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Relaxation behaviour of the tyrosine Y-D radical in photosystem II: evidence for strong dipolar interaction with paramagnetic centers in the S-1 and S-2 states

Authors
Publisher
Royal Society of Chemistry
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Keywords
  • Chemistry

Abstract

Inversion recovery (T-1) and microwave power saturation studies have been performed, between 4 and 25 K, on the EPR signal from the stable tyrosyl radical, Y-D(.), in photosystem II core complex preparations from higher plants. Measurements are reported from the dark stable S-1 and first turnover S-2 states of the photosystem catalytic Mn cluster and in two cryoprotectant regimes; sucrose and ethylene glycol/glycerol. The inversion recovery kinetics show a dominant, non exponential decay component which is well described by a through space dipolar relaxation model, with a weak exponential decay background (similar toan order of magnitude less than the dipolar rate). The dipolar relaxation rate is only modestly temperature dependent and shows no consistent dependence on S state or cryoprotectant. In contrast, the background rate shows a S state dependence, consistent with an interaction between Y-D(.) and the Mn cluster in the multiline S-2 state, over a distance of similar to30 Angstrom. The fraction of centers exhibiting the dipolar relaxation component appears to be temperature dependent, but S state independent and consistent with the presence of a fast relaxing species interacting with Y-D(.). The present results and the possible nature of this interacting species are discussed in comparison with earlier Y-D(.) relaxation studies on photosystem II membrane samples.

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