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研究生: 高彰隆
Kao, Chang-Long
論文名稱: 選擇性乙醯基化γ-環糊精靜相於高效率液相層析及毛細管電層析之研究
Native and Selectively Acetylated γ-cyclodextrin as Stationary Phases for μ-HPLC and CEC
指導教授: 桂椿雄
Kuei, Chun-Hsiung
學位類別: 碩士
Master
系所名稱: 理學院 - 化學系
Department of Chemistry
論文出版年: 2005
畢業學年度: 93
語文別: 英文
論文頁數: 51
中文關鍵詞: 環糊精
外文關鍵詞: cyclodextrin
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  •   將選擇性乙醯基化之γ環糊精以3-glycidoxypropyltrimethoxy silane (GPTMOS)之矽烷化合物鍵結於粒徑5μm矽膠粒子上,將之充填入100μm內徑融矽石英管柱並藉溶膠-凝膠反應製備成整體管柱。利用高效率液相層析及毛細管電層析對多環芳香族分離混合物、1-phenylethane-1,2-diol及 dansyl serine對掌異構物化合物進行分離。結果顯示對多環芳香族滯留時間因分析物於動相之溶解度及主-客錯合物穩定度造成不同滯留順序。對於1-phenylethanol, 1-phenylethane-1,2-diol及 dansyl serine對掌異構物化合物而言,1-phenylethanol 於2,3-乙醯基化之γ環糊精較2,3-乙醯基化之β環糊精有較好解析,1-phenylethane-1, 2diol於2,3-及2-乙醯基化之γ環糊精則顯示不同解析能力,dansyl serine於γ環糊精則具有基線解析。相較於β環糊精,γ環糊精空腔較大且具彈性結構有助於乙醯基化之γ環糊精解析對掌異構物化合物。

      Native and selectively acetylated γ-cyclodextrins were synthesized as chiral stationary phases. Compound, 3-glycidoxypropyltrimethoxy silane (GPTMOS), is used to modify the hydroxyl groups of 6-positions of γ-cylcodextrins for bonding on silica gel.A piece of 100 I.D.μm fused silica capillary (10 to 20 ㎝) was packed with thoses particles, and then proceeding sol-gel reaction to produce monolithic columns for CEC an μ-HPLC.

      Results show different retention order for polyaromatic hydrocarbons (PAHs) influenced by the stability of analytes-CDs inclusion complex, solubility of analytes in mobile phase. Results also show dansyl serine with native γ-cyclodextrin has baseline resolution which is better than native β- cyclodextrin. 1-phenylethanol was better resolved with 2, 3-O-diacetyl-γ-cyclodextrin than 2, 3-O-diacetyl-β- cyclodextrin. 1-phenylethane-1, 2diol was resolved by native γ-cyclodextrin, 2, 3-O-diacetyl-γ-cyclodextrin and 2-O-acetyl-γ-cyclodextrin.

      It is due to the fact that γ-cyclodextrin has the wider cavity width and more flexible than β-cyclodextyrin, which the modification of acetyl groups – more stereo than methyl at different positions of hydroxyl groups of γ-cycyclodextrin facilitate chiral recognition.

    Chinese Abstract..............................................................Ⅰ English Abstract..............................................................Ⅱ Context.......................................................................Ⅲ List of Tables................................................................Ⅴ List of Figures...............................................................Ⅵ Chapter 1 Introduction.........................................................1 1-1 Chirality and The Importance of Chiral Separation..........................1 1-2 Chiral Selectors or Chiral Sationary Phases(CSPs)..........................2 1-2.1 Pi-Pi interactions - acceptor and donor..................................3 1-2.2 Ligand exchange type.....................................................4 1-2.3 Affinity type............................................................4 1-2.4 Macrocycles..............................................................4 1-2.4.1 Macrocylclic antibodies................................................4 1-2.4.2 Crown ether............................................................5 1-2.5 Molecular imprint........................................................5 1-2.6 Polysaccharides..........................................................6 1-2.6.1 Cellulose..............................................................6 1-2.6.2 Cyclodextrins..........................................................6 1-3 Modes in Chiral Separations and Chromatographic Methods....................9 1-3.1 Modes in chiral separations..............................................9 1-3.2 Chromatography method:μ-HPLC and CEC...................................10 1-4 Monolithic Columns for chromatography.....................................12 1-4.1 Organic-Based Monoliths.................................................12 1-4.2 Silica-Based Monoliths..................................................13 1-5 Aims of Studies...........................................................14 Chapter 2 Experimental section................................................15 2-1 Instrument and Reagents...................................................15 2-1.1 Instrument..............................................................15 2-1.2 Reagents.............................................................15 2-2 Station Phases Synthesis..................................................18 2-2.1 Silyl ether protection of hydroxyl groups in cyclodextrins..............18 2-2.2 Acetyl derivative of cyclodextrins......................................18 2-2.3 Immobilization on Silica Gels...........................................18 2-3 Preparation of Monolithic Column..........................................19 2-3.1 Pretreatment of capillaries.............................................19 2-3.2 Packing.................................................................19 2-3.3 Sole-Gel Process........................................................19 2-4 Pretreatment of Columns...................................................19 2-5 Pretreatment of analytes and reagents.....................................19 Chapter 3 Results and Discussions.............................................21 3-1 Identification of compounds...............................................21 3-2 Mechanisms................................................................27 3-2.1 Silyl ether protection and remove in cyclodextrin.......................27 3-2.2 Selective modifications of cyclodextrin.................................27 3-2.3 2-O à 3-O silyl migration in cyclodextrin..............................29 3-2.4 Acetyl derivative cyclodextrin..........................................30 3-3 On Monolithic Columns.....................................................30 3-3.1 Gelation................................................................31 3-3.2 Aging...................................................................31 3-4 On Column performance.....................................................33 3-4.1 Retention of Polyaromatic Hydrocarbons..................................34 3-4.2 Retention of Chiral Compounds...........................................38 Chapter 4 Conclusions and further study.......................................45 4-1 Conclusions...............................................................45 4-2 further study.............................................................46 References....................................................................47

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