| 研究生: |
張雅婷 Chang, Ya-Ting |
|---|---|
| 論文名稱: |
含希夫鹼之芳香噁二唑衍生物的合成及其在螢光化學感測器之應用 Aromatic 1,3,4-Oxadiazolyl Derivative with Terminal Schiff Base Groups: Synthesis and Fluorescent Chemosensory Characteristics Toward Zinc Ion |
| 指導教授: |
陳雲
Yun, Chen |
| 學位類別: |
碩士 Master |
| 系所名稱: |
工學院 - 化學工程學系 Department of Chemical Engineering |
| 論文出版年: | 2018 |
| 畢業學年度: | 106 |
| 語文別: | 中文 |
| 論文頁數: | 80 |
| 中文關鍵詞: | 螢光感測器 、希夫鹼 、光誘導電子轉移 、鋅離子 、TICT |
| 外文關鍵詞: | sensor, oxadiazolyl, Schiff base, photo-induced electron transfer, zinc ion, solvent effect, TICT |
| 相關次數: | 點閱:67 下載:3 |
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近年來螢光感測器應用於對金屬離子的感測越來越受到關注,金屬離子維持人體許多功能的運行,金屬離子在人體中的量過多或過少均會造成危害,因此檢測金屬離子在環境中的含量變得極其重要。相較於其他測定金屬離子的儀器,螢光感測器有許多優點,例如:容易操作、成本低、量測時間短。
本研究合成出含希夫鹼之噁二唑衍生物O1作為金屬離子螢光感測器
, O1因光誘導電子轉移(photo-induced electron transfer, PET)的作用,螢光強度低。於乙醇/水(7:1, v/v)中探討對金屬離子的辨識能力及形成錯合物的機制,鋅離子選擇性地增強螢光強度(λem = 465 nm,33倍),造成此現象的原因是O1與鋅離子作用使光誘導電子轉移被抑制,進而造成螢光增強。同時螢光光譜產生藍位移,推測是鋅離子與電子給予imine基(-C=N-)氮原子的強作用,提高了激發態與基態間的能量差。由Job plot實驗得到O1與鋅離子形成錯合物的配位比例是1:2,由濃度滴定實驗得到偵測極限(LOD)是3.08×10-8M。O1在pH = 6到pH = 11的環境下皆可有效地感測鋅離子。在可逆性方面,加入強螯合化合物Na2EDTA抓走結合的Zn2+,導致螢光隨時間淬熄,隨後再加入Zn2+可觀察到螢光恢復增強現象,顯示O1是具良好可逆性的感測材料。利用TICT(English)理論解釋溶劑效應,溶劑極性越大,放光波長紅移現象越明顯,在UV燈照射下可用肉眼觀察到顏色從藍色變化成青綠色。溫度的影響則是O1-Zn2+在室溫時的放光強度,明顯高於高溫時。
A novel fluorescent sensor O1, containing oxadiazolyl core and two terminal imine (azomethime) moieties, was synthesized by the Suzuki coupling reaction and imine condensation. O1 exhibits weak fluorescence owing to photo-induced electron transfer (PET) and C=N isomerization. In the presence of Zn2+, the fluorescence “turns on” and its intensity increases significantly with increasing concentration of Zn2+. The chemical structure of O1 was satifactorily characterized by 1H NMR and MALDI/TOF-MS spectra. 1H NMR and FTIR spectral results confirm the formation of O1-Zn2+complex. Moreover, the Job plot reveals formation of the O1–Zn2+ complex with 1:2 stoichiometry. In the presence of strong chelating Na2EDTA the O1-Zn2+ fluorescence quenches significantly. The binding constant and limit of detection (LOD) are 6.7×108 M-2and 3.08×10-8M, respectively, estimated from titration data.
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