大氣壓力質譜法(Ambient Mass Spectrometry, AMS) 具有快速、高通量、即時偵測及操作簡單等特點，且操作環境皆在大氣壓下進行，樣品可直接偵測且不須繁複的前處理，而近年來更以快速、直接偵測為發展的目標而產生了許多不同樣式的設計。直接式電噴灑探針(Direct electrospray probe, DEP )是以為了避免以傳統電噴灑游離法分析樣品時，容易使管線阻塞或是殘留的問題，並且能夠快速地轉換樣品直接分析及清理為目標所發展。
2012年改良後的直接式電噴灑探針外觀因筆型的設計而使整體結構簡單化，並增加了操作的便利性，能夠更快速的替換樣品與分析，而由於前端取樣探針尺寸較小(O. D. 0.27 mm)，因此可以精確的採取樣品的細部結構，使其分析具有空間分布的意義，並且能夠克服不平整的樣品表面；此外，採樣過程對樣品的傷害不劇烈，因此能夠應用於活體植物上化學成分變化的分析。本研究的第一部份即是利用2012年改良後的直接式電噴灑探針對不同曲面的樣品進行偵測；偵測對象包括進口香吉士上表皮殘留的防黴劑、馬鈴薯的生物鹼分布切面、食物的黴菌區分、以及綠豆藥物吸收的監測。
第二部分的研究則是改良直接式電噴灑探針，雖然直接式電噴灑探針發展至今已具備了許多優點，但仍然有一些問題需要改進；像是探針無法控制溶液的流動以及接地裝置設計上的一些小缺失，而這些問題都會影響數據的再現性。藉由加裝溶液控制閥與改良接地裝置，結果顯示，舊式的直接式電噴灑探針由於缺乏溶液控制閥，因此它的RSD值大於20%；而新式直接式電噴灑探針，其RSD值為14.9%，改善了再現性不佳的問題。

Ambient mass spectrometry is a technique used to directly analyze samples without sophisticated pretreatment under ambient conditions. Thus, it has many advantages such as fast and real-time analyte detection, high-throughput sample analysis, and easy operation. Several different ambient ionization techniques have been developed recently. Direct electrospray probe (DEP) ionization mass spectrometry is one such technique developed to prevent and overcome problems with traditional electrospray ionization mass spectrometry (ESI-MS), such as clogging and carryover in the electrospray capillary.
A simplified pen-like DEP was developed as an improvement of previous designs, increasing the simplicity of operation and decreasing analysis times. The tiny sampling probe (0.27 mm in diameter) was able to analyze small sample areas, increasing spatial resolution and overcoming problems with uneven sample surfaces. In addition, the tiny sampling probe resulted in minimal sample damage, so that DEP was used in in vivo studies of analytes in plants.
The first part of this study discusses the applications of DEP for different samples, including detection of fungicides on the surfaces of Sunkist oranges, observation of glycoalkaloids in the bulbs of potatoes, distinction between different molds in foods, and the monitoring of metabolites of medicines in mung bean plants.
The second part of this study details the development of different DEP probes. Although the pen-like DEP is easy to use and clean, it is unable to continuously hold the ESI solution stored in the probe, and did not have a fixed probe holder, which affected the electrospray plume and therefore experimental reproducibility. These problems were solved by adding a valve at the front of the probe to control the flow of ESI solution
from the end of the probe and by constructing a fixed probe holder. The relative standard deviations (RSD) of acetaminophen using the new and old DEP were 14.9 % and greater than 20 %, respectively, indicating an improved reproducibility due to changes in the probe and holder designs.

論文審定書 i
謝誌 ii
摘要 iii
Abstract iv
目錄 vi
圖目錄 ix
表目錄 xiii
第一章 緒論 1
1.1 前言 1
1.2 傳統真空游離法 5
1.2.1 電子撞擊游離法 (Electron Ionization, EI) 5
1.2.2 化學游離法 (Chemical Ionization, CI) 5
1.2.3 場游離法 (Field Ionization, FI) 6
1.3 現代生物質譜法 6
1.3.1 基質輔助雷射脫附游離法 (Matrix-assisted Laser Desorption Ionization, MALDI )33 6
1.3.2 電噴灑游離法 (Electrospray Ionization, ESI )32, 34 8
1.4 大氣壓力質譜法(Ambient mass spectrometry)40 10
1.4.1 直接脫附/游離法 (Direct Desorption/Ionization) 13
1.4.2 兩步驟游離法 (Two-step ionization) 16
1.4.3 直接式游離法 (Direct Ionization, DI) 17
1.5 論文目標 30
第二章 實驗 31
2.1 實驗藥品與試劑 31
2.1.1 試劑 31
2.1.2 藥品 31
2.2 儀器裝置 31
2.2.1 直接式電噴灑探針游離源 (Direct Electrospray Probe, DEP ) 31
2.2.2 質譜儀 32
2.3 藥品配製 32
第三章 結果與討論 33
3.1 第一部份:直接式電噴灑探針於不同曲面上的應用 33
3.1.1 實驗介紹 33
3.1.2 樣品分析 34
3.2 第二部分:直接式電噴灑探針的改良 58
3.2.1 實驗設計 58
3.2.2 實驗結果 61
第四章 結論 64
第五章 參考文獻 65

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