S-state dependence of the calcium requirement and binding characteristics in the oxygen-evolving complex of photosystem II.

Abstract:

:The functional role of the Ca (2+) ion in the oxygen-evolving complex of photosystem II is not yet clear. Current models explain why the redox cycle of the complex would be interrupted after the S 3 state without Ca (2+), but the literature shows that it is interrupted after the S 2 state. Reinterpretation of the literature on methods of Ca (2+) depletion [Miqyass, M., van Gorkom, H. J., and Yocum, C. F. (2007) Photosynth. Res. 92, 275-287] led us to propose that all S-state transitions require Ca (2+). Here we confirm that interpretation by measurements of flash-induced S-state transitions in UV absorbance. The results are explained by a cation exchange at the Ca (2+) binding site that, in the absence of the extrinsic PsbP and PsbQ polypeptides, can occur in minutes in low S-states and in seconds in high S-states, depending on the concentration of the substituting cation. In the S 2(K (+)) or S 2(Na (+)) state a slow conformational change occurs that prevents recovery of the slow-exchange situation on return to a lower S-state but does not inhibit the S-state cycle in the presence of Ca (2+). The ratio of binding affinities for monovalent vs divalent cations increases dramatically in the higher S-states. With the possible exception of S 0 to S 1, all S-state transitions specifically require Ca (2+), suggesting that Ca (2+)-bound H 2O plays an essential role in a H (+) transfer network required for H (+)-coupled electron transfer from the Mn cluster to tyrosine Z.

journal_name

Biochemistry

journal_title

Biochemistry

authors

Miqyass M,Marosvölgyi MA,Nagel Z,Yocum CF,van Gorkom HJ

doi

10.1021/bi8006059

subject

Has Abstract

pub_date

2008-07-29 00:00:00

pages

7915-24

issue

30

eissn

0006-2960

issn

1520-4995

journal_volume

47

pub_type

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