臺灣博碩士論文加值系統

本實驗室過去發現間位胺基取代類綠螢光蛋白發光團能有效地提高螢光量子產率，例如：m-DMABDI在正己烷中的螢光量子產率高達0.46，並在質子性溶劑中具螢光淬滅的特性，這一類的發光團也被成功的應用至人類乳腺上皮細胞做細胞顯影，在細胞中呈現綠色螢光。
本論文內容指在將m-DMABDI做結構修飾成化合物1-4，利用非共軛 π-π 作用力，希望使其放光能更加紅位移。在結構設計上保留了間位胺基取代效應來提高螢光量子產率，以及在質子、非質子性環境中具有螢光量子產率的高度對比差異。根據Hirayama’s rule，期望能夠藉形成分子內激發錯合體得到放光紅移並高亮度的發光團，並在發光團的部位加上酯基做為m-D1Aa的前驅物；於是我們在m-DMABDI間位的胺基上修飾上苯乙基團 (n = 3)或苯丙基團 (n = 4)，除了希望使放光紅位移之外，並嘗試了解碳鏈長度在這個系統與Hirayama’s rule的關係；另外，嘗試在苯環的對位接上推、拉電子基 (-OMe、-CN)，利用增強或減弱施予體的強度改變發光團的放光波長。目前研究的結果顯示，我們所設計的分子1-4在常溫下觀測不到因分子內激發錯合體形成所造成的紅位移放光，化合物3、4因取代基效應各自藍位移及紅移大約10 nm；而我們發現化合物1在180 K低溫的環境下，螢光放光紅位移了30 nm。

Meta-Amino substituted green fluorescence protein chromophores (GFPc) such as m-DMABDI displays strong fluorescence in non-polar aprotic solvents (e.q., ϕ_f = 0.46 in n-Hex)as a result of the “meta-amino substituent effect” but undergoes fluorescence quenching in protic solvents due to solvent–solute H-bonding interactions. This type of chromophore has been applied in bioimaging, which showed green fluorescence in the hydrophobic regions of human mammary epithelial cells. However, fluorescent dyes with green emission might be interfered by autofluorescence of the biological samples. In order to avoid this problem, developing chromophores of red-shifted emission is necessary.
In this thesis, we modified the structure of m-DMABDI to four compounds 1-4 to introduce non-covalent π-π interactions for the red shift of fluorescence. Because of the meta-amino effect, the feature of high fluorescence quantum yield and high different fluorescence quantum yield between the protic and aprotic solvent are retained. Also, introducing the ester group to the imidazolinone is to enhance the water solubility upon hydrolyzed to the corresponding acid. According to the Hirayama’s rule, the fluorescence could be red-shifted upon the formation of intramolecular exciplex. The ethylbenzene (1) and propylbenzene (2) system provide the correlation of the chain length and the emission wavelength; Introducing the electron withdrawing cyano (3) and electron donating methoxy (4) to would change the donor-acceptor strength. Our results show that there are no red-shifted emission between compound 1-4 in the room temperature. Cause of the meta-amino effect, compound 3, 4 shows blue and red shift fluorescence respectively, and compound 1 is red-shifted by 30 nm at 180 K.

謝誌 i
摘要 v
Abstract vi
目錄 viii
圖目錄 xi
表目錄 xv
附圖目錄 xvi
第一章 引言 1
1-1 電磁輻射簡介 1
1-2 光物理行為 2
1-2-1 螢光量子產率 4
1-2-2 吸收度 4
1-2-3 生命期 5
1-2-4 溶劑化顯色效應(Solvatochromism) 6
1-3 光學異構化作用 7
1-4 聚集引致發光 9
1-5 生物螢光 12
1-6綠色螢光蛋白 (Green Fluorescent Proteins) 14
1-6-1 綠色螢光蛋白發光團 (Green Fluorescent Protein Chromophores) 17
1-7 綠色螢光蛋白發光團衍生物 (類GFPc) 19
1-7-1 鎖式結構 (structure confinement) 19
1-7-2 環境效應 (environment confinement) 20
1-7-3 電子效應 (kinetic confinement) 22
1-8 胺基取代之類綠色螢光蛋白發光團 23
1-9 類綠螢光蛋白發光團衍生物之細胞顯影應用 27
1-10 黃色螢光蛋白 (Yellow Fluorescent Proteins) 30
1-11 Hirayama’s rule 31
1-12 研究動機 35
第二章 結果與討論 36
2-1 目標化合物之合成與結構 36
2-1-1 目標化合物1和 2的合成 36
2-1-2 目標化合物3和 4的合成 39
2-1-3 目標化合物之結構 48
2-2 發光團之光學性質探討 51
2-2-1 吸收光譜 51
2-2-2 螢光光譜 56
2-2-3 螢光量子產率與生命期 60
2-2-4 聚集引致發光測試與固態粉末放光 62
2-2-5 化合物1之變溫吸收與放光光譜 64
第三章 結論 68
第四章 實驗儀器與方法 69
4-1 實驗藥品及溶劑 69
4-2 實驗儀器與方法 70
4-2-1 核磁共振光譜儀 (Nuclear Magnetic Resonance，400 MHz) 70
4-2-2 紫外光/可見光吸收光譜儀 (Ultraviolet/Visible Spectrophotometer) 71
4-2-3 螢光光譜儀 (Fluorescence Spectrometer) 71
4-2-4 螢光量子產率測量步驟 72
4-2-5 聚集引致發光測量步驟 73
4-2-6 紅外線吸收光譜儀(FT-Infrared Spectrometer) 74
4-2-7 高解析度質譜儀 (High resolution Mass) 74
4-2-8 X-ray 單晶繞射體 (Single-crystal X-ray Spectrometer) 74
4-2-9 溶點測定儀 75
4-2-10 溶劑純化系統 75
4-3 化合物之合成步驟 75
第五章 參考資料 87
附圖 95

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