隨著大氣質譜技術蓬勃發展，不同功能之大氣游離源也相繼被報導，又因進樣/脫附方式不同，可以分為熱脫附、雷射脫附、及氣動式霧化進樣系統。其中熱脫附方法適合應用於中高揮發性的小分子檢測、而雷射脫附方法適合非揮發性的大分子檢測，氣動式霧化方法則適合用於檢測具揮發性或熱不穩定特性的小分子。本篇的研究目標，即是開發出一種能同時以熱脫附或是雷射脫附將分析物脫附的大氣質譜法，並應用於檢測高分子聚合物與植物中的生物鹼。
研究第一部分，為建立一套全新的游離源系統－雷射輔助熱脫附電噴灑游離質譜法，該系統包含連續式紅外雷射裝置、銅管加熱裝置、溫控氮氣流裝置與電噴灑游離裝置等四大組件。由於該游離源裝置可提供高功率的雷射脫附、熱穩定的銅管加熱和可控溫的輔助氣流導引，因此該系統能同時具備偵測非揮發性及揮發性分析物的能力，藉以提高大氣質譜法在分析領域上的用途。內容也將闡述該大氣游離裝置的機制原理與最適化儀器相關的各類參數，包含具有良好的分析重複性、高靈敏度的檢測能力，以及建立一套操作的標準流程。
研究第二部分，則將雷射輔助熱脫附電噴灑游離質譜法應用於材料科學與食品安全領域上。材料科學方面，針對高分子聚合物材料進行分析，首先以高分子聚合物標準品建立其指紋圖譜資料庫，提供後續來自日常生活中的材料鑑定依據。此外，在真實樣品之分析上，可以應用在鑑定塑膠食品包裝之聚合物組成以及由材料行購買之塑料製品。食品安全方面，針對馬鈴薯中的生物鹼進行檢測，在發芽的馬鈴薯中能快速檢測到龍葵鹼和卡茄鹼兩種植物鹼的訊號。過往文獻指出龍葵鹼及卡茄鹼佔綠馬鈴薯中配醣生物鹼總量的95%以上，是最主要的成分而且加熱還無法分解，一旦攝取過量的綠馬鈴薯就有急性中毒的危險。因此若能建立一套早期鑑定配醣生物鹼的方法，將有助於防止這類中毒的悲劇再發生。

With the rapid development of ambient mass spectrometry (AMS), different functions of ambient ionization have also been reported. Based on the different sampling/desorption methods, AMS can be classified as thermal desorption, laser desorption, and gas stream methods. Thermal desorption was used to characterize volatile or semi-volatile compounds in liquid or solid samples, while laser desorption was applied to detect non-volatile samples. The method of gas stream was developed to determine volatile and thermally unstable compounds in solution. The purpose of this thesis is to develop a new ambient ionization technique called thermal desorption and laser desorption electrospray ionization mass spectrometry (LD+TD-ESI/MS), which is capable of analyzing polymer materials and alkaloids in plants.
Thermal desorption and laser desorption electrospray ionization mass spectrometry comprised a continuous infrared laser device, a copper tube heating device, a temperature controlled nitrogen stream device and an electrospray ionization device. Since the ion source provided high power for laser desorption, thermally stable to be heated, and temperature-controlled auxiliary to transfer analytes, the system can be simultaneously detected non-volatile and volatile analytes. Herein, the ionization mechanism will be explained in detail and performances related to instrumentation will also be optimized, including its repeatability, reproducibility, sensitivity, and robust procedure.
In the second part, LD+TD-ESI/MS was used for direct analysis of the polymer materials. Firstly, a complete database of polymer material was established. Various plastic products commonly used in daily life were directly analyzed. The resultant polymers, in addition to additives of the samples, were rapidly characterized. In addition, LD+TD-ESI/MS can also detect alkaloids. In potato with sprouts, the signals of both α-chaconine and α-solanine can be detected. According to the previous literature, potatoes contain toxic compounds known as glycoalkaloids, of which the most prevalent are α-chaconine and α-solanine. It is pointed out that α-chaconine and α-solanine account for more than 95% of the total amount of glycoalkaloids. Additionally, they cann’t be decomposed by heating. Once the excessive intake of glycoalkaloids is in danger of acute poisoning. Thus, the rapid identification of glycoalkaloids will help prevent the recurrence of such poisoning tragedies.

論文審定書 i
中文摘要 ii
Abstract iii
目錄 v
圖目錄 viii
表目錄 xii
縮寫用語對照表 xiii
第1章、緒論 1
1.1前言 1
1.2質譜儀 1
1.3大氣壓游離法 3
1.4大氣質譜法 4
1.4.1直接脫附/游離法 5
1.4.2直接游離法 7
1.4.3兩步驟游離法 8
1.5論文目標 16
第2章、雷射輔助熱脫附電噴灑游離質譜法之開發 17
2.1前言 17
2.1.1研究目的 17
2.2藥品配制及實驗裝置 19
2.2.1儀器設備 19
2.2.2實驗試劑與藥品 25
2.2.3實驗設計 26
2.3結果與討論 29
2.3.1 ESI毛細管電壓 29
2.3.2 ESI霧化氣體 30
2.3.3乾燥氣體流速 31
2.3.4輔助氣體流速 32
2.3.5溫控氮氣流裝置之溫度 33
2.3.6 連續式雷射輸出功率 34
2.3.7 銅管溫度 35
2.3.8雷射至銅管加熱裝置之距離 36
2.3.9 建立標準流程 37
2.3.10重複性實驗 39
2.3.11不同模式之標準品訊號 40
2.4結論 42
第3章、雷射輔助熱脫附電噴灑游離法應用於鑑定高分子材料 44
3.1前言 44
3.1.1研究目的 44
3.2藥品配制及實驗裝置 45
3.2.1儀器設備 45
3.2.2實驗試劑與藥品 47
3.2.3樣品配制 49
3.2.4實驗設計 50
3.3結果與討論 51
3.3.1分別以LD + TD-ESI、ELDI和TD-ESI檢測標準品 51
3.3.2 比較LD + TD-ESI、ELDI和TD-ESI三者的偵測極限 53
3.3.3以LD + TD-ESI分析高分子材料 54
3.4結論 58
第4章、雷射輔助熱脫附電噴灑游離法應用於監測馬鈴薯中配醣生物鹼 59
4.1前言 59
4.1.1研究目的 59
4.2藥品配制及實驗裝置 60
4.2.1儀器設備 60
4.2.2實驗試劑與藥品 64
4.2.3樣品配制 66
4.2.4實驗設計 67
4.3結果與討論 69
4.3.1分別以TD-ESI、ELDI和LD + TD-ESI檢測標準品 69
4.3.2比較LD + TD-ESI和ELDI兩者的偵測極限 70
4.3.3以LD + TD-ESI監測馬鈴薯中配醣生物鹼 71
4.3.4以LC/MS/MS驗證 79
4.4結論 81
第5章、結論 82
第6章、參考文獻 83

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