結合類綠色螢光蛋白發光團與二芳基乙烯分子的雙重調控螢光分子開關

具有間位胺基取代效應的類綠色螢光蛋白發光團在非質子性溶劑中有高的螢光量子產率，不過因為發光團會與質子性溶劑形成氫鍵，使發光團多了一條激發態質子轉移的去活化路徑，因此具有在質子性溶劑中螢光淬熄的特性。在各式光致變色分子中，二芳基乙烯分子中的 dithienylethene (DTE)分子具有光致開合環的特性與良好的熱穩定性，而且無論是開環或合環產物皆展現良好的疲勞阻抗性，所以常被應用在分子開關上。本論文主要內容為結合具有間位胺基取代效應的類綠色螢光蛋白發光團與 dithienylethene (DTE)分子，合成出兩個具有雙重調控螢光系統的分子開關化合物DTE-m-D1A1 與DTE’-m-D8A1，希望在液態中可以透過改變溶劑的極性來調控其螢光開與關，而在聚集狀態下則是透過分子的光致開合環特性來調控其螢光開與關。由結果顯示 DTE-m-D1A1 與DTE’-m-D8A1 雖然在液態以及聚集狀態下皆可以滿足我的分子設計概念，但是由於dithienylethene (DTE)分子中的噻吩結構會淬熄綠色螢光蛋白發光團的螢光，造成分子先天的螢光偏弱，進而影響到聚集引致發光的轉換效率，使螢光開關間的轉換不甚完美。了解造成螢光開關轉換效率差的原因之後，未來也可以透過取代噻吩結構來提高螢光開關的轉換效率。此外，本論文也同時探討了會淬熄綠色螢光蛋白發光團螢光的基團，無論是在液態、聚集狀態下或是具有胺基酸的環境下，建立基本的資料庫有利於後續研究的進行。

關鍵字

綠色螢光蛋白發光團；二芳基乙烯分子；聚集引致發光

並列摘要

Meta-amino-substituted green fluorescence protein chromophore (GFPc) (m-DMABDIs) are highly emissive in aprotic solvents. However hydrogen bonding interactions between the chromophore and protic solvents could induce a fast nonradiative decay process that quenches the fluorescence. Among the various types of photochromic molecules, dithienylethene (DTE) derivatives are the most promising systems for applications as molecular switches, because they undergo ring-closing and ring-opening reactions when irradiated with UV and visible light repeatedly, with an excellent thermal stability and a high degree of fatigue resistance. This thesis aims to take the advantage of m-DMABDI chromophore and dithienylethene switch to form two fluorescent molecular switches, name DTE-m-D1A1 and DTE’-m-D8A1, that can be operated in both solution and in the aggregates. The on-off fluorescence switches rely on the solvent proticity, and the on-off switch in the aggregate form relies on the ring-closing and ring-opening reactions of the dithienylethene moiety. The results show that DTE-m-D1A1 and DTE’-m-D8A1 perform the expected properties, but the thiophene groups of dithienylethene lower the fluorescence of the chromophore, making the efficiency of AIE not ideal and thus the low on-off fluorescent ratio in the aggregates. A non-thiophene switch might improve the performance. We also systematically investigated the potential quenchers of m-DMABDI to facilitate the future design of related systems.

並列關鍵字

GFP chromophore ； dithienylethene ； aggregation induced emission

參考文獻

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結合類綠色螢光蛋白發光團與二芳基乙烯分子的雙重調控螢光分子開關

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