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C6H的衍生物:C6H-Aldehyde以及C6H-Imine，以1H-NMR核磁共振光譜與FTIR光譜鑑定其結構，以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，並與作者Sisi Wang等人之香豆素衍生物CuCIN做比較。

研究結果顯示，相較於未環化結構的香豆素CuCIN，具有剛性胺基環化結構的香豆素C6H-Imine具有較好的UV-Vis吸收及螢光特性。此外，C6H-Imine的結構可設計為銅離子之光學感測器，當添加銅離子時，其能靈敏地辨認，肉眼可看到C6H-Imine溶液的顏色由黃色變成紅色。其中當銅離子添加，可看見吸收光譜藍移，且螢光強度降低了3倍，這些結果說明C6H-Imine對於銅離子具有高的選擇性及靈敏度，顯示C6H-Imine在螢光感測銅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, C6H-Aldehyde and C6H-Imine) were characterized by 1H-NMR and FTIR spectra. The photophysical properties of the C6H-Imine were studied by absorption and steady-state fluorescence spectroscopy in acetonitrile, and compared with the CuCIN.

The photophysical results showed that the C6H-Imine with rigid amine cyclization has a relatively good UV-Vis absorption and fluorescence characteristics than the CuCIN. The C6H-Imine was designed and used as an optical chemosensor for metal ions and could recognize Cu2+ sensitively in acetonitrile solution. Upon addition of Cu2+, the color of the solution of C6H-Imine changed from yellow to red, respectively, and it could easily observed by naked eyes. The addition of Cu2+ into the acetonitrile solution of the C6H-Imine, a blue shift of the absorption band was observed and emission band was turned off 3-fold in the fluorescence intensity. The results showed that the C6H-Imine has good selectivity and sensitivity and could be found potential applications in fluorescent chemosensor of Cu2+.

目錄
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
摘要…………………………………..………………………………………..iii
Abstract……………………………………………………………..………….iv
目錄…………………………………………………………………………….v
圖目錄……….………………………………………………….....…………viii
表目錄…………...……………………………………………. .………..……xi
第一章 緒論…………………………………………………………………...1
第二章 文獻回顧……………………………………………………………...3
2-1 認識香豆素及其應用……………………………………………….3
2-2 香豆素的合成……………………………………………………….5
2-2-1 Perkin反應…………………………………………………...5
2-2-2 Pechmannn縮合反應………………………………………...6
2-2-3 Knoevenagel縮合反應……………………………………….6
2-2-4 Witting反應………………………………………………..7
2-2-5 Claisen反應…………………………………………………..8
2-2-6 Vilsmeier Haack反應………………………………………...9
2-2-7 Petersen Olefination反應…………………………………….9
2-3 有機光化學………………………………………………………..10
2-4 螢光光譜原理……………………………………………………..13
2-4-1 螢光及磷光………………………………………………….13
2-4-2 影響螢光的因素…………………………………………….18
2-5 化學感測器………………………………………………………...22
2-5-1 感測器組成………………………………………………….23
2-5-2 分子辨識…………………………………………………….24
2-5-3 信號轉換…………………………………………………….26
2-5-4 感測器作用機制…………………………………………….27
2-6 Cu2+螢光感測器………...…………..……………………………..31
2-7 研究動機…………………………..…………………………..…..35
第三章 實驗方法…………………………………………………………...38
3-1 實驗藥品…………………………………………………………..38
3-2 儀器設備…………………………………………………………..41
3-3 實驗流程…………………………………………………………..43
3-3-1 以8-Hydroxyjulolidine為起始物合成9-Formyl-8- hydroxyjulolidine……....……………43
3-3-2 以9-Formyl-8-hydroxyjulolidine合成C6H……....………44
3-3-3 以C6H合成C6H-Aldehyde…....………………………...45
3-3-4 以C6H-Aldehyde合成C6H-Imine……………………….46
第四章 結果與討論….…………………………………………………….47
4-1 以8-Hydroxyjulolidine為起始物合成9-Formyl-8-hydroxyjulolidine…………………………...47
4-2 以9-Formyl-8-hydroxyjulolidine合成C6H……………………...51
4-3 以C6H合成C6H-Aldehyde……………………………………...55
4-4 以C6H-Aldehyde合成C6H-Imine………………………………59
4-5 化合物光物理性質分析…………………………………………..62
4-6 C6H-Imine應用於金屬離子之螢光感測分析……………….…..66
4-7 C6H-Imine應用於銅離子感測……………….…………………..72
第五章 結論………………………………………………………………...75
參考文獻……………………………………………………………………...76
附錄…………………………………………………………………………..80
 
圖目錄
圖2-1、香豆素的結構………………………………………………………...3
圖2-2、Perkin反應合成香豆素………………………………………………5
圖2-3、Pechmannn縮合反應合成香豆素…………………………………...6
圖2-4、Knoevenagel縮合反應合成香豆素………………………………….6
圖2-5、Witting反應合成香豆素……………………………………………..7
圖2-6、Claisen反應合成香豆素……………………………………………..8
圖2-7、Petersen Olefination反應合成香豆素……………………………….9
圖2-8、甲醛的分子軌域示意圖…….……………………………………….11
圖2-9、電磁輻射全譜、引發過程的類型、相應的光譜學名詞術語…..…...12
圖2-10、描述一般吸收、發光及非輻射躍遷的Jablonski圖……….………..15
圖2-11、雜環化合物的螢光性……………………………………....………..19
圖2-12、感測器的組成………...……………………………………………..23
圖2-13、化學感測器單元作用示意圖………...……………………………..23
圖2-14、互補結構示意圖………………………………………..…………...25
圖2-15、PET探針對離子的傳遞機制圖…………………….……………...28
圖2-16、ICT之螢光傳遞機制……………………….………………………29
圖2-17、羅丹明衍生物檢測金屬離子的螢光強度…………….……………32
圖2-18、羅丹明衍生物檢測Cu2+的螢光光譜….………..………….………..32
圖2-19、氨基脲衍生物檢測Cu2+催化水解機制……………………………..33
圖2-20、氨基脲衍生物檢測Cu2+的螢光光譜………...……….……………..33
圖2-21、萘二甲醯亞胺衍生物檢測金屬離子的螢光強度…….…………....34
圖2-22、萘二甲醯亞胺衍生物檢測Cu2+的螢光光譜……….………….…..34
圖2-23、香豆素C-35、C-355及C-153的分子結構……….…………..……..35
圖4-1、9-Formyl-8-hydroxyjulolidine之1H NMR光譜圖………………...48
圖4-2、9-Formyl-8-hydroxyjulolidine之FTIR光譜圖…………………….49
圖4-3、9-Formyl-8-hydroxyjulolidine合成的反應機制……………………50
圖4-4、C6H之1H NMR光譜圖……………………………………………52
圖4-5、C6H之FTIR光譜圖………………………………………………..53
圖4-6、C6H合成的反應機制………………………………………………54
圖4-7、C6H-Aldehyde之1H NMR光譜圖…...……………………………56
圖4-8、C6H-Aldehyde之FTIR光譜圖…………………………………….57
圖4-9、C6H-Aldehyde合成的反應機制……………………………………58
圖4-10、C6H-Imine之FTIR光譜圖……………………………………….60
圖4-11、C6H-Imine合成的反應機制………………………………………61
圖4-12、CuCIN與C6H-Imine之結構比較……………………….…….…63
圖4-13、CuCIN與C6H-Imine之UV-Vis吸收光譜圖………………………64
圖4-14、CuCIN與C6H-Imine之螢光光譜圖………..………………………64
圖4-15、C6H-Imine與等濃度(1×10-4 M)金屬離子在可見光下之觀測圖…66
圖4-16、C6H-Imine在等濃度(1×10-4 M)不同金屬離子下之UV-Vis吸收光譜圖…………………………………………………………….68
圖4-17、C6H-Imine在等濃度(1×10-4 M)不同金屬離子下之螢光光譜圖……………………………………………………………...…68
圖4-18、C6H-Imine在等濃度(1×10-4 M)銅離子與不同金屬離子下之UV-Vis吸收光譜圖……………………………………………………70
圖4-19、C6H-Imine在等濃度(1×10-4 M)銅離子與不同金屬離子下之螢光光譜圖……………………………………………………………70
圖4-20、C6H-Imine在等濃度(1×10-4 M)銅離子與不同金屬離子下之螢光強度比較 圖…………………………………………………………....71
圖4-21、C6H-Imine在不同濃度的銅離子之UV-Vis吸收光譜圖…………..73
圖4-22、C6H-Imine在不同濃度的銅離子之螢光光譜圖……….…………..73
圖4-23、C6H-Imine在不同濃度的銅離子之螢光強度變化……….………..74
Scheme 2-1、CuCIN的合成反應路徑………………………………………36
Scheme 2-2、C6H-Imine的合成反應路徑………………………………….37
Scheme 3-1、9-Formyl-8-hydroxyjulolidine的合成路徑…………………...43
Scheme 3-2、C6H的合成路徑………………………………………………44
Scheme 3-3、C6H-Aldehyde的合成路徑…………………………………...45
Scheme 3-4、C6H-Imine的合成路徑……………………………………….46
 
表目錄
表2-1、香豆素C-35、C-355及C-153在乙醇中的螢光性質……………..35
表3-1、實驗藥品…….……………………………………………………….38
表3-2、實驗儀器…….……………………………………………………….40
表4-1、CuCIN與C6H-Imine之光物理數據………………………………65

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