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研究生:李逸祺
研究生(外文):Yat-Chi Li
論文名稱:以2,3-O-(4-丁醇基)-β-環糊精衍生物作為靜相應用於整體管柱上的製備與性質研究
論文名稱(外文):Syntheses and Properties of2,3-O-(4-Hydroxybutyl)-β-Cyclodextrin derivativesused as stationary phase for monolithic column
指導教授:桂椿雄桂椿雄引用關係
指導教授(外文):Chun-Hsiung Kuei
學位類別:碩士
校院名稱:國立成功大學
系所名稱:化學系碩博士班
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2005
畢業學年度:93
語文別:中文
論文頁數:60
中文關鍵詞:環糊精
外文關鍵詞:cyclodextrin
相關次數:
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摘 要
  將β-環糊精(β-cyclodextrin)各葡萄糖單體上C(2)、C(3)位置之二級羥基衍生化成丁醇基,並將GPTMS 與環糊精衍生物C(6)位置反應,接上silica 粒子,最後脫去保護基,完成在環糊精上衍生化長鏈羥基的目的,所有步驟皆以NMR 定性。完成反應之silica 衍生物粒子以高壓填入空的熔融矽膠毛細管,利用整體管柱技術,製備μ-HPLC的新靜相管柱;製備方法是將毛細管內壁表面活化後,填入3μm 靜相粒子,再注入TMOS 與EtMOS 混合膠體,並進行縮和反應,將3μm 矽膠粒子固定在毛細管柱中,形成整體管柱。實驗中解決過去充填3 μm 靜相粒子所遇到的瓶頸,同時改善製備整體管柱時,管柱內容易產生氣泡,造成管柱不連續的問題。

  所製備的整體管柱利用一系列多環芳香烴(PAHs),經由分離參數的改變,測定其滯留時間變化,以評估新型靜相的性質。研究發現以下三點結果:1.該反應路徑能以高產率進行一系列環糊精衍生化反應。2.修正充填技術後的乾式充填法,可提高充填3μm 粒子成功率。3.注入11 種濃度為100 ppm 的PAHs 分析物,以體積比為40%的氰甲烷的水溶液,偵測分析波長為240、254、280nm。測試結果顯示新靜相阻塞空腔口,對於PAHs 分離效果不理想。
Abstract
 In this study, we focus on transferring the functional groups in each glucoses-linked of β-cyclodextrin, especially on the hydroxyl groups of the C2 and C3 positions as well as the C6 terminal hydroxyl group.
First, the hydroxyl group in C2 and C3 positions have used synthesized by 1-bromo-butanol to be the primary butanol species.

 On the other hand, to combine the silica particle molecule linked the primary alcohol at C6 position by using GPTMS and continued deprotecting the functional groups. All synthesized intermediate compounds were independently and conduct spectroscopy characterization including 1H-NMR and 13C-NMR.

 The terminal silica-linked β-cyclodextrin was added into the fuse capillary by high-pressure and using monolithic column technique,to prepared newly column for μ-HPLC. In addition, the prepared method by re-actively inside surface of capillary, added stationary phase and the gel combined TMOS with EtMOS for condensation reaction for 3 μm silica
particles bonding at surface in capillary to be a monolithic column. In past experiences, the method of packing 3 μm silica particle molecules into prepared-column were difficult problems, and we have salve this problem, by the way , we have saw out the bubble problem
when we make up a column, that will cause the broken wall in the column.

 As result, this study was developed three excellent points. The first, we can synthesized the different protect groups of β-cyclodextrin in good yields. The second, we revised the technique of drying packing column in
good yields when we packing 3μm silica particle. The third, we loading the PAHs compounds to test the column, the data seems that the CD’s hole was block up, and the result was not fit in with early supposition.
第一章 緒論
1-1 環糊糖精的介紹-----------------------------------1
1-1.1 環糊糖精的介紹-----------------------------------1
1-1.1.1 環糊精的結構及來源--------------------------1
1-1.1.2 cyclodextrin 的立體結構----------------------2
1-1.1.3 cyclodextrin 的性質--------------------------4
1-1.2 環糊糖精及其衍生物在過去文獻上之研究------------6
1-1.2.1 環糊精上面羥基衍生化的方法-------------------7
1-1.2.2 不同位置上羥基衍生化的選擇-------------------8
1-1.3 環糊精應用於層析分離----------------------------10
1-2 毛細管整體管柱--------------------------------------12
1-2.1 整體管柱-----------------------------------------12
1-2.2 管柱充填技術簡介---------------------------------15
1-3 研究目的-------------------------------------------20
1-3.1 衍生化2,3-hydroxybutoxy-CD 之研究目的-------------20
1-3.2 以monolithic column 作為管柱技術之研究目的--------21
1-3.3 以μ-HPLC-UV 作為主要分離方法之研究目的------------21
第二章 實驗部分
2-1 實驗架構-------------------------------------22
2-1.1 環糊精衍生化研究----------------------------------22
2-1.2 管柱製備研究、新型靜相評估-------------------------23
2-2 實驗-----------------------------------------25
2-2.1 β-環糊精衍生化步驟-------------------------------25
C6 保護基反應步驟-----------------------------------25
反應前趨物(BrBuOTHP)製備---------------------------26
環糊精衍生化保護基部份-----------------------------27
去保護基(TBDMS)部分--------------------------------28
鍵結矽膠粒子部分----------------------------------29
去保護基部分(THP)--------------------------------32
2-2.2 管柱製備------------------------------------------33
2-2.2.1 管柱活化------------------------------------33
2-2.2.2 管柱充填------------------------------------33
2-2.2.3 膠體配製與填膠------------------------------35
2-2.2.4 膠體熟化------------------------------------35
2-2.2.5 管柱沖提------------------------------------36
2-2.3 管柱測試------------------------------------------38
第三章 實驗結果與討論---------------------------41
3-1 環糊精衍生化探討---------------------------------41
3-1.1 溶劑的選擇對反應結果探討研究---------------------41
3-1.2 保護基TBDMSCl 特性--------------------------------42
3-1.3 反應前趨物(BrBuOTHP)製備結果與探討---------------43
3-1.4 衍生化後產物結果(已去部分TBDMS 保護基)與探討------44
3-1.5 鍵結上靜相支撐物之探討----------------------------45
3-1.6 衍生化與未衍生化鍵結上粒子多寡原因探討-------------47
3-1.7 去保護基部分(THP)結果與探討------------------------47
3-2 管柱製備探討
3-2.1 靜相粒子含水率對管柱充填成功率影響-----------------48
3-2.2 管柱末端阻擋方式對充填成功率影響-------------------49
3-2.3 膠體選擇與填膠技術對於管柱影響探討-----------------49
3-2.4 管柱成膠條件對管柱影響探討-------------------------50
3-2.5 管柱清洗與條件化對管柱影響探討---------------------51
3-3 分離結果與靜相探討
3-3.1 乙晴/水比例不同對於PAHs 衍生物分離效果探討--------51
3-3.2 環糊精衍生物靜相與文獻中環糊精靜相之比較----------53
第四章 結論與未來展望-----------------------------54
參考文獻------------------------------------------------55
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