Photoionization and electron radical recombination dynamics in photoactive yellow protein investigated by ultrafast spectroscopy in the visible and near-infrared spectral region.

Photoionization and electron radical recombination dynamics in photoactive yellow protein investigated by ultrafast spectroscopy in the visible and near-infrared spectral region.
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通过可见光和近红外光谱区的超快光谱研究光敏黄色蛋白的光电离和电子自由基重组动力学。

DOI:
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发表时间:
2013
影响因子:
3.3
通讯作者:
M. Groot
M. Groot
中科院分区:
化学3区
文献类型:
--
作者:
Jingyi Zhu;Laura Paparelli;M. Hospes;J. Arents;J. Kennis;I. V. van Stokkum;K. Hellingwerf;M. Groot

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利用超快光谱技术研究了光敏黄蛋白(PYP)内生色团的光致电离。观察到从约550至850 nm延伸的吸收带,并归因于溶剂化电子,在吸收两个400 nm光子后从对羟基肉桂酸阴离子发色团射出。全局动力学分析表明,溶剂化电子吸收衰减分两个阶段:约10 ps的较短阶段和超过3 ns的较长阶段。从基于扩散模型的模拟中,我们得出结论,在野生型PYP中,电子的扩散速率约为0.8 μ(2)/ps,并且电子被喷射到距离发色团仅几埃的短距离处。生色团-蛋白质口袋为电子提供了一个类似水的局域环境,由于生色团周围不同位置的突变对电子复合动力学的影响不同,因此我们认为溶剂化电子可以为研究PYP内部的局域介电环境提供一种新的方法,从而有助于理解蛋白质在光异构化过程中的作用。
Photoinduced ionization of the chromophore inside photoactive yellow protein (PYP) was investigated by ultrafast spectroscopy in the visible and near-infrared spectral regions. An absorption band that extended from around 550 to 850 nm was observed and ascribed to solvated electrons, ejected from the p-hydroxycinnamic acid anion chromophore upon the absorption of two 400 nm photons. Global kinetic analysis showed that the solvated electron absorption decayed in two stages: a shorter phase of around 10 ps and a longer phase of more than 3 ns. From a simulation based on a diffusion model we conclude that the diffusion rate of the electron is about 0.8 Å(2)/ps in wild type PYP, and that the electron is ejected to a short distance of only several angstroms away from the chromophore. The chromophore-protein pocket appears to provide a water-similar local environment for the electron. Because mutations at different places around the chromophore have different effect on the electron recombination dynamics, we suggest that solvated electrons could provide a new method to investigate the local dielectric environment inside PYP and thus help to understand the role of the protein in the photoisomerization process.
DOI: 10.1039/c2cp41718a
发表时间: 2012-01-01
影响因子: 3.3
作者:
Lincoln, Craig N.;Fitzpatrick, Ann E.;van Thor, Jasper J.
通讯作者: van Thor, Jasper J.
DOI: 10.1016/s0006-3495(89)82703-1
发表时间: 1989-09-01
影响因子: 3.4
作者:
MEYER, TE;TOLLIN, G;CUSANOVICH, MA
通讯作者: CUSANOVICH, MA