臺灣博碩士論文加值系統

本論文利用時間相關單光子技術系統（Time-Correlated Single Photon Counting; TCSPC）來研究紫質衍生物 Protoporphyrin (IX) Zinc (II) (ZnPP) 在THF溶液、不同pH值之水溶液、氧化鋁奈米管 (Anodized Aluminum Oxcide Nanotube, AAO ) 內以及與脫輔基肌紅蛋白 (Apo-myoglobin, Apo-Mb) 結合後的動態學。在THF溶液中，我們發現ZnPP分子產生聚集後，在螢光光譜上除了紫質原有的放光頻帶Q(0,0)及Q(0,1)以外，在此兩頻帶的中間隱含了一個新的頻帶。在生命期的測量方面，我們發現其螢光衰減曲線包含了兩個指數函數衰減：短時間的衰減生命期為0.4 ns而長時間的衰減生命期為2.2 ns。經由變化溶液的濃度，我們得知前者隨濃度愈高所佔的比例亦愈大，故推測0.4 ns為ZnPP的聚集體 (aggregates) 進行分子間能量轉移 (intermolecular energy transfer) 之時間常數，而2.2 ns則為ZnPP的單體進行系統間轉換過程（ intersystem crossing）之時間常數。
我們觀測ZnPP在氧化鋁奈米管內因為聚集所產生的螢光淬熄現象 (fluorescence quenching)，遠比其在THF溶液中更為嚴重。藉由改變實驗的條件，例如溶液的濃度、浸泡樣品的時間及氧化鋁奈米管之孔徑大小，可以變化分子產生聚集的形式，造成其在吸收、螢光光譜及激發態生命期上的變化。另外，我們嘗試將ZnPP和脫輔基肌紅蛋白結合在緩衝溶液 (buffer) 中，以改善ZnPP容易聚集的特性。我們並改變緩衝溶液之pH值，探討pH值對於ZnPP聚集在靜態及瞬態光譜上的影響。藉由比較此兩者的光譜及動力學結果的差異，可推測ZnPP與Apo-Mb結合的形式，同時我們也利用時間—解析螢光非等向性光譜 (time-resolved fluorescence anisotropy) 的技術來探討其動力行為。

The aggregation behaviors of Protoporphyrin (IX) Zinc (II) (ZnPP) in solutions, inside anodized aluminum oxide (AAO) nanoporous environments, and in combination with apomyoglobin (Apo-Mb) have been observed by using time-correlated single photon counting (TCSPC) technique. In ZnPP / THF solution, we observed a new band in addition to the Q (0,0) and Q (0,1) bands in the emission spectrum, and the fluorescence decays can be well described by a bi-exponential decay function with time coefficients of ~0.4 ns and ~2 ns. By observation of the change of the transients as a function of the concentration of the ZnPP / THF solution, we assign the fast and slow decay times being due to the intermolecular energy transfer of the aggregated molecules, and the S1→T1 intersystem crossing (ISC), respectively. Inside AAO, the fluorescence of ZnPP was significantly quenched. Changing the different experimental conditions such as the initial ZnPP / THF concentration, the sample immersion time, and the radial size of the AAO nanotubes, we discussed the observed relaxation dynamics. On the other hand, ZnPP molecules bound to Apo-myoglobin in buffer solution have shown sharp and red-shifted spectral feature in comparison with that of ZnPP in free buffer solutions. We studied the dynamics of the ZnPP˙Apo-Mb complex using the technique of time-resolved fluorescence anisotropy.

中文摘要 i
英文摘要 iii
誌謝 iv
目錄 v
表目錄 viii
圖目錄 x
附錄目錄 xviii

第一章、緒論 1
1-1 紫質分子的自我組裝 1
1-2 紫質的分子間作用力 3
1-3 紫質的聚集形式 6
1-3-1 H-聚集 6
1-3-2 J-聚集 8
1-3-3 分子之激子偶和模型 11
1-4 氧化鋁奈米材料的應用 13
1-5 本論文的研究 14

第二章、實驗技術 16
2-1 時間相關單光子計數系統 16
2-2 電子元件 19
2-2-1 分數式時間鑑別器 19
2-2-2 時間-振幅轉換器 19
2-2-3 類比-數位轉換器 21
2-2-4 多頻道分析儀 21
2-2-5 可調節式延遲器 21
2-2-6 雙光柵光譜儀 21
2-3 雷射光源 22
2-4 時間—解析螢光非等向性光譜技術 22
2-5 紫外-可見光光譜儀 25
2-5-1 電荷偶和裝置 26
2-6 螢光光譜儀 27
2-7 資料分析 27
2-8 樣品處理 28
2-8-1 氧化鋁奈米管的製成 29

第三章、紫質在有機溶液中及陽極氧化鋁奈米環境下的光譜及動力學 32
3-1 ZnPP在THF溶液中之吸收及螢光光譜 32
3-2 ZnPP在THF溶液中之S1激發態生命期 38
3-3 ZnPP在AAO奈米管內之聚集行為 43
3-3-1 ZnPP/ AAO的靜態吸收及螢光光譜 46
3-3-2 ZnPP/ AAO的瞬態螢光光譜及其激發態動力學 50
3-3-3 浸泡時間的影響 57

第四章、紫質在不同pH值水溶液中及與脫輔基肌紅蛋白結合下的光譜及動力學 63
4-1 樣品配置 64
4-2 ZnPP在不同pH值下之吸收及螢光光譜 65
4-3 ZnPP在不同pH值下之S1激發態生命期 69
4-4 ZnPP-Mb錯合物之吸收及螢光光譜. 74
4-5 ZnPP-Mb錯合物之瞬態螢光光譜 77
4-6 ZnPP-Mb錯合物的時間—解析螢光非等向性動力學 80

第五章、結論 83
附錄 84

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