臺灣博碩士論文加值系統

本篇論文設計並合成出具合作效應的離子感測器，研究架構以萘醯亞胺 (1,8-naphthalimide) 為螢光發光發射團，則做為辨識單元選用；含氮、氧、硫之冠醚 (dithiodioxomonoaza) 作為捕捉金屬離子的辨識單元。另外設計一組對照組，探討並用以確認捕捉金屬離子的位置為含氮、氧、硫之冠醚，而非其他位置。冠醚分子與螢光團鍵結所產生的共軛鍵，金屬離子被捕抓後造成電荷轉移，使得會有顏色變化效果，可用以肉眼快速偵測。因此，化合物的結構經由NMR來確定結構的正確性後，利用UV-vis-NIR和螢光光譜其來測定化學感測器的效能外，還能利用肉眼辨識的方法來偵測其效果，其偵測極限為1×10-5 M。
本章即針對我們所設計合成的兩個螢光探針的結果顯示：在觀測下加入特定金屬離子後以UV-vis-NIR吸收光譜與顏色改變以及螢光放射光譜變化，化合物(I)符合我們的預期效果，並不會參與任何離子結合。化合物(II)，經由與各金屬離子的滴定、競爭性實驗中可得知螢光探針對汞離子及鉻離子具有較好的結合能力與選擇性，並且靈敏度可達到ppb等級，且化合物與汞離子的反應只需18秒。故我們的化合物具有雙重辨識離子能力優勢，並且能藉由pH值的不同來初步篩選出兩種離子，由此證明此感測器具有快速篩選及符合化學感測器高經濟效益的目的。

In this thesis, the design and synthesis issued by the cooperative effect of ion sensors, research framework to 1,8-naphthalimide photoluminescence emission corporation, as a recognition unit selection; dithiodioxomonoaza as the capture metal ion recognition unit. In addition to design a control group to explore and to confirm the capture of the location of the metal ions for nitrogen, oxygen, sulfur crown ether, rather than the other locations. Crown ether molecules with the fluorophore binding conjugate, resulting from charge transfer, so there will be color change effects available to the naked eye can quickly detect metal ions arrested grasp. Therefore, the structure of the compounds to determine the correctness of the structure through NMR spectroscopy, UV-vis-NIR and fluorescence spectroscopy to the determination of the chemical sensor performance, but also to the naked eye identification method to detect the effect of its The detection limit of 1 × 10-5 M.
This chapter, namely the results of the two fluorescent probes designed and synthesized for our show: UV-vis-NIR absorption spectra and color change, as well as changes in the fluorescence emission spectra, compound (I) added to the specific metal ions under observation in line with our the desired results, and will not participate in any ion binding. Compound (II), via titration with the metal ion competition experiments can be learned fluorescent probes for mercury ion and chromium ion binding capacity and selectivity, and sensitivity to achieve the ppb level, and compounds with mercury ion reaction is only 18 seconds. Therefore, our compounds have the advantage of dual recognition ion capacity, and by different pH values the initial screening of the two ions, thus proving that this sensor has a fast screening and compliance with high economic efficiency of the chemical sensors.

中文摘要……………………………………………………………………………………… I
英文摘要……………………………………………………………………………………… II
誌謝…………………………………………………………………………………………… III
目錄…………………………………………………………………………………………… VI
表目錄………………………………………………………………………………………… VIII
圖目錄………………………………………………………………………………………… IX

第一章 緒論 ………………………………………………………………………… 1
1-1 前言 ………………………………………………………………… 1
1-2 汞之基本資料 ……………………………………………………… 1
1-3 鉻之基本介紹………………………………………………………… 3
1-4 研究目的……………………………………………………………… 4
第二章 研究背景與文獻回顧 ………………………………………………………… 8
2-1 分子辨識單…………………………………………………………… 8
2-2 活感測器之組成與原理………………………………………………… 10
2-2-1 化學感應分子…………………………………………………… 12
2-2-1-1 化學感應器的定義…………………………………………… 12
2-2-1-2 螢光離子感測器 …………………………………………… 15
2-2-2 接受區設計 ……………………………………………………… 15
2-3 冠醚類分子介紹……………………………………………………… 16
2-4 螢光探針介紹………………………………………………………… 21
2-5 螢光發光原理………………………………………………………… 21
2-5-1 光誘導電子轉移(Photoinduced Electron Transfer)……………… 25
2-5-2 光誘導內部電荷轉移(Internal Charge Transfer)………………… 29
第三章 實驗材料、設備與方法………………………………………………………… 37
3-1 實驗架構 …………………………………………………………… 37
3-2 實驗試劑……………………………………………………………… 38
3-3 儀器設備及工具軟體………………………………………………… 42
3-4 金屬離子探針之合成設計……………………………………………. 49
3-3-1 化合物(I)之合成………………………………………………… 50
3-3-2 化合物(II)之合成………………………………………………… 51
第四章 結果與討論…………………………………………………………………….. 54
4-1 金屬離子探針合成設計探討………………………………………… 54
4-1-1 化合物(I)金屬離子探針之合成探 …………………………… 54
4-1-2 化合物(II)金屬離子探針之合成探討…………………………… 56
4-2 化合物 (I)的光譜研究與結果討論………………………………… 59
4-2-1 化合物(I)對各金屬離子選擇性測定…………………………… 60
4-2-2 化合物(I)對汞與鉻離子反應時間測定………………………… 62
4-2-3 化合物(II)的光譜研究與結果討論……………………………… 63
4-3 化合物(II)的光譜研究與結果討論………………………………… 64
4-3-1 化合物(II)對汞離子反應時間測定……………………………… 65
4-3-2 化合物(II)對汞離子之靈敏度測定……………………………… 67
4-3-3 化合物(II)對各金屬離子選擇性測定…………………………… 70
4-3-4 化合物(II)對各金屬離子競爭性測定…………………………… 72
4-3-5 化合物(II)對汞離子pH之適用範圍…………………………… 75
4-3-6 化合物(II)對汞離子的肉眼偵測極限…………………………… 76
4-3-7 化合物(II) 對鉻離子反應時間測定…………………………… 77
4-3-8 化合物(II)對鉻離子之靈敏度測定……………………………… 79
4-3-9 化合物(II) 對各金屬離子競爭性測定 ………………………… 82
4-3-10 化合物(II) 對鉻離子pH之適用範圍………………………… 84
4-3-11 化合物(II)對鉻離子的肉眼偵測極限…………………………… 85
4-4 化合物(II)之螢光譜結果與討論…………………………………… 86
4-4-1 化合物(II)對各金屬離子的螢光強度變化……………………… 86
第五章 結論…………………………………………………………………………… 99
第六章 參考文獻……………………………………………………………………… 100

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