臺灣博碩士論文加值系統

1.本研究使用Finnigan公司之GCQplus離子阱質譜儀，進行氣相離子/分子反應。由於藥物本身結構上的官能基對於藥性有很大的影響，換言之，官能基的位置、種類、數目及其大小對於藥物在生物體中的反應性有顯著的不同。因此，本實驗將藉由單純的氣相反應來瞭解藥物化合物的反應本質。本研究可以對藥物化合物的結構與反應性的關係作更深一層的了解。實驗使用四種黃素母酮（flavones）及一種二氧化黃色素母酮(flavanones)的藥物化合物，分別是Baicalein、Chrysin、Morin、Fisetin及Naringenin。這類化合物具有抵抗癌症和抗氧活性的功效亦可作為抗HIV的活性抑制劑。
本實驗利用外部游離法之離子阱質譜儀並加上CAD技術，以二甲基醚(DME)作為化學游離試劑氣體。DME在游離區中主要可生成CH3O=CH2+（m/z=45）及CH3OHCH3+（m/z=47）兩種離子，進而可與分析物形成許多的離子/分子產物，雖然黃素母酮類化合物產生微量之[M+47]+ Adduct ion，由於Finnigan GCQplus 具有超微量分析的特性，因此能成功地進行CAD的實驗。實驗結果顯示：五種黃素母酮類化合物可分別與OH官能基或雙鍵形成[M+13]+以及在第9號位置的氧或第4號位置C=O的氧上形成[M+15]+的離子/分子產物。此外，第2號及第3號碳之間雙鍵和第3號碳上OH基的存在與否，對於生成子離子的碎片形式有很大的影響，除了常見的掉H2O和CO以外，亦可見到母離子有中央斷裂的模式存在。壓力效應方面，分別控制不同壓力之DME試劑氣體，進行離子/分子反應，實驗結果可以觀察到，較高壓力下，較有利於生成[M+H]+離子。本研究除了可以了解這些藥物其結構與反應性的關係外，產物離子的解離途徑與反應機構，亦可由串聯質譜的分析中詳細被研究。此外，將藉由理論計算方法輔助反應機構的推導。
2.本研究利用Finnigan公司之GCQplus離子質譜儀的ECD(Electron Capture Detection)的功能，研究一系列結構相似之鹵化物取代之苯二甲酐(Phthalic anhydride)及其衍生物(Phthalimide)。針對不同的鹵素取代位置以及取代基種類，採用甲烷負離子化學游離法。由於鹵素原子具有較高之電子親和力，因此可以捕捉游離源區甲烷所產生低能量之二次電子，形成負離子，進而選擇分離出產物離子並進行碰撞活化解離母離子斷裂的位置以及負電荷在化合物結構中的分佈狀況和轉移情形。
研究成果為：溴原子比氯及氟原子有更大的電子捕捉能力，而且溴化物形成負離子後，容易掉溴負離子，使得結構趨向穩定，由於氯、溴具有明顯的同位素峰，能夠應用於碎片離子的鑑定。此外，進行改變游離源區壓力、溫度以及選擇不同試劑氣體(CH4、O2)的實驗，證明此三項變因會影響負離子圖譜的結果。Phthalic anhydride及Phthalimide本身具有捕捉電子的能力，可以從碎片的解離情形知道，負電荷主要分佈在苯環上，即使強電子親和力之鹵素取代基亦不容易將負電荷帶走。鹵素取代基的位置、種類、數目以及主結構上原子的不同，亦導致其結果的差異，因此，對於同分異構物的確認上，可以提供極佳的可信度。另外發現部份化合物ECD的結果有Dimer生成。
研究的結果將可提供學術界有關此儀器應用於負離子研究的訊息，對於環境化學方面，污染物以及有毒物質常含有氯的官能基，本儀器所使用之負離子化學游離法，能夠提供極高的靈敏度以及選擇性，利用Tandem in Time 串聯質譜儀的優點，鑑定分析物之碎片型態。

2.Electron Capture Detection Mass Spectrometry is a sensitive and selective technique for the analysis of compounds containing electrophilic functional groups.
It has been used extensively for the analysis of many classes of compounds in the traditional mass spectrometers but none was reported from the ion trap mass spectrometer since the traditional ion trap MS can not perform negative ion analysis. However, in this study we have examined a series of Phthalic anhydride and their derivatives by electron capture detection in the ion trap tandem mass spectrometers with an external source (the Finnigan GCQplus). The GCQ is the first commercial benchtop ion trap mass spectrometer with the capability to perform negative ion analysis.
In this study, a series of halogenated Phthalic anhydride and their derivatives will be examined. Methane was used as the reagent gas. Since these halogenated compounds possess higher electron affinities, negative ions can be formed perdominantly through a resonance electron capture process. Besides, using the tandem in time ion trap mass spectrometry can select a specific m/z of ion to perform MS/MS. Then the selected precursor ions dissociate by the collisional activation technique. From the fragments of parent ion, the structure of ions can be determined. These noval experiments can provide valuable results for negative ions which could not be detected by an traditional internal ionization ion trap mass spectrometer in the past.

Pci
1.Abstract
2.Introduction
3.Experiment
4.Discussion
Nci
1.Abstract
2.Introduction
3.Experiment
4.Discussion

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