層析系統因可分離複雜組成的樣品而被廣泛的應用在各分析領域中，一般而言，氣相層析儀多用以分析具揮發性的小分子，而液相層析儀則可分析熱不穩定小分子及生化大分子。傳統氣相層析質譜儀及早期開發之液相層析質譜法使用電子游離法 ( Electron ionization, EI ) 、化學游離法 ( Chemical ionization, CI ) 或是快速原子撞擊游離法 ( Fast atom bombardment, FAB ) 游離分析物。因為三種游離源都是在真空環境下運作，因此操作氣相及液相層析儀時載流氣體及沖提液體的流速都需要考慮到，以維持真空穩定度，這也促使科學家開始嘗試將GC及LC與大氣壓力游離技術 ( Atmospheric Pressure Ionization, API ) 結合，開發操作更方便的新式GC/MS及LC/MS介面。
大氣壓力游離技術如電噴灑游離法 ( Electrospray Ionization, ESI ) 、大氣壓力化學游離法 ( Atmospheric pressure chemical ionization, APCI ) 及大氣壓力光游離法 ( Atmospheric Pressure Photoionization, APPI ) 等，可在一大氣環境下操作，並獲得完整的分析物訊號。近年來，有研究團隊將ESI與plasma-APCI結合，開發出一套ESI/plasma-APCI游離源，此新式游離源可同時進行ESI及APCI游離機制，將樣品中所含各式極性與非極性分析物游離，大幅提高質譜檢測的能力。
因此本研究目的是將LC/MS與GC/MS連接介面整合在同一介面，並使用ESI/plasma-APCI方法游離分析物，開發出一套可在大氣壓力環境下分析極性及非極性之氣相層析及液相層析質譜介面。此介面藉由一加熱傳輸管線將經氣相層析儀分離之化合物傳送至游離區域內，經液相層析分離之樣品溶液則以Nebulizer導入游離區，游離源部分則是將ESI及plasma-APCI整合成一複合式游離源，並藉由切換複合式游離源之DC電壓 ( 提供ESI帶電荷液滴產生 ) 及AC電壓 ( 提供plasma-APCI電漿產生 ) 來改變游離源的操作模式(i) ESI-only、(ii) ESI/plasma-APCI dual、(iii) plasma-APCI-only。
直鏈烷類 ( Straight-chain Alkanes ) 及甲酯化脂肪酸 ( FAMEs ) 的混合樣品，經由氣相層析儀分離後使用複合模式游離源 ( ESI/plasma-APCI mode )，可同時偵測到經plasma-APCI游離的直鏈烷類氧化訊號[M+O-3H]+，及經ESI游離的質子化甲酯化脂肪酸離子訊號[M+H]+。液相層析儀結合ESI/plasma-APCI游離源分析胜肽混合物，可偵測到經ESI游離之多價電荷離子訊號，及經plasma-APCI介電粒子還原之單價電荷離子訊號。最後也將此介面應用於汽油、精油、香水及植物萃取液等真實樣品的分析，證實此介面能快速更換游離模式的操作，有助於同時分析具有極性及非極性分析物之複雜樣品。

Chromatography systems can separate complicated sample then sequentially importing to detector, so now are widely used in various fields. Generally, gas chromatograph ( GC ) is suitable for analysis of volatile small molecules, and liquid chromatography ( LC ) is suitable for analysis thermal instability molecular, biochemical macromolecules. Traditional gas chromatography and liquid chromatography mass spectrometry utilize electron, chemical ionization or fast atom bombardment techniques for ionization. However, sample analysis using these techniques is performed under a vacuum. Thus, the flow rate of mobile phase in GC and LC is limited. Coupling GC and LC to atmospheric pressure ionization ( API ) methods is therefore of interest to scientists.
API methods such as electrospray ionization ( ESI ) , atmospheric pressure chemical ionization ( APCI ) , and atmospheric pressure photoionization ( APPI ) would generate intact analyte ions. In the recent year, new ESI/plasma-APCI source that combines an ESI and plasma-APCI has been developed to simultaneously characterize polar and non-polar compounds, greatly improving the capability of MS detector
In this study, a new GC+LC/MS that integrated GC/MS and LC/MS interfaces together was developed. The aforementioned, ESI/ plasma-APCI source was utilized for ionization of analytes from GC and LC columns. The gaseous analytes from GC column were delivered to the ionization region through a heated transfer line; whereas effluent from LC column was sprayed by a nebulizer. The ESI/ plasma-APCI ion source was operated in ESI-only, dual ESI/plasma-APCI, or plasma-APCI-only mode to analyze the separated compounds.
This GC-ESI/plasma-APCI/MS interface was used to analyze straight-chain alkanes and fatty acid methyl esters (FAMEs). Straight-chain alkanes were generated by plasma-APCI, protonated FAMEs were generated by ESI. In ESI/plasma-APCI mode, [M+O-3H]+ ion of analytes characterize in ESI-only and plasma-APCI-only mode were all detected. LC-ESI/plasma-APCI/MS was used to detect peptide mixtures. Because the peptide multiply-charged ions generated by ESI were reacted with negative species generated by plasma, the peptide ions with lower charge number were detected. Singly and multiply-charged analyte ions can be detected in ESI/plasma-APCI mode. In addition, gasoline, essential oil and leaf extract were tested.

論文審定書 i
論文公開授權書 ii
誌謝 iv
中文摘要 v
英文摘要 vii
目錄 ix
圖目錄 xii
表目錄 xvii
第一章、緒論 1
一、層析分離系統 1
1、氣相層析儀 1
2、液相層析儀 3
二、質譜儀 6
1、真空游離源 7
2、大氣壓力游離法 11
三、層析系統與質譜儀結合的發展歷史 22
1、氣相層析儀結合質譜儀的發展歷史 22
2、液相層析儀結合質譜儀的發展歷史 24
3、雙重層析系統與雙重游離源 28
四、研究動機與論文目標 31
第二章、層析系統連接ESI/plasma-APCI雙游離源之介面開發 32
一、實驗部份 32
1、儀器設備 32
2、化學試劑 34
3、實驗樣品之製備 36
二、結果與討論 36
1、層析系統連接大氣游離源之介面開發 36
2、ESI/plasma-APCI雙游離源之建立 37
3、ESI/plasma-APCI實驗參數最佳化之探討 39
三、結論 43
第三章、氣相層析結合ESI/plasma-APCI雙游離源 44
一、實驗部份 44
1、實驗樣品之製備 44
二、結果與討論 44
1、以氣相層析結合ESI/plasma-APCI雙游離源質譜法分析標準品 44
2、以氣相層析結合ESI/plasma-APCI雙游離源質譜法分析真實樣品 51
三、結論 54
第四章、液相層析結合ESI/plasma-APCI雙游離源 55
一、實驗部份 55
1、實驗樣品之製備 55
二、結果與討論 55
1、以液相層析結合ESI/plasma-APCI雙游離源質譜法分析標準品 55
2、以液相層析結合ESI/plasma-APCI雙游離質譜法分析真實樣品 59
三、結論 62
總結 63
參考文獻 64

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