類綠螢光蛋白發光團的取代基效應對發光性質影響之研究

綠螢光蛋白有相當高的螢光量子產率~0.79，但是發光團單獨在溶液中螢光量子產率卻極低。我們實驗室開發之間位胺基取代類綠螢光蛋白發光團m-DMABDI在正己烷中則有相當高的螢光量子產率~0.46。取代基如何影響m-DMABDI螢光量子產率為本論文之研究目的。焠熄m-DMABDI螢光的兩種原因分別為E-Z異構化以及氫鍵所導致的質子轉移，因此本論文從此二方面進行研究與討論。 E-Z異構化是激發態S1跨越活化能來到P1*態而進行，若P1*態視為雙鍵部分的電荷分離的情形，我們預期鄰位具有氰基取代的m-DMABDI衍生物，由於氰基的拉電子效應會使P1*能態上升而不利於異構化反應。另外，m-DMABDI衍生物容易與質子性溶劑產生氫鍵而造成螢光焠熄，先前實驗室曾以長碳鏈修飾而創造疏水性環境而螢光增強，我們也將此設計在氰基取代的m-DMABDI上。本論文另一工作為延續先前實驗室OH系列化合物之氫鍵效應研究工作，探討溫度變化對於此系列且分子內氫鍵發光團之吸光及螢光的影響。隨著老年化社會的來臨，造成阿茲海默症主因的類澱粉變性蛋白 (amyloid)的相關研究是當前熱門議題，因此我們嘗試利用m-DMABDI衍生物作為偵測類澱粉變性蛋白的螢光探針。

關鍵字

綠色螢光蛋白發光團；取代基效應

並列摘要

Meta-amino-substituted green fluorescence protein chromophore (GFPc) (m-DMABDIs) are emissive in aprotic solvents. However hydrogen bonding interactions between the chromophores and protic solvents could induce a fast non-radiative decay process and quench the fluorescence. This thesis is aimed to investigate the fluorescence behave of m-DMABDIs. The E-Z isomerization in the S1 state competes with the fluorescence of GFPc. The meta-amino group could largely increase the barrier for the isomerization and thus enhance the fluorescence. We designed a cyano substituted m-DMABDI to further increase the torsional barrier and to enhance the fluorescence. Another part of this work is to study the intramolecular H-bonded systems, the OH series, by investigating the variable temperature electronic absorption and emission spectra. As the chromophores are sensitive to H-bonding condition, we choose amyloid protein, which plays an important role in Alzheimer's disease, to investigate if the m-DMABDIs could turn on the fluorescence in response to amyloid protein

並列關鍵字

GFP ； green fluorescence protein-like chromophores ； substituent effect

參考文獻

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國際替代計量

類綠螢光蛋白發光團的取代基效應對發光性質影響之研究

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