毛細管電層析(capillary electrochromatography，CEC)是結合毛細管電泳(CE)和液相層析(HPLC)的一種新分離技術，CEC藉由在毛細管內加入靜相，並在毛細管兩端施加高壓電場以產生電滲流帶動動相溶液進行分析，故其分離機制含括毛細管內分析物之電泳遷移速率的差異，以及分析物在固定相與動相之間的分佈係數不同。由於CEC兼具CE的高分離效率和HPLC的動、靜相間高選擇性等優點，因此近年來CEC的發展極為快速並廣受重視。然而CEC的應用仍以分析中性化合物為主，在電活性陰離子(如S2-和CN-)方面的分析應用則尚未有文獻報導。
本實驗是利用毛細管電層析結合電化學安培偵測法進行電活性陰離子(如S2-、Br-、CN-、I-和S2O32-等)之分析研究，而所使用的CEC管柱是開管式管柱(open-tubular column)，其優點是製備簡單，易與其他偵測器連結。藉由dynamic毛細管修飾法，將陽離子界面活性劑DDAB (didodecyldimethylammonium bromide)修飾至毛細管內壁上，除可使電滲流(EOF)的流動方向反轉(與陰離子之電泳流同向)以縮短分析時間外，對分離而言，管壁上的陽離子界面活性劑亦提供陰離子交換位置；在離子交換和電泳兩種不同的分離機制相互作用下，更增加分離陰離子的選擇性。
本實驗使用長50 cm、內徑25 μm的熔融矽毛細管，以30 mM H3BO3 (pH 9.24)作為分離電解質溶液，在以固定式(- 15 kV)或兩段式(-15 kV / -28 kV)的分離電壓下，以銀微電極(直徑 100 μm)結合定電位安培偵測法(偵測電位為+0.1 V vs. Ag/AgCl)，成功地將EOF反向並同時分析具電活性的無機陰離子：S2-、Br-、CN-、I-和S2O32-。實驗結果發現，各待測陰離子之電泳遷移時間之再現性都很好(RSD < 3 %)，至於波峰電流之再現性，除了CN-之RSD值為10 %之外，其他陰離子則亦皆良好 (RSD 2.5∼4.5 %)。在分析過程中，以甲醇溶液證明以DDAB修飾的開管式毛細管柱能提供系統穩定的電滲流，電滲流遷移率之再現性極佳(RSD＝1.1 %，n = 30)，因此可將此方法應用至定量分析上。分析標準樣品溶液所得校正曲線的線性關係還不錯(r ＞ 0.995以上)，但測得之理論板數約在2500∼7000則較差。
偵測極限各為：S2- 4.2 ppb；Br- 10 ppb；CN- 9.4 ppb；I- 120 ppb；S2O32- 110 ppb。最後也對其他陰離子：SCN-、Cl- 、SO42-、NO2-、Cl-、NO3- 、SO42-和ClO4-所可能產生的干擾和影響進行一系列探討，並成功地將此分析方法應用在真實樣品如飲水機和礦泉水水樣的回收率及對陽明山溫泉水中S2-含量的定量分析。

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摘要………………………………………………………………………….Ⅰ
謝誌………………………………………………………………………….Ⅲ
目錄………………………………………………………………………….Ⅳ
圖目………………………………………………………………………….Ⅶ
表目………………………………………………………………………….Ⅹ
壹、緒論..………………………………………………………………….…1一、毛細管電層析法……………………………………………………...1
二、毛細管電層析法原理…………………………………………….…...3
1. 毛細管電泳原理…………………………………………………....3
2. 高效能液相層析法原理……………………………………………9
三、毛細管電層析法之管柱類型……………………………………….11
1. 開管式管柱………………………………………………………..13
2. 填充式管柱………………………………………………………..16
3. 連續式管柱………………………………………………………..17
四、界面活性劑及其吸附機制………………………………………….18
五、毛細管電泳法分析陰離子………………………………….………24
1. Normal EOF……………………………………………………….26
2. Reduced EOF……………………………………………………...26
3. Reversed EOF……………………………………………………..26
六、毛細管電層析分析陰離子…………………………………………26
七、 離子層析法分析電活性陰離子…………………………………...28
八、研究目的…………………………………………………………...29

貳、實驗部分……………………………………………………………….33
一、儀器設備……………………………………………………………33
二、藥品及溶液之配製…………………………………………………36
三、銀微電極之製作…..………………………………………………..40
四、實驗過程 …………………………………………………………..41

參、結果與討論…………………………………………………………….45
一、實驗條件最佳化……………………………………………………45
1. 偵測電位之選擇…………………………………………………..45
2. 界面活性劑之濃度對陰離子分離的影響………………………..50
3. 分離電解質溶液之pH對陰離子分離的影響…………………...50
4. 配製樣品溶液的pH值對陰離子分離的影響…………………...54
5. 分離電解質溶液之濃度對陰離子分離的影響…………………..57
6. 分離電壓對陰離子分離的影響…………………………………..57
7. 樣品注入時間對陰離子訊號大小及分離的影響………………..60
8. 兩段式分離電壓…………………………………………………..60
9. 實驗最佳化條件…………………………………………………..60
二、系統之再現性………………………………………………………65
三、電滲流的穩定性……………………………………………………68
1. 電滲流的證據……………………………………………………68
2. 電滲流的再現性…………………………………………………70
四、校正曲線及偵測極限………………………………………………70
五、其他陰離子的干擾…………………………………………………75
1. 干擾陰離子的電化學性質………………………………………75
2. 干擾陰離子之干擾探討…………………………………………79
3. 樣品溶液含干擾陰離子之影響…………………………………79
4. 樣品溶液中含NO3-、SO42-、ClO4-的干擾探討……………….85
5. 分離電解質溶液添加競爭陰離子的探討………………………85
六、真實樣品分析………………………………………………………88
1.飲用水的水樣……………………………………………………..88
2.溫泉水的水樣……………………………………………………..97
肆、結論.…………………………………………………………………100
伍、參考文獻.……………………………………………………………..101
陸、簡歷…………………………………………………………………...105

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