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Comparison of the electron spin polarized spectrum found in plant photosystem I and in iron-depleted bacterial reaction centers with time-resolved K-band EPR; evidence that the photosystem I acceptor A1 is a quinone
Authors:J Petersen  D Stehlik  P Gast  M Thurnauer
Institution:(1) Department of Physics, Free University Berlin, FB 20 WE 1B, D-1000, 33 Berlin, FRG;(2) Department of Chemistry, The University of Chicago, 60637 Chicago, IL, USA;(3) Chemistry Division, Argonne National Laboratory, 60439 Argonne, IL, USA
Abstract:The suggestion that the electron acceptor A1 in plant photosystem I (PSI) is a quinone molecule is tested by comparisons with the bacterial photosystem. The electron spin polarized (ESP) EPR signal due to the oxidized donor and reduced quinone acceptor (P 870 + Q-) in iron-depleted bacterial reaction centers has similar spectral characteristics as the ESP EPR signal in PSI which is believed to be due to P 700 + A 1 - , the oxidized PSI donor and reduced A1. This is also true for better resolved spectra obtained at K-band (sim24 GHz). These same spectral characteristics can be simulated using a powder spectrum based on the known g-anisotropy of reduced quinones and with the same parameter set for Q- and A1 -. The best resolution of the ESP EPR signal has been obtained for deuterated PSI particles at K-band. Simulation of the A1 - contribution based on g-anisotropy yields the same parameters as for bacterial Q- (except for an overall shift in the anisotropic g-factors, which have previously been determined for Q-). These results provide evidence that A1 is a quinone molecule. The electron spin polarized signal of P700 + is part of the better resolved spectrum from the deuterated PSI particles. The nature of the P700 + ESP is not clear; however, it appears that it does not exhibit the polarization pattern required by mechanisms which have been used so far to explain the ESP in PSI.Abbreviations hf hyperfine - A0 A0 acceptor of photosystem I - A1 A1 acceptor of photosystem I - Brij-58 polyoxyethylene 20 cetyl ether - CP1 photosystem I particles which lack ferridoxin acceptors - ESP electron spin polarized - EPR electron paramagnetic resonance - I intermediary electron acceptor, bacteriopheophytin - LDAO lauryldimethylamine - N-oxide, P700 primary electron donor of photosystem I - PSI photosystem I - P700 T triplet state of primary donor of photosystem I - P870 primary donor in R. sphaeroides reaction center - Q quinore-acceptor in photosynthetic bacteria - RC reaction center
Keywords:bacterial quinone acceptor  electron paramagnetic resonance  electron spin polarization  photosystem I  PSI acceptor A1  time-resolved EPR
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