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、硝基還原反應以及胺醛縮合反應合成香豆素Coumarin 6H衍生物(C6H-NO2、C6H-NH2與化合物A)，以1H-NMR、FTIR光譜和MASS質譜鑑定其結構，並用吸收光譜及螢光光譜研究這些香豆素染料在二氯甲烷及乙腈/水溶劑中的光物理性質。
此外，化合物A的結構設計可作為鋅離子及鈷離子之光學感測器，當添加鋅離子及鈷離子，其能靈敏地辨認，肉眼就可以看到化合物A乙腈/水溶液的顏色由黃變成橘色。而其中鋅離子的添加，可看見吸收光譜的紅移以及出現475 nm等吸收點，螢光放射則呈現藍移，並且大大地增強其螢光強度，這些結果顯示化合物A在螢光感測鋅離子的應用有很大的潛力。

In this study, coumarin 6H derivatives (C6H-NO2, C6H-NH2 and compound A) had been successfully synthesized by Vilsmeier reaction, Knoevenagel condensation, reduction and condensation of primary amine and aldehyde. The structures of these coumarin dyes were characterized by 1H-NMR, FTIR and MASS spectra. The photophysical properties of these dyes were studied by absorption and steady-state fluorescence spectroscopy in dichloromethane and acetonitrile/water (9:1).
The compound A was designed and used as an optical chemosensor for metal ion and could recognize Zn2+ and Co2+ sensitively in acetonitrile/water (9:1) solution. Upon addition of Zn2+ and Co2+, the color of the solution of compound A changed from yellow to orange and it could easily observed by naked eyes. The addition of Zn2+ into the acetonitrile/water solution of the compound A, a red shift of the absorption band was observed with a isosbetic point at 475 nm while the emission band blue-shifted and induced the enhancement in the fluorescence intensity. The results showed that the compound A could be found potential applications in fluorescent chemosensor of Zn2+.

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
明志科技大學學位論文授權書…………………………………………...……iii
誌謝………………………………………………………………………...……iv
摘要…………………………………………………………………..……...…...v
Abstract………………………………………………………………………...vi
目錄…………………………………………………………………………...vii
圖目錄………………………………………………………...…………….…ix
表目錄……………………………………………………………………..…...xii
第一章 緒論……………………………………………………….…………….1
第二章 文獻回顧……………………………. ………………………….……...2
2-1 香豆素簡介………………………………………………….……………2
2-2 香豆素的合成………………………………………………….…………3
2-3 螢光染料………………………………………………………….………7
2-4 有機光化學…………………………………………………...…………11
2-4-1 螢光及磷光………………………………………………….……13
2-4-2 量子產率………………………………………………….………15
2-4-3 影響螢光的因素………………………………………….………15
2-5 化學感測器……………………………………………………...………16
2-5-1 感測器的組成…………………………………………………….17
2-5-2 分子辨識………………………………………………………….19
2-5-3 感測器作用機制……………………………………………….…22
2-6 研究動機……………………………………………………29
第三章 實驗方法………………………………………………………...…….32
3-1 實驗藥品…………………………………………………………..…….32
3-2 儀器設備…………………………………………………………...……34
3-3 實驗流程…………………………………………………………...……36
3-3-1 以8-hydroxyjulolidine為起始物微波合成9-formyl-8-hydroxyjulolidine……………...…………….….……36
3-3-2 以9-formyl-8-hydroxyjulolidine為起始物合成C6H-NO2………………………………………….………..……..37
3-3-3 以C6H-NO2為起始物合成C6H-NH2…………………………...38
3-3-4 以C6H-NH2為起始物合成Compound A……………………..…39
3-3-5 C6H-NO2、C6H-NH2與Compound A光物理性質之研究……..40
第四章 結果與討論………………………………………….……………..….41
4-1 以8-hydroxyjulolidine為起始物微波合成9-formyl-8-hydroxyjulolidine…………………………....……….….…41
4-2 以9-formyl-8-hydroxyjulolidine為起始物合成 C6H-NO2……………46
4-3 以C6H-NO2為起始物合成C6H-NH2………………….……………....51
4-4 以C6H-NH2為起始物合成Compound A……………………………...55
4-5 合成物的光物理性質分析…………………………………………...…60
4-6 Compound A作用於金屬離子感測.......................................................65
第五章 結論...…………………………..……..………………………….……74
參考文獻……………………………………………………………..………....75

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