Ultrafast 2D-IR spectroelectrochemistry of flavin mononucleotide
Ultrafast 2D-IR spectroelectrochemistry of flavin mononucleotide
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DOI：
10.1063/1.4916916
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发表时间：
2015-06-07
影响因子：
4.4
通讯作者：
Bredenbeck, Jens
中科院分区：
文献类型：
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作者：
El Khoury, Youssef;van Wilderen, Luuk J. G. W.;Bredenbeck, Jens
我们展示了超快二维红外（2D-IR）光谱耦合到溶液中的电化学，并将其应用于黄素单甘肽，氧化还原蛋白质的重要辅因子。为此，我们设计了一个光谱电化学电池优化的2D-IR测量反射和测量的氧化和还原形式的黄素montobenzide的时间依赖性的2D-IR光谱。数据显示在两个氧化还原物种的不同振动模式之间的非谐耦合和振动能量转移。这些信息是无法访问的氧化还原控制的稳态FTIR光谱。2D-IR光谱提供了广泛的应用，如亚皮秒结构测定，通过能量转移的IR谱带分配，通过2D光谱中的带连接性解开反应混合物，以及溶剂化动力学和化学交换的测量，现在可以在受控的氧化还原电位下进行探索。这项技术的发展还为研究氧化还原蛋白质的动力学开辟了新的视野。(C)2015 AIP Publishing LLC.
We demonstrate the coupling of ultrafast two-dimensional infrared (2D-IR) spectroscopy to electrochemistry in solution and apply it to flavin mononucleotide, an important cofactor of redox proteins. For this purpose, we designed a spectroelectrochemical cell optimized for 2D-IR measurements in reflection and measured the time-dependent 2D-IR spectra of the oxidized and reduced forms of flavin mononucleotide. The data show anharmonic coupling and vibrational energy transfer between different vibrational modes in the two redox species. Such information is inaccessible with redox-controlled steady-state FTIR spectroscopy. The wide range of applications offered by 2D-IR spectroscopy, such as sub-picosecond structure determination, IR band assignment via energy transfer, disentangling reaction mixtures through band connectivity in the 2D spectra, and the measurement of solvation dynamics and chemical exchange can now be explored under controlled redox potential. The development of this technique furthermore opens new horizons for studying the dynamics of redox proteins. (C) 2015 AIP Publishing LLC.