【摘要】：咔唑類(lèi)衍生物是一類(lèi)具有大共軛系統(tǒng)的物質(zhì),常用于構(gòu)建分子內(nèi)電荷轉(zhuǎn)移(ICT),這類(lèi)物質(zhì)被廣泛用作供電子基團(tuán)并且表現(xiàn)出較大的Stocks位移。近些年,由于熒光測(cè)定技術(shù)具備簡(jiǎn)單、無(wú)創(chuàng)性、高靈敏性以及快速的響應(yīng)等優(yōu)點(diǎn),利用咔唑及其衍生物合成新的發(fā)色團(tuán)以及熒光探針已引起研究者們的廣泛興趣。本論文合成了三種咔唑類(lèi)化合物,并對(duì)其用于檢測(cè)CN~-、HSO_3~-、ClO~-以及pH進(jìn)行系統(tǒng)的研究。主要內(nèi)容如下:第一章:簡(jiǎn)單地介紹了超分子化學(xué)和分子識(shí)別及其熒光探針的概念,由此引入咔唑類(lèi)熒光探針,并對(duì)咔唑類(lèi)熒光探針及其研究進(jìn)展進(jìn)行了具體介紹。第二章:報(bào)道了一種在500 nm-650 nm范圍內(nèi)有廣泛發(fā)射的水溶性咔唑熒光探針(探針1),它通過(guò)3-甲醛-N-乙基咔唑和2,3-二甲基苯并噻唑碘化物而合成,能夠檢測(cè)CN~-,HSO_3~-和極堿性pH。在此,CN~-和HSO_3~-都是通過(guò)1,4-加成反應(yīng)機(jī)理進(jìn)行。在DMSO體系中,比率型熒光探針(探針1)對(duì)CN~-顯示了高靈敏性和選擇性,CN~-加入前后,顯示了兩個(gè)完全分離的發(fā)射峰(Δλ=199 nm)。在水溶液體系中,探針1對(duì)HSO_3~-和極堿性pH也顯示了極好的光譜性質(zhì)。探針1對(duì)CN~-,HSO_3~-和極堿性pH都顯示了大的Stocks位移,好的穩(wěn)定性,快速響應(yīng)等優(yōu)點(diǎn)。探針1在細(xì)胞內(nèi)CN~-和HSO_3~-熒光成像也成功地被實(shí)施。最后,大腸桿菌的熒光共聚焦成像也證實(shí)了探針1能在生物系統(tǒng)內(nèi)檢測(cè)堿性pH的變化。第三章:報(bào)道了一種用于檢測(cè)CN~-的比率型咔唑熒光探針(探針2),它通過(guò)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~-通過(guò)加成C=N雙鍵上的C原子機(jī)理進(jìn)行。CN~-加成前后,探針2出現(xiàn)兩個(gè)完全分離的發(fā)射峰,顏色也發(fā)生明顯的變化。熒光滴定中,探針2對(duì)CN~-顯示了高選擇性,大Stocks位移,并且可以用于定量檢測(cè)低濃度的CN~-。最后,探針2成功地被用于細(xì)胞內(nèi)CN~-熒光成像。第四章:報(bào)道了一種新型的咔唑熒光探針(探針3),它對(duì)ClO~-具有明顯增強(qiáng)的熒光響應(yīng)。響應(yīng)機(jī)理為ClO~-的氧化橋連乙烯基。在水"乙醇(4/1,v/v)體系中探針3對(duì)ClO~-顯示了高靈敏性和選擇性,ClO~-加入前后,肉眼觀察下,探針溶液由黃色變?yōu)闊o(wú)色,紫外燈下探針溶液由黃色變?yōu)樗{(lán)色。此外,探針3在細(xì)胞內(nèi)對(duì)ClO~-表現(xiàn)出令人滿(mǎn)意的光學(xué)特性,意味著探針3可應(yīng)用于生物體系內(nèi)檢測(cè)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.
【學(xué)位授予單位】：山西大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O657.3

【參考文獻(xiàn)】

相關(guān)期刊論文 前3條

1 張仕祿;趙波;冉利;秦大斌;羅杰偉;;一種新型咔唑衍生物的合成及識(shí)別性能研究[J];化學(xué)試劑;2014年10期

2 房旭彬;房雷;茍少華;;咔唑及其衍生物合成方法研究進(jìn)展[J];有機(jī)化學(xué);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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本文編號(hào)：2291487