Analysis of the spin-polarized electron spin echo of the [P700+A1-] radical pair of photosystem I indicates that both reaction center subunits are competent in electron transfer in cyanobacteria, green algae, and higher plants

Santabarbara, Stefano, Kuprov, Ilya, Hore, P.J., Casal, Antonio, Heathcote, Peter and Evans, Michael C.W. (2006) Analysis of the spin-polarized electron spin echo of the [P700+A1-] radical pair of photosystem I indicates that both reaction center subunits are competent in electron transfer in cyanobacteria, green algae, and higher plants. Biochemistry, 45 (23), 7389-7403. (doi:10.1021/bi060330h).

Abstract

The decay of the light-induced spin-correlated radical pair [P700+A1-] and the associated electron spin echo envelope modulation (ESEEM) have been studied in either thylakoid membranes, cellular membranes, or purified photosystem I prepared from the wild-type strains of Synechocystis sp. PCC 6803, Chlamydomonas reinhardtii, and Spinaceae oleracea. The decay of the spin-correlated radical pair is described in the wild-type membrane by two exponential components with lifetimes of 2?4 and 16?25 ?s. The proportions of the two components can be altered by preillumination of the membranes in the presence of reductant at temperatures lower than 220 K, which leads to the complete reduction of the iron?sulfur electron acceptors FA, FB, and FX and partial photoaccumulation of the reduced quinone electron acceptor A1A-. The “out-of-phase” (OOP) ESEEM attributed to the [P700+A1-] radical pair has been investigated in the three species as a function of the preillumination treatment. Values of the dipolar (D) and the exchange (J) interactions were extracted by time-domain fitting of the OOP-ESEEM. The results obtained in the wild-type systems are compared with two site-directed mutants of C. reinhardtii [Santabarbara et al. (2005) Biochemistry 44, 2119?2128], in which the spin-polarized signal on either the PsaA- or PsaB-bound electron transfer pathway is suppressed so that the radical pair formed on each electron transfer branch could be monitored selectively. This comparison indicates that when all of the iron?sulfur centers are oxidized, only the echo modulation associated with the A branch [P700+A1A-] radical pair is observed. The reduction of the iron?sulfur clusters and the quinone A1 by preillumination treatment induces a shift in the ESEEM frequency. In all of the systems investigated this observation can be interpreted in terms of different proportions of the signal associated with the [P700+A1A-] and [P700+A1B-] radical pairs, suggesting that bidirectionality of electron transfer in photosystem I is a common feature of all species rather than being confined to green algae.

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Contributors

Author: Ilya Kuprov

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