直接在大氣壓力下進行樣品分析已成為目前質譜游離法的發展趨勢。大氣壓力游離法具有進樣方便、分析快速的特性，並可簡化繁雜的樣品前處理步驟。現今已有多種大氣壓力游離技術被開發，可依照不同的樣品形態(固、液、氣態)，分別使用不同的大氣壓力游離技術進行分析，達到快速偵測其化學成分的目的，因為一般有機合成反應及生化反應均是在液相中進行，本研究的目的是利用兩種大氣壓力游離法(Liquid ELDI及RF-DART)來監測化學反應中樣品組成的變化。
液相電噴灑輔助雷射脫附游離法(Liquid Electrospray-assisted Laser Desorption Ionization, Liquid ELDI)，它是利用UV-雷射照射含有碳粉的液體表面，碳粉吸收雷射能量，並傳遞給周圍分子以進行脫附， 由雷射脫附出的分子， 再藉由電噴灑游離法(Electrospray Ionization, ESI)進行後游離的動作。當以Liquid ELDI分析有機溶劑中的標準品時，無論是在極性較高的甲醇(MeOH)溶液中，或是非極性的正己烷(n-hexane)等六種不同極性的有機溶劑中，均可偵測到分析物的訊號。在連續監測液相化學反應的實驗中，本研究分析了加成消去反應、藥物非共價鍵結反應、金屬螯合反應及螢光衍生化反應，結果可成功地利用此技術監控化學反應中反應物及生成物的隨反應時間增加，離子訊號的消長情形。使用UV-雷射進行Liquid ELDI分析時，需在溶劑中加入惰性基質碳粉。在分析含有羥基(-OH)官能基的溶劑，則可使用IR-雷射系統，將液相樣品脫附，不需在溶劑中加入碳粉，本研究以IR Liquid ELDI來監測cytochrome C的消化水解反應(tryptic digestion)。
第二部份是以交頻-即時直接分析游離法(Radio Frequency-Direct Analysis in Real Time, RF-DART)監測化學反應，RF-DART是利用電漿生成的介穩態氦氣分子與空氣中的水分子碰撞，生成水合離子 (H3O+、(H2O)n+H+)，水合離子再與氣相分析物進行離子分子反應，而產生分析物離子。其優勢在於能直接快速的偵測樣品中揮發性的組成，因RF-DART游離同時具有熱脫附作用，在分析低揮發性的甘油(glycerol)，仍可偵測到樣品訊號。以RF-DART監測甘油與醋酸之酯化反應，可依序得到單取代、雙取代、三取代的產物訊號，此外在
RF-DART游離源前裝置上一加熱探針，分析2-甲氧基苯胺、2-甲硫基苯胺的熱裂解反應時，可得到脫氫(M˙)+及其他熱裂解產物之訊號。

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論文摘要..............................................................................Ⅰ
目錄......................................................................................Ⅲ
圖目錄..................................................................................Ⅴ
壹、 緒論............................................................................01
一、 前言............................................................................01
二、 液相電噴灑輔助雷射脫附游離法(Liquid
Electrospray-assisted laser desorption ionization,
Liquid ELDI)...……...........................................................02
三、 交頻-即時直接分析游離法(Radio Frequency-Direct
Analysis in Real Time, RF-DART)………………........09
四、 各式化學反應監測方法介紹...................................14
五、 論文目標...................................................................25
貳、 實驗...........................................................................27
一、 液相電噴灑輔助雷射脫附游離質譜法裝置...........27
二、 交頻-即時直接分析游離法裝置.............................31
三、 化學藥品與分析樣品..............................................34
四、 藥品配置、實驗參數及實驗步驟..........................35
參、 結果與討論..............................................................38
一、 第一部份：以Liquid ELDI 進行連續式化學反應的監
測.......................................................................................38
二、 第二部份：以RF-DART 進行連續式化學反應的監
測.......................................................................................63
肆、 結論..........................................................................75
伍、 參考資料..................................................................76

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