TY - JOUR
T1 - Energy-dispersive X-ray emission spectroscopy using an X-ray free-electron laser in a shot-by-shot mode
AU - Alonso-Mori, Roberto
AU - Kern, Jan
AU - Gildea, Richard J.
AU - Sokaras, Dimosthenis
AU - Weng, Tsu Chien
AU - Lassalle-Kaiser, Benedikt
AU - Tran, Rosalie
AU - Hattne, Johan
AU - Laksmono, Hartawan
AU - Hellmich, Julia
AU - Glöckner, Carina
AU - Echols, Nathaniel
AU - Sierra, Raymond G.
AU - Schafer, Donald W.
AU - Sellberg, Jonas
AU - Kenney, Christopher
AU - Herbst, Ryan
AU - Pines, Jack
AU - Hart, Philip
AU - Herrmann, Sven
AU - Grosse-Kunstleve, Ralf W.
AU - Latimer, Matthew J.
AU - Fry, Alan R.
AU - Messerschmidt, Marc M.
AU - Miahnahri, Alan
AU - Seibert, M. Marvin
AU - Zwart, Petrus H.
AU - White, William E.
AU - Adams, Paul D.
AU - Bogan, Michael J.
AU - Boutet, Sébastien
AU - Williams, Garth J.
AU - Zouni, Athina
AU - Messinger, Johannes
AU - Glatzel, Pieter
AU - Sauter, Nicholas K.
AU - Yachandra, Vittal K.
AU - Yano, Junko
AU - Bergmann, Uwe
PY - 2012/11/20
Y1 - 2012/11/20
N2 - The ultrabright femtosecond X-ray pulses provided by X-ray free-electron lasers open capabilities for studying the structure and dynamics of a wide variety of systems beyond what is possible with synchrotron sources. Recently, this "probe-before-destroy"approach has been demonstrated for atomic structure determination by serial X-ray diffraction of microcrystals. There has been the question whether a similar approach can be extended to probe the local electronic structure by X-ray spectroscopy. To address this, we have carried out femtosecond X-ray emission spectroscopy (XES) at the Linac Coherent Light Source using redox-active Mn complexes. XES probes the charge and spin states as well as the ligand environment, critical for understanding the functional role of redox-active metal sites. Kβ1,3 XES spectra of Mn II and Mn2III,IVcomplexes at room temperature were collected using a wavelength dispersive spectrometer and femtosecond X-ray pulses with an individual dose of up to >100 MGy. The spectra were found in agreement with undamaged spectra collected at low dose using synchrotron radiation. Our results demonstrate that the intact electronic structure of redox active transition metal compounds in different oxidation states can be characterized with this shotby-shot method. This opens the door for studying the chemical dynamics of metal catalytic sites by following reactions under functional conditions. The technique can be combined with X-ray diffraction to simultaneously obtain the geometric structure of the overall protein and the local chemistry of active metal sites and is expected to prove valuable for understanding the mechanism of important metalloproteins, such as photosystem II.
AB - The ultrabright femtosecond X-ray pulses provided by X-ray free-electron lasers open capabilities for studying the structure and dynamics of a wide variety of systems beyond what is possible with synchrotron sources. Recently, this "probe-before-destroy"approach has been demonstrated for atomic structure determination by serial X-ray diffraction of microcrystals. There has been the question whether a similar approach can be extended to probe the local electronic structure by X-ray spectroscopy. To address this, we have carried out femtosecond X-ray emission spectroscopy (XES) at the Linac Coherent Light Source using redox-active Mn complexes. XES probes the charge and spin states as well as the ligand environment, critical for understanding the functional role of redox-active metal sites. Kβ1,3 XES spectra of Mn II and Mn2III,IVcomplexes at room temperature were collected using a wavelength dispersive spectrometer and femtosecond X-ray pulses with an individual dose of up to >100 MGy. The spectra were found in agreement with undamaged spectra collected at low dose using synchrotron radiation. Our results demonstrate that the intact electronic structure of redox active transition metal compounds in different oxidation states can be characterized with this shotby-shot method. This opens the door for studying the chemical dynamics of metal catalytic sites by following reactions under functional conditions. The technique can be combined with X-ray diffraction to simultaneously obtain the geometric structure of the overall protein and the local chemistry of active metal sites and is expected to prove valuable for understanding the mechanism of important metalloproteins, such as photosystem II.
KW - Energy-dispersive XES
KW - Femtosecond x-ray spectroscopy
KW - Kβ emission lines
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U2 - 10.1073/pnas.1211384109
DO - 10.1073/pnas.1211384109
M3 - Article
C2 - 23129631
AN - SCOPUS:84869843028
SN - 0027-8424
VL - 109
SP - 19103
EP - 19107
JO - Proceedings of the National Academy of Sciences of the United States of America
JF - Proceedings of the National Academy of Sciences of the United States of America
IS - 47
ER -