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系統識別號 U0026-1607201812515800
論文名稱(中文) 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
論文名稱(英文) Aromatic 1,3,4-Oxadiazolyl Derivative with Terminal Schiff Base Groups: Synthesis and Fluorescent Chemosensory Characteristics Toward Zinc Ion
校院名稱 成功大學
系所名稱(中) 化學工程學系
系所名稱(英) Department of Chemical Engineering
學年度 106
學期 2
出版年 107
研究生(中文) 張雅婷
研究生(英文) Ya-Ting Chang
學號 N36051227
學位類別 碩士
語文別 中文
論文頁數 80頁
口試委員 指導教授-陳雲
口試委員-劉瑞祥
口試委員-吳逸謨
口試委員-許梅娟
口試委員-吳知易
中文關鍵字 螢光感測器  希夫鹼  光誘導電子轉移  鋅離子  TICT 
英文關鍵字 sensor  oxadiazolyl  Schiff base  photo-induced electron transfer  zinc ion  solvent effect  TICT 
學科別分類
中文摘要 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。
英文摘要 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.
論文目次 摘要 I
致謝 XVI
目錄 XVII
圖目錄 XX
表目錄 XXIV
流程目錄 XXIV
第一章 緒論 2
1-1 前言 2
1-2 感測器介紹 3
1-2-1化學感測器 3
1-2-2 金屬離子感測 3
1-2-3 螢光感測器 4
1-3 感測器的特性 5
1-3-1靈敏度 5
1-3-2 選擇性 6
1-3-3 可逆性 6
1-3-4 準確性 7
第二章 文獻回顧 8
2-1 螢光原理介紹 8
2-1-1 分子失活過程 9
2-3 螢光感測器的訊號傳遞與作用機制 15
2-3-1光誘導電子轉移(photo-induced electron transfer, PET) 16
2-3-2光誘導的電荷轉移 (photo-induced charge transfer, PCT) 17
2-3-3光誘導能量轉移(photo-induced energy transfer) 19
2-3-4 激發雙體(excimer)或激發複合體(exciplex)的形成 20
2-3-5 聚集誘導放光(aggregation induced emission) 21
2-3-6 C=N異構化(isomerization) 22
2-3-7激發態分子內質子轉移(excited state intramolecular proton transfer, ESIPT) 23
2-3-8扭曲的分子內電荷轉移 (twisted intramolecular charge transfer, TICT) 24
2-4 希夫鹼(Schiff base) 26
2-4-1 以希夫鹼作為辨識基團之感測器介紹 28
2-5反應機制 31
2-5-1 Suzuki coupling Reaction 31
2-5-2 Miyaura Borylation Reactions 32
2-6 研究動機 33
第三章 實驗內容 34
3-1 實驗裝置與設備 34
3-2 鑑定測量儀器 35
3-3感測器O1與金屬離子溶液配制 37
3-4 實驗藥品與材料 38
3-5反應步驟與結果 40
第四章 結果與討論 43
4-1化合物鑑定 43
4-1-1 核磁共振光譜 (NMR) 43
4-1-2 基質輔助雷射脫附游離飛行質譜儀 (MALDI/TOF-MS) 44
4-1-3 紅外線光譜儀 (FTIR) 49
4-2 光學性質 50
4-2-1 探討感測器O1對不同金屬的感測 50
4-2-2 機制解釋光譜變化 53
4-2-3 濃度滴定實驗 54
4-2-4 Job plot 56
4-2-5 偵測極限 (Detection limit) 57
4-2-6 結合常數計算 58
4-2-7 雙離子競爭實驗 59
4-2-8 化學感測器在不同pH 值的影 60
4-3 化學感測器O1的可逆性 63
4-4 O1-Zn2+ 錯合物之核磁共振圖譜 64
4-5 O1-Zn2+錯合物之FTIR圖譜 65
4-6 TICT solvent effect of O1-Zn2+ 66
4-7 O1-Zn2+ 與溫度的變化 70
第五章 結論 71
參考文獻 72
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