Photodetachment spectra of deprotonated fluorescent protein chromophore anions.

Photodetachment spectra of deprotonated fluorescent protein chromophore anions.
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去质子化荧光蛋白发色团阴离子的光脱离光谱。

DOI:
10.1021/jp3058349
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发表时间:
2012
期刊:
The journal of physical chemistry. A
影响因子:
--
通讯作者:
Mooney CR
Mooney CR
中科院分区:
--
文献类型:
--
作者:
Mooney CR

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在电喷雾离子源中产生绿色和青色荧光蛋白的孤立模型阴离子发色团,并且使用光电子成像记录它们的光分离光谱。垂直光剥离能量为2.85(10)和4.08(10)eV的模型绿色荧光蛋白发色团阴离子已被测量,对应于从阴离子的基态电子态的自由基的基态和第一激发电子态的光剥离,分别。对于模型青色荧光蛋白发色团阴离子,垂直光剥离能量为2.88(10)和3.96(10)eV的已被测量,分别对应于从阴离子的基态电子态到中性自由基的基态和第一激发电子态的剥离。我们还发现证据表明,发色团阴离子的电子激发态的自电离与直接光剥离竞争。为了比较和基准我们的测量,垂直光剥离能量的去质子化的苯酚和吲哚阴离子也被记录和提出。量子化学计算支持我们的作业。我们在分离的蛋白质发色团阴离子作为电子供体的背景下讨论了我们的结果,这是它们潜在的生物学功能之一。
Isolated model anion chromophores of the green and cyan fluorescent proteins were generated in an electrospray ion source, and their photodetachment spectra were recorded using photoelectron imaging. Vertical photodetachment energies of 2.85(10) and 4.08(10) eV have been measured for the model green fluorescent protein chromophore anion, corresponding to photodetachment from the ground electronic state of the anion to the ground and first excited electronic states of the radical, respectively. For the model cyan fluorescent protein chromophore anion, vertical photodetachment energies of 2.88(10) and 3.96(10) eV have been measured, corresponding to detachment from the ground electronic state of the anion to the ground and first excited electronic states of the neutral radical, respectively. We also find evidence suggesting that autoionization of electronically excited states of the chromophore anions competes with direct photodetachment. For comparison and to benchmark our measurements, the vertical photodetachment energies of deprotonated phenol and indole anions have also been recorded and presented. Quantum chemistry calculations support our assignments. We discuss our results in the context of the isolated protein chromophore anions acting as electron donors, one of their potential biological functions.
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