Structure, ligands and substrate coordination of the oxygen-evolving complex of photosystem II in the S 2 state: a combined EPR and DFT study
Date
2014
Authors
Lohmiller, Thomas
Krewald, Vera
Perez-Navarro, Montserrat
Retegan, Marius
Rapatskiy, Leonid
Nowaczyk, Marc M.
Boussac, Alain
Neese, Frank
Lubitz, Wolfgang
Pantazis, Dimitrios A.
Journal Title
Journal ISSN
Volume Title
Publisher
Royal Society of Chemistry
Abstract
The S2 state of the oxygen-evolving complex of photosystem II, which consists of a Mn4O5Ca cofactor, is EPR-active, typically displaying a multiline signal, which arises from a ground spin state of total spin ST = 1/2. The precise appearance of the signal varies amongst different photosynthetic species, preparation and solvent conditions/compositions. Over the past five years, using the model species Thermosynechococcus elongatus, we have examined modifications that induce changes in the multiline signal, i.e. Ca2+/Sr2+-substitution and the binding of ammonia, to ascertain how structural perturbations of the cluster are reflected in its magnetic/electronic properties. This refined analysis, which now includes high-field (W-band) data, demonstrates that the electronic structure of the S2 state is essentially invariant to these modifications. This assessment is based on spectroscopies that examine the metal centres themselves (EPR, 55Mn-ENDOR) and their first coordination sphere ligands (14N/15N- and 17O-ESEEM, -HYSCORE and -EDNMR). In addition, extended quantum mechanical models from broken-symmetry DFT now reproduce all EPR, 55Mn and 14N experimental magnetic observables, with the inclusion of second coordination sphere ligands being crucial for accurately describing the interaction of NH3 with the Mn tetramer. These results support a mechanism of multiline heterogeneity reported for species differences and the effect of methanol [Biochim. Biophys. Acta, Bioenerg., 2011, 1807, 829], involving small changes in the magnetic connectivity of the solvent accessible outer MnA4 to the cuboidal unit Mn3O3Ca, resulting in predictable changes of the measured effective 55Mn hyperfine tensors. Sr2+ and NH3 replacement both affect the observed 17O-EDNMR signal envelope supporting the assignment of O5 as the exchangeable μ-oxo bridge and it acting as the first site of substrate inclusion.
Description
Keywords
ligand, oxygen, photosystem II, chemical structure
Citation
Collections
Source
Physical Chemistry Chemical Physics
Type
Journal article
Book Title
Entity type
Access Statement
Open Access
License Rights
Creative Commons Attribution 3.0 Unported Licence.
Restricted until
Downloads
File
Description