XANES (X-ray Absorption Near-Edge Structure) in Biophysics


Photosynthetic enzymes containing manganese have been studied by XANES for many years, and various model structures of the photosynthetic oxygen evolving manganese cluster have been proposed. High-resolution XANES with light illumination experiments have recently provided new insight on Mn valency. The first observation of a cyclic shift of the Mn K-edge associated with laser illumination showed that the oxidation state of Mn does oscillate during a four-electron cycling reaction induced by photons, corresponding to the well known "oxygen clock" mechanism proposed by Joliot & Kok.

Mn K-XANES spectra for O2-evolving photosystem II (PSII) membranes after a series of flashes, which demonstrates the first observation of a cyclic shift of the Mn K-edge associated with laser illumination. These results evidenced that the oxidation state of Mn does oscillate during a four-electron cycling reaction induced by photons.

Oscillation of the Mn K-edge energy of PSII membranes under single-turnover flashes. The half-height energies of Mn K-edge spectra after zero to five flashes ( ) were compared with the simulated values ().
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