本文選題：離子液體 + 毛細管電泳　； 參考：《重慶大學》2011年博士論文

【摘要】：毛細管電泳具有分析速度快、分離效率高、樣品用量少等特點。室溫離子液體由于低熔點、良好的導電性、電化學窗口寬、特殊溶解性,已廣泛應用于毛細管電泳分離分析。咪唑型離子液體因其獨特結(jié)構(gòu),能吸附在毛細管壁,影響毛細管電泳電滲流大小和方向。離子液體與其它分子間存在廣泛分子間作用,如:靜電作用、氫鍵、范德華力、色散力、n-π作用,π-π作用等,作為毛細管電泳添加劑,能與介質(zhì)中包括分析物、環(huán)糊精、表面活性劑等成分作用,改變分析物Z/M值或分配特性,提供一種新的分離機制,所以咪唑型離子液體是毛細管電泳方法應用最多一種類型。論文在總結(jié)離子液體相關(guān)性質(zhì)和應用基礎(chǔ)上,第一部分嘗試以非手性離子液體作輔助添加劑,探討其對手性藥物分離分析影響;第二部分通過疏水離子液體1-丁基-3-甲基咪唑六氟磷酸鹽([BMIM]PF6)與表面活性劑作用形成水包離子液體微乳液或者離子液體修飾膠束,與毛細管微乳液電動色譜(MEEKC)或膠束電動色譜(MEKC)相結(jié)合,研究這種新型微乳液和膠束在手性和非手性分離中的特性。具體內(nèi)容主要有: (1)建立了以水溶性非手性離子液1-正丁基-3-甲基咪唑鹽酸鹽([BMIM]C1)為添加劑,β-環(huán)糊精及其衍生物作為手性選擇劑的毛細管區(qū)帶電泳方法,分離了氯霉素前體、普萘洛爾、沙丁胺醇三種手性藥物對映體。結(jié)果表明:緩沖液中沒有添加[BMIM]CI的條件下,藥物只能部分分離,添加離子液體后三種藥物都實現(xiàn)了基線分離,在此基礎(chǔ)上考察了手性選擇劑濃度、離子液體種類和濃度、緩沖溶液pH、分離電壓等因素對手性分離度的影響。 (2)為了探討非手性離子液體對手性藥物分離的影響機理,應用熒光光譜方法測定了緩沖液介質(zhì)加入離子液體條件下,兩種氯霉素前體對映體與β-環(huán)糊精結(jié)合常數(shù),與無離子液體條件結(jié)合常數(shù)比較,并從微觀上分析探索作用機制。 (3)吐溫-20(Tween-20)作為非離子型表面活性劑本身對中性化合物不能實現(xiàn)分離,通過與離子液體之間作用使膠束帶有電荷。建立了基于以非離子型Tween-20為表面活性劑,1-丁基-3-甲基咪唑六氟磷酸鹽([BMIM]PF6)為油相形成水包離子液體微乳液分離四種中性化合物和四種喹諾酮藥物MEEKC新方法。并對緩沖液pH值、離子濃度和表面活性劑用量、離子液體用量等因素對分離的選擇性進行了討論。在此基礎(chǔ)上,比較其與環(huán)己烷為油相、SDS為表面活性劑組成的微乳液對分離對象選擇性異同。 (4)以非離子型Tween-20為表面活性劑,1-丁基-3-甲基咪唑六氟磷酸鹽([BMIM]PF6)為油相形成水包離子液體微乳液,把這種新型微乳液引入毛細管微乳液電動色譜(MEEKC),以β-環(huán)糊精衍生物作為手性選擇劑,建立了在酸性條件下分離氯霉素前體、氧氟沙星手性藥物毛細管微乳液電動色譜方法,同時考察微乳液組成等條件對分離的影響,并對其分離機制進行了初步研究。該方法保留了毛細管微乳液電動色譜可控條件多、理論塔板數(shù)高等優(yōu)點,由于采用非離子型表面活性劑避免了對電滲流的抑制,可在酸性環(huán)境中對藥物實現(xiàn)分離。 (5)通過陰離子表面活性劑十二烷基硫酸鈉(SDS)與疏水性離子液體1-正丁基-3-甲基咪唑六氟磷酸鹽之間作用形成了離子液體修飾的SDS膠束,建立了新的膠束毛細管電動色譜方法,采用該方法分離8種喹諾酮藥物混合物,并對微乳液PH值、緩沖液離子濃度、表面活性劑量、離子液體量等因素對分離的選擇性進行了討論。結(jié)果表明這種新型膠束與未被修飾SDS對分離的選擇性存在差異。
[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.
【學位授予單位】：重慶大學
【學位級別】：博士
【學位授予年份】：2011
【分類號】：R341

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相關(guān)期刊論文 前7條

1 王月伶;胡中波;袁倬斌;;離子液體修飾毛細管膠束電動色譜法分離測定槲皮素、綠原酸和異槲皮甙[J];分析化學;2006年12期

2 劉建芳;隋曉t，

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