title: Structure-based simulation of linear optical spectra of the CP43 core antenna of photosystem II.
abstract: The linear optical spectra (absorbance, linear dichroism, circular dichroism, fluorescence) of the CP43 (PsbC) antenna of the photosystem II core complex (PSIIcc) pertaining to the S(0) → S(1) (Q(Y)) transitions of the chlorophyll (Chl) a pigments are simulated by applying a combined quantum chemical/electrostatic method to obtain excitonic couplings and local transition energies (site energies) on the basis of the 2.9 Å resolution crystal structure (Guskov et al., Nat Struct Mol Biol 16:334-342, 2009). The electrostatic calculations identify three Chls with low site energies (Chls 35, 37, and 45 in the nomenclature of Loll et al. (Nature 438:1040-1044, 2005). A refined simulation of experimental spectra of isolated CP43 suggests a modified set of site energies within 143 cm(-1) of the directly calculated values (root mean square deviation: 80 cm(-1)). In the refined set, energy sinks are at Chls 37, 43, and 45 in agreement with earlier fitting results (Raszewski and Renger, J Am Chem Soc 130:4431-4446, 2008). The present structure-based simulations reveal that a large part of the redshift of Chl 37 is due to a digalactosyldiacylglycerol lipid. This finding suggests a new role for lipids in PSIIcc, namely the tuning of optical spectra and the creation of an excitation energy funnel towards the reaction center. The analysis of electrostatic pigment-protein interactions is used to identify amino acid residues that are of potential interest for an experimental approach to an assignment of site energies and energy sinks by site-directed mutagenesis.
authors.affiliation: Institut für Theoretische Physik, Johannes Kepler Universität Linz, Altenberger Str. 69, 4040, Linz, Austria. Frank.Mueh@jku.at
authors.forename: Frank
authors.initials: F
authors.lastname: Müh
authors.forename: Mohamed El-Amine
authors.initials: Mel-A
authors.lastname: Madjet
authors.forename: Thomas
authors.initials: T
authors.lastname: Renger
mesh_terms: D002734:Chlorophyll / Q000737:chemistry; D000077194:Chlorophyll A; D003198:Computer Simulation; D004563:Electrochemistry; D004735:Energy Transfer; D008027:Light; D008055:Lipids / Q000737:chemistry; D008958:Models, Molecular; D009154:Mutation; D045332:Photosystem II Protein Complex / Q000737:chemistry* / Q000235:genetics; D011487:Protein Conformation; D013057:Spectrum Analysis
chemical_list: D008055:Lipids; D045332:Photosystem II Protein Complex; C083100:photosystem II, chlorophyll binding protein, CP-43; D002734:Chlorophyll; D000077194:Chlorophyll A