The Effect of Conjugation on the Competition between Internal Conversion and Electron Detachment: A Comparison between Green Fluorescent and Red Kaede Protein Chromophores.

The Effect of Conjugation on the Competition between Internal Conversion and Electron Detachment: A Comparison between Green Fluorescent and Red Kaede Protein Chromophores.
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共轭对内部转换和电子脱离之间竞争的影响:绿色荧光和红色 Kaede 蛋白发色团的比较。

DOI:
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发表时间:
2017
影响因子:
5.7
通讯作者:
H. Fielding
H. Fielding
中科院分区:
化学2区
文献类型:
--
作者:
Jamie Tay;M. Parkes;K. Addison;Y. Chan;Lijuan Zhang;H. Hailes;Philip C Bulman Page;S. Meech;L. Blancafort;H. Fielding

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Kaede是一种绿色荧光蛋白(GFP)的类似物,是一种绿色到红色的光转换荧光蛋白,在生物成像中用作体内“光学荧光剂”。红色Kaede蛋白的荧光量子产率低于GFP,表明增加缀合修饰电子弛豫途径。使用阴离子光电子能谱和电子结构计算的组合,我们发现,孤立的红色Kaede蛋白质发色团在气相中的咪唑环去质子化,不像GFP发色团是去质子化的苯酚环。我们发现了一个有效的电子弛豫途径的证据,从更高的电子激发态的红色Kaede发色团的S1状态,这是无法访问的GFP发色团。发现从S1的高振动态的快速自脱离与到基态电子态的内部转换有效地竞争。
Kaede, an analogue of green fluorescent protein (GFP), is a green-to-red photoconvertible fluorescent protein used as an in vivo "optical highlighter" in bioimaging. The fluorescence quantum yield of the red Kaede protein is lower than that of GFP, suggesting that increasing the conjugation modifies the electronic relaxation pathway. Using a combination of anion photoelectron spectroscopy and electronic structure calculations, we find that the isolated red Kaede protein chromophore in the gas phase is deprotonated at the imidazole ring, unlike the GFP chromophore that is deprotonated at the phenol ring. We find evidence of an efficient electronic relaxation pathway from higher-lying electronically excited states to the S1 state of the red Kaede chromophore that is not accessible in the GFP chromophore. Rapid autodetachment from high-lying vibrational states of S1 is found to compete efficiently with internal conversion to the ground electronic state.
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