||A Turn-on Fluorescent Sensor Based on Schiff base-containing Triazole for Zn2+ Detection
||Department of Chemical Engineering
photo-induced electron transfer
， S1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(4:1, 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，53倍)，造成此現象的原因是S1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S1與鋅離子形成錯合物的配位比例是1:3，由濃度滴定實驗得到偵測極限(LOD)是1.23 × 10-7 M。另外，S1與鋅離子形成錯合物造成顏色改變可直接以肉眼辨識，以Na2EDTA測試S1之可逆性，發現螢光強度的回復性佳，且S1在pH = 4.2到pH = 11的環境下皆可有效地感測鋅離子。
A Schiff base-containing fluorescent sensor S1 was synthesized by Suzuki coupling reaction. The structure is characterized by 1H NMR and MALDI/TOF-MS. S1 was developed for the detection of Zn2+ ion in EtOH-H2O solution. It exhibited weak fluorescence due to photo-induced electron transfer (PET). However, the strong fluorescent emission can be observed in the prescence of Zn2+ (20 eq) with over 53-fold enhancement at 465 nm. Furthermore, the blue shift in emission are attributed to the coordination of imine nitrogen with Zn2+ which increase the band gap between the excited state and ground state. The stoichiometric ratio between S1 and Zn2+ is 1:3 obtained by Job plot. The limit of optical detection (LOD) is 1.23 × 10-7 M derived from titration experiment. The formation of S1-Zn2+ is chemically reversible and the color change could be directly observed by naked eye. In addition, S1 showed good sensing ability under wide pH value ranging from 4.2 to 11.
第一章 緒論. 1
1-1 前言 1
1-2 感測器介紹 2
1-2-1 化學感測器 2
1-2-2 金屬離子感測 3
1-2-3 螢光感測器 3
1-3 感測器的特性 4
1-3-2 選擇性 5
1-3-3 可逆性 5
1-3-4 準確性 6
第二章 文獻回顧 7
2-1 螢光原理介紹 7
2-1-1 分子失活過程 8
2-1-2 影響螢光的因素 10
2-2 溶劑效應 14
2-3 螢光感測器的訊號傳遞與作用機制 16
2-3-1光誘導電子轉移 (photoinduced electron transfer，PET) 16
2-3-2光誘導的電荷轉移 (photoinduced charge transfer，PCT) 17
2-3-3光誘導能量轉移(photoinduced 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
2-4 希夫鹼(Schiff base) 25
2-4-1 以希夫鹼作為辨識基團之感測器介紹 26
2-5 Suzuki coupling反應 29
2-6 研究動機 30
第三章 實驗內容 31
3-1 實驗裝置與設備 31
3-2 鑑定測量儀器 32
3-3 感測器S1與金屬離子溶液配製 34
3-4 實驗藥品與材料 35
3-5 反應流程 37
3-6 單體合成 39
第四章 結果與討論 42
4-1 單體結構鑑定 42
4-1-1 核磁共振光譜 (NMR) 42
4-1-2基質輔助雷射脫附游離飛行質譜儀 (MALDI/TOF-MS) 44
4-2 光學性質探討 51
4-2-1 感測器S1對不同金屬離子的感測能力 51
4-2-2 光譜變化的機制探討 54
4-2-3 濃度滴定實驗 55
4-2-4 Job plot實驗 57
4-2-5 結合常數計算 58
4-2-6 偵測極限(Detection limit) 59
4-2-7 雙離子實驗 60
4-2-8 感測器S1在不同pH值下的影響 61
4-3 S1-Zn2+錯合物核磁共振圖譜 64
4-5 感測器S1作為Zn2+試紙 67
第五章 結論 68
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