臺灣博碩士論文加值系統

本研究以8-Hydroxyjulolidine為起始物，利用Vilsmeier反應、Knoevenagel縮合反應、水解反應以及醛胺縮合反應分別合成出一系列C6H的衍生物：C6H-Ethyl ester、C6H、C6H-Aldehyde以及C6H-Imine，以1H-NMR核磁共振光譜、FTIR光譜以及MASS質譜鑑定其結構，利用UV-Vis吸收光譜及螢光光譜研究這些香豆素染料在乙腈溶劑中的光物理性質，並與本實驗室許瑞宏學長之香豆素衍生物C6H-Imine(methyl)做比較。
研究結果顯示，比起C6H-Imine(methyl)，C=N鍵上沒有甲基的C6H-Imine有較好的UV-Vis吸收以及螢光特性。此外，C6H-Imine的結構設計可作為鋅離子、鎂離子及鈷離子之光學感測器，當添加鋅離子、鎂離子及鈷離子時，其能靈敏地辨認，肉眼就可以看到C6H-Imine溶液的顏色由黃色分別變成螢光綠(鋅與鎂離子)及深紫紅色(鈷離子)。其中鋅與鎂離子的添加，可看見吸收光譜的紅移以及出現450 nm等吸收點，且螢光強度分別增強了4倍及7倍，這些結果顯示C6H-Imine在螢光感測鋅、鎂離子的應用具有很大的潛力。

In this study, coumarin derivative (C6H-Imine) had been successfully synthesized by Vilsmeier reaction, Knoevenagel condensation, hydrolysis and condensation of amine and aldehydes. The structures of these coumarin dyes (C6H-Ethyl ester, C6H, C6H-Aldehyde and C6H-Imine) were characterized by 1H-NMR, FTIR and MASS spectra. The photophysical properties of the C6H-Imine were studied by absorption and steady-state fluorescence spectroscopy in acetonitrile, and compared with the C6H-Imine(methyl).
The photophysical results showed that the C6H-Imine without a methyl group on C=N has a relatively good UV-Vis absorption and fluorescence characteristics than the C6H-Imine(methyl). The C6H-Imine was designed and used as an optical chemosensor for metal ions and could recognize Zn2+, Mg2+and Co2+ sensitively in acetonitrile solution. Upon addition of Zn2+, Mg2+ and Co2+, the color of the solution of C6H-Imine changed from yellow to bright green (for Zn2+, Mg2+) and to purple (for Co2+), respectively, and it could easily observed by naked eyes. The addition of Zn2+ and Mg2+ into the acetonitrile solution of the C6H-Imine, a red shift of the absorption band was observed with an isosbestic point at 450 nm and emission band was enhanced in the fluorescence intensity. The results showed that the C6H-Imine could be found potential applications in fluorescent chemosensor of Zn2+ and Mg2+.

明志科技大學碩士學位論文指導教授推薦書 i
明志科技大學碩士學位論文口試委員審定書 ii
致謝 iii
摘要 iv
Abstract v
目錄 vi
圖目錄 ix
表目錄 xiv
第一章 緒論 1
第二章 文獻回顧 2
2-1 香豆素簡介及其應用 2
2-2 香豆素的合成 3
2-2-1 Perkin 反應 3
2-2-2 Pechmann 反應 4
2-2-3 Knoevenagel 縮合反應 5
2-2-4 Claisen 反應 5
2-2-5 Wittig 反應 6
2-2-6 Vilsmeier Haack 反應 7
2-2-7 Petersen Olefination 反應 7
2-3 有機光化學 8
2-4 螢光光譜原理 10
2-4-1 螢光及磷光 10
2-4-2 影響螢光及磷光的因素 12
2-5 化學感測器 15
2-5-1 感測器組成 15
2-5-2 分子辨識 16
2-5-3 信號轉換 17
2-5-4 感測器作用機制 18
2-6 香豆素螢光感測器 22
2-7 研究動機 27
第三章 實驗方法 30
3-1 實驗藥品 30
3-2 儀器設備 34
3-3 實驗流程 36
3-3-1 以8-Hydroxyjulolidine為起始物合成9-Formyl-8-hydroxyjulolidine 36
3-3-2 以9-Formyl-8-hydroxyjulolidine合成C6H-Ethyl ester 37
3-3-3 以C6H-Ethyl ester 水解成C6H 38
3-3-4 以C6H合成C6H-Aldehyde 39
3-3-5 以C6H-Aldehyde合成C6H-Imine 40
第四章 結果與討論 41
4-1 以8-Hydroxyjulolidine為起始物合成9-Formyl-8-hydroxyjulolidine 41
4-2 以9-Formyl-8-hydroxyjulolidine合成C6H-Ethyl ester 46
4-3 以C6H-Ethyl ester水解成C6H 51
4-4 以C6H合成C6H-Aldehyde 56
4-5 以C6H-Aldehyde合成C6H-Imine 61
4-6 化合物光物理性質分析 66
4-7 C6H-Imine應用於金屬離子之螢光感測分析 70
4-7-1 C6H-Imine應用於鋅離子感測 74
4-7-2 C6H-Imine應用於鎂離子感測 77
4-7-3 C6H-Imine應用於鈷離子感測 80
4-7-4 C6H-Imine應用於鉀離子感測 82
第五章 結論 84
參考文獻 85
附錄 88

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