【作者】 阴永光；

【导师】 夏之宁；

【作者基本信息】 重庆大学 ， 分析化学， 2005， 硕士

【摘要】 近年来非水毛细管电泳作为毛细管电泳一个新的分支发展迅速,其优势日益引起人们的关注。由于非水溶剂相对于水的物理性质的变化,通常其中的静电相互作用变强,而疏溶剂相互作用变弱。因此在非水溶剂中添加剂与样品中各组分之间的相互作用与水相介质中有很大差异。利用这种差异可以提高非水毛细管电泳分离的选择性。本论文研究了利用非水介质中的静电相互作用与疏溶剂相互作用,实现了不同种类的非离子化物质的非水毛细管电泳分离。本论文由两部分构成: 第一部分着重研究了利用静电相互作用分离酚类与胺类化合物。这一部分包括了第2、3、4 章。在论文第2 章,以乙腈-甲醇为混合溶剂,十六烷基三甲基溴化铵为添加剂,对三种萘类衍生物α-萘胺、α-萘酚、β-萘酚进行了分离,讨论了分离的机理、添加剂浓度、溶剂组成对分离的影响以及CTAB 作为添加剂的特点。最后,对分析纯β-萘酚样品进行了非水毛细管电泳分析。在论文第3 章,以短链四烷基溴化铵(四乙基溴化铵与四丁基溴化铵)为添加剂,在乙腈中基于静电相互作用对多种非离解酚类化合物进行了毛细管电泳分离分析。研究表明四烷基溴化铵添加剂的分离能力与烷基链长度相关,烷基链越短分离能力越强。此外还考察了添加剂浓度以及缓冲液中少量水对分离的影响。研究表明酚的分子结构影响静电相互作用强度,通过对酚类分子结构的分析可以对分离结果进行初步预测。在论文的第4 章,主要以四乙基溴化铵为添加剂,通过溴阴离子与苯胺类化合物的静电相互作用,对苯胺、对-甲苯胺、联苯胺、邻苯二胺以及邻、间、对-硝基苯胺进行非水毛细管电泳分离分析。考察了缓冲液中水与甲醇的存在对分离的影响,表明缓冲液中电子受体的存在可使分离恶化。对分离的机理进行了考察,进一步初步确认了溴离子与苯胺类物质发生静电作用的作用位点为氨基。第二部分包括第5 章,主要研究了利用非水介质中添加剂与分析物之间的疏溶剂相互作用对邻苯二甲酸酯类物质的分离。以SDS 为胶束相,以甲酰胺为非水介质,采用非水胶束电动力色谱,在15 min 内实现了邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯的分离。研究表明,由于非水溶剂中疏溶剂作用的减弱,非水胶束电动力色谱在分离强疏水性化合物方面具有一定优势。更多还原

【Abstract】 Non-aqueous capillary electrophoresis, as a new branch of capillary electrophoresis, witnesses great development in recent years. Because of the different physiochemical properties of non-aqueous solvents, the interaction between molecules or ions is much difference with aqueous media. Usually, the electrostatic interaction becomes stronger, while solvophobic interaction weaker. That difference can be used to improve the selectivity of separation. In this thesis, through electrostatic interaction and solvophobic interaction of additive-analyte, the separation of non-ionic compounds was demonstrated. This thesis mainly includes two parts. In the first part, the separation of phenol and aniline compounds using electrostatic interaction of addictive-analyte was studied. This part consists of Chapter 2, 3, and 4. In chapter 2, the separation of three derivatives of naphthalin, i.e. α-naphthylamine, α-naphthol and β-naphthol, was studied using cetyltrimethyl ammonium bromide, CTAB as additive in methanol/acentonitrile media. The mechanism of separation, and the effect of concentration of CTAB, composition of solvent and the characteristic of CTAB were discussed. And analytical grade reagent, β-naphthol, was analyzed by non-aqueous capillary electrophoresis. In chapter 3, the separation of non-ionic phenols was studied in acentonitrile based on electrostatic interaction using short chain tetra-alkyl ammonium bromide as additive. The research reveals that acentonitrile is a kind of appropriate solvent for electrostatic interaction. The separation using tetra-alkyl ammonium bromide with different alkyl suggested tetra-alkyl ammonium bromide with shorter alkyl chain might have higher separation efficiency. The addition of water and methanol into running solution deteriorates the separation. The study reveals that the structures of phenols have great influence on the strength of electrostatic interaction of phenol-Br-. Through analysis of phenols’structure, we can predict the result of separation primarily. In chapter 4, the separation of anilines, including m-nitroaniline, o-nitroaniline, p-nitroaniline, p-toluidine, aniline, benzidine and o-phenylenediamine, using tetra-ethyl ammonium bromide, TEAB as additive in acentonitrile based on the electrostatic interaction of additive-analyte was studied by non-aqueous capillary electrophoresis. The influence of water and methanol in running solution on the separation was investigated. The research on the mechanism of the interaction revealed that it is the amino group that interacts with the bromide anion. In the second part, Chapter 5, the separation of dialkyl phthalates by non-aqueous micellar electrokinetic chromatography (NAMEKC) in formamide media based on solvophobic interaction was investigated. The separation of three kinds of priority pollutions by U.S. Environmental Protection Agency (EPA), i.e. dimethyl phthalate, diethyl phthalate and dibutyl phthalate, was realized in 15 min using sodium dodecyl sulfate, SDS micelle as pseudo-stationary phase in formamide under optimized conditions. The study suggested that NAMEKC has great potential in the separation of hydrophobic compounds.更多还原