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研究生： 鄧名志
Teng, Ming-Chih
論文名稱： 環糊精及膠體穩定度對整體毛細管柱製備之研究
The Study of Cyclodextrin and Stability of Sol-Gel for Preparation of Monolithic Column
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： 2003
畢業學年度： 91
語文別： 中文
論文頁數： 69
中文關鍵詞： 環糊精 、鏡相異構物 、整體管柱
外文關鍵詞： cyclodextrin, chiral, monolithic column
相關次數： 點閱：101  下載：1 
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    • 層析分離效率順應時代需求逐年提高，身為層析心臟的管柱對於分離效率之影響力甚鉅，因此管柱開發之研究至今仍屹立不搖，近年來在管柱製備的技術上有一項新技術，此技術是將靜相粒子填入管柱之後，再填入矽膠單體，將管柱內壁、支撐物及靜相化為一體，此管柱稱為整體管柱（Monolithic column）或溶膠管柱（Sol-gel column）。此管柱改善了開管式毛細管柱對分析物之容積量小，及填充式毛細管柱在固定靜相技術上的缺點。
    由於許多的生化藥物及食品添加物具有鏡相異構物，大部分異構物對於生物體的生化反應具有特異性，且鏡相異構物無法以一般之分離方法分離，使得鏡相異構物的分離變得格外的重要，因此利用環糊精分離鏡相異構物。
    本研究將-環糊精二級羥基甲基化及一級羥基丙烯基化形成2,3-di-O-methyl-6-O-propenyl--CD，衍生化完成之環糊精以1H-NMR及IR鑑定結果，環糊精衍生物鍵結於粒徑3m矽膠粒子上，完成後將此靜相粒子填充於內徑100m毛細管柱中，並將Octyltrimethoxysilane（OTMOS）和Tetramethoxysilane（TMOS）所組成的膠體填入管柱中，粒子固定後利用超臨界二氧化碳及氰甲烷清洗管柱。
    上述管柱以毛細管電層析對Carvone鏡相異構物、Naphthalene及Anthracene進行測試，此整體管柱對Carvone具有完全分離的效果。理論板數最高可達到210,000 plates /m，且管柱壽命初步可達到4個月。

    A new technique for preparing capillary packed column is reported in recent years. The stationary phase particles is packed into a capillary column and sol-gel injected to proceed cross-linking reaction, which will bond stationary phase particles in the column and make the inner walls of column, supports and stationary phase into one unity. This kind of column is called monolithic column or sol-gel column. The sample capacity is higher than open tubular column. It was improved drawbacks associated with packed capillary column.
    Many biochemical drugs and food additives have chiral isomers and most isomers have their functions on biochemical reactions of organism, separation of chiral isomers is of value. Cyclodextrins (CDs) and its derivatives have had excellent performance on the separation of chiral isomers in analytical chemistry since a decade ago.
    -Cyclodextrin (-CD) was methylated to form 2,3-di-O-methyl-6-O- propenyl--CD, which was bonded to 3m silica particles to produce stationary phase particles needed for a column. The number and position of the methyl groups in -CD were verified by 1H-NMR and IR. These particles were packed into a capillary column under high pressure CO2. Then fill 9% (v/v) sol-gel solution into column. The compositions of the sol-gel solution were octyltrimethoxysilane (OTMOS) and tetramethoxy- silane (TMOS). After gelling and aging, the column was dried with supercritical CO2.
    Capillary electrochromatography of the monolithic column was examined. Its maximum theoretical plate number was as high as 210,000 plates/m. It could completely separate chiral isomers of carvone. The life of column could initially last for 4 months.

    謝誌----------I 中文摘要----------III 英文摘要----------IV 目錄----------VI 表目錄----------IX 圖目錄----------X 第一章 緒論----------1 1-1毛細管柱簡介----------3 1-1-1管壁材質簡介----------3 1-1-2開管式毛細管柱----------4 1-1-3填充式毛細管柱----------6 1-1-4整體毛細管柱----------7 第二章 鏡相異構物分離簡介----------11 2-1鏡相異構物定義----------11 2-2鏡相異構物對生物體之效應----------12 2-3鏡相異構物之分離----------14 2-4環糊精簡介----------17 2-4-1環糊精的性質----------17 2-4-2環糊精於靜相上之應用----------19 2-5研究目的----------21 第三章 實驗操作----------22 3-1儀器設備及藥品----------22 3-1-1儀器設備----------22 3-1-2藥品----------23 3-2環糊精及矽膠衍生化----------26 3-2-1環糊精衍生化----------26 3-2-2矽膠粒子氫化----------27 3-2-3環糊精及矽膠粒子鍵結----------28 3-3膠體耐度測試----------29 3-3-1膠體配置----------29 3-3-2膠體耐度測試----------30 3-4管柱製備----------31 3-4-1管柱前處理----------31 3-4-2靜相粒子之充填----------31 3-4-3靜相粒子之固定----------32 3-4-4管柱上機前處理----------34 3-5管柱測試----------35 3-5-1緩衝溶液製備----------35 3-5-2配置分析物----------35 3-5-3實驗操作----------35 第四章 結果與討論----------37 4-1環糊精衍生化及其鍵結於矽膠粒子之探討----------37 4-1-1環糊精之衍生化----------37 4-1-2環糊精衍生化之反應機制----------37 4-1-3矽膠粒子衍生化及環糊精鍵結----------39 4-1-4環糊精衍生化之鑑定----------40 4-1-5環糊精鍵結於矽膠粒子之鑑定----------42 4-2膠體耐度測定探討----------46 4-2-1相同膠體比例對不同pH溶液之耐度探討----------46 4-2-2相同pH溶液對不同膠體比例之耐度探討----------47 4-3管柱製備探討----------59 4-3-1靜相充填技術探討----------59 4-3-2填膠技術及成膠因素探討----------60 4-4 管柱效能探討----------61 4-4-1分析效率----------61 4-4-2解析度----------62 第五章 結論----------65 第六章 未來展望----------66 參考文獻----------67

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