本研究開發出一個創新的對稱型同軸式雙游離源，該系統整合了平衡常壓氦氣電漿游離源以及電噴灑游離源，以同時游離極性和非極性的分析物。傳統直線型同軸式雙游離源因為電漿出口將殘留的淨電壓，因此在雙游離源模式下，電噴灑游離將受到該淨電壓之干擾，而無法與電漿游離源穩定共存。本研究透過對稱式電極設計，其利用兩電極上之反向高壓交流電，使電漿產生中心處之電位為零，以消除電漿出口之淨電壓，成功地解決雙游離源無法共存的問題。結果顯示，本研究所發展之雙游離源，可穩定操作長達100分鐘，且平均離子濃度高達109 ion∙cm-3，足以適用於大部分質譜游離偵測之應用。本研究亦測試四個影響該雙游離源系統之四項參數進行實驗分析，其包含電漿與電噴灑源之幾何設計、電噴灑電壓、電噴灑溶液注射速率以及產生電漿之氦氣流量，並以數位顯微鏡觀察噴灑情形，成功地優化該雙游離源系統之穩定性，並增加產生之總離子濃度。本研究並配置易揮發的化合物、市售農藥、市售成藥、長碳鏈烷類和水溶性及脂溶性之維他命標準品以及複方中草藥天然物做為待測物，以驗證該雙游離源之質譜偵測效能，結果顯示該系統可在單電漿模式、單電噴灑模式以及雙游離源模式下，成功量測到分析物的成份，並可同時量測到適合電噴灑游離偵測之極性物質和適合電漿游離之非極性物質，大幅增加質譜系統之偵測能力。本研究所發展之系統，未來將可應用於食品安全檢測、空氣汙染監控、藥品成分分析…等領域。

This work develops an innovative symmetric coaxial dual ion source combining a balanced atmospheric helium plasma ion source and an electrospray ion source to simultaneously detect both polar and nonpolar chemical compounds. The traditional linear-type coaxial dual ion source suffers the drawback of floating voltage at the plasma outlet of the glass tube. When the dual ion source is working at dual ion source mode, the high floating voltage at the plasma outlet of the glass tube will interfere the ESI source which leads to unstable signals. In order to solve this problem, the balanced electrode design of the symmetric coaxial dual ion source was introduced to eliminate the floating voltage by changing the drive phase of the plasma generator. The results show that after 100 minutes of continuous testing in the dual source mode, the ESI source can constantly produce ions with the existence of plasma source due to the elimination of floating voltage and the dual source can provide more than 109 ion∙cm-3 ion intensity that can apply for most of the ambient mass spectrometry applications. In order to optimize the symmetric coaxial dual source’s stability and increase the total ion intensity, four important parameters including the geometric design of the plasma source and the ESI source, ESI spray voltage, the injection rate of ESI solutions, and the flow rate of helium as the carrier gas for producing plasma have been studied through the results of MS results and the pictures were taking by the digital microscope. Standards of volatile organic compounds, pesticide, cold syrup, Chinese herbal medicine, vitamins, tetradecane and hexadecane were used for testing in three different modes including plasma-only, ESI-only, and dual ion source modes. Results show that the developed dual source successfully detect the analytes and can both detect polar and nonpolar compounds which substantially improve the abilities of MS system. The developed system can apply in food safety testing, air pollution monitoring, and pharmaceutical composition analysis.

論文審定書 i
論文授權書 ii
致謝 iii
中文摘要 iv
Abstract v
目錄 vii
圖目錄 x
表目錄 xii
符號表 xiii
簡寫表 xiv
第一章 緒論 1
1.1 前言 1
1.2 環境質譜游離法 5
1.3 電噴灑游離法簡介 6
1.3.1 脫附電噴灑游離法 7
1.3.2 直接式電噴灑探針 8
1.4 常壓電漿游離法簡介 9
1.4.1 即時直接分析法 10
1.4.2 低溫電漿游離法 11
1.4.3 介電質放電游離法 11
1.4.4 介電質放電游離法 12
1.5 論文架構 13
第二章 動機目的及原理 15
2.1 電噴灑游離原理 15
2.1.1 霧化 15
2.1.2 去溶劑 16
2.1.3 游離 16
2.2 電漿游離原理 17
2.3 電噴灑游離與電漿游離之比較 18
2.4 現有之複合游離源介紹 19
2.4.1 市面上已存在之複合型游離源 19
2.4.2 同軸式雙游離源 20
2.5 對稱型介電質放電電漿游離源 21
2.6 研究動機與目的 22
2.6.1 研究動機 22
2.6.2 研究目的 22
第三章 實驗與方法 23
3.1 實驗藥品及樣品 23
3.2 實驗裝置 23
3.2.1 氦氣流量計 23
3.2.2 方型撓式超薄電熱片 24
3.2.3 光譜儀 24
3.2.4 離子阱質譜儀 25
3.2.5 數位攝影設備 26
3.2.6 電漿高壓交流模組及電噴灑直流高壓輸出 26
3.3 同軸雙游離源裝置的設計 27
3.4 熔融矽毛細管口徑對電噴灑之影響 28
3.5 同軸雙游離源系統架構 29
3.6 同軸雙游離源之參數探討 30
3.6.1 毛細管與玻璃管出口間距對離子濃度之影響 30
3.6.2 電噴灑電壓對離子濃度之影響 32
3.6.3 電噴灑溶液注射速率 33
3.6.4 氦氣流量對離子濃度之影響 33
第四章 實驗結果與討論 35
4.1 光譜量測 35
4.2 兩種裝置之離子濃度比較圖 36
4.3 三種模式下之特徵背景質譜圖 37
4.4 單電漿模式樣品分析 40
4.4.1 量測易揮發之小分子化合物 40
4.4.2 量測複方中草藥之成分 41
4.5 單電噴灑模式樣品分析 42
4.5.1 市售農藥之成分量測 42
4.5.2 市售感冒糖漿之成分量測 43
4.6 雙游離源模式樣品分析 44
4.6.1 水溶性及脂溶性維他命量測 44
4.6.2 兩種裝置對氧化物的影響 46
第五章 結論與未來展望 48
5.1 結論 48
5.2 未來展望 49
參考文獻 50
自述 53

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