L-edge x-ray absorption spectroscopy of dilute systems relevant to metalloproteins using an X-ray free-electron laser

  • L-edge spectroscopy of 3d transition metals provides important electronic structure information and has been used in many fields. However, the use of this method for studying dilute aqueous systems, such as metalloenzymes, has not been prevalent because of severe radiation damage and the lack of suitable detection systems. Here we present spectra from a dilute Mn aqueous solution using a high-transmission zone-plate spectrometer at the Linac Coherent Light Source (LCLS). The spectrometer has been optimized for discriminating the Mn L-edge signal from the overwhelming 0 K-edge background that arises from water and protein itself, and the ultrashort LCLS X-ray pulses can outrun X-ray induced damage. We show that the deviations of the partial-fluorescence yield-detected spectra from the true absorption can be well modeled using the state-dependence of the fluorescence yield, and discuss implications for the application of our concept to biological samples.

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Author:Rolf Mitzner, Jens Rehanek, Jan Kern, Sheraz Gul, Johan Hattne, Taketo Taguchi, Roberto Alonso-Mori, Rosalie Tran, Christian Weniger, Henning Schröder, Wilson Quevedo, Hartawan Laksmono, Raymond G. Sierra, Guangye Han, Benedikt Lassalle-Kaiser, Sergey Koroidov, Katharina Kubicek, Simon Schreck, Kristjan Kunnus, Maria Brzhezinskaya, Alexander Firsov, Michael P. Minitti, Joshua J. Turner, Stefan Möller, Nicholas K. Sauter, Michael J. Bogan, Dennis Nordlund, William F. Schlotter, Johannes Messinger, Andrew Borovik, Simone Techert, Frank M. F. de Groot, Alexander FöhlischORCiDGND, Alexei Erko, Uwe Bergmann, Vittal K. Yachandra, Philippe Wernet, Junko Yano
ISSN:1948-7185 (print)
Parent Title (English):The journal of physical chemistry letters
Publisher:American Chemical Society
Place of publication:Washington
Document Type:Article
Year of first Publication:2013
Year of Completion:2013
Release Date:2017/03/26
First Page:3641
Last Page:3647
Funder:Office of Science, Office of Basic Energy Sciences (OBES), Division of Chemical Sciences, Geosciences, and Biosciences (CSGB) of the Department of Energy (DOE) [DE-AC02-050CH11231]; LBNL Laboratory Directed Research and Development award; NIH [GM50781, GM055302]; Alexander von Humboldt Foundation; Ruth L. Kirschstein National Research Service Award [F32GM100595]; OBES; CSGB of the DOE [DE-AC02-76SF00515]; LCLS; SLAC Laboratory Directed Research and Development award; Volkswagenstiftung Peter Paul Ewald fellowship; Swedish Energy Agency (Energimyn-digheten); K&A Wallenberg Foundation (Artificial Leaf Umea); Umea University (Solar Fuels Umea); Stanford University through the Stanford Institute for Materials Energy Sciences (SIMES); Lawrence Berkeley National Laboratory (LBNL), University of Hamburg through the BMBF priority program [FSP 301]; Center for Free Electron Laser Science (CFEL); BMBF project "Next generation instrumentation for ultrafast X-ray science at accelerator-driven photon source" [05K12CB4]; Helmholtz Virtual Institute "Dynamic Pathways in Multidimensional Landscapes"; European Community [PCIG10-GA-2011-297905]; [SFB755-DFG]
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie
Peer Review:Referiert