標題: | 含芘三唑取代之苯醌芳杯及其衍生物之離子感測研究 Triazole Functionalized Calix[4]quinone Derivatives as Highly Selective Ion Sensor |
作者: | 倪湘茹 鍾文聖 Ni, Xiang-Ru Chung, Wen-Sheng 應用化學系碩博士班 |
關鍵字: | 芳杯;苯醌;偶氮;螢光;芘;calixarene;quinone;azobenzene;flurescence;pyrene |
公開日期: | 2016 |
摘要: | 在本研究中利用點擊化學修飾芳杯下緣,引入芘為螢光發射基團,並延續實驗室陳映蓉學姐的意外發現,利用過量的過氯酸鐵,有效合成出苯醌芳杯之骨架,衍生出更加多樣性的分子。故在本研究中,合成下緣為芘三唑取代的苯醌芳杯之衍生化合物3336。由實驗結果,我們發現化合物33,因其骨架改變,使其螢光放射強度減弱,進而影響其光學性質;化合物34對Zn2+與Cd2+離子有單體激態雙體的螢光變化;化合物35原本預期可以做為雙調控的離子感測器,因其合成上的困難,因此沒有後續的感測探討;化合物36對於Ca2+與Pb2+離子有較明顯的選擇性,錯合前後可造成顏色的變化;另外,化合物36加入陰離子如F-、AcO-及H2PO4-,亦可以由肉眼觀察其顏色變化。此外,我們更進一步利用氫核磁共振光譜探討化合物34與化合物36之離子錯合模型,並相互印證比較其差異。 In this study, we modified the lowerrim of the calix[4]arene by attaching distal pyrene unit as the fluorophore through the click chemistry of pyrene azides with 25, 27bispropargyl calix[4]arene. Based on the methods developed by Ms. YingJung Chen, we successfully synthesized the unique skeleton of calix[4]quinone and its derivatives 3336. Based on the results from UVVis spectroscopy and fluorescence spectrometry, we found that fluorescence emission intensity decreased, because more flexible structure will cause energy lost in the cases of 33; 34 possesses an efficient excimer formation and emission, and the fluorescent spectra changes observed upon addition of various metal ions show that 34 is selective for Cd2+ and Zn2+ over other metal ions; Owing to the low yield of 35, we didn’t investigate the allosteric effect of 35. In addition, compound 36 was found to change color when anion such as F-, AcO- and H2PO4- was added to its solution. Moreover, we further investigate the complexation models by using NMR titration spectroscopy. |
URI: | http://etd.lib.nctu.edu.tw/cdrfb3/record/nctu/#GT070352527 http://hdl.handle.net/11536/138835 |
顯示於類別: | 畢業論文 |