title: Protein modifications affecting triplet energy transfer in bacterial photosynthetic reaction centers.
abstract: The efficiency of triplet energy transfer from the special pair (P) to the carotenoid (C) in photosynthetic reaction centers (RCs) from a large family of mutant strains has been investigated. The mutants carry substitutions at positions L181 and/or M208 near chlorophyll-based cofactors on the inactive and active sides of the complex, respectively. Light-modulated electron paramagnetic resonance at 10 K, where triplet energy transfer is thermally prohibited, reveals that the mutations do not perturb the electronic distribution of P. At temperatures > or = 70 K, we observe reduced signals from the carotenoid in most of the RCs with L181 substitutions. In particular, triplet transfer efficiency is reduced in all RCs in which a lysine at L181 donates a sixth ligand to the monomeric bacteriochlorophyll B(B). Replacement of the native Tyr at M208 on the active side of the complex with several polar residues increased transfer efficiency. The difference in the efficiencies of transfer in the RCs demonstrates the ability of the protein environment to influence the electronic overlap of the chromophores and thus the thermal barrier for triplet energy transfer.
authors.affiliation: Center for Mechanistic Biology and Biotechnology and Chemistry Division, Argonne National Laboratory, Illinois 60439, USA. laible@anl.gov
authors.forename: P D
authors.initials: PD
authors.lastname: Laible
authors.forename: V
authors.initials: V
authors.lastname: Chynwat
authors.forename: M C
authors.initials: MC
authors.lastname: Thurnauer
authors.forename: M
authors.initials: M
authors.lastname: Schiffer
authors.forename: D K
authors.initials: DK
authors.lastname: Hanson
authors.forename: H A
authors.initials: HA
authors.lastname: Frank
mesh_terms: D019943:Amino Acid Substitution; D002338:Carotenoids / Q000378:metabolism*; D002734:Chlorophyll / Q000378:metabolism; D003198:Computer Simulation; D019281:Dimerization; D004578:Electron Spin Resonance Spectroscopy; D004735:Energy Transfer; D008027:Light; D045342:Light-Harvesting Protein Complexes; D008956:Models, Chemical; D008958:Models, Molecular; D016297:Mutagenesis, Site-Directed; D045322:Photosynthetic Reaction Center Complex Proteins / Q000737:chemistry* / Q000378:metabolism*; D017354:Point Mutation; D011487:Protein Conformation; D011994:Recombinant Proteins / Q000737:chemistry / Q000378:metabolism; D012242:Rhodobacter sphaeroides / Q000378:metabolism*
chemical_list: D045342:Light-Harvesting Protein Complexes; D045322:Photosynthetic Reaction Center Complex Proteins; D011994:Recombinant Proteins; D002734:Chlorophyll; D002338:Carotenoids