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 O 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.
Institute for Methods and Instrumentation for Synchrotron Radiation Research, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany.
Rolf
R
Mitzner
Institute for Nanometre Optics and Technology, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany.
Jens
J
Rehanek
Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States ; LCLS, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
Jan
J
Kern
Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Sheraz
S
Gul
Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Johan
J
Hattne
Department of Chemistry, University of California-Irvine, 1102 Natural Sciences II, Irvine, California 92697, United States.
Taketo
T
Taguchi
LCLS, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
Roberto
R
Alonso-Mori
Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Rosalie
R
Tran
Institute for Methods and Instrumentation for Synchrotron Radiation Research, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany.
Christian
C
Weniger
Institute for Methods and Instrumentation for Synchrotron Radiation Research, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany ; Institut für Physik und Astronomie, Universität Potsdam, 14476 Potsdam, Germany.
Henning
H
Schröder
Institute for Methods and Instrumentation for Synchrotron Radiation Research, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany.
Wilson
W
Quevedo
Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
Hartawan
H
Laksmono
Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
Raymond G
RG
Sierra
Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Guangye
G
Han
Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Benedikt
B
Lassalle-Kaiser
Institutionen för Kemi, Kemiskt Biologiskt Centrum, Umeå Universitet, 901 87 Umeå, Sweden.
Sergey
S
Koroidov
Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States ; Structural Dynamics of (Bio)Chemical Systems, Deutsches Elektronen-Synchtrotron (DESY), Notkestrasse 85, 22607 Hamburg, Germany.
Katharina
K
Kubicek
Institute for Methods and Instrumentation for Synchrotron Radiation Research, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany ; Institut für Physik und Astronomie, Universität Potsdam, 14476 Potsdam, Germany.
Simon
S
Schreck
Institute for Methods and Instrumentation for Synchrotron Radiation Research, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany ; Institut für Physik und Astronomie, Universität Potsdam, 14476 Potsdam, Germany.
Kristjan
K
Kunnus
Institute for Nanometre Optics and Technology, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany.
Maria
M
Brzhezinskaya
Institute for Nanometre Optics and Technology, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany.
Alexander
A
Firsov
LCLS, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
Michael P
MP
Minitti
LCLS, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
Joshua J
JJ
Turner
LCLS, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
Stefan
S
Moeller
Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Nicholas K
NK
Sauter
Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
Michael J
MJ
Bogan
SSRL, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
Dennis
D
Nordlund
LCLS, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
William F
WF
Schlotter
Institutionen för Kemi, Kemiskt Biologiskt Centrum, Umeå Universitet, 901 87 Umeå, Sweden.
Johannes
J
Messinger
Department of Chemistry, University of California-Irvine, 1102 Natural Sciences II, Irvine, California 92697, United States.
Andrew
A
Borovik
Max Planck Institute for Biophysical Chemistry, 37077 Göttingen, Germany ; Structural Dynamics of (Bio)Chemical Systems, Deutsches Elektronen-Synchtrotron (DESY), Notkestrasse 85, 22607 Hamburg, Germany.
Simone
S
Techert
Inorganic Chemistry and Catalysis, Utrecht University, 3584 CG Utrecht, The Netherlands.
Frank M F
FM
de Groot
Institute for Methods and Instrumentation for Synchrotron Radiation Research, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany ; Institut für Physik und Astronomie, Universität Potsdam, 14476 Potsdam, Germany.
Alexander
A
Föhlisch
Institute for Nanometre Optics and Technology, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany.
Alexei
A
Erko
LCLS, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
Uwe
U
Bergmann
Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Vittal K
VK
Yachandra
Institute for Methods and Instrumentation for Synchrotron Radiation Research, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany.
Philippe
P
Wernet
Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Junko
J
Yano
Excited States; Photochemistry; Spectroscopy