查尔酮衍生物氰离子探针的合成与性能研究
发布时间：2018-07-18 14:06
【摘要】：氰化物拥有可怕的毒性,威胁着人类以及动物的生命安全,但是它又广泛应用在很多工业制品的生产过程中。因此,如何设计出能够灵敏识别氰离子的探针,成为众多学者研究的重点。本论文设计合成了查尔酮衍生物和香豆素查尔酮衍生物两类共16种氰离子荧光探针,系统研究了它们的光物理性质和氰离子识别性质。合成的两类探针化合物分子结构如下图所示:(1)查尔酮类化合物1-8(2)香豆素查尔酮类化合物9-16:本论文合成的16种化合物中得到了3个化合物的单晶,分别是化合物1、9和13。系统分析了这三种化合物的晶体结构,通过分析发现,化合物1和9具有较好的晶体平面性。化合物13的二面角比较大,平面性不佳。这也是化合物13荧光不好的原因。在查尔酮类化合物体系中,硝基查尔酮化合物1和2的特点是可以实现在水环境中对氰离子的识别,水环境中(CH3CN-H2O(1:1,v/v))氰离子检测限分别为0.20μM(1)和0.19μM(2)符合WHO的规定。二乙胺基香豆素硝基查尔酮化合物3的特点是颜色比较深,在加入CN-前后可以实现肉眼识别。键合机理分析表明化合物1,2,4,5和7,化合物与氰离子之间发生了迈克尔反应,氰离子键合在碳碳双键上。而含二乙胺基香豆素基团的查尔酮化合物3和8,化合物与氰离子之间也发生了迈克尔反应,氰离子键合在香豆素4-位上。通过对比化合物6和7对氰离子的原位核磁图发现吲哚氢基团的化合物6与氰离子的响应机理不是迈克尔加成反应而是氨基和羟基上的氢与氰离子之间产生反应,实现氰离子识别。在香豆素查尔酮类化合物体系中,化合物9-16的特点是,这8个化合物不仅可以实现对CN-的识别,而且还可以实现对Cu2+的识别。此外这一类化合物的颜色比较深,在加入离子前后,化合物的颜色变化比较明显,可以实现肉眼识别。特别的是吡咯烷化合物13-16是在合成化合物9-16的时候意外得到的产物,这四个化合物结构新颖。化合物与氰离子之间的作用机理也是迈克尔反应,对氰离子的识别位点发生在了共轭桥的碳碳双键上(9-12)或香豆素的4-位(14和16)。化合物对铜离子的键合机理是发生了配位作用。
[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.
【学位授予单位】：济南大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O657.3
本文编号：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.
【学位授予单位】：济南大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O657.3
【参考文献】
相关期刊论文 前1条
1 黄志平;李书海;李慧卓;曾凯;;氰根离子荧光检测方法的研究进展[J];广东化工;2009年06期
，本文编号：2132138
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