本研究提出利用低成本的定性濾紙，與3D列印製造技術，製作一個整合電噴灑游離質譜偵測，於快速檢測卡匣系統，並成功透過創新二維紙層析分離，將待測物成分分離、再濃縮，經由電噴灑游離法脫附、游離後，透過質譜偵測、分析，應用於生醫與食品樣本的檢測。因此本研究選用市售孔徑2.5 µL之定性濾紙，再透過自行設計與雷雕機切割為40×5.0 mm2與紙片尖端角度60o之紙片，作為卡匣樣本傳遞與偵測之微流道，結合電噴灑游離法進行即時的檢測，且其成本低廉、取得容易，是個檢測即時、攜帶式、拋棄式檢測裝置。而本研究所提出的二維紙層析，不需要經過其他設備或是複雜的操作，只需要透過紙纖維本身的毛細作用力，即可以完成樣本成分的分離與濃縮。待測物經由兩個維度之紙層析後，質譜所偵測到之離子訊號強度，大幅的提升了100倍外，訊雜比也增加了1.73倍，證實二維層析讓樣本成分被濃縮，同時能將殘渣或雜質剔除，以提升質譜偵測分析之解析度。實驗結果顯示，系統在標準品對乙醯氨基酚與維生素B2之檢測極限可以達到1.0 ppb；在噴灑穩定度量測上，在尖端角度60o之紙片陣列上施加1.26×106 V/m的電場條件下，可得到電噴灑游離離子強度為1010 ions/cm3，並持續兩分鐘以上之穩定噴灑。利用兩個維度之紙層析分離，成功分離亞甲基藍及甲基紫兩種指示劑，能夠在過程中直接觀察到分離效果，並於質譜偵測應證其分離效能。於茶葉、大蒜實驗中，人為摻雜了10.0 ppm之巴拉刈，經過了層析分離後，成功的被質譜偵測。最後，選用市場購買之青蔥，直接萃取其汁液，經過層析後，偵測到了派美尼以及伏寄普兩種農藥訊號。本研究成功開發一快速檢測卡匣，整合進樣前處理、二維紙層析、電噴灑游離，在標準品與天然物皆有良好的靈敏度，農藥的偵測上也成功量測，其訊號之訊雜比皆能達到7.31 dB以上，表示此快速檢測卡匣，於生醫與食品安全檢測應用上，有著極大的潛力。

This research successfully presents a lateral flow cassette combined with electrospray ionization (ESI) for rapid mass spectrometry detection of ambient samples. The developed aims to substitute conventional food-safety examination approaches such as high performance liquid chromatography tandem mass spectrometer (HPLC/MS) and gas chromatography tandem mass spectrometer (GC/MS). The cassette is demonstrated with the ingredient separation and electrospray process of the ambient liquid samples under unique cassette-based two-dimensional (2-D) paper chromatography scheme. Liquid sample is directly applied on the cassette for sample separation with paper chromatography and then concentrated with the second paper chromatography for enhancing the detection performance of ESI. Results show that the electrospray ion intensity is enhanced for 100 times higher after the 2-D paper chromatography process for sample enrichment. The whole process can be done in 30 min on a patterned filter paper. The time and cost for food-safety examination can be dramatically reduced with the developed method. The experimental results also indicated that the developed cassette exhibits a lower limit of detection (LOD) of 1.0 ppb for detecting acetaminophen and vitamin B2. The intensity for ESI on the paper tips is as high as 1010 ions/ cm3 for the paper tip of 60o. Several samples including like Chinese herbal medicines (cinnamon), raw vegetables (garlic, green onion), clinical medicines (acetaminophen, chlorpheniramine), paraquat-spiked garlic sample are used to evaluate the performance of the developed method. Moreover, two pesticides of pyrimethanil (fungicide) and fluazifop-butyl (herbicides) in raw fresh green onion are detected with high SNR (signal to noise ratio) of 4.77 dB. The developed method has shown its potential on rapid food-safety examination compared to conventional HPLC/MS & GC/MS.

論文審定書 i
論文授權書 ii
致謝 iv
中文摘要 v
Abstract vi
目錄 vii
圖目錄 ix
表目錄 xiii
符號表 xiv
簡寫表 xv
第一章 緒論 1
1.1 前言 1
1.2 快速檢測卡匣系統簡介 2
1.2.1 快速檢測卡匣的介紹與回顧 2
1.2.2 酵素結合免疫吸附分析法 7
1.2.3 快速檢測卡匣效能評斷 9
1.3大氣壓力質譜法 12
1.4 電噴灑游離法 14
1.4.1 脫附電噴灑游離法 14
1.4.2 直接電噴灑探針 15
1.4.3 紙噴灑游離法 16
1.5 研究動機與目的 19
1.6 論文架構 20
第二章 實驗原理 21
2.1 毛細作用力 21
2.2 紙層析 22
2.3 電噴灑游離法 27
第三章 實驗設計與架構 30
3.1 快速檢測卡匣設計與製作 30
3.1.1 紙片設計與製作 32
3.1.2 卡匣電極設計與製作 34
3.2 紙層析分離系統 35
3.3 紙噴灑游離偵測系統 36
3.4 實驗系統架構 37
3.5 實驗設計與檢測目標 39
3.6 實驗溶液配置 41
第四章 實驗結果與討論 43
4.1 紙片尖端角度特性分析 43
4.2 紙層析分離參數分析 46
4.3 檢測卡匣系統偵測極限 48
4.4 紙層析分離後量測 51
4.4.1 標準藥品層析分離 52
4.4.2 天然物層析分離 56
4.5 二維層析分離效能比較 59
4.5.1 直接量測與層析後量測比較 59
4.5.2 一、二維層析後量測比較 62
4.6 天然物快速檢測 65
4.7 天然物農藥快速檢測 67
第五章 結論與未來展望 70
5.1 結論 70
5.2 未來展望 72
參考文獻 73
自述 79

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