咔唑类荧光探针的合成及应用研究
发布时间：2018-10-24 12:59
【摘要】：咔唑类衍生物是一类具有大共轭系统的物质,常用于构建分子内电荷转移(ICT),这类物质被广泛用作供电子基团并且表现出较大的Stocks位移。近些年,由于荧光测定技术具备简单、无创性、高灵敏性以及快速的响应等优点,利用咔唑及其衍生物合成新的发色团以及荧光探针已引起研究者们的广泛兴趣。本论文合成了三种咔唑类化合物,并对其用于检测CN~-、HSO_3~-、ClO~-以及pH进行系统的研究。主要内容如下:第一章:简单地介绍了超分子化学和分子识别及其荧光探针的概念,由此引入咔唑类荧光探针,并对咔唑类荧光探针及其研究进展进行了具体介绍。第二章:报道了一种在500 nm-650 nm范围内有广泛发射的水溶性咔唑荧光探针(探针1),它通过3-甲醛-N-乙基咔唑和2,3-二甲基苯并噻唑碘化物而合成,能够检测CN~-,HSO_3~-和极碱性pH。在此,CN~-和HSO_3~-都是通过1,4-加成反应机理进行。在DMSO体系中,比率型荧光探针(探针1)对CN~-显示了高灵敏性和选择性,CN~-加入前后,显示了两个完全分离的发射峰(Δλ=199 nm)。在水溶液体系中,探针1对HSO_3~-和极碱性pH也显示了极好的光谱性质。探针1对CN~-,HSO_3~-和极碱性pH都显示了大的Stocks位移,好的稳定性,快速响应等优点。探针1在细胞内CN~-和HSO_3~-荧光成像也成功地被实施。最后,大肠杆菌的荧光共聚焦成像也证实了探针1能在生物系统内检测碱性pH的变化。第三章:报道了一种用于检测CN~-的比率型咔唑荧光探针(探针2),它通过N-乙基咔唑-3-甲醛和1,1,2-三甲基-3-乙基-1H-苯并吲哚碘化物而合成。CN~-通过加成C=N双键上的C原子机理进行。CN~-加成前后,探针2出现两个完全分离的发射峰,颜色也发生明显的变化。荧光滴定中,探针2对CN~-显示了高选择性,大Stocks位移,并且可以用于定量检测低浓度的CN~-。最后,探针2成功地被用于细胞内CN~-荧光成像。第四章:报道了一种新型的咔唑荧光探针(探针3),它对ClO~-具有明显增强的荧光响应。响应机理为ClO~-的氧化桥连乙烯基。在水"乙醇(4/1,v/v)体系中探针3对ClO~-显示了高灵敏性和选择性,ClO~-加入前后,肉眼观察下,探针溶液由黄色变为无色,紫外灯下探针溶液由黄色变为蓝色。此外,探针3在细胞内对ClO~-表现出令人满意的光学特性,意味着探针3可应用于生物体系内检测ClO~-。
[Abstract]:Carbazole derivatives are a class of compounds with large conjugate systems. They are often used to construct intramolecular charge transfer (ICT), and are widely used as electron donor groups and exhibit large Stocks shifts. In recent years, due to the advantages of simple, non-invasive, highly sensitive and rapid response, the use of carbazole and its derivatives to synthesize new chromophore and fluorescent probes has attracted extensive interest of researchers. In this paper, three carbazole compounds were synthesized and used for the detection of CN~-,HSO_3~-,ClO~- and pH. The main contents are as follows: in chapter 1, the concepts of supramolecular chemistry and molecular recognition and their fluorescent probes are briefly introduced, and carbazole fluorescent probes are introduced, and the research progress of carbazole fluorescent probes is introduced in detail. Chapter 2: a widely emitting water-soluble carbazole fluorescent probe (probe 1) with a range of 500 nm-650 nm is reported. It is synthesized by 3- formaldehyde-N-ethylcarbazole and 2-trimethylbenzothiazolium iodide. It can be used to detect CN~-,HSO_3~- and extremely basic pH.. In this case, both CN~- and HSO_3~- are carried out through the mechanism of 1 ~ 4-addition reaction. In DMSO system, the ratio fluorescence probe (probe 1) showed high sensitivity and selectivity to CN~-. Before and after the addition of CN~-, two completely separated emission peaks (螖 位 = 199 nm).) were shown. Probe 1 also showed excellent spectral properties for HSO_3~- and very basic pH in aqueous solution. Probe 1 shows the advantages of large Stocks shift, good stability and fast response to both CN~-,HSO_3~- and very basic pH. Probe 1 was also successfully performed in intracellular CN~- and HSO_3~- fluorescence imaging. Finally, the fluorescence confocal imaging of Escherichia coli confirmed that probe 1 could detect the changes of alkaline pH in biological system. Chapter 3: a ratio carbazole fluorescent probe (probe 2) for the detection of CN~- is reported. It is synthesized by N- ethylcarbazole-3- formaldehyde and 1httrimethyl-3-ethyl-1H-benzindole-iodide. CN~- is synthesized by adding C proto on Con N double bond. Before and after the CN~- addition, Probe 2 showed two completely separated emission peaks and obvious changes in color. In fluorescence titration, probe 2 showed high selectivity to CN~-, large S tocks shift, and could be used for quantitative detection of low concentration CN~-.. Finally, probe 2 was successfully used for intracellular CN~- fluorescence imaging. Chapter 4: a novel carbazole fluorescence probe (probe 3) is reported, which has a significantly enhanced fluorescence response to ClO~-. The response mechanism is the oxidation bridge of ClO~- with vinyl group. Probe 3 showed high sensitivity and selectivity to ClO~- in the water (4 / 1 / v / v) system. Before and after the addition of ClO~-, the probe solution changed from yellow to colorless, and the probe solution changed from yellow to blue under ultraviolet lamp. In addition, probe 3 showed satisfactory optical properties to ClO~- in cells, which meant that probe 3 could be used to detect ClO~-. in biological system.
【学位授予单位】：山西大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3
本文编号：2291487
[Abstract]:Carbazole derivatives are a class of compounds with large conjugate systems. They are often used to construct intramolecular charge transfer (ICT), and are widely used as electron donor groups and exhibit large Stocks shifts. In recent years, due to the advantages of simple, non-invasive, highly sensitive and rapid response, the use of carbazole and its derivatives to synthesize new chromophore and fluorescent probes has attracted extensive interest of researchers. In this paper, three carbazole compounds were synthesized and used for the detection of CN~-,HSO_3~-,ClO~- and pH. The main contents are as follows: in chapter 1, the concepts of supramolecular chemistry and molecular recognition and their fluorescent probes are briefly introduced, and carbazole fluorescent probes are introduced, and the research progress of carbazole fluorescent probes is introduced in detail. Chapter 2: a widely emitting water-soluble carbazole fluorescent probe (probe 1) with a range of 500 nm-650 nm is reported. It is synthesized by 3- formaldehyde-N-ethylcarbazole and 2-trimethylbenzothiazolium iodide. It can be used to detect CN~-,HSO_3~- and extremely basic pH.. In this case, both CN~- and HSO_3~- are carried out through the mechanism of 1 ~ 4-addition reaction. In DMSO system, the ratio fluorescence probe (probe 1) showed high sensitivity and selectivity to CN~-. Before and after the addition of CN~-, two completely separated emission peaks (螖 位 = 199 nm).) were shown. Probe 1 also showed excellent spectral properties for HSO_3~- and very basic pH in aqueous solution. Probe 1 shows the advantages of large Stocks shift, good stability and fast response to both CN~-,HSO_3~- and very basic pH. Probe 1 was also successfully performed in intracellular CN~- and HSO_3~- fluorescence imaging. Finally, the fluorescence confocal imaging of Escherichia coli confirmed that probe 1 could detect the changes of alkaline pH in biological system. Chapter 3: a ratio carbazole fluorescent probe (probe 2) for the detection of CN~- is reported. It is synthesized by N- ethylcarbazole-3- formaldehyde and 1httrimethyl-3-ethyl-1H-benzindole-iodide. CN~- is synthesized by adding C proto on Con N double bond. Before and after the CN~- addition, Probe 2 showed two completely separated emission peaks and obvious changes in color. In fluorescence titration, probe 2 showed high selectivity to CN~-, large S tocks shift, and could be used for quantitative detection of low concentration CN~-.. Finally, probe 2 was successfully used for intracellular CN~- fluorescence imaging. Chapter 4: a novel carbazole fluorescence probe (probe 3) is reported, which has a significantly enhanced fluorescence response to ClO~-. The response mechanism is the oxidation bridge of ClO~- with vinyl group. Probe 3 showed high sensitivity and selectivity to ClO~- in the water (4 / 1 / v / v) system. Before and after the addition of ClO~-, the probe solution changed from yellow to colorless, and the probe solution changed from yellow to blue under ultraviolet lamp. In addition, probe 3 showed satisfactory optical properties to ClO~- in cells, which meant that probe 3 could be used to detect ClO~-. in biological system.
【学位授予单位】：山西大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3
【参考文献】
相关期刊论文 前3条
1 张仕禄;赵波;冉利;秦大斌;罗杰伟;;一种新型咔唑衍生物的合成及识别性能研究[J];化学试剂;2014年10期
2 房旭彬;房雷;苟少华;;咔唑及其衍生物合成方法研究进展[J];有机化学;2012年07期
3 ;A novel carbazole-based fluorescent probe:3,6-Bis-[(N-ethylcarbazole-3-y1)-propene-1-keto]-N-ethylcarbazole[J];Chinese Chemical Letters;2010年01期
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