title: Electron transfer between exogenous electron donors and reaction center of photosystem 2.
abstract: Transfer of electrons between artificial electron donors diphenylcarbazide (DPC) and hydroxylamine (NH2OH) and reaction center of manganese-depleted photosystem 2 (PS2) complexes was studied using the direct electrometrical method. For the first time it was shown that reduction of redox-active amino acid tyrosine Y(Z)(.) by DPC is coupled with generation of transmembrane electric potential difference (DeltaPsi). The amplitude of this phase comprised ~17% of that of the DeltaPsi phase due to electron transfer between Y(Z) and the primary quinone acceptor Q(A). This phase is associated with vectorial intraprotein electron transfer between the DPC binding site on the protein-water interface and the tyrosine Y(Z)(.). The slowing of DeltaPsi decay in the presence of NH2OH indicates effective electron transfer between the artificial electron donor and reaction center of PS2. It is suggested that NH2OH is able to diffuse through channels with diameter of 2.0-3.0 A visible in PS2 structure and leading from the protein-water interface to the Mn(4)Ca cluster binding site with the concomitant electron donation to Y(Z)(.). Because the dielectrically-weighted distance between the NH2OH binding site and Y(Z)(.) is not determined, the transfer of electrons from NH2OH to Y(Z)(.) could be either electrically silent or contribute negligibly to the observed electrogenicity in comparison with hydrophobic donors.
authors.affiliation: Belozersky Institute of Physico-Chemical Biology, Lomonosov Moscow State University, Moscow, 119991, Russia. mamedov@genebee.msu.ru
authors.forename: M D
authors.initials: MD
authors.lastname: Mamedov
authors.forename: V N
authors.initials: VN
authors.lastname: Kurashov
authors.forename: I O
authors.initials: IO
authors.lastname: Petrova
authors.forename: A A
authors.initials: AA
authors.lastname: Zaspa
authors.forename: A Yu
authors.initials: AY
authors.lastname: Semenov
mesh_terms: D001665:Binding Sites; D004160:Diphenylcarbazide / Q000737:chemistry*; D004579:Electron Transport; D019811:Hydroxylamine / Q000737:chemistry*; D008345:Manganese / Q000378:metabolism; D008564:Membrane Potentials; D010084:Oxidation-Reduction; D045332:Photosystem II Protein Complex / Q000378:metabolism*; D017434:Protein Structure, Tertiary; D014443:Tyrosine / Q000378:metabolism
chemical_list: D045332:Photosystem II Protein Complex; D004160:Diphenylcarbazide; D019811:Hydroxylamine; D014443:Tyrosine; D008345:Manganese