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Pulse Q-band EPR and ENDOR spectroscopies of the photochemically generated monoprotonated benzosemiquinone radical in frozen alcoholic solution.


ABSTRACT: Quinones are essential cofactors in many physiological processes, among them proton-coupled electron transfer (PCET) in photosynthesis and respiration. A key intermediate in PCET is the monoprotonated semiquinone radical. In this work we produced the monoprotonated benzosemiquinone (BQH(•)) by UV illumination of BQ dissolved in 2-propanol at cryogenic temperatures and investigated the electronic and geometric structures of BQH(•) in the solid state (80 K) using EPR and ENDOR techniques at 34 GHz. The g-tensor of BQH(•) was found to be similar to that of the anionic semiquinone species (BQ(•-)) in frozen solution. The peaks present in the ENDOR spectrum of BQH(•) were identified and assigned by (1)H/(2)H substitutions. The experiments reconfirmed that the hydroxyl proton (O-H) on BQH(•), wh

SUBMITTER: Flores M 

PROVIDER: S-EPMC3432317 | biostudies-literature | 2012 Aug

REPOSITORIES: biostudies-literature