Soft x-ray absorption spectroscopy of metalloproteins and high-valent metal-complexes at room temperature using free-electron lasers. Kubin, M., Kern, J., Gul, S., Kroll, T., Chatterjee, R., Löchel, H., Fuller, F. D., Sierra, R. G., Quevedo, W., Weniger, C., Rehanek, J., Firsov, A., Laksmono, H., Weninger, C., Alonso-Mori, R., Nordlund, D. L., Lassalle-Kaiser, B., Glownia, J. M., Krzywinski, J., Moeller, S., Turner, J. J., Minitti, M. P., Dakovski, G. L., Koroidov, S., Kawde, A., Kanady, J. S., Tsui, E. Y., Suseno, S., Han, Z., Hill, E., Taguchi, T., Borovik, A. S., Agapie, T., Messinger, J., Erko, A., Föhlisch, A., Bergmann, U., Mitzner, R., Yachandra, V. K., Yano, J., & Wernet, P. Structural Dynamics, 4(5):054307, September, 2017.
Soft x-ray absorption spectroscopy of metalloproteins and high-valent metal-complexes at room temperature using free-electron lasers [link]Paper  doi  abstract   bibtex   
X-ray absorption spectroscopy at the L-edge of 3d transition metals provides unique information on the local metal charge and spin states by directly probing 3d-derived molecular orbitals through 2p-3d transitions. However, this soft x-ray technique has been rarely used at synchrotron facilities for mechanistic studies of metalloenzymes due to the difficulties of x-ray-induced sample damage and strong background signals from light elements that can dominate the low metal signal. Here, we combine femtosecond soft x-ray pulses from a free-electron laser with a novel x-ray fluorescence-yield spectrometer to overcome these difficulties. We present L-edge absorption spectra of inorganic high-valent Mn complexes (Mn ∼ 6–15 mmol/l) with no visible effects of radiation damage. We also present the first L-edge absorption spectra of the oxygen evolving complex (Mn4CaO5) in Photosystem II (Mn < 1 mmol/l) at room temperature, measured under similar conditions. Our approach opens new ways to study metalloenzymes under functional conditions.
@article{kubin_soft_2017,
	title = {Soft x-ray absorption spectroscopy of metalloproteins and high-valent metal-complexes at room temperature using free-electron lasers},
	volume = {4},
	issn = {2329-7778},
	url = {https://doi.org/10.1063/1.4986627},
	doi = {10.1063/1.4986627},
	abstract = {X-ray absorption spectroscopy at the L-edge of 3d transition metals provides unique information on the local metal charge and spin states by directly probing 3d-derived molecular orbitals through 2p-3d transitions. However, this soft x-ray technique has been rarely used at synchrotron facilities for mechanistic studies of metalloenzymes due to the difficulties of x-ray-induced sample damage and strong background signals from light elements that can dominate the low metal signal. Here, we combine femtosecond soft x-ray pulses from a free-electron laser with a novel x-ray fluorescence-yield spectrometer to overcome these difficulties. We present L-edge absorption spectra of inorganic high-valent Mn complexes (Mn ∼ 6–15 mmol/l) with no visible effects of radiation damage. We also present the first L-edge absorption spectra of the oxygen evolving complex (Mn4CaO5) in Photosystem II (Mn \&lt; 1 mmol/l) at room temperature, measured under similar conditions. Our approach opens new ways to study metalloenzymes under functional conditions.},
	number = {5},
	urldate = {2024-12-10},
	journal = {Structural Dynamics},
	author = {Kubin, Markus and Kern, Jan and Gul, Sheraz and Kroll, Thomas and Chatterjee, Ruchira and Löchel, Heike and Fuller, Franklin D. and Sierra, Raymond G. and Quevedo, Wilson and Weniger, Christian and Rehanek, Jens and Firsov, Anatoly and Laksmono, Hartawan and Weninger, Clemens and Alonso-Mori, Roberto and Nordlund, Dennis L. and Lassalle-Kaiser, Benedikt and Glownia, James M. and Krzywinski, Jacek and Moeller, Stefan and Turner, Joshua J. and Minitti, Michael P. and Dakovski, Georgi L. and Koroidov, Sergey and Kawde, Anurag and Kanady, Jacob S. and Tsui, Emily Y. and Suseno, Sandy and Han, Zhiji and Hill, Ethan and Taguchi, Taketo and Borovik, Andrew S. and Agapie, Theodor and Messinger, Johannes and Erko, Alexei and Föhlisch, Alexander and Bergmann, Uwe and Mitzner, Rolf and Yachandra, Vittal K. and Yano, Junko and Wernet, Philippe},
	month = sep,
	year = {2017},
	pages = {054307},
}
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