基于离子液体相互作用毛细管电泳新方法

发布时间：2018-06-30 03:47

本文选题：离子液体 + 毛细管电泳　；参考：《重庆大学》2011年博士论文

【摘要】：毛细管电泳具有分析速度快、分离效率高、样品用量少等特点。室温离子液体由于低熔点、良好的导电性、电化学窗口宽、特殊溶解性,已广泛应用于毛细管电泳分离分析。咪唑型离子液体因其独特结构,能吸附在毛细管壁,影响毛细管电泳电渗流大小和方向。离子液体与其它分子间存在广泛分子间作用,如:静电作用、氢键、范德华力、色散力、n-π作用,π-π作用等,作为毛细管电泳添加剂,能与介质中包括分析物、环糊精、表面活性剂等成分作用,改变分析物Z/M值或分配特性,提供一种新的分离机制,所以咪唑型离子液体是毛细管电泳方法应用最多一种类型。论文在总结离子液体相关性质和应用基础上,第一部分尝试以非手性离子液体作辅助添加剂,探讨其对手性药物分离分析影响;第二部分通过疏水离子液体1-丁基-3-甲基咪唑六氟磷酸盐([BMIM]PF6)与表面活性剂作用形成水包离子液体微乳液或者离子液体修饰胶束,与毛细管微乳液电动色谱(MEEKC)或胶束电动色谱(MEKC)相结合,研究这种新型微乳液和胶束在手性和非手性分离中的特性。具体内容主要有: (1)建立了以水溶性非手性离子液1-正丁基-3-甲基咪唑盐酸盐([BMIM]C1)为添加剂,β-环糊精及其衍生物作为手性选择剂的毛细管区带电泳方法,分离了氯霉素前体、普萘洛尔、沙丁胺醇三种手性药物对映体。结果表明:缓冲液中没有添加[BMIM]CI的条件下,药物只能部分分离,添加离子液体后三种药物都实现了基线分离,在此基础上考察了手性选择剂浓度、离子液体种类和浓度、缓冲溶液pH、分离电压等因素对手性分离度的影响。 (2)为了探讨非手性离子液体对手性药物分离的影响机理,应用荧光光谱方法测定了缓冲液介质加入离子液体条件下,两种氯霉素前体对映体与β-环糊精结合常数,与无离子液体条件结合常数比较,并从微观上分析探索作用机制。 (3)吐温-20(Tween-20)作为非离子型表面活性剂本身对中性化合物不能实现分离,通过与离子液体之间作用使胶束带有电荷。建立了基于以非离子型Tween-20为表面活性剂,1-丁基-3-甲基咪唑六氟磷酸盐([BMIM]PF6)为油相形成水包离子液体微乳液分离四种中性化合物和四种喹诺酮药物MEEKC新方法。并对缓冲液pH值、离子浓度和表面活性剂用量、离子液体用量等因素对分离的选择性进行了讨论。在此基础上,比较其与环己烷为油相、SDS为表面活性剂组成的微乳液对分离对象选择性异同。 (4)以非离子型Tween-20为表面活性剂,1-丁基-3-甲基咪唑六氟磷酸盐([BMIM]PF6)为油相形成水包离子液体微乳液,把这种新型微乳液引入毛细管微乳液电动色谱(MEEKC),以β-环糊精衍生物作为手性选择剂,建立了在酸性条件下分离氯霉素前体、氧氟沙星手性药物毛细管微乳液电动色谱方法,同时考察微乳液组成等条件对分离的影响,并对其分离机制进行了初步研究。该方法保留了毛细管微乳液电动色谱可控条件多、理论塔板数高等优点,由于采用非离子型表面活性剂避免了对电渗流的抑制,可在酸性环境中对药物实现分离。 (5)通过阴离子表面活性剂十二烷基硫酸钠(SDS)与疏水性离子液体1-正丁基-3-甲基咪唑六氟磷酸盐之间作用形成了离子液体修饰的SDS胶束,建立了新的胶束毛细管电动色谱方法,采用该方法分离8种喹诺酮药物混合物,并对微乳液PH值、缓冲液离子浓度、表面活性剂量、离子液体量等因素对分离的选择性进行了讨论。结果表明这种新型胶束与未被修饰SDS对分离的选择性存在差异。
[Abstract]:Capillary electrophoresis has the characteristics of fast analysis, high separation efficiency and less sample use. Room temperature ionic liquids have been widely used in capillary electrophoresis separation and analysis due to low melting point, good electrical conductivity, wide electrochemical window and special solubility. The imidazole ionic liquid can be adsorbed on capillary wall and affect capillary electrophoresis because of its unique structure. The size and direction of electroosmotic seepage. There are extensive intermolecular interactions between ionic liquids and other molecules, such as electrostatic action, hydrogen bond, Fan Dehua force, dispersion force, n- PI action, Pi Pi action and so on. As a capillary electrophoresis additive, it can change the Z/M value or distribution characteristics of the analyte, including analyte, cyclodextrin, surface active agent and so on. For a new separation mechanism, the imidazole ionic liquid is the most widely used type of capillary electrophoresis. On the basis of summarizing the related properties and applications of ionic liquids, the first part attempts to use the chiral ionic liquids as auxiliary additives to explore the influence of the separation and analysis of their chiral drugs; the second part is through the hydrophobic ionic liquid. 1- butyl -3- methylimidazole six fluorophosphate ([BMIM]PF6) and surfactant formed water package ionic liquid microemulsion or ionic liquid modified micelle, combined with capillary microemulsion electrokinetic chromatography (MEEKC) or micellar electrokinetic chromatography (MEKC) to study the characteristics of the new microemulsion and micelle in chiral and chiral separation. The main contents are as follows:
(1) a capillary zone electrophoresis method was established for the separation of chloramphenicol precursors, propranolol and salbutamol by capillary zone electrophoresis with 1- n-butyl -3- methylimidazolate ([BMIM]C1) as an additive, beta cyclodextrin and its derivatives as chiral selectors. The results showed that no [BMIM was added to the buffer solution. On the condition of]CI, the drugs can only be partially separated. After adding ionic liquids, the three kinds of drugs have been separated from the baseline. On this basis, the effects of chiral selector concentration, ionic liquid type and concentration, buffer solution pH, separation voltage and other factors are investigated.
(2) in order to investigate the influence mechanism of chiral separation of antichiral ionic liquids, the binding constants of the two chloramphenicol precursor enantiomers and beta cyclodextrins were determined by fluorescence spectroscopy, and the mechanism of the interaction between the enantiomers of chloramphenicol precursors and the non ionic liquid conditions was compared.
(3) Twain -20 (Tween-20) can not separate the neutral compound as a nonionic surfactant itself, and the micelle is charged by the action between the ionic liquid and the ionic liquid. Based on the non ionic Tween-20 as the surface active agent, the 1- butyl -3- methidazole six fluoro phosphate ([BMIM]PF6) is used as the oil phase to form the aqueous microemulsion. A new MEEKC method for separating four neutral compounds and four quinolone drugs was separated. The selectivity of the buffer solution, pH value, ion concentration, the dosage of surfactant and the amount of ionic liquid, was discussed. On this basis, the selection of microemulsion with cyclohexane as oil phase and SDS as surface active agent was selected. Sexual similarities and differences.
(4) using non ionic Tween-20 as surface active agent and 1- butyl -3- methidazole six fluorophosphate ([BMIM]PF6) as oil phase to form water package ionic liquid microemulsion, the new microemulsion was introduced into capillary microemulsion electrokinetic chromatography (MEEKC), and a beta cyclodextrin derivative was used as chiral selector, and the separation of chloramphenicol precursor under acidic conditions was established. The method of capillary microemulsion electrokinetic chromatography with ofloxacin chiral drugs was used to investigate the effect of the composition of microemulsion on the separation and the separation mechanism was preliminarily studied. This method retained the advantages of the capillary microemulsion electrokinetic chromatography with many controllable conditions and high theoretical plate number, and avoided the use of non ionic surfactants. The inhibition of electroosmotic flow can achieve separation of drugs in acidic environment.
(5) an ionic liquid modified SDS micelle was formed by the interaction between the anionic surfactant sodium alkyl sulfate (SDS) and the hydrophobic ionic liquid 1- n-butyl -3- methidazole six fluorophosphate, and a new micellar capillary electrokinetic chromatography was established. This method was used to separate 8 quinolone mixtures, and the pH value of the microemulsion was slow. The separation selectivity of the ion concentration, the surface active dose and the ionic liquid amount was discussed. The results showed that the selectivity of the new micelle and the non modified SDS were different.
【学位授予单位】：重庆大学
【学位级别】：博士
【学位授予年份】：2011
【分类号】：R341

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