| 研究生: |
林盈如 Lin, Ying-Ju |
|---|---|
| 論文名稱: |
含冠醚基團之芴衍生物:合成、鑑定與螢光感測特性研究 Fluorene-Based Chemosensor Containing Crown Ether Groups: Synthesis, Characterization, Optical Properties and Application |
| 指導教授: |
陳雲
Chen, Yun |
| 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: | 2011 |
| 畢業學年度: | 99 |
| 語文別: | 英文 |
| 論文頁數: | 76 |
| 中文關鍵詞: | 螢光感測器 、冠醚分子 、芴 |
| 外文關鍵詞: | Fluorescent chemosensor, Crown ether, Fluorene, Stern-Volmer constant |
| 相關次數: | 點閱:128 下載:2 |
| 分享至: |
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本研究合成含冠醚(monoaza-15-crown-5)以及芴衍生物(fluorene)之螢光感測器(FTC),並探討其對金屬陽離子的辨識能力。當加入鐵離子,吸收光譜及螢光光譜呈現藍位移,可推測為鐵離子與冠醚作用,引發光誘導電荷轉移(PCT)。螢光強度的下降可推測為發光團被激發後能量轉移給鐵離子,引發淬熄效應。在多種離子干擾下,FTC對Fe3+仍具有高度的選擇性。其敏感性相對於文獻也顯著提升,可與高分子螢光感測器相比。(Ksv = 1.59×105 M-1) 由於FTC可溶於常用有機溶劑以及高極性溶劑,例如:氯仿、甲苯、甲醇、丙酮…等,因此可應用於水溶液的偵測,提升了感測器之應用性。而其敏銳的螢光感測能力,加入鐵離子後造成溶液顏色變化,可由肉眼辨識鐵離子的存在。
To improve the sensitivity and application in aqueous solution of chemosensor towards Fe3+, we synthesized a chemosensor (FTC) based on conjugated fluorene core, which contains three crown ether moieties (monoaza-15-crown-5). The FTC is satisfactorily characterized by 1H NMR, COSY, NOESY, 13C NMR, FT-IR and elemental analysis. The FTC is soluble in common organic solvents such as chloroform and toluene, even in high polar solvents such as methanol and N,N-dimethylformamide (DMF). Therefore, the FTC is applicable in aqueous contaminated solution.
The electrochemical properties were investigated by cyclic voltammetry (CV), with the HOMO and LUMO levels were estimated to be -5.88 eV and -2.88 eV, respectively.
Fluorescence spectral variations in the presence of different metal ions and concentrations were used to elucidate the selectivity and sensitivity, respectively. The absorption and fluorescence spectra shift hypsochromically (blue-shift) in the presence of Fe3+, which has been attributed to the photoinduced charge transfer (PCT) process between electron-donor (amino) and electron-acceptor (fluorene core). Also the fluorescence quenching was observed, which is resulted from energy transfer from fluorophore to Fe3+ directly. As the concentration of Fe3+ is increased, the collision between fluorophore and Fe3+ is raised, leading to significant decrease in fluorescence intensity. The sensitivity (Stern-Volmer constant: Ksv) of FTC towards Fe3+ reached 1.59×105 M-1 in THF/H2O (9/1 v/v). The characteristic fluorescence responses of FTC upon the addition of Fe3+ lead to the color changes which is detectable by naked eye.
The presence of hydrochloric results in absorption blue-shift and fluorescence quenching, attributed to the protonation of nitrogen atom of monoaza-15-crown-5 moiety.
The FTC exhibits specific recognition to Fe3+ with very high sensitivity. Accordingly, it is a promising chemical sensor for Fe3+.
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