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Primary Electronic and Vibrational Dynamics of Cytochrome c Observed by Sub-10 fs NUV Laser Pulses.
The Journal of Physical Chemistry B ( IF 3.3 ) Pub Date : 2020-08-27 , DOI: 10.1021/acs.jpcb.0c05959
Ying Kuan Ko,Atsushi Yabushita,Takayoshi Kobayashi

The primary reaction mechanism of cytochrome c (Cyt c) was elucidated for two redox forms of ferric (oxidized) and ferrous (reduced) Cyt c by measuring their transient absorption (TA) spectra using a homemade sub-10 fs broadband NUV laser pulses system. The TA traces measured in the broad probe wavelength region were analyzed by the global analysis method to study the electronic dynamics. The difference of relaxation dynamics dependent on the excitation bandwidth enabled us to elucidate that the 2.5 ps component in ferrous Cyt c can be assigned to intramolecular vibration energy redistribution and not to vibrational cooling, which was not clear until this work. The temporal resolution of 10 fs observes TA signal modulation caused by the molecular vibration in the time domain, which can be used to calculate the instantaneous frequency of the molecular vibration mode. The observed vibrational dynamics has visualized that the heme structure changes in 0.8 ps for ferric Cyt c and in >1.0 ps for ferrous Cyt c. These estimated lifetimes of vibrational dynamics reflect vibrational relaxation in the ground state of ferric Cyt c and electronic transition from the S2 state to the S1 state in ferrous Cyt c, respectively.

中文翻译:

亚10 fs NUV激光脉冲观察到的细胞色素c的主要电子和振动动力学。

通过使用自制的低于10 fs宽带NUV激光脉冲系统测量其瞬态吸收(TA)光谱,阐明了细胞色素c(Cyt c)的主要反应机理,阐明了铁氧体(氧化的)和亚铁(还原的)Cyt c的两种氧化还原形式。。通过全局分析方法分析了在宽探针波长范围内测得的TA迹线,以研究电子动力学。弛豫动力学的差异取决于激励带宽,这使我们能够阐明亚铁Cyt c中的2.5 ps分量可以将其分配给分子内的振动能量重新分配,而不是分配给振动冷却,这在这项工作之前还不清楚。10 fs的时间分辨率可观察到由时域中的分子振动引起的TA信号调制,可用于计算分子振动模式的瞬时频率。所观察到的振动动力学已可视化了血红素结构在0.8 PS为铁细胞色素改变Ç和在> 1.0 PS为亚铁细胞色素C ^。这些估计的振动动力学寿命反映铁细胞色素的基态振动弛豫Ç在亚铁细胞色素和电子跃迁从S2状态到S1状态Ç,分别。
更新日期:2020-09-24
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