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研究生: 陳雯雄
Wen-Xiong Chen
論文名稱: 液相層析質譜法對色胺類衍生物之分析研究
Analysis of tryptamines by Liquid-Chromatography/Mass Spectrometry
指導教授: 林震煌
Lin, Cheng-Huang
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2008
畢業學年度: 96
語文別: 中文
中文關鍵詞: 液相層析質譜儀阿達瑪轉換色胺類濫用藥物
論文種類: 學術論文
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  • 本研究以LC-ESI/MS (liquid chromatography-electrospray ionization/mass spectrometry,液相層析電噴灑質譜儀)分析色胺類濫用藥物,歸納出色胺類濫用藥物的特徵譜峰。在ESI游離模式下,一級胺類(α-methyltryptamine, AMT;5-methoxy-α-methyltryptamine, 5-MeO-AMT)與三級胺類(N,N-dimethyltryptamine, DMT; N,N-diethyltryptamine, DET; N,N-dipropyltryptamine, DPT; N,N-dibutyltryptamine, DBT; N,N-diisopropyltryptamine, DIPT; 5-methoxy-N,N-dimethyltryptamine, 5-MeO-DMT; 5-methoxy-N,N-di-isopropyltryptamine, 5-MeO-DIPT)藥物,可觀察到兩種特殊斷裂途徑。此兩種斷裂途徑分別為α-斷裂(α-cleavage)和β-斷裂(β-cleavage),可做為刑事鑑定的特徵峰。此外,為了改善色胺類的偵測靈敏度,本研究引用阿達瑪轉換(Hadamard Transform)技術來提高訊號/雜訊的比值。實驗中使用了一個高效能液相層析(High Performance Liquid Chromatography, HPLC)幫浦與一個高壓精密注射泵來完成進樣的工作。將阿達瑪序列由電腦經RS232介面傳輸到注射泵,使樣品溶液與HPLC流析溶劑,可按照阿達瑪序列的方式,流入Tee connector再進入分離管柱。分析物經管柱分離以後,以ESI的方式,可在SIM (selected ion monitoring)或SRM (selected reaction monitoring)的模式下讀取數據。以DMT為測試樣品,在阿達瑪序列n = 1023 時,訊號/雜訊的比值可提高約一個數量級。

    Characteristic mass fragmentation of 9 tryptamine standards, including a-methyltryptamine, 5-methoxy-a-methyltryptamine, N,N-dimethyltryptamine, N,N-diethyltryptamine, N,N-dipropyltryptamine, N,N-dibutyltryptamine, N,N-diisopropyltryptamine, 5-methoxy-N,N-dimethyltryptamine and 5-methoxy-N,N-diisopropyltryptamine, were investigated and compared by means of LC-ESI/MS (liquid chromatography-electrospray ionization/mass spectrometry). As a result, the protonated molecular ion ([M+H]+) and two types of fragments produced from the α-cleavage and β-cleavage processes, were found to be characteristic and useful in the rapid screening and confirmation of tryptamine derivatives. Furthermore, in order to improve signal-to-noise (S/N) ratio, Hadamard transform (HT) technique was applied. Novel sample injection device was developed to achieve multiple sample injections, where a syringe pump and Tee connector were employed. The injection device permitted precise successive injections, resulting in clearly modulated chromatograms encoded by Hadamard matrices. After inverse Hadamard transformation of the encoded chromatogram, the S/N ratios of the signals were substantially improved compared with those expected from theoretical values.

    目錄 中文摘要……………………………………………………………………………Ⅰ 英文摘要……………………………………………………………………………Ⅱ 目錄…………………………………………………………………………………Ⅲ 第一章 緒論……………………………………………………………………… 1 1-1 研究目的………………………………………………………………… 1 1-2 液相層析質譜儀近況…………………………………………………… 1 1-3 阿達瑪轉換法…………………………………………………………… 2 1-4 分析物簡介……………………………………………………………… 2 第二章 分析方法及原理……………………………………………………………5 2-1 高效能液相層析法簡介……………………………………………………5 2-2 液相層析電灑質譜儀………………………………………………………6 2-2-1 液相層析質譜儀簡介……………………………………………6 2-2-2 電灑游離法簡介…………………………………………………6 2-2-3 離子阱質量分析器簡介…………………………………………8 2-3 阿達瑪轉換法………………………………………………………………8 第三章 儀器、藥品與實驗方法…………………………………………………13 3-1 Thermo LCQ 液相層析質譜儀…………………………………………13 3-1-1 以直接注射進樣………………………………………………13 3-1-2 以HPLC串聯質譜儀進樣………………………………………13 3-1-3 阿達瑪進樣裝置………………………………………………13 3-1-4 阿達瑪進樣步驟與方法………………………………………16 3-2 LabVIEW圖控程式………………………………………………………19 3-3 質量校正液配製與質量校正……………………………………………21 3-3-1 質量校正液的配製……………………………………………21 3-2-2 質量校正………………………………………………………21 3-4 儀器與周邊設備列表……………………………………………………24 3-5 藥品列表…………………………………………………………………26 第四章 結果與討論………………………………………………………………28 4-1 以LC-ESI/MS直接注射法對色胺類濫用藥物的分析…………………28 4-2 以HPLC進樣方式對色胺類濫用藥物的分析……………………………42 4-2-1 條件測試………………………………………………………42 4-2-2 DMT檢量線製作與色胺類偵測極限……………………………44 4-2-3 真實樣品的偵測………………………………………………47 4-3 以阿達瑪進樣對色胺類濫用藥物的分析………………………………50 4-3-1 阿達瑪LC-UV測試………………………………………………………50 4-3-2 阿達瑪LC-MS進樣時間測試…………………………………54 4-3-3 阿達瑪進樣與阿達瑪序列比較………………………………55 4-3-4 比較單點進樣與阿達瑪轉換…………………………………56 4-3-5 以SRM模式偵測下來做阿達瑪進樣與轉換……………………60 第五章 結論………………………………………………………………………62 論文發表……………………………………………………………………………63 參考文獻……………………………………………………………………………64

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