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研究生: 張景翔
Jing-Shan Chiang
論文名稱: 液相微萃取法於環境水樣及尿液之微量有機污染物分析方法之研究與開發
Determination of trace organic contaminants in environment using liquid-phase microextraction
指導教授: 黃賢達
Shang-Da Huang
口試委員:
學位類別: 博士
Doctor
系所名稱: 理學院 - 化學系
Department of Chemistry
論文出版年: 2008
畢業學年度: 96
語文別: 中文
論文頁數: 132
中文關鍵詞: 液相微萃取分散式液液微萃取動態頂空單滴微萃取鹵素醚類安非他命芳香胺氣相層析電子捕捉偵測器火焰離子化偵測器質譜儀化學衍生中空纖維
外文關鍵詞: Liquid-phase microextraction, Dispersive liquid -iquid microextraction, Dynamic headspace single-drop microextraction, Haloether, Amphetamine, Aromatic amine, Gas-Chromatography, Electron capture detector, Flame ionization detector, Mass Spectrometer, Chemical Derivatization, Hollow Fiber
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  • 中文摘要
    近年來在分析化學方法上強調綠色化學、快速、簡便與耗費成本低的分析技術,傳統的液液相萃取法或固相萃取法等,對於分析環境中之微量有機污染物有著花費大量時間或有機溶劑的缺點。因此本論文的研究方向為液相微萃取方法搭配分散式液液微萃取方法的開發搭配液相層析儀和氣相層析儀之分析方法,並將其應用在環境中水樣與人體尿液中微量有機物之測定,以下為各章節之主題與概要說明。
    第一章為緒論,說明在發展經濟同時保護環境的重要性,提出分析方法之必要性與本論文研究之目的,並介紹本實驗室使用過及相關之部份分析方法或原理。
    第二章為動態式液相微萃取法 (dynamic liquid phase microextraction) 分析環境中水樣之鹵素醚類,液相微萃取法是近年來新興的一種樣品前處理技術,萃取相為微量有機溶劑,相較於商業化固相微萃取之吸附纖維的價格低廉許多,同時也具有樣品前濃縮的效果。研究中探討電子捕捉偵測器 (ECD) 與火焰離子化偵測器 (FID) 對這四種鹵素醚類之靈敏度,最後再比較液相微萃與固相微萃取之精密度及靈敏度。
    第三章是同步萃取-衍生的頂空液相微萃取 (head-space liquid phase microextraction) 技術應用在人體尿液中的安非他命及搖頭丸之分析,文中說明一般分析濫用藥物的萃取方法,並討論本研究開發出之同時衍生/萃取的實驗裝置所達到的良好結果,除了有效的分析時間,方法的簡便與靈敏度的提升外,並探討各項萃取參數之最佳化條件與此技術之實際應用性,顯示可分析尿液中超微量濃度之濫用藥物。
    第四章之內容為化學衍生法結合分散式液液微萃取 (dispersive liquid-liquid microextraction) 技術,並應用於水溶液樣品中微量芳香胺之分析。分散式液液微萃取是近年來新興的一種樣品前處理方法,萃取相為微量有機溶劑,萃取時間極短同時具備高靈敏度。研究中探討先衍生後萃取與同步萃取/衍生的結果,並討論分散式液液微萃取法的各項最佳化參數。
    第五章內容是開發動態式頂空單滴微萃取 (dynamic single-drop microextractio) 技術與其應用。研究中探討開發動態式頂空單滴微萃取方法的過程中,萃取溶劑在注射針尖持續維持液滴而移到針壁,經由稍做改變後發現也只有離子液體可以進行動態式頂空單滴微萃取,因此選擇離子液體做為萃取溶劑來萃取尿液中的多環芳香族碳氫化合物。研究中探討各項萃取參數之最佳化條件,以及此技術之實際應用性。
    第六章則將上述開發的數種分析方法做簡單的整理,並展望未來分析技術可能的進展與應用。


    Abstract
    The development of faster, simpler and economic sample-preparation techniques is an important issue in chemical analysis. In this work, four analytical methods base liquid-phase microextraction (LPME) and dispersive liquid-liquid microextraction (DLLME) were described. The developed methods have been applied to the analysis of trace pollutants and abuse drugs in different sample matrices such as lake, river or human urine.
    Liquid phase microextraction method, which included hollow fiber liquid-phase microextraction (HF-LPME), single-drop microextraction (SDME), were investigated in the chapter one, chapter two, and chapter four. This methodology provided to be extremely simple, low cost and virtually solvent-free sample-preparation technique, which provided a high degree of selectivity and enrichment. The results show that these sample-preparation coupled with GC-ECD or GC-MS could determinate the trace organic pollutants in the ppb level.
    The DLLME developed by Yaghoub Assadi in 2006 has emerged as a virtually time-free alternative for extraction time to conventional liquid-liquid extraction and solid-phase extraction even SPME and LPME procedures. It involves the partition of analytes between the aqueous and extremely small organic drop and the surface area between the aqueous and organic drop is enhanced dramatically. Thus the extraction time is reduced effectively. Second chapter describes the development of DLLME technique where extraction and derivatization were carried out in one-step. In this work, the derivatizating reagent was added into extraction solvent so that the analytes can be derivatized as the partition of analytes into extraction solvent was carried out. This technique was applied to the analysis of amphetamine and methylenedioxyamphetamine in urine sample from abusers.

    目錄 中文摘要 Abstract 第一章 緒論 1 - 1 前言………………………………………………1 1 - 2 固相微萃取法 …………………………………2 1 - 2 – 1 萃取原理 …………………………………3 1 - 2 – 2 直接浸入式固相微萃取 …………………3 1 – 2 –3 頂空固相微萃取 …………………………4 1 – 3 液相微萃取法 …………………………………4 1 - 3 - 1 中空纖維薄膜液相微萃取…………………5 1 - 3 - 2 中空纖維兩相之液相微萃取………………5 1 - 3 - 3 中空纖維三相之液相微萃取………………6 1 - 3 - 4 單滴微萃取法………………………………7 1 - 3 - 5 分散式液液微萃取…………………………8 第二章 利用液相微萃取法分析水樣中之鹵素醚類 2 – 1 前言……………………………………………18 2 – 2 實驗部份………………………………………20 2 – 2 – 1 試藥 ……………………………………20 2 – 2 – 2 器材 ……………………………………21 2 – 2 – 3分析儀器…………………………………21 2 – 2 – 4 樣品配製 ………………………………22 2 – 2 – 5 萃取步驟 ………………………………22 2 – 3 結果與討論……………………………………24 2 – 3 – 1 萃取溶劑的選擇 ………………………24 2 – 3 – 2 萃取時間 ………………………………24 2 – 3 – 3 攪拌速率 ………………………………25 2 – 3 – 4 萃取溫度 ………………………………25 2 – 3 – 5 離子強度的影響 ………………………26 2 – 3 – 6 萃取溶劑使用量與注射量的探討 ……26 2 – 3 – 7 檢量線及方法偵測極限 ………………27 2 – 3 – 8 回收率與濃縮倍率 ……………………27 2 – 3 – 9 真實樣品 ………………………………28 2 - 4 與文獻分析方法的比較 ………………………29 2 – 5 結論……………………………………………30 第三章 以同步萃取/衍生之頂空液相微萃取法分析分析尿液中之安非他命與搖頭丸 3 – 1 前言……………………………………………43 3 – 1 – 1 安非他命類藥物之性質 ………………43 3 – 1 – 2 分析方法 ………………………………44 3 – 1 – 3 固相微萃取結合化學衍生法 …………45 3 – 2 實驗部份………………………………………47 3 – 2 – 1 試藥 ……………………………………47 3 – 2 – 2 器材 ……………………………………48 3 – 2 – 3 分析儀器 ………………………………49 3 – 2 – 4 萃取步驟 ………………………………49 3 – 3 結果與討論……………………………………51 3 – 3 – 1 萃取溶劑的選擇 ………………………51 3 – 3 – 2 樣品基質修飾之探討 …………………51 3 – 3 – 3 攪拌速率的影響 ………………………52 3 – 3 – 4 萃取溫度 ………………………………52 3 – 3 – 5 萃取時間 ………………………………52 3 – 3 – 6 氯化鈉的添加 …………………………53 3 – 3 – 7 檢量線、方法偵測極限與回收率 ……53 3 – 3 – 8 絕對回收率與精密度 …………………54 3 – 3 – 9 真實樣品 ………………………………54 3 - 4分析方法比較……………………………………56 3 – 5 結論……………………………………………57 第四章 利用分散液液微萃取法分析河川中芳香族胺類化合物 4 – 1 前言……………………………………………72 4 – 2 實驗部份………………………………………74 4 – 2 - 1 試藥………………………………………74 4 – 2 – 2 器材 ……………………………………75 4 – 2 – 3 分析儀器 ………………………………75 4 – 2 – 4 萃取步驟 ………………………………76 4 – 3 結果與討論……………………………………77 4 – 3 – 1 化學衍生法 ……………………………77 4 – 3 – 2 萃取步驟評估 …………………………77 4 – 3 – 3 萃取溶劑的選擇 ………………………78 4 – 3 – 4 分散試劑的選擇 ………………………78 4 – 3 – 5分散試劑用量的選擇……………………78 4 – 3 – 6萃取試劑用量的選擇……………………79 4 – 3 – 7 水樣pH值的探討 ………………………79 4 – 3 – 8 萃取/衍生溫度的探討…………………79 4 – 3 – 9萃取/衍生時間的探討 …………………80 4 – 3 – 10 檢量線、方法偵測極限與回收率……80 4 – 3 – 11 真實樣品………………………………81 4 – 4 結論……………………………………………82 第五章 利用液相微萃取分析尿液中的多環芳香族碳氫化合物 5 – 1 前言……………………………………………97 5 – 2 實驗部份 ……………………………………100 5 – 2 – 1 藥品……………………………………100 5 – 2 – 2 器材……………………………………101 5 – 2 – 3 分析儀器………………………………101 5 – 2 – 4 萃取步驟………………………………102 5 – 3 結果與討論 …………………………………103 5 – 3 –1 萃取溶劑的選擇 ………………………103 5 – 3 –2 萃取溫度的選擇 ………………………103 5 – 3 –3 攪拌速率的選擇 ………………………104 5 – 3 –4 離子效應的探討 ………………………104 5 – 3 –5 萃取時間的選擇 ………………………104 5 – 3 –6 方法評估 ………………………………104 5 – 3 – 7 檢量線、方法偵測極限與精密………105 5 – 3 –8 真實樣品 ………………………………105 5 – 4 結論 …………………………………………107 第六章 結論與展望 …………………………………120 參考文獻………………………………………………124

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