TY - JOUR A1 - Mitzner, Rolf A1 - Rehanek, Jens A1 - Kern, Jan A1 - Gul, Sheraz A1 - Hattne, Johan A1 - Taguchi, Taketo A1 - Alonso-Mori, Roberto A1 - Tran, Rosalie A1 - Weniger, Christian A1 - Schröder, Henning A1 - Quevedo, Wilson A1 - Laksmono, Hartawan A1 - Sierra, Raymond G. A1 - Han, Guangye A1 - Lassalle-Kaiser, Benedikt A1 - Koroidov, Sergey A1 - Kubicek, Katharina A1 - Schreck, Simon A1 - Kunnus, Kristjan A1 - Brzhezinskaya, Maria A1 - Firsov, Alexander A1 - Minitti, Michael P. A1 - Turner, Joshua J. A1 - Möller, Stefan A1 - Sauter, Nicholas K. A1 - Bogan, Michael J. A1 - Nordlund, Dennis A1 - Schlotter, William F. A1 - Messinger, Johannes A1 - Borovik, Andrew S. A1 - Techert, Simone A1 - de Groot, Frank M. F. A1 - Föhlisch, Alexander A1 - Erko, Alexei A1 - Bergmann, Uwe A1 - Yachandra, Vittal K. A1 - Wernet, Philippe A1 - Yano, Junko T1 - L-edge x-ray absorption spectroscopy of dilute systems relevant to metalloproteins using an X-ray free-electron laser JF - The journal of physical chemistry letters N2 - 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. Y1 - 2013 U6 - https://doi.org/10.1021/jz401837f SN - 1948-7185 VL - 4 IS - 21 SP - 3641 EP - 3647 PB - American Chemical Society CY - Washington ER -