博碩士論文 90223021 詳細資訊




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姓名 陳鑫昌(Hsin-Chang Chen)  查詢紙本館藏   畢業系所 化學學系
論文名稱 利用毛細管電泳結合線上濃縮方法分離奈磺酸鹽之機制探討
(Analysis of naphthalenesulfonate compounds by cyclodextrin-mediated capillary electrophoresis with sample stacking)
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摘要(中) 本研究主要是建立樣品線上濃縮技術(on-line concentration)以提高毛細管電泳(CE)的靈敏度。毛細管電泳是近年來相當受到重視的分析技術,但往往受限於毛細管的光徑長度,使得在以UV的偵測上,無法有效降低分析的偵測極限。利用樣品線上濃縮技術來提高靈敏度的方式,不必更改或更換任何儀器設備,以達到簡便且經濟的需求。其原理是增加毛細管中樣品的進樣量,以不同方式將樣品聚集濃縮,提高樣品的相對濃度。
奈磺酸鹽類(Naphthalene Sulfonates)是指磺酸根取代基在奈丸的不同位置上取代所形成之位置異構物,在製藥與化學工業的產品製造上均被廣泛使用。由於這類化合物具有很高的水溶性與穩定性,易隨水流四處擴散,加上廢水處理無法適當降解這類化合物,以致這些物質隨廢水排放入自然水環境中,進而污染水源及影響環境生態。此外由於一般的毛細管區帶電泳(CZE)並無法有效分離位置異構物,因此將利用毛細管環糊精修飾區帶電泳對位置異構物進行分析,以達有效分離。
研究中將改良反向電極極性堆積模式(Reverse Electrode Polarity Stacking Mode、REPSM),對樣品進行堆積進而分離,並改變緩衝溶液中b-、g-環糊精之組成成份及比例,以求分離達到最佳化。在最佳的樣品堆積分離條件下,方法偵測極限可達到4mg/L。遷移時間與波峰的再現性也因加入內標準品而有顯著的改善,此分析物的定性與定量更加精密。此方法亦成功應用至飲用水之微量分析。
摘要(英) This study systematically investigates the optimal conditions for analyzing the positional isomers of multi-charged naphthalenesulfonate compounds by cyclodextrin-mediated capillary electrophoresis (CE). Specifically, this work employs large-volume sample injection with the electrode polarity switching technique. The most effective separation and sample stacking conditions was 15 mM borate buffer with a mixture of b- and g-cyclodextrin (CD) (concentration ratio 3:7 mM) at pH 9.2 and 25℃, and the sample hydrodynamic injection of up to 60 seconds at 3 psi (around 1802 nL). Significant selective and sensitive improvements were observed and a more than 100-fold enrichment was achieved (based on peak area). The reproducibility of migration time and quantitative results of stacking CE can be improved by using internal standards. The quantitation limits of these naphthalenesulfonate isomers, based on a signal-to-noise (S/N) ratio above 10, can be reached about 4 mg/L with UV detection. This method was successfully applied to determine the trace amount of naphthalenesulfonate isomers in a spiked drinking water sample.
關鍵字(中) ★ 樣品堆積
★ 環糊精
★ 奈磺酸鹽
★ 毛細管電泳
關鍵字(英) ★ sample stacking
★ capillary electrophoresis
★ cyclodextrin
★ naphthalenesulfonate
論文目次 中文摘要----------------------------------------------------------------------Ⅰ
英文摘要----------------------------------------------------------------------Ⅲ
目錄--------------------------------------------------------------------------Ⅳ
表目錄------------------------------------------------------------------------Ⅶ
圖目錄------------------------------------------------------------------------Ⅷ
第一章 前言---------------------------------------------------------------- 1
1-1 研究的緣起---------------------------------------------------------- 1
1-2 研究目標------------------------------------------------------------ 3
第二章 文獻回顧------------------------------------------------------------ 4
2-1 毛細管電泳分析法---------------------------------------------------- 4
2-1-1 毛細管柱-- -------------------------------------------------------- 5
2-1-2 基本原理- --------------------------------------------------------- 6
2-1-3 毛細管電泳儀之裝置 ----------------------------------------------- 10
2-1-4 線上樣品堆積 ----------------------------------------------------- 11
2-2 環糊精 -------------------------------------------------------------14
2-3 內標準品 ---------------------------------------------------------- 19
2-4 奈磺酸鹽類 -------------------------------------------------------- 20
2-5 國內外之相關研究 -------------------------------------------------23
第三章 實驗步驟與樣品分析 ---------------------------------------------- 26
3-1 實驗藥品與儀器設備 -----------------------------------------------26
3-1-1 實驗藥品 ---------------------------------------------------------26
3-1-2 儀器設備 ---------------------------------------------------------28
3-2 實驗步驟
3-2-1 奈磺酸鹽位置異構物分析 -------------------------------------------- 29
3-2-1.1 標準品的製 -- -------------------------------------------- 29
3-2-1.2 緩衝溶液的製備- ------------------------------------------ 30
3-2-1.3 毛細管的處理---------------------------------------------- 30
3-2-1.4 實驗操作條件---------------------------------------------- 31
第四章 結果與討論 -------------------------------------------------------- 33
4-1 紫外光偵檢器之波長選擇 - ----------------------------------------- 33
4-2 環糊精對NS異構物分離的影響 ---------------------------------------- 36
4-2-1 一般CZE分離------------------------------------------------------ 36
4-2-2 樣品堆積--------------------------------------------------------- 36
4-2-3 有機修飾劑------------------------------------------------------- 37
4-2-4 毛細管環糊精修飾區帶電泳結合樣品堆積之分離----------------------- 37
4-3 緩衝溶液之pH值與濃度的影響 -----------------------------------------39
4-4 最佳樣品堆積條件 ---------------------------------------------------46
4-5 操作條件再現性之探討 -----------------------------------------------49
4-6 檢量線之製作與理論板數 ---------------------------------------------50
4-7 真實水樣之測試 -----------------------------------------------------57
第五章 結論 -------------------------------------------------------------- 62
參考文獻 ------------------------------------------------------------------- 63
表目錄
表2-1 環糊精的性質---------------------------------------------------------- 18
表3-1 毛細管電泳儀(CE)設定參數-------------------------------------32
表4-1 奈磺酸鹽類之結構式、縮寫及其波峰之符號代表--------------34
表4-2 連續8次進樣結果之再現性-----------------------------------------51
表4-3 日與日之間之再現性 -----------------------------------------------52
表4-4 奈磺酸鹽類異構物標準品之感應因子線性關係-----------------54
表4-5 理論板數-----------------------------------------------------------------56
表4-6 不同樣品之電導度值 -----------------------------------------------61
圖目錄
圖2-1 毛細管柱內壁表面矽醇基Si-OH解離示意圖----------------------6
圖2-2 毛細管內壁之Stern電雙層模型--------------------------------------7
圖2-3 毛細管內之電位變化圖 -----------------------------------------------8
圖2-4 流體流動剖面圖 --------------------------------------------------------9
圖2-5 毛細管電泳儀裝置圖--------------------------------------------------10
圖2-6 線上樣品堆積之機制示意圖-----------------------------------------13
圖2-7 環糊精結構通式--------------------------------------------------------17
圖2-8 偶氮染料分解反應式--------------------------------------------------20
圖4-1 奈磺酸鹽之UV吸收圖譜--------------------------------------------35
圖4-2 以一般CZE分離方法分離奈磺酸鹽位置異構物之電泳圖 --41
圖4-3 不同種類環糊精對分析物分離效果的影響之電泳圖-----------42
圖4-4 添加有機修飾劑於硼酸鹽緩衝溶液之分析物電泳圖-----------43
圖4-5 添加不同比例b-與g-環糊精於緩衝溶液中之電泳圖------------44
圖4-6 硼酸鹽緩衝溶液濃度對遷移時間及吸收峰影響之電泳圖-----45
圖4-7 樣品堆積與分離時之電流圖-----------------------------------------46
圖4-8 線上濃縮技術REPSM與一般CE進樣之靈敏度差異---------48
圖4-9 奈磺酸鹽類異構物標準品之檢量線--------------------------------53
圖4-10 奈磺酸鹽類異構物標準品之儀器偵測極限電泳圖 -----------55
圖4-11 添加10 mg/L標準品於飲用水樣品之電泳圖--------------------59
圖4-12 不同電導度之樣品堆積與分離時的電流圖 --------------------60
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指導教授 丁望賢(Wang-Hsien Ding) 審核日期 2003-7-14
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