| 研究生: |
程靖雯 Chen, Jing-Wen |
|---|---|
| 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:
反應機制的探討 Copper-ion-induced Cyclization Reaction of Green Fluorescent Protein Chromophore Derivatives: Discussion on Reaction Mechanism |
| 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: | 2025 |
| 畢業學年度: | 113 |
| 語文別: | 中文 |
| 論文頁數: | 92 |
| 中文關鍵詞: | 銅離子(Ⅱ) 、環化反應 、反應機制 |
| 外文關鍵詞: | copper(II), cyclization, mechanism |
| 相關次數: | 點閱:52 下載:0 |
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在過去的研究中,黃世昱學長嘗試使用o-ABDI的衍生物o-DHPBDI與銅(II)試劑進行螯合反應意外得到環化產物DHPIO,當時並未對其真正之反應機制深入探討。也發現到相較起始物o-DHPBDI其螢光量子產率也有提升。
本文中原先將針對此o-DHPBDI環合反應的機制深入探討,藉由加入自由基捕捉劑TEMPO觀察到能夠阻斷2種環化產物生成,通過再結晶的方式得產物HMTA其真實結構,推測此環合反應確實經過自由基路徑,然而從原先環化產物結構DHPIO、DHPIO-Cl發現與HMTA存在明顯的不同,推測TEMPO可能作為氧化劑開啟另一條新的環化路徑,而HMTA為主產物產率最高達70.5%,解決了原先o-DHPBDI環合反應存在大量副產物DHPIO-Cl。
最後在電子吸收及螢光放射光譜觀察到因為HMTA結構更具剛性相較於o-DHPBDI產生明顯藍移的現象,也因為旋轉及振動自由度皆明顯下降,其螢光量子產率也比原先環化產物DHPIO、DHPIO-Cl增加了10倍之多。
In previous research, Huang Shiyu tried to use o-DHPBDI and copper (II) reagent for chelation reaction and accidentally obtained cyclization product DHPIO. At that time, the actual reaction mechanism was not deeply explored. It was also found that the fluorescence quantum yield was also improved compared with the starting material o-DHPBDI.
In this paper, the reaction mechanism of this cyclization reaction was originally studied in depth. By adding the free radical scavenger TEMPO, it was observed that the formation of two cyclization products could be blocked. It was speculated that this cyclization reaction did go through the free radical pathway. However, the original cyclization product structures DHPIO and DHPIO-Cl were found to be significantly different from HMTA. TEMPO may act as an oxidant to start another new cyclization reaction. The yield of HMTA as the main product is as high as 70.5%, which solves the problem of the original o-DHPBDI cyclization reaction with a large amount of by-product DHPIO-Cl.
Finally, in the electronic absorption and fluorescence emission spectra, it was observed that HMTA had a more rigid structure than o-DHPBDI and produced a significant blue shift. Also, because the rotational and vibrational freedoms were significantly reduced, its fluorescence quantum yield is also 10 times higher than that of the original cyclization products DHPIO and DHPIO-Cl.
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