查爾酮衍生物氰離子探針的合成與性能研究
發(fā)布時(shí)間：2018-07-18 14:06
【摘要】：氰化物擁有可怕的毒性,威脅著人類以及動(dòng)物的生命安全,但是它又廣泛應(yīng)用在很多工業(yè)制品的生產(chǎn)過(guò)程中。因此,如何設(shè)計(jì)出能夠靈敏識(shí)別氰離子的探針,成為眾多學(xué)者研究的重點(diǎn)。本論文設(shè)計(jì)合成了查爾酮衍生物和香豆素查爾酮衍生物兩類共16種氰離子熒光探針,系統(tǒng)研究了它們的光物理性質(zhì)和氰離子識(shí)別性質(zhì)。合成的兩類探針化合物分子結(jié)構(gòu)如下圖所示:(1)查爾酮類化合物1-8(2)香豆素查爾酮類化合物9-16:本論文合成的16種化合物中得到了3個(gè)化合物的單晶,分別是化合物1、9和13。系統(tǒng)分析了這三種化合物的晶體結(jié)構(gòu),通過(guò)分析發(fā)現(xiàn),化合物1和9具有較好的晶體平面性�；衔�13的二面角比較大,平面性不佳。這也是化合物13熒光不好的原因。在查爾酮類化合物體系中,硝基查爾酮化合物1和2的特點(diǎn)是可以實(shí)現(xiàn)在水環(huán)境中對(duì)氰離子的識(shí)別,水環(huán)境中(CH3CN-H2O(1:1,v/v))氰離子檢測(cè)限分別為0.20μM(1)和0.19μM(2)符合WHO的規(guī)定。二乙胺基香豆素硝基查爾酮化合物3的特點(diǎn)是顏色比較深,在加入CN-前后可以實(shí)現(xiàn)肉眼識(shí)別。鍵合機(jī)理分析表明化合物1,2,4,5和7,化合物與氰離子之間發(fā)生了邁克爾反應(yīng),氰離子鍵合在碳碳雙鍵上。而含二乙胺基香豆素基團(tuán)的查爾酮化合物3和8,化合物與氰離子之間也發(fā)生了邁克爾反應(yīng),氰離子鍵合在香豆素4-位上。通過(guò)對(duì)比化合物6和7對(duì)氰離子的原位核磁圖發(fā)現(xiàn)吲哚氫基團(tuán)的化合物6與氰離子的響應(yīng)機(jī)理不是邁克爾加成反應(yīng)而是氨基和羥基上的氫與氰離子之間產(chǎn)生反應(yīng),實(shí)現(xiàn)氰離子識(shí)別。在香豆素查爾酮類化合物體系中,化合物9-16的特點(diǎn)是,這8個(gè)化合物不僅可以實(shí)現(xiàn)對(duì)CN-的識(shí)別,而且還可以實(shí)現(xiàn)對(duì)Cu2+的識(shí)別。此外這一類化合物的顏色比較深,在加入離子前后,化合物的顏色變化比較明顯,可以實(shí)現(xiàn)肉眼識(shí)別。特別的是吡咯烷化合物13-16是在合成化合物9-16的時(shí)候意外得到的產(chǎn)物,這四個(gè)化合物結(jié)構(gòu)新穎。化合物與氰離子之間的作用機(jī)理也是邁克爾反應(yīng),對(duì)氰離子的識(shí)別位點(diǎn)發(fā)生在了共軛橋的碳碳雙鍵上(9-12)或香豆素的4-位(14和16)�；衔飳�(duì)銅離子的鍵合機(jī)理是發(fā)生了配位作用。
[Abstract]:Cyanide has terrible toxicity and threatens human and animal life, but it is widely used in many industrial products. Therefore, how to design a probe that can sensitively identify cyanide ions has become the focus of many scholars. In this paper, 16 kinds of cyanide fluorescent probes were designed and synthesized, and their photophysical and cyanide recognition properties were systematically studied. The molecular structures of the two kinds of probe compounds are as follows: (1) Chalcone compounds 1-8 (2) coumarin compounds 9-16: in this paper, three single crystals were obtained from 16 compounds, I. e., compounds 1, 9 and 13, respectively. The crystal structures of these three compounds were systematically analyzed. It was found that compounds 1 and 9 had better crystal planarity. Compound 13 has a large dihedral angle and poor planarity. This is also the reason for the poor fluorescence of compound 13. In the system of chalcone compounds, nitro chalcone compounds 1 and 2 can recognize cyanide ions in water environment. The detection limits of cyanide ions in water environment (CH3CN-H2O (1: 1v / v) are 0.20 渭 M (1) and 0.19 渭 M (2), respectively. Diethylaminocoumarin nitrochalcone compound 3 is characterized by dark color and can be recognized by naked eyes before and after the addition of CN-. The analysis of the bonding mechanism showed that the compounds 1 / 2 / 4 / 5 and 7 / 5 reacted with the cyanide ion and the cyanide ion was bonded to the carbon / carbon double bond. However, chalcone compounds 3 and 8 with diethylaminocoumarin group also reacted with cyanide ions, and the cyanide ions were bonded to coumarin 4- site. By comparing the in situ NMR of compounds 6 and 7 for cyanide ions, it was found that the response mechanism of compound 6 of indole group to cyanide ion was not the Michael addition reaction but the reaction between hydrogen and cyanide ions on amino and hydroxyl groups. Cyanide ion recognition is realized. The characteristic of compound 9-16 in the system of coumarin chalcone compounds is that the eight compounds can not only recognize CN-, but also recognize Cu2. In addition, the color of this kind of compounds is dark, the color changes of the compounds are obvious before and after the addition of ions, which can be recognized by naked eyes. In particular, pyrrolidine compound 13-16 is an unexpected product in the synthesis of compounds 9-16. These four compounds have novel structures. The mechanism of interaction between compounds and cyanide ions is also Michael reaction. The recognition sites of cyanide ions occur on the carbon-carbon double bond of conjugate bridge (9-12) or on the 4- sites (14 and 16) of coumarin. The bond mechanism of the compound to copper ion is that the coordination occurs.
【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】：2016
【分類號(hào)】：O657.3
本文編號(hào)：2132138
[Abstract]:Cyanide has terrible toxicity and threatens human and animal life, but it is widely used in many industrial products. Therefore, how to design a probe that can sensitively identify cyanide ions has become the focus of many scholars. In this paper, 16 kinds of cyanide fluorescent probes were designed and synthesized, and their photophysical and cyanide recognition properties were systematically studied. The molecular structures of the two kinds of probe compounds are as follows: (1) Chalcone compounds 1-8 (2) coumarin compounds 9-16: in this paper, three single crystals were obtained from 16 compounds, I. e., compounds 1, 9 and 13, respectively. The crystal structures of these three compounds were systematically analyzed. It was found that compounds 1 and 9 had better crystal planarity. Compound 13 has a large dihedral angle and poor planarity. This is also the reason for the poor fluorescence of compound 13. In the system of chalcone compounds, nitro chalcone compounds 1 and 2 can recognize cyanide ions in water environment. The detection limits of cyanide ions in water environment (CH3CN-H2O (1: 1v / v) are 0.20 渭 M (1) and 0.19 渭 M (2), respectively. Diethylaminocoumarin nitrochalcone compound 3 is characterized by dark color and can be recognized by naked eyes before and after the addition of CN-. The analysis of the bonding mechanism showed that the compounds 1 / 2 / 4 / 5 and 7 / 5 reacted with the cyanide ion and the cyanide ion was bonded to the carbon / carbon double bond. However, chalcone compounds 3 and 8 with diethylaminocoumarin group also reacted with cyanide ions, and the cyanide ions were bonded to coumarin 4- site. By comparing the in situ NMR of compounds 6 and 7 for cyanide ions, it was found that the response mechanism of compound 6 of indole group to cyanide ion was not the Michael addition reaction but the reaction between hydrogen and cyanide ions on amino and hydroxyl groups. Cyanide ion recognition is realized. The characteristic of compound 9-16 in the system of coumarin chalcone compounds is that the eight compounds can not only recognize CN-, but also recognize Cu2. In addition, the color of this kind of compounds is dark, the color changes of the compounds are obvious before and after the addition of ions, which can be recognized by naked eyes. In particular, pyrrolidine compound 13-16 is an unexpected product in the synthesis of compounds 9-16. These four compounds have novel structures. The mechanism of interaction between compounds and cyanide ions is also Michael reaction. The recognition sites of cyanide ions occur on the carbon-carbon double bond of conjugate bridge (9-12) or on the 4- sites (14 and 16) of coumarin. The bond mechanism of the compound to copper ion is that the coordination occurs.
【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】：2016
【分類號(hào)】：O657.3
【參考文獻(xiàn)】
相關(guān)期刊論文 前1條
1 黃志平;李書(shū)海;李慧卓;曾凱;;氰根離子熒光檢測(cè)方法的研究進(jìn)展[J];廣東化工;2009年06期
，本文編號(hào)：2132138
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