(I) 以芘為橋連之雙芳杯系列衍生物的膠體性質研究; (II) 芳杯下緣以蒽為橋連之環氧化加成反應研究

Abstract

第一部份我們利用點擊反應合成出一系列以芘為橋連基團的雙芳杯化合物15，16和17，希望能夠利用芘的π-π堆疊作用力提高成膠的能力，並以化合物18作為對照。針對上述化合物作膠體測試後，發現化合物15能夠與二甲基甲醯胺、甲苯和對二甲苯形成凝膠，其中在二甲基甲醯胺裡有最低臨界膠體濃度1.0 w/v %─為一超級凝膠體。我們利用核磁共振光譜、紫外可見光及螢光光譜、紅外光光譜、掃描式電子顯微鏡、穿透式電子顯微鏡及共軛焦雷射掃描顯微鏡等作一系列的實驗量測或形貌的拍攝，綜合所得資料對此一化合物的成膠能力加以探討。 第二部分以芳杯為骨架的單態氧感測器為主題，此類化合物在文獻上鮮少報導，我們利用點擊反應在芳杯下緣修飾以蒽為架橋之芳杯化合物25，並以化合物23作為控制化合物。以365 nm和350 nm波長之光源激發進行環氧加成，並利用核磁共振光譜針對化合物的反應性與安定性進行研究。

In the first part, we have synthesized a series of pyrene-bridged biscalix[4]arenes 15, 16 and 17 by click reaction. We wish to increase the ability of forming gels via the π-π stacking interaction of the pyrene group. Compound 18 was used as a control compound. The biscalix[4]arene 15 was found to form gels in dimethylformamide, toluene, and p-xylene. The critical gelation concentration was found to be 1 w/v % in dimethylformamide, which meant it was a supergelator. To gain insight into the gelation properties of compound 15, we used NMR, IR, UV-Vis, fluorescence spectroscopy, SEM, TEM and Confocal Laser Scanning Microscopy to study the morphology of related gelation. The subject of the second part of this Thesis was about the synthesis of a calix[4]aren-based singlet oxygen sensor. These type of compounds were rarely reported in the literature. Compound 25, with an anthracene-bridged calix[4]arene on its lower rim was synthesized by click reaction. Compound 23 was a control compound. UV light of 365 nm and 350 nm was used as irradiation source for the cyclooxidation. The reactivity and stability of the photooxidation products was monitored by NMR spectroscopy.