于化合物13来说,仅有Cys的加入可以引起化合物荧光强度发生明显的增强。因此它对Cys的检测显示了明显的优势。
[Abstract]:As probes, small molecular fluorescent compounds have gradually become a convenient and effective means of detection in biological, environmental and other fields, so the research and development of small molecular probes have become more and more important. Focusing on some important substances, coumarin and flavonoids were synthesized as probes by a simple and efficient synthetic method. The photophysical properties of compounds for the detection of specific substances were studied respectively. The corresponding recognition effect was analyzed and the corresponding recognition mechanism was explored. (1) six coumarin amides were synthesized in coumarin compounds 1-6 (2) flavonoids 7-13 coumarin system. That is compound 1-6. In the design, synthesis, characterization and study of these fluorescent probes, not only six new probes were obtained which can specifically recognize cyanide ions, but also two compounds (compounds 4 and 6) were obtained. It was found that all of the six compounds could recognize cyanide ions in acetonitrile, which not only showed that the absorption spectra and fluorescence spectra of the compounds changed obviously with the addition of cyanide ions, The change of color and fluorescence of the solution before and after the addition of cyanide ion can be observed by naked eye. For example, the solution colors of compounds 3, 4 and 6 can become colorless with the addition of cyanide ions, and the fluorescence of the solutions of compounds 3 and 6 can be quenched by the addition of cyanide ions. The fluorescence of compound 4 solution becomes stronger with the addition of cyanide ion. In the system of flavonoids, seven derivatives of flavonoids were synthesized, that is, compounds 7-13. It was found that these compounds could be detected under different conditions. It is found that compound 7-9 can not only realize selective recognition of cyanide ions but also detect and recognize copper ions in acetonitrile. Moreover, the recognition can be realized not only by the changes of UV absorption and fluorescence spectra, but also by observing the changes of the color and fluorescence of the solution before and after the addition of the corresponding ions. In the studies of compounds 10 and 11, it is found that these two compounds can recognize specific metal ions in buffer solution. Compound 10 can recognize both copper and zinc ions. Copper ions can quench the fluorescence of the compounds and the addition of zinc ions can obviously enhance the fluorescence of the compounds. The corresponding changes in color and fluorescence are also visible to the naked eye. Compound 11 can uniquely recognize copper ions and has a particularly low limit of absorption and fluorescence detection for copper ions. Compounds 12 and 13 were designed and synthesized to recognize specific amino acids. It was found that the absorption of compound 12 was also quenched with the addition of nickel ion. After adding cysteine (Cys) or homocysteine, the absorption and fluorescence of (Hcy) recovered obviously. For compound 13, only the addition of Cys can significantly enhance the fluorescence intensity of the compound. Therefore, its detection of Cys shows obvious advantages.
【学位授予单位】：济南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3
本文编号：2392791
[Abstract]:As probes, small molecular fluorescent compounds have gradually become a convenient and effective means of detection in biological, environmental and other fields, so the research and development of small molecular probes have become more and more important. Focusing on some important substances, coumarin and flavonoids were synthesized as probes by a simple and efficient synthetic method. The photophysical properties of compounds for the detection of specific substances were studied respectively. The corresponding recognition effect was analyzed and the corresponding recognition mechanism was explored. (1) six coumarin amides were synthesized in coumarin compounds 1-6 (2) flavonoids 7-13 coumarin system. That is compound 1-6. In the design, synthesis, characterization and study of these fluorescent probes, not only six new probes were obtained which can specifically recognize cyanide ions, but also two compounds (compounds 4 and 6) were obtained. It was found that all of the six compounds could recognize cyanide ions in acetonitrile, which not only showed that the absorption spectra and fluorescence spectra of the compounds changed obviously with the addition of cyanide ions, The change of color and fluorescence of the solution before and after the addition of cyanide ion can be observed by naked eye. For example, the solution colors of compounds 3, 4 and 6 can become colorless with the addition of cyanide ions, and the fluorescence of the solutions of compounds 3 and 6 can be quenched by the addition of cyanide ions. The fluorescence of compound 4 solution becomes stronger with the addition of cyanide ion. In the system of flavonoids, seven derivatives of flavonoids were synthesized, that is, compounds 7-13. It was found that these compounds could be detected under different conditions. It is found that compound 7-9 can not only realize selective recognition of cyanide ions but also detect and recognize copper ions in acetonitrile. Moreover, the recognition can be realized not only by the changes of UV absorption and fluorescence spectra, but also by observing the changes of the color and fluorescence of the solution before and after the addition of the corresponding ions. In the studies of compounds 10 and 11, it is found that these two compounds can recognize specific metal ions in buffer solution. Compound 10 can recognize both copper and zinc ions. Copper ions can quench the fluorescence of the compounds and the addition of zinc ions can obviously enhance the fluorescence of the compounds. The corresponding changes in color and fluorescence are also visible to the naked eye. Compound 11 can uniquely recognize copper ions and has a particularly low limit of absorption and fluorescence detection for copper ions. Compounds 12 and 13 were designed and synthesized to recognize specific amino acids. It was found that the absorption of compound 12 was also quenched with the addition of nickel ion. After adding cysteine (Cys) or homocysteine, the absorption and fluorescence of (Hcy) recovered obviously. For compound 13, only the addition of Cys can significantly enhance the fluorescence intensity of the compound. Therefore, its detection of Cys shows obvious advantages.
【学位授予单位】：济南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3
【参考文献】
相关硕士学位论文 前1条
1 扶燕;基于罗丹明6G的Schiff碱类金属离子荧光探针的研究[D];郑州大学;2014年
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