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研究生: 方晴
Ching Fang
論文名稱: 毛細管電泳螢光光譜法對尿液中低濃度毒品3,4-亞甲雙氧甲基安非他命(3,4-MDMA)與麥角二乙胺(LSD)之分析研究
Determination of 3,4-Methylenedioxymethamphetamine and Lysergic Acid Diethylamide in Urine by Capillary Electrophoresis/Fluorescence Spectroscopy
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: 2002
畢業學年度: 90
語文別: 中文
中文關鍵詞: 毛細管電泳螢光光譜法亞甲雙氧甲基安非他命尿液麥角二乙胺
英文關鍵詞: LSD
論文種類: 學術論文
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  • 3,4-methylenedioxymethamphetamine(3,4-MDMA)是一種強烈中樞神經興奮劑。本研究發現使用非水相毛細管泳層析/螢光分析法,可提供一種快速、有效的分離條件。利用加入3,4-MDMA-D5為內標物,依照分析物個別的電泳遷移時間與譜峰高度,直接對吸毒者尿液中代謝出的3,4-MDMA濃度做定量分析,每次偵測的時間僅約5分鐘,偵測極限可到1 ppm(5.2 ×10-6 M),輔以簡單的液-液萃取法可使偵測極限降至50 ppb(S/N = 3)。
    Lysergic acid diethylamide(LSD)對人體大腦和神經中樞系統具有強大的危害性,受此藥物刺激會產生幻覺及脫離現實感。本研究針對LSD、iso-Lysergic acid diethylamide(iso-LSD)與Lysergic acid N,N-methylpropylamide(LAMPA)建立標準的分析方法。由實驗結果顯示,使用最佳化分離條件為100 mM SDS、50 mM磷酸溶液及3 mM Brij-30並加入Acetonitrile-Methanol-Water(5:35:60, v/v)緩衝溶液組成。此外,本實驗應用毛細管電泳掃集法(sweeping)與陽離子選擇性完全注射掃集MEKC法(CSEI-sweep-MEKC),可使偵測極限(S/N = 3)降至~20 ppb和~60 ppt。最後,本研究以水相毛細管電泳/低溫(77 K)螢光光譜偵測法與GC/MS偵測法應用於檢測嗑藥者尿液與一粒砂毒品中LSD的定性與定量分析。

    3,4-methylenedioxyamphetamine (3,4-MDMA) is a strong central nervous system stimulant. Using nonaqueous capillary electrophoresis/fluorescence detection, the precision of the method was evaluated by measuring the repeatability and intermediate precision of migration time and corrected peak height by comparison with a 3,4-MDMA-D5 internal standard. It is possible to determine this drug at a level of 1 ppm without any pre-treatment in less than 5 min. After liquid-liquid extraction, the sample can be condensed and a detection limit of 3,4-MDMA in urine of 50 ppb (S/N = 3) can be achieved.
    Lysergic acid diethylamide (LSD) is a powerful psychedelic drug that produces temporary hallucinations and a schizophrenic psychotic state The separation and on-line concentrations of LSD, iso-lysergic acid diethylamide (iso-LSD) and lysergic acid N, N-methylpropylamide (LAMPA) in human urine also were investigated by capillary electrophoresis-fluorescence spectroscopy using a mixture of acetonitrile-methanol-water solution (5:35:60, v/v) containing sodium dodecyl sulfate (100 mM), phosphate (50 mM), and Brij-30 (3 mM). To improve sensitivity, a technique involving sweeping and cation-selective exhaustive injection-sweep-micellar electrokinetic chromato-
    graphy (CSEI-sweep-MEKC) were also used for on-line concentration which resulted in detection limits of ~ 20 ppb and ~ 60 ppt, respectively. The separation and on-line identification of LSD in tablets were also investigated by capillary electrophoresis-fluorescence spectroscopy at 77 K and GC/MS.

    中文摘要 Ⅰ 英文摘要 Ⅱ 目錄 Ⅲ 圖目錄 Ⅵ 表目錄 Ⅷ 第一章、緒論 1 1-1. 分析物簡介 1 1-1-1. 3,4-MDMA 1 1-1-2. LSD 3 1-2. 研究目的 5 1-2-1. 3,4-MDMA濫用藥物 5 1-2-1. LSD類濫用藥物 7 第二章、分析方法與原理 11 2-1 毛細管電泳分析法之發展歷程 11 2-2 毛細管電泳分析法之基本原理 14 2-2-1. 電泳分離與電泳遷移率 14 2-2-2. 電滲流 15 2-2-3. 管柱分離效率 20 2-3 毛細管電泳層析法的分離模式 21 2-3-1. 毛細管區帶電泳(CZE) 22 2-3-2. 微胞電動毛細管層析(MEKC) 24 2-4 線上濃縮技術 28 2-4-1. 毛細管電泳掃集法(sweeping) 30 2-4-2. 陽離子選擇性完全注射掃集MEKC法 (CSEI-sweep-MEKC) 33 2-5 低溫(77 K)螢光光譜分析法 35 2-6 氣相層析質譜儀之原理與應用 39 2-7 固相萃取法 41 第三章、儀器及藥品 43 3-1 自組式毛細管電泳螢光分析儀 43 3-2 自組式螢光光譜儀 46 3-3 毛細管電泳/低溫(77 K)螢光偵測系統 48 3-4 儀器及週邊設備列表 50 3-5 藥品 53 3-6 分析物的基本性質 55 第四章、非水相毛細管電泳/螢光光譜法快速偵測尿液中低濃度3,4-MDMA:與GC/MS之比較 56 4-1 非水相毛細管電泳法 56 4-2 分離條件之適宜性評估 60 4-2-1. 檢量線製作 60 4-2-2. 再現性 60 4-3 吸毒者尿液中3,4-MDMA的定量分析 64 4-3-1. 尿液樣品的保存及前處理 64 4-3-2. 快速定量吸毒者尿液中3,4-MDMA濃度 64 4-4 毛細管電泳法與GC/MS偵測法比較 68 4-4-1. 尿液樣品的萃取與衍生反應 68 4-4-2. CE和GC/MS分析結果比較 70 第五章、毛細管電泳/螢光光譜法對尿液中低濃度LSD定性與定量分析 法的研究 72 5-1 LSD類化合物室溫之光譜性質 72 5-2 On-line低溫(77K)螢光光譜之鑑定 74 5-2-1. 最佳化分離條件的確立 74 5-2-2. 標準品on-line 77 K螢光光譜鑑定 81 5-3 線上濃縮技術 83 5-3-1. 毛細管電泳掃集法最佳樣品堆積條件 83 5-3-1-1. 進樣時間 83 5-3-1-1-1. 溶液的製備 83 5-3-1-1-2. 最佳進樣長度的測量 86 5-3-1-2. 檢量線製作 89 5-3-1-3. 操作條件再現性的探討 91 5-3-1-4. 偵測極限 93 5-3-2. 陽離子選擇性完全注射掃集MEKC法最佳樣品堆積條件 95 5-3-2-1. 進樣時間 95 5-3-2-1-1. 溶液的製備 95 5-3-2-1-2. 最佳進樣時間的測量 96 5-3-2-2. 檢量線製作 99 5-3-2-3. 操作條件再現性的探討 101 5-3-2-4. 偵測極限 103 5-3-3. Sweeping技術與CSEI-sweep-MEKC技術之比較 105 5-4 尿液中LSD的偵測 106 5-4-1. 尿液的萃取---液液萃取 106 5-4-1-1. 液液萃取 106 5-4-1-2. 液液萃取回收率 107 5-4-2. 尿液的萃取---固相萃取 108 5-4-2-1. 固相萃取 108 5-4-2-2. 固相萃取回收率 109 5-4-3. 結合線上濃縮技術偵測尿液萃取液 113 5-4-3-1. Sweeping技術測量尿液萃取液 113 5-4-3-2. CSEI-sweep-MEKC技術測量尿液萃取液 114 5-5 一粒砂毒品的定性分析 117 5-5-1. 一粒砂毒品簡介 117 5-5-2. 一粒砂毒品的前處理 119 5-5-3. 一粒砂毒品的分析及on-line 77 K光譜指紋比對 119 5-5-3-1. 一粒砂毒品(一)的偵測 119 5-5-3-2. 一粒砂毒品(二)的偵測 123 第六章、結論 127 發表論文 129 參考文獻 131 附錄 137 附錄1 管制藥品的分級 137 附錄2 管制藥品登記證 144 附錄3 3,4-MDMA及其他類似化合物之lifetime數據 145 附錄3-1 3,4-MDMA之lifetime數據 145 附錄3-2 2,3-MDMA之lifetime數據 145 附錄3-3 3,4-MDA之lifetime數據 146 附錄3-4 MDEA之lifetime數據 146 附錄3-5 3,4-BDB之lifetime數據 147 附錄3-6 3,4-MBDB之lifetime數據 147 附錄4 動物實驗 148 附錄5 毒品濫用之尿液檢定標準(節錄) 153 附錄6 重要實驗藥品庫存量 156

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