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• W2004661331 abstract "Four quanta of light, absorbed by Photosystem II (PS II), drive the catalytic center of oxygen evolution (OEC) through five transitions which are named S 0 ⇒S 1 to S 3 ⇒S 4 →S 0 [1] . Manganese (Mn 4 ), tyrosine (Y Z ) and a chemically ill-defined compound, X, serve as redox cofactors. Transient optical absorption spectra of PS II core particles have led us to propose that the same cofactor X is oxidized on S 2 ⇒S 3 in controls and on S 1 * ⇒S 2 * in Cl − -depleted centers [2] . In this work this particular transition was scrutinized by monitoring UV-transients, proton release and transmembrane electrochromism, both in Cl − -depleted and in control thylakoids. The oxidation of X by Y Z ox caused biphasic proton release: the fast component ( t 1/2 ≈35 μs) was attributable to electrostatically induced pK-shifts of peripheral amino acid residues. It was transient and disappeared concomittantly with the rise of the slow component ( t 1/2 ≈220 μs) that was attributed to proton liberation from X itself. The stoichiometric extent of `chemical' proton release per X ⋅ was 1:1. The transfer of a proton from X into the lumen of thylakoids was electrogenic with a relative extent of 10% of the one attributable to the formation of the charge pair Y Z ox /Q A − . The oxidation of X by Y Z ox , proton release and the 10% rise of the transmembrane voltage were all characterized by the same half-rise time of 220 μs. We propose that the membrane embedded X, after its oxidation and deprotonation during S 2 ⇒S 3 , serves as the postulated hydrogen acceptor during the final oxygen evolving step S 3 ⇒S 4 →S 0 ." @default.
• W2004661331 created "2016-06-24" @default.
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• W2004661331 date "1997-07-01" @default.
• W2004661331 modified "2023-10-18" @default.
• W2004661331 title "Cofactor X of photosynthetic water oxidation: electron transfer, proton release, and electrogenic behaviour in chloride-depleted Photosystem II" @default.
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• W2004661331 doi "https://doi.org/10.1016/s0005-2728(97)00042-x" @default.
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