Structural Dynamics (Sep 2017)
Soft x-ray absorption spectroscopy of metalloproteins and high-valent metal-complexes at room temperature using free-electron lasers
- Markus Kubin,
- Jan Kern,
- Sheraz Gul,
- Thomas Kroll,
- Ruchira Chatterjee,
- Heike Löchel,
- Franklin D. Fuller,
- Raymond G. Sierra,
- Wilson Quevedo,
- Christian Weniger,
- Jens Rehanek,
- Anatoly Firsov,
- Hartawan Laksmono,
- Clemens Weninger,
- Roberto Alonso-Mori,
- Dennis L. Nordlund,
- Benedikt Lassalle-Kaiser,
- James M. Glownia,
- Jacek Krzywinski,
- Stefan Moeller,
- Joshua J. Turner,
- Michael P. Minitti,
- Georgi L. Dakovski,
- Sergey Koroidov,
- Anurag Kawde,
- Jacob S. Kanady,
- Emily Y. Tsui,
- Sandy Suseno,
- Zhiji Han,
- Ethan Hill,
- Taketo Taguchi,
- Andrew S. Borovik,
- Theodor Agapie,
- Johannes Messinger,
- Alexei Erko,
- Alexander Föhlisch,
- Uwe Bergmann,
- Rolf Mitzner,
- Vittal K. Yachandra,
- Junko Yano,
- Philippe Wernet
Affiliations
- Markus Kubin
- Institute for Methods and Instrumentation for Synchrotron Radiation Research, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany
- Jan Kern
- Molecular Biophysics and Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA
- Sheraz Gul
- Molecular Biophysics and Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA
- Thomas Kroll
- Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA
- Ruchira Chatterjee
- Molecular Biophysics and Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA
- Heike Löchel
- Institute for Nanometre Optics and Technology, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany
- Franklin D. Fuller
- Molecular Biophysics and Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA
- Raymond G. Sierra
- Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA
- Wilson Quevedo
- Institute for Methods and Instrumentation for Synchrotron Radiation Research, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany
- Christian Weniger
- Institute for Methods and Instrumentation for Synchrotron Radiation Research, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany
- Jens Rehanek
- Institute for Nanometre Optics and Technology, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany
- Anatoly Firsov
- Institute for Nanometre Optics and Technology, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany
- Hartawan Laksmono
- Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA
- Clemens Weninger
- Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA
- Roberto Alonso-Mori
- Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA
- Dennis L. Nordlund
- Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA
- Benedikt Lassalle-Kaiser
- Synchrotron SOLEIL, L'Orme des Merisiers, Saint-Aubin, 91191 Gif-sur-Yvette, France
- James M. Glownia
- Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA
- Jacek Krzywinski
- Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA
- Stefan Moeller
- Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA
- Joshua J. Turner
- Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA
- Michael P. Minitti
- Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA
- Georgi L. Dakovski
- Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA
- Sergey Koroidov
- Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA
- Anurag Kawde
- Institutionen för Kemi, Kemiskt Biologiskt Centrum, Umeå Universitet, SE 90187 Umeå, Sweden
- Jacob S. Kanady
- Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA
- Emily Y. Tsui
- Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA
- Sandy Suseno
- Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA
- Zhiji Han
- Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA
- Ethan Hill
- Department of Chemistry, University of California-Irvine, 1102 Natural Sciences II, Irvine, California 92697-2025, USA
- Taketo Taguchi
- Department of Chemistry, University of California-Irvine, 1102 Natural Sciences II, Irvine, California 92697-2025, USA
- Andrew S. Borovik
- Department of Chemistry, University of California-Irvine, 1102 Natural Sciences II, Irvine, California 92697-2025, USA
- Theodor Agapie
- Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA
- Johannes Messinger
- Institutionen för Kemi, Kemiskt Biologiskt Centrum, Umeå Universitet, SE 90187 Umeå, Sweden
- Alexei Erko
- Institute for Nanometre Optics and Technology, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany
- Alexander Föhlisch
- Institute for Methods and Instrumentation for Synchrotron Radiation Research, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany
- Uwe Bergmann
- Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA
- Rolf Mitzner
- Institute for Methods and Instrumentation for Synchrotron Radiation Research, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany
- Vittal K. Yachandra
- Molecular Biophysics and Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA
- Junko Yano
- Molecular Biophysics and Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA
- Philippe Wernet
- Institute for Methods and Instrumentation for Synchrotron Radiation Research, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany
- DOI
- https://doi.org/10.1063/1.4986627
- Journal volume & issue
-
Vol. 4,
no. 5
pp. 054307 – 054307-16
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 < 1 mmol/l) at room temperature, measured under similar conditions. Our approach opens new ways to study metalloenzymes under functional conditions.
