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研究生: 蕭仁傑
Hsiao, Jen-Chieh
論文名稱: 銅離子引發綠色螢光蛋白發光團類似物之環化反應:鄰位胺基上取代基的效應
Copper-ion-induced Ring-closure Reactions of Green Fluorescent Protein Chromophore Derivatives:Effects from Substituents on the alpha-Amino Group
指導教授: 宋光生
Sung, Kuang-Sen
學位類別: 碩士
Master
系所名稱: 理學院 - 化學系
Department of Chemistry
論文出版年: 2023
畢業學年度: 111
語文別: 中文
論文頁數: 46
中文關鍵詞: 銅(II)環化取代基
外文關鍵詞: copper(II), cyclization, substituent
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  • 在過去的研究中,實驗室的黃世昱學長嘗試使用o-ABDI的衍生物與銅(II)錯合物進行養晶的過程中得到環化的產物,在過去的文獻當中也有使用銅離子做為添加物所進行的含氮雜環合成反應,這展現了銅(II)作為添加物進行環化的可能性。
    在本文中將研究以綠色螢光蛋白衍生物o-ABDI為起始物進行親核取代改變其鄰位上的取代基,再與銅(II)進行環化反應並觀察含有不同取代基對於反應的影響,還有產物的光譜性質差異。
    我們使用o-ABDI以及其鄰位取代基改變為帶有立體障礙、酸鹼性或拉電子基的取代基進行環化反應,發現環化後的產物在吸收光譜上與過去實驗室將具有diol moiety的化合物進行環化後的光譜有相似的結果,都產生藍移的現象,並且這樣的現象也出現在螢光光譜上。

    In the past research, Shih-Yu Huang, a senior in the laboratory, used o-ABDI derivatives and copper(II) complexes to obtain cyclized products, instead of expecting crystal product. In the past literature, there are also nitrogen-containing heterocycle synthesis reactions using copper ions as additives, which shows the possibility of copper(II) as additives for cyclization.
    In this paper, we try to change the substituent on the ortho-position of o-ABDI derivatives and observe the effects of different substituents on the cyclization reaction and try to figure out the influence of o-ABDI derivatives with different substituents and the different in the spectral properties of the products.

    中文摘要 i 致謝 xiii 表目錄 xvi 圖目錄 xvii 第I部分 序論 1 I-1 人工合成綠色螢光蛋白發光團(p-HBDI) 1 I-2 提高合成綠色螢光蛋白發光團及衍生物螢光的方法 2 I-3 銅離子性質簡介9 3 I-4 以金屬為添加物進行的反應 4 I-4-1 銅(II)催化反應 4 I-4-2 o-ABDI衍生物環化反應 6 I-5 實驗動機 8 第II部分 結果與討論 9 II-1 綠色螢光蛋白衍生物o-ABDI及其衍生物環化的合成路徑 9 II-2 取代基變化對於反應的影響 10 II-3 含不同取代基的光譜性質 11 II-3-1 取代基及環化對光譜性質的影響 12 II-4 結論 15 第III部分 實驗儀器及實驗方法 17 III-1 實驗儀器 17 III-1-1 核磁共振光譜儀(Nuclear Magnetic Resonance Spectrometer) 17 III-1-2 高解析質譜儀(High Resolution Mass Spectrometry, ESI-MS) 17 III-1-3 紫外-可見光光譜儀(UV-Vis Spectrometry, PerkinElmer) 17 III-1-4 螢光放射光譜儀(Fluorescence Spectrometer, PerkinElmer, LS 45) 17 III-2 綠色螢光蛋白衍生物的合成 18 III-2-1 合成o-ABDI四步驟20 18 III-2-2 合成o-NHABDI步驟22 20 III-2-3 合成o-BBDDI步驟22 20 III-2-4 合成m-DPABDI步驟22 21 III-2-5 o-NHABDI環化 22 III-2-6 o-BBDDI環化 22 III-2-7 o-ABDI環化 23 III-2-8 m-DPABDI環化 23 III-3 o-ABDI及其衍生物環化後基本物理性質的測定 24 III-3-1 吸收光譜的測定及莫爾吸收係數的計算 24 III-3-2 螢光光譜測定 24 III-3-3 標準液校正以及計算螢光量子產率 24 第IV部分 參考文獻 25 第V部分 附錄 28

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