1H Hyperfine Interactions in the Mn-Cluster of Photosystem II in the S-2 State Detected by Hyperfine Sublevel Correlation Spectroscopy

36 Pag., 1 Tabl., 7 Fig. The definitive version is available at: http://pubs.acs.org/journal/jpcbfkA study of the hydrogen hyperfine couplings of the Mn-cluster of the oxygen-evolving complex of Photosystem II in the S2 state of the Kok cycle by means of hyperfine sublevel correlation spectroscopy was achieved. Features corresponding to hyperfine interaction of at least two hydrogen nuclei were detected. Combining our results with previous ENDOR data, hyperfine constants were determined, and by using a model for the structure and electronic spin state of the Mn-cluster, relevant structural information of the S2 state was obtained. This new information can be used for improving our knowledge about the structure and function of the Mn-cluster during light-driven water oxidation reaction in oxygenic photosynthetic organisms.This work was supported by the Spanish Ministry of Science and Innovation (projects MAT2008-03461 and AGL2008-00377) and Gobierno de Aragn (DGA-GC E33 and DGA-GE B18).Peer reviewe