大氣質譜法（Ambient Mass Spectrometry，AMS）為近年來廣泛被開發的技術領域，由於此項技術的游離源本身具有一定的選擇性，加上質譜儀可根據各分析物分子及其碎片離子的質荷比（m/z）進行高效率之分離，使得使用大氣質譜法進行分析時，樣品的處理步驟大幅降低，縮減樣品分析的周轉時間，提升分析效能。熱脫附電噴灑游離法（thermal desorption-electrospray ionization，TD-ESI）即是一例，它是利用一個探針對樣品進行採樣，然後將探針置入高溫爐把分析物熱脫附，同時以載流氮氣將較易揮發的物質帶入電噴灑游離區域進行游離，最後導入質譜儀進行偵測。採樣時僅需以探針沾附液體樣品或在固體樣品表面輕刮，非常簡單與快速。熱脫附時高沸點物質因沸點差異被留滯於採樣探針上與分析物分離因而大幅降低分析時的基質干擾、進而得以免除層析分離步驟。上述特點再結合質譜的高特異性快速偵測，使得熱脫附電噴灑游離質譜分析法具備快速篩檢的潛力。
基於熱脫附電噴灑游離質譜法所具備快速篩檢的潛力，本研究首先將針對食用魚及數種水果樣本表面上分析物建立熱脫附電噴灑游離質譜分析方法，然後根據該方法以金屬環探針自樣品表面快速採樣、檢測、獲取樣品表面上不同位置分析物訊號，最終完成建構分析物於樣品表面分佈圖。論文的另一個部分則是結合快速棉棒採樣法與TD-ESI/MS技術建立快速篩檢方法，並以這個方法應用在水果農藥殘留、房屋內家具擺飾設施表面附著之毒害物質做系統性的快速篩檢分析，以這個方法所得結果再與常規方法所用的GC-MS與LC-MS結果進行比較確認，結果顯示以棉棒採樣法結合TD-ESI/MS的快篩技術的確適於進行快速、簡單與靈敏的檢測。

In recent years, the field of ambient mass spectrometry (AMS) has been widely developed. Due to good selectivity of ionization source and high mass specificity of mass spectrometry (MS) according to charge ratio (m/z) of analyte molecule ion and its product ion, the sample pretreatment steps can therefore be reduced greatly, shorten sample analaysis turn-around time and speedup the throughput. Thermal desorption-electrospray ionization mass spectrometry (TD-ESI/MS) is an example of AMS technique. TD-ESI/MS adopt a sample probe to collect analyte from bulk sample then loaded into a thermal desorption chamber to desorb the collected analytes to gas phase. Desorbed analyte is then carried by heated N2 carrier gas to electrospray region and ionized therein following MS detection. The sample probe can simply dip in sample solution to collect aqueous sample or gently scrap on surface of bulk solid sample. Matrix effects during the analytical course can be reduced since high boiling point substance will not be vaporized during the early desorption step. All these advantages plus high specificity and quick mass spectrometry detection make TD-ESI/MS technique a good option of screening mean.
　　Base on the potential of screening ability of TD-ESI/MS, the research here presented a method developed by combing metal ring sample collection probe and TD-ESI/MS to collect and detect analytes on different positions of sample surface. The sample surface distribution diagram is then created base on the detected signals. Another part of this research is incorporated cotton swab sample collection manner to TD-ESI/MS for systematic collection and detection of residual pesticides of fruits and toxins adsorbed on the surface of indoor furniture or decorations. The results were also compared to conventional analysis method (LCMS and GCMS). It shown that cotton swab combined with TD-ESI/MS is practicable for quick, simple and sensitive sample detection.

論文審定書 i
論文公開授權書 ii
誌謝 iii
中文摘要 v
英文摘要 vi
目錄 vii
圖目錄 x
表目錄 xiii
第一章、緒論 1
第一節、前言 1
第二節、熱脫附電噴灑游離法 3
第三節、結合質譜技術之前處理方法 5
一、固相萃取（solid phase extraction，SPE） 6
二、分散式固相萃取（dispersive solid phase extraction，dSPE） 7
三、QuEChERS（Quick, Easy, Cheap, Effective, Rugged, and Safe） 8
第四節、應用於分子影像之質譜技術 10
第五節、論文目標 12
第二章、實驗方法 13
第一節、藥品與試劑 13
一、試劑 13
二、藥品 13
三、配製方法 14
第二節、儀器設備與軟體設定 16
一、質譜儀及離子掃描模式設定 16
二、熱脫附電噴灑游離質譜儀及參數設定 19
三、液相層析質譜儀及參數設定 20
四、氣相層析質譜儀 21
第三章、開發以熱脫附電噴灑質譜法建構表面分子影像及應用 23
第一節、實驗方法 23
一、樣品資訊 23
二、以金屬環探針採樣之最適化探討及不同樣品之採樣策略 24
第二節、質譜影像建構軟體 27
第三節、樣本與目標分析物用途 28
第四節、分析物分佈實驗可行性評估 31
第五節、建構各式樣品之分子影像 33
一、蔬果表皮分子影像 33
二、食用魚外皮分子分佈 39
第六節、影像方法建立與應用之結論 44
第四章、棉棒採樣結合TD-ESI/MS之方法開發 45
第一節、實驗方法 45
一、採樣棉棒來源及清洗方法 45
二、製備模擬樣品之方法 46
第二節、方法最適化探討 48
一、以棉棒吸附樣品表面分析物 48
二、將棉棒上沾附分析物脫除 51
三、基質效應之探討 53
四、訊號強度與含量關係之探討 56
五、檢液保存能力探討 60
第三節、方法建立之結論 62
第五章、快速採樣方法結合TD-ESI/MS技術對殘餘農藥的檢測 63
第一節、實驗方法 63
一、樣本、購入時間及地點 63
二、以棉棒採集分析物之流程 63
三、QuEChERS前處理流程 65
第二節、蔬果殘餘農藥之檢測應用及比較 66
一、以棉棒採樣法結合TD-ESI/MS 66
二、以QuEChERS結合TD-ESI/MS 72
第六章、快速採樣方法結合TD-ESI/MS技術對室內有害物質的檢測 76
第一節、實驗方法 76
一、目標分析物的性質及相關用途 76
二、採樣地點、時間及採樣方式 79
三、以棉棒採集養品的流程 80
第二節、以棉棒採樣法結合TD-ESI/MS做大規模樣品採樣及探討 81
一、代表性採樣位置的質譜圖 81
二、分析物與採樣面積之關係 83
三、分析物訊號隨時間之變化 84
四、分析物在空間中之分佈情形 86
五、棉棒採樣進行大規模篩檢之結論 88
六、以GC/MS進行方法驗證 89
第七章、結論 91
第八章、附錄 93
第九章、參考文獻 102

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