有機錫化合物係指以錫(Sn)原子為中心而周圍鍵結烷基或苯基的化合物(RnSnX4-n)，已被廣泛地使用在工業與農業上，例如做為塑膠安定劑、船舶防汙劑、農藥及殺蟲劑等，其中又以有三個取代基的三有機錫化合物應用最廣。
有機錫化合物大都具有毒性，其毒性大小又隨不同的化學型態(Chemical Form)而有所不同，所以定量分析不同型態的有機錫化合物，要比測定錫總量更有意義。文獻中，用以測定三有機錫物種的方法，主要有氣相層析(GC)及液相層析(LC)，但毛細管電泳有分離效率高與樣品使用量少的優點，近年也被應用於有機錫的分析，但偵測法都侷限於紫外光(UV)吸收法及螢光法(FL)；本實驗室曾以毛細管電泳連接差式脈衝安培法(Differential Pulsed Amperometry)測定有機錫物種，但只能分析三種三有機錫化合物。因此本研究的目的是要藉由改善分離電解質組成與電化學偵測方式，使其不但能夠同時分析五種三有機錫化合物，而且可以達成更低的偵測極限。
本實驗使用內徑10 μm、長50 cm 的 fused silica 毛細管，以2 mM 4-aminopyridine + 175 mM HAc + 10% MeOH (pH 3.0) 溶液作為分離電解質，標準樣品配在MeOH 中，施加22 kV 分離電壓進行分離；並在毛細管
出口以 100 μm 金汞膜微電極以 wall-jet 的方式進行對位，使用三電位脈衝(波)安培偵測法(Triple Pulsed Amperometric Detection, triple PAD)偵測三甲基錫 ( (CH3)3Sn+, TMT)、三乙基錫( (C2H5)3Sn+, TET)、三丙基錫( (C3H7)3Sn+, TPT)、三丁基錫( (C4H9)3Sn+, TBT )、 三苯基錫( (C6H5)3Sn+,TPhT) 等五種三有機錫化合物。Triple PAD 的偵測原理如下：在E1 = 0.0 V 時，電極表面的吸附物被清除；在E2 = -1.3 V 時，三有機錫化合物還原(R3Sn+ --> R3Sn-)並沉積在金汞膜電極表面；在E3 = 0.0 V 時，原本沉積在電極表面的三有機錫還原物(R3Sn-)被氧化而測得氧化電流，殘餘的三有機錫還原產物將在下一循環的E1 電位被清除，並重複進行上述反應。
藉由以上實驗條件，可成功地分離並偵測到上述五種三有機錫化合物，其電泳遷移時間之再現性良好(RSD% < 1%)，而波峰電流訊號之再現性(RSD%)則皆 < 6%。而分析物濃度在2 ∼ 20 μM 時測得之校正曲線之線性相關係數皆在0.996 以上，各物種的偵測極限(S/N = 3)分別為：三甲基錫(0.53 μM)、三乙基錫(0.15 μM)、三丙基錫(0.19 μM)、三丁基錫(0.40 μM)、三苯基錫(0.97 μM)。最後利用本分析方法對港口底泥標準參考樣品進行分析，可成功測定其中的三丁基錫。

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摘要……………………………………………… I
謝誌……………………………………………… III
目錄……………………………………………… IV
圖目……………………………………………… VI
表目……………………………………………… VIII
壹、緒論
　一、有機錫化合物簡介……………………… 1
　二、測定有機錫化合物的方法……………… 3
　三、結合電化學偵測法分析有機錫化合物… 6
　四、三電位脈衝安培法……………………… 9
　五、研究目的………………………………… 12
貳、實驗部分
　一、儀器設備………………………………… 13
　二、藥品……………………………………… 17
　三、溶液之製備……………………………… 19
　四、金汞膜微電極的製作與再生…………… 22
　五、實驗過程………………………………… 24
&#21442;、結果與討論
　一、分離條件之選擇………………………… 29
　　1. 分離電解質之探討……………………… 29
　　2. 使用有機溶劑之探討…………………… 34
　　3. 分離電壓之探討………………………… 37
　　4. 樣品注入時間之探討…………………… 37
　二、偵測電位之選擇………………………… 39
　　1. 三有機錫化合物的電化學特性之探討… 39
　　2. 三電位脈衝安培偵測法測定三有機錫化
　　　物之電位條件探討……………………… 44
　三、系統之再現性、校正曲線與偵測極限… 58
　四、港口底泥標準參考樣品中三有機錫化合物
　　　之分析……………………………………… 63
肆、結論………………………………………… 72
伍、參考文獻…………………………………… 73
陸、附錄
　一、三丁基錫之電化學反應模式…………… 79
　二、單丁基錫與二丁基錫的電化學特性之探討 82
　三、不同pH值之分離電解質溶液中所含的
　　　醋酸濃度………………………………… 84
　四、樣品堆積對五種三有機錫化合物訊號
　　　增大的倍數……………………………… 84
柒、簡歷………………………………………… 86

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