臺灣博碩士論文加值系統

本研究運用8-羥基喹啉分子與二價金屬鎂離子螯合成MgQ₂錯合物為螢光材料，並輔以傅立葉紅外線光譜儀、質譜、紫外/可見吸收光譜及螢光光譜儀器鑑定其特徵。另外運用溶膠-凝膠法將MgQ₂錯合物、金屬半導體氧化鋅(ZnO)及不同重量百分比之聚乙烯吡咯酮(PVP)混合製成複合感測材料薄膜，赓續以製備之材料分別與三硝基甲苯(TNT)、苦味酸 (PA)、史帝芬酸(Styphenic Acid)、2,6-二硝基甲苯(2,6-DNT)、2,3-二硝基甲苯(2,3-DNT) 及3,4-二硝基甲苯(3,4-DNT)等6種火炸藥行感測實驗，由實驗數據顯示所製備之螢光材料對DNT,TNT,PA及Styphenic Acid等6種火炸藥具有顯著之螢光消光感測靈敏性，因此，這些複合材料及MgQ₂錯合物可嘗試運用於火炸藥感測之研究，而其材料之螢光消光反應現象則以火炸藥蒸氣壓、化合物之間相互反應及材料能階理論解釋之。

In the present work, The fluorescent MgQ₂ complex, containing bis-(8-hydroxyquinoline) and magnesium(Ⅱ) was synthesized. The complexes were characterized by Fourier transform infrared Spectroscopy(FTIR), Mass Spectroscopy, Ultra-Violet Visible Spectroscopy(U.V) and Fluorescent Spectrum. In addition, the sol-gel method has been employed in the fabrication of composite sensing films consisting of bis-(8-hydroxyquinoline)magnesium, Znic oxide(ZnO) and polyvinyl -pyrrolidone(PVP). These films were examined for applications to detect explosives
compounds such as 2,4,6-trinitrotoluene(TNT), picric acid(PA), styphenic acid, 2,3-dinitrotoluene(2,3-DNT), 2,6-dinitrotoluene (2,6-DNT) and 3,4-dinitrotoluene
(3,4-DNT). The composite thin film showed high fluorescence quenching sensitivity towards DNT, TNT, PA and Styphnic Acid, indicating that composite sensing films consisting of emissive bis-(8-hydroxyquinoline)magnesium are potentially useful chemosensor for detecting explosives. The relative sensitivity of fluorescence quenching of emissive materials by the explosives has been rationalized in terms of the vapor pressure of the explosives, the interaction of the emissive compound and the analyles, and the relative energy levels of the emissive materials.

誌謝. ii
摘要 iii
ABSTRACT iv
目錄 v
表目錄 viii
圖目錄 ix
1. 緒論 1
1.1 前言 1
1.2 研究動機 2
1.3 研究目的 4
2. 文獻回顧 5
2.1 火炸藥偵檢 5
2.2 火炸藥偵檢技術 6
2.3 化學發光檢測 7
2.4 分子發光原理 13
2.5 分子軌域理論 15
2.6 電子躍遷 17
2.7 螢光原理 17
2.7.1 振動弛緩 20
2.7.2 內能轉換 21
2.7.3 螢光放射 21
2.7.4 外部轉換 21
2.7.5 系統跨越 21
2.7.6 磷光發射 22
2.8 量子產率 22
2.9 影響螢光的因素 23
2.9.1 溫度效應 23
2.9.2 pH值對螢光的影響 23
2.9.3 磁性分子及金屬的影響 23
2.9.4 取代基效應 24
2.9.5 分子結構的影響 25
2.9.6 重原子效應 25
2.9.7 氫鍵對螢光的影響 25
2.9.8 激發複合體生成 26
2.9.9 溶劑效應 26
2.9.10 濃度消光效應 27
2.10 螢光消光理論 27
2.10.1 螢光消光 27
2.10.2 能量轉移 28
2.10.3 光誘導電子轉移 32
3. 實驗 33
3.1 實驗研究架構流程 33
3.2 實驗藥品器材 34
3.3 實驗儀器設備 34
3.4 實驗步驟 35
3.4.1 合成 35
3.4.2 火炸藥飽和蒸氣壓螢光消光試驗 37
3.4.3 火炸藥溶液混合螢光消光試驗 40
4. 結果與討論 42
4.1 有機金屬錯合物材料合成鑑定 42
4.1.1 紫外光∕可見光光譜分析 42
4.1.2 紅外光譜及質譜分析 43
4.1.3 螢光光譜分析 45
4.2 複合材料之圖譜分析 48
4.2.1 紫外光∕可見光光譜分析 48
4.2.2 螢光光譜分析 51
4.3 火炸藥飽和蒸氣壓螢光消光試驗 52
4.3.1 MgQ₂有機金屬錯合物材料螢光消光結果分析 52
4.3.2 6種不同複合材料螢光消光結果分析 57
4.4 各檢測材料比較 81
4.5 有機金屬錯合物作為火炸藥溶液檢測材料 84
4.5.1 螢光光譜變化分析 84
4.5.2 紫外∕可見光譜吸收變化分析 88
4.6 檢測試樣與待測分析物螢光消光作用機制探討 94
5.結論 95
參考文獻 97
自傳 102

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