理學院: 化學研究所指導教授: 汪根欉沈家安Shen, Chia-AnChia-AnShen2017-03-022018-07-102017-03-022018-07-102016http://ntur.lib.ntu.edu.tw//handle/246246/272149本研究以有機合成的方式，設計出一具有疊氮基之離子性有機共軛藍光分子，並利用電子顯微鏡（Electron microscopy）及動態光散射儀（Dynamic light scattering）鑑定，此分子可於有機溶劑丙酮中自組裝形成粒徑介於100–300 nm 之間的中空囊泡狀（Vesicle-like）奈米球。另外可藉由改變分子所處之溶劑環境，來影響分子自組裝作用力之間的平衡，藉此系統性探討奈米球之生成機制。 此外，我們進一步將此分子進行速配化學（Click chemistry），目的是在奈米球表面修飾上具特殊功用的基團或分子。本研究選用的速配化學反應是利用銅金屬離子催化末端炔與疊氮基進行合環反應（Cu-catalyzed alkyne-azide coupling, CuAAC），合成出一新型離子性有機共軛自組裝分子T3-4im-2OH，以核磁共振光譜以及質譜鑑定，並透過改變溶劑環境來探討其自組裝行為，以及檢視此分子是否對金屬離子有鉗合能力而改變其奈米結構。 另一方面，我們也利用 CuAAC 反應將一綠色發光團（NI）鍵結至離子性共軛藍光分子上，由於我們設計之離子性共軛藍光分子之放光光譜與NI分子之吸光光譜重疊範圍大，故所得之產物T3-4im-2NI分子會進行分子內與分子間之螢光共振能量轉移。藉由比較形成微結構前後之能量轉移效率與電子顯微影像分析，我們期望能對於探討此離子性有機共軛系統之自組裝行為提供更進一步的證據。 針對應用的部份，我們將硼酸分子鍵結至離子性共軛藍光分子上，得到一新型離子性有機共軛分子T3-4im-2BA。根據文獻，硼酸會在水溶液中快速與雙醇基團鍵結，於是我們透過電子顯微影像分析，發現具有雙醇基之葡萄糖與多巴胺會與之作用，並改變其奈米結構，而我們也進一步利用能量轉移來佐證此行為會於溶液態中發生。In this research, we designed a highly fluorescent -conjugated organic molecule T3-4im-2Az with ionic self-assembly motifs and azide groups for further functionalization. The molecule spontaneously assembles into hollow vesicle-like nano-spheres with a diameter of ca. 200 nm in acetone solutions, which was characterized by electron microscope and dynamic light scattering. The copper(I)-catalyzed Huisgen 1,3-dipolar cycloaddition, which is commonly known as “click reaction”, was exploited to functionalize T3-4im-2Az to obtain the model compound T3-4im-2OH. We systematically investigated the self-assembly mechanism of T3-4im-2OH through the manipulation of non-covalent interactions by varying the solvent composition. In another experiment, we used the click reaction to incorporate T3-4im-2Az with a green fluorophore, which enables the product, T3-4im-2NI to possess intramolecular FRET ability. We expect to examine more deeply into the self-assembly mechanism of this system by measuring the FRET efficiency under different self-assembly conditions. For further application, we choose to use T3-4im-2Az incorporating with boronic acid moieties. Boronic acid is well-known to interact with diol functionalities, and as such, we examined the influences of dopamine and glucose on the newly synthesized T3-4im-2BA system. Before adding dopamine/glucose, T3-4im-2BA can self-assemble into intact nanospheres, which collapse upon the addition of dopamine/glucose. We look forward to the application of this system on dopamine/glucose sensing in biological systems.6533244 bytesapplication/pdf論文公開時間: 2019/8/2論文使用權限: 同意有償授權(權利金給回饋學校)自組裝速配化學能量轉移雙醇Self-AssemblyClick chemistryEnergy transferDiolthesis10.6342/NTU201601517http://ntur.lib.ntu.edu.tw/bitstream/246246/272149/1/ntu-105-R03223105-1.pdf