Abstract
The secondary acceptor A1 of the electron transport chain(s) of photosystem (PS) I is a phylloquinone (vitamin K1, VK1). Pulse electron paramagnetic resonance and electron nuclear double resonance (ENDOR) experiments at X-band frequencies were performed on the photoaccumulated acceptor radical A ·−1 and the radical pair state P ·+700 A ·−1 in PS I ofThermosynechococcus elongatus. The data obtained were compared with data from the respective radical anion of VK1 in organic solvents. The unusualg tensor magnitude of A ·−1 is explained by the hydrophobic binding pocket of this radical. The hyperfine couplings and the spin (and charge) density distribution is very different for A .−1 in PS I and VK ·−1 in frozen alcoholic solution. This is attributed to a rather strong one-sided hydrogen bond to A ·−1 . The presence of a hydrogen bond to A ·−1 has only a minor effect ong. The hyperfine coupling constants of A ·−1 determined from the radical pair spectra deviate only slightly from those derived from photoaccumulated A ·−1 in PS I treated with dithionite at high pH. ENDOR resonances of the proton in a H bond were detected and an estimate of the strength and geometry of this bond to A ·−1 was obtained. The significance of the hydrogen bond and other (hydrophobic) interactions of A1 with the surrounding are briefly discussed.
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Teutloff, C., Bittl, R. & Lubitz, W. Pulse ENDOR studies on the radical pair P +·700 A ·−1 and the photoaccumulated quinone acceptor A ·−1 of photosystem I. Appl. Magn. Reson. 26, 5–21 (2004). https://doi.org/10.1007/BF03166559
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DOI: https://doi.org/10.1007/BF03166559