||Aromatic 1,3,4-Oxadiazolyl Derivative with Terminal Schiff Base Groups: Synthesis and Fluorescent Chemosensory Characteristics Toward Zinc Ion
||Department of Chemical Engineering
photo-induced electron transfer
， 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.
第一章 緒論 2
1-1 前言 2
1-2 感測器介紹 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
1-3-2 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
2-5-1 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
3-4 實驗藥品與材料 38
第四章 結果與討論 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
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