【摘要】：小分子熒光化合物作為探針在生物、環(huán)境等領(lǐng)域中已經(jīng)逐漸成為一種方便有效的檢測(cè)手段,因此小分子探針的研究和開發(fā)顯得越來越重要。本論文著眼于當(dāng)前一些具有重要檢測(cè)意義的物質(zhì),采用簡(jiǎn)便、高效的合成方法目標(biāo)性的合成了香豆素和黃酮類兩類熒光化合物作為探針。分別研究了化合物對(duì)特定物質(zhì)檢測(cè)的光物理性質(zhì),分析了相應(yīng)的識(shí)別效果并探究了相應(yīng)的識(shí)別機(jī)制。(1)香豆素酰胺類化合物1-6(2)黃酮類化合物7-13香豆素體系中,合成了六個(gè)香豆素酰胺類化合物,即化合物1-6。在此類熒光探針的設(shè)計(jì)、合成、表征以及研究的過程中,不僅得到了六個(gè)可以特異性識(shí)別氰離子的新型探針還得到了兩個(gè)化合物的晶體結(jié)構(gòu)(化合物4和6)。實(shí)驗(yàn)發(fā)現(xiàn),六個(gè)化合物均可以在乙腈中實(shí)現(xiàn)對(duì)氰離子的識(shí)別,這不僅表現(xiàn)在化合物的吸收光譜以及熒光光譜會(huì)隨著氰離子加入發(fā)生明顯的變化,還表現(xiàn)在化合物加入氰離子前后溶液顏色以及熒光的變化可以通過肉眼觀察到。例如,化合物3、4和6的溶液顏色都可以隨著氰離子的加入變?yōu)闊o色,此外化合物3和6的溶液的熒光會(huì)由于氰離子的加入發(fā)生猝滅,而化合物4溶液的熒光會(huì)隨著氰離子的加入變得更強(qiáng)。黃酮體系中,合成了七個(gè)黃酮衍生物,即化合物7-13。通過對(duì)此類化合物進(jìn)行不同的修飾后,發(fā)現(xiàn)此類化合物在不同的條件下可以實(shí)現(xiàn)對(duì)不同物質(zhì)的檢測(cè)。實(shí)驗(yàn)發(fā)現(xiàn)化合物7-9在乙腈中不僅可以實(shí)現(xiàn)對(duì)氰離子的選擇性識(shí)別還可以實(shí)現(xiàn)對(duì)銅離子的檢測(cè)識(shí)別,而且識(shí)別現(xiàn)象不僅可以通過紫外吸收和熒光光譜的變化得以實(shí)現(xiàn)還可以通過肉眼觀察加入相應(yīng)離子前后相應(yīng)的溶液顏色以及熒光的變化來實(shí)現(xiàn)。對(duì)于化合物10和11的研究中發(fā)現(xiàn)這兩個(gè)化合物可以實(shí)現(xiàn)在緩沖溶液中對(duì)特定金屬離子的識(shí)別�；衔�10可以同時(shí)識(shí)別銅離子和鋅離子,銅離子可以使化合物本身的熒光發(fā)生猝滅而鋅離子的加入可以使化合物的熒光發(fā)生明顯的增強(qiáng)。相應(yīng)的顏色和熒光的變化同樣是肉眼可見的�；衔�11可以單一性的識(shí)別銅離子,并且對(duì)銅離子具有特別低的吸收和熒光檢測(cè)限�；衔�12和13的設(shè)計(jì)與合成是為了實(shí)現(xiàn)對(duì)特定氨基酸的識(shí)別。實(shí)驗(yàn)發(fā)現(xiàn)化合物12加入鎳離子后吸收在發(fā)生明顯變化的同時(shí)熒光也發(fā)生了猝滅,在此基礎(chǔ)上加入半胱氨酸(Cys)或同型半胱氨酸后(Hcy)后吸收和熒光都會(huì)發(fā)生明顯的恢復(fù)現(xiàn)象。對(duì)于化合物13來說,僅有Cys的加入可以引起化合物熒光強(qiáng)度發(fā)生明顯的增強(qiáng)。因此它對(duì)Cys的檢測(cè)顯示了明顯的優(yōu)勢(shì)。
[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.
【學(xué)位授予單位】：濟(jì)南大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O657.3

【參考文獻(xiàn)】

相關(guān)碩士學(xué)位論文 前1條

1 扶燕;基于羅丹明6G的Schiff堿類金屬離子熒光探針的研究[D];鄭州大學(xué);2014年

，

本文編號(hào)：2392791