- 學位論文
(1) 固有掌性芳杯螢光感測器之合成與光學純化及其掌性分子辨識 (2) 下緣鄰位蒽三唑及酯基取代芳杯螢光感測器之合成及其金屬離子辨識
(1) Syntheses and Optical Resolution of Inherently Chiral Fluorescent Calix[4]arenes and Their Chiral Recognition (2) Syntheses of Calix[4]arenes with Lower-rim Anthryl-triazole and Ester Groups for Metal Ions Sensing Studies
摘要
本論文主要分為兩個研究主題，分別探討螢光固有掌性芳杯化合 物的合成與光學純化，與其對掌性分子的辨識能力；以及探討下緣含 鄰位蒽三唑及酯基取代芳杯衍生物對於金屬離子的錯合能力。 第一部分中，我們設計合成了芳杯下緣AABH取代模式的固有掌 性芳杯化合物 40，並成功的找到了1-苯基乙基胺(R-form 與S-form) 當作掌性輔助試劑，利用化學法將外消旋化合物 40a 與 40b 進行拆 分，得到光學純的固有掌性芳杯化合物 41-44。並且，我們藉由化合 物 41的晶體結構，判定一系列固有掌性芳杯化合物之絕對組態。另 外，我們結合即合化學，將螢光基團引入結構中作為訊號傳遞的感應 端，利用光學純的螢光固有掌性芳杯來對掌性分子作辨識。 第二部分中，我們合成了一系列下緣不同數目的蒽三唑五員雜環 與酯基的芳杯衍生物 49 與 51，初步研究結果顯示，在溶劑系統為 甲醇比氯仿99:1的環境下，對金屬離子Ag+與Hg2+有好的辨識能力。 經由與化合物 57 相互比較，證實了當蒽三唑與酯基取代的數量增加 時，能夠有效的提升主體分子對金屬離子的錯合能力，錯合常數介於 103至1010 (M-1)。
並列摘要
In this thesis, my research is focused on two topics. the first part is the synthesis and optical recognition of fluorescent inherently chiral calix[4]arenes and their chiral recognition. The second part is the synthesis of cailx[4]arenes with lower-rim triazole and ester groups as cationic binding site and anthracene as the fluorophores. In part one, we synthesized novel calix[4]arene of AABH-type with inherent chirality through the reaction of racemic calix[4]arene derivatives 40a and 40b with 1-phenylethylamine (both R-form and S-form), follow by the separation of the diastereomers by column chromatography. Compounds 41-44 are optically pure inherently chiral calix[4]arenes. Based on the X-ray structure of 41, we could determine the absolute configurations of all three chiral cailx[4]arenes. We farther modified the lower-rim propargyl groups by Click Chemistry to add an anthracene groups as the fluorophores. The optically pure inherently chiral calyx[4]arenes were used for chiral recognition studies. In second part, we synthesized a series of calix[4]arenes with lower-rim triazole and ester groups as the cationic binding sites, and anthracene as the fluorophores. When a cosolvent of methanol and chloroform (v/v = 99:1), both compound 49 and 51 have good selectivity toward Ag+ and Hg2+. Compared with 57, we confirmed that when thenumber of triazole and ester groups increased, their binding ability toward metal ions increased. The binding construct about 103~1010 (M-1).