臺灣博碩士論文加值系統

本論文研究合成一系列由苯胺三聚體合成之化學感測器。含有硫脲基鍵結位置的Colorimetric dual responsive sensor (CDRS) 化學感測器能夠同時感測CN-陰離子和pH。含有光學活性中心之硫脲基鍵結位置的Cation-Amino acid sensor (CAS) 化學感測器能夠感測陽離子與胺基酸。CDRS可以在含20%水量之DMSO混合溶劑中能夠辨識CN-，顏色變化從橙色至紫色。CAS在含50%含水量的DMSO溶劑 (中性) 中能夠感測到Ag+, Cu2+, Fe3+，加入Ag+顏色從淡紫色變成棕色、加入Cu2+變成紫色與加入Fe3+變成紫紅色，CAS亦能在10%含水量DMSO溶劑中能夠辨識到L-Tryptophan產生藍色螢光，其他胺基酸則無反應。這些變化可由目視觀察。透過紫外-可見光光譜儀來進行CN¯對於CDRS的定量分析以及Ag+, Cu2+, Fe3+對於CAS的定量分析。可以藉由1H NMR滴定實驗來觀察感測材料與待測離子兩者之間的氫鍵作用力與去質子化作用。在其他競爭性離子之存在下CDRS與CAS仍然能夠感測到待測離子，說明化學感測材料對於特定離子具有高度的選擇性。CDRS與CAS在不同酸鹼值之環境亦有顏色上之變化。此外，我們也將CDRS和CAS塗布在濾紙上製備成方便攜帶與檢測之試紙，提供低成本且能夠以肉眼直接辨識生活中有毒離子存在的檢測方法。本研究亦評估化學感測材料CDRS對陰離子以及化學感測材料CAS對於不同陽離子的鍵結常數與感測極限。

We’ve successfully synthesized a series of efficient chemical sensors, including two aniline trimer based colorimetric chemical sensors. Colorimetric dual responsive sensor (CDRS) with thiourea binding site can sense CN- anion and changes in pH. Cation-Amino acid sensor (CAS) with chiral thiourea binding site can sense Ag+, Cu2+, Fe3+ and L- Tryptophan. Upon addition of CN- to CDRS in 30% aqueous DMSO, the colorimetric response of solution of CDRS showed a color change from orange to purple. For CAS, upon addition of Ag+, Cu2+, and Fe3+ to it in 50% aqueous DMSO respectively, the colorimetric response of solution of CAS exhibited a color change from light purple to brown, purple, and fuchsia, respectively. Moreover, upon addition of L-Tryptophan to CAS in 10% aqueous DMSO, it showed blue fluorescence. However, no response was observed by adding other amino acid. The results can be recognized by naked eye.
The quantative analysis of CN- by CDRS, and quantative analysis of Ag+, Cu2+, Fe3+ by CAS can be achieved by UV-Vis. Spectrometer. The interaction between receptor and analyte ions was realized by 1H NMR spectroscopic titration. CDRS and CAS have shown appreciable selectivity in the presence of multiple ions. In different pH environments, CDRS and CAS also have differnt color change. The CN- anion in aqueous solution can be recognized by solid test kits of CDRS. The Ag+, Cu2+, Fe3+ cations in aqueous solution can be recognized by solid test kits of CAS. The binding constants, detection limits of different receptor toward various ions were also studied.

摘要 i
Abstract iii
目錄 iv
圖目錄 vi
表目錄 ix
第一章 緒論 1
1.1前言 1
1.1.1 氰化物 1
1.1.2 銅離子 2
1.1.3 銀離子 2
1.1.4 鐵離子 2
1.1.5 L-色胺酸 3
1.2研究動機與目的 4
第二章 理論原理與文獻回顧 6
2.1化學感測材料簡介 6
2.1.1 辨識單元 6
2.1.2 信號傳遞單元 7
2.2化學感測材料的設計原理 8
2.2.1鍵結位置-信號單元法 (Binding Site-Signaling Subunit Approach) 8
2.2.2置換法 (Displacement Approach) 9
2.2.3 Chemodosimeter法 (Chemodosimeter Approach) 10
2.3螢光化學感測材料之機制 12
2.3.1光誘導電子轉移 (PET) 12
2.3.2電子能量轉移 (EET) 13
2.3.3分子內電荷轉移 (ICT) 14
2.3.4單體-激態複合物形成 (Monomer-Excimer Formation) 15
2.4化學感測材料之文獻回顧 17
2.4.1苯胺衍生物為基底的陰離子感測材料 17
2.4.2苯胺衍生物為基底的陽離子感測材料 24
第三章 實驗部分 29
3.1實驗流程圖 29
3.1.1 化學感測材料CDRS實驗流程圖 29
3.1.2 化學感測材料CAS實驗流程圖 29
3.2檢測儀器 30
3.3實驗儀器與藥品溶劑 32
3.3.1實驗藥品 32
3.3.2實驗溶劑 35
3.4合成與檢測 36
3.4.1 Aniline trimer合成 (AT) 36
3.4.2 Colorimetric dual responsive sensor合成 (CDRS) 37
3.4.3 Cation-Amino acid sensor合成 (CAS) 39
3.5化學感測材料與離子溶液之配製 41
3.5.1 CDRS與陰離子溶液之配置 41
3.5.2 CAS與陽離子溶液之配置 41
3.5.3 CAS與銅離子與胺基酸離子溶液之配置 41
3.6化學感測材料與陰離子的感測機制之實驗方法 42
3.7 Benesi-Hildebrand Method 43
3.8感測極限 45
3.9 Job’s Method 46
第四章 實驗結果與討論 47
4.1 硫脲系統CDRS之特性 47
4.1.1化學感測材料CDRS對陰離子之顏色變化計量測試 47
4.1.2化學感測材料CDRS對陰離子的感測機制 54
4.1.3化學感測材料CDRS在多重陰離子中之感測能力 56
4.1.4試紙製備與應用 57
4.1.5化學感測材料CDRS之pH值感測 59
4.1.6化學感測材料CDRS之雙重感測 ( pH值、陰離子) 61
4.2光學硫脲系統CAS之特性 63
4.2.1化學感測材料CAS對陽離子之顏色變化計量測試 63
4.2.2化學感測材料CAS對陽離子之感測機制 75
4.2.3化學感測材料CAS在多重陽離子中之感測能力 77
4.2.4試紙製備與應用 78
4.2.5化學感測材料CAS之pH值感測 79
4.2.6化學感測材料CAS之雙重感測特性 ( pH值、陽離子) 81
4.2.7化學感測材料CAS之雙重選擇性感測(陽離子、胺基酸) 84
第五章 結論 86
參考文獻 88

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