邻苯二酚乙胺与环境友好型溶剂的相互作用研究

发布时间：2019-03-04 09:15

【摘要】：由于工业废水和生活污水的污染,天然水中会含有一些酚类和胺类物质。人体长期摄入含酚的水会引起失眠,贫血等中毒症状。因此检测该类物质的含量有重要的意义。邻苯二酚乙胺是一种重要的生物分子,结构中含有酚羟基和氨基,且对环境污染小。以邻苯二酚乙胺为例,对其性能和含量的检测进行详细的研究可以为其它酚、胺类化合物提供一些理论依据。此外,测定性质和含量时需选用合适的溶剂,溶剂性质和溶剂效应(如介电效应、盐效应、离解作用、溶剂与溶质的相互作用等)会对溶质性质、化学反应过程以及反应产物有着重要影响。研究邻苯二酚乙胺与溶剂的相互作用,可为环境化学、药物化学和生命科学等领域的酚类和胺类物质的研究及应用提供理论依据。本文选择了在邻苯二酚乙胺检测中经常用到的小分子溶剂水和离子液体两种环境友好型溶剂为研究对象,利用电化学和核磁共振实验方法研究了它们与邻苯二酚乙胺盐酸盐(3,4-Dihydroxyphenethylamine hydrochloride,简写为DH)的相互作用。探讨两种溶剂对DH微环境的影响；并用量子化学方法对水与DH形成的氢键复合物进行了密度泛函计算和拓扑分析。首先,利用循环伏安法和核磁共振研究了水、离子液体对DH性质的影响及其相互作用。实验结果表明：水对DH具有一定的稳定作用,能在一定程度上抑制邻苯二酚乙胺的电氧化。随着DH浓度的增大,DH与溶剂的相互作用程度增强。而离子液体的咪唑环与DH的苯环之间则主要存在π-π堆积相互作用,二者相互作用的结果使DH更容易发生电氧化,从而增强了其电化学活性。其次,采用密度泛函理论研究了水与质子化的邻苯二酚乙胺(DH+)及邻苯二酚乙胺之间的氢键作用,对水与其形成氢键复合物的几何构型进行了优化,对形成的各种氢键复合物的一系列参数进行了理论探讨。发现二者之间氢键的形成有效的保护了邻苯二酚乙胺上的两个羟基,使其上面的H难以脱去,在一定程度上抑制了邻苯二酚乙胺的电氧化,增强了邻苯二酚乙胺的稳定性。最后通过分子中原子理论(AIM)对水与DH+的计算结果进行了拓扑分析,进一步证实了氢键的存在。理论和实验结果一致。探究邻苯二酚乙胺分子与环境友好型溶剂的相互作用方式可以为废水中其它复杂酚、胺类化合物的萃取,分离等操作选择合适的溶剂提供参考,并减少实验过程中对环境的污染；对环境污染中残留邻苯二酚乙胺的去除以及废水中酚类,胺类物质的检测也具有重要的指导意义。
[Abstract]:Natural water contains some phenols and amines because of the pollution of industrial wastewater and domestic sewage. Long-term intake of phenol-containing water can cause insomnia, anemia and other poisoning symptoms. Therefore, it is of great significance to detect the content of this kind of substances. Catechol ethylamine is an important biomolecule, which contains phenolic hydroxyl and amino groups, and has little pollution to the environment. Taking catechol ethylamine as an example, a detailed study on its performance and content can provide some theoretical basis for other phenols and amines. In addition, appropriate solvents should be selected for the determination of properties and contents, and solvent properties and solvent effects (such as dielectric effect, salt effect, dissociation effect, solvent-solute interaction, etc.) will affect solute properties. The chemical reaction process and the reaction product have important influence. The study of the interaction between catecholamines and solvents can provide a theoretical basis for the research and application of phenols and amines in the fields of environmental chemistry, drug chemistry and life sciences. In this paper, two environment-friendly solvents, water and ionic liquid, which are commonly used in the determination of catecholamines, are chosen as the research objects. The interaction between them and catechol ethylamine hydrochloride (3,4-dihydroxyphenethylamine hydrochloride, abbreviated as DH) was studied by electrochemical and nuclear magnetic resonance (NMR) methods. The effects of two solvents on the micro-environment of DH were investigated, and the density functional calculation and topological analysis of the hydrogen-bonded complexes formed by water and DH were carried out by quantum chemistry. Firstly, the effects of water and ionic liquids on the properties of DH and their interactions were studied by cyclic voltammetry and nuclear magnetic resonance (NMR). The experimental results show that water can stabilize DH and inhibit the electrooxidation of catechol ethylamine to a certain extent. With the increase of DH concentration, the interaction between DH and solvent increased. However, there is a 蟺-蟺 stacking interaction between the imidazole ring of ionic liquids and the benzene ring of DH. The results of the two interactions make DH more prone to electrooxidation and thus enhance its electrochemical activity. Secondly, the hydrogen bonding between water and protonated catechol ethylamine (DH) and catechol ethylamine was studied by density functional theory (DFT), and the geometric configuration of hydrogen bond complex formed between water and protonated catechol ethylamine was optimized. A series of parameters of various hydrogen bond complexes are discussed theoretically. It was found that the formation of hydrogen bond effectively protected the two hydroxyl groups on catechol ethylamine, which made it difficult to remove the H above it, inhibited the electrooxidation of catechol ethylamine to a certain extent, and enhanced the stability of catechol ethylamine. Finally, the topological analysis of the calculation results of water and DH is carried out by means of the atom theory (AIM) in molecules, and the existence of hydrogen bonds is further confirmed. The theoretical and experimental results are in agreement with each other. Exploring the interaction mode between catechol ethylamine molecule and environment friendly solvent can provide a reference for the extraction and separation of other complex phenol and amine compounds in wastewater, and provide reference for the selection of appropriate solvents for the extraction and separation of other complex phenol and amine compounds in wastewater. And reduce the environmental pollution during the experiment; It is also of great significance for the removal of residual catechol ethylamine in environmental pollution and the detection of phenols and amines in wastewater.
【学位授予单位】：河南大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：X832

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