Water molecules coupled to the redox-active tyrosine Y(D) in photosystem II as detected by FTIR spectroscopy

Biochemistry
Ryouta TakahashiTakumi Noguchi

Abstract

The redox-active tyrosine YD (D2-Tyr160) in photosystem II (PSII) serves as a side-path electron donor to P680. When YD is oxidized, a proton is released from phenolic OH, and a neutral radical YD* is formed. A hydrogen bond network around YD must be deeply involved in the mechanism of the YD reaction. In this study, we have detected water molecules structurally coupled to YD by means of Fourier transform infrared (FTIR) spectroscopy. Light-induced YD*/YD FTIR difference spectrum of a hydrated film of the PSII core complexes from Thermosynechococcus elongatus showed major signals at 3636(-)/3617(+) and 3594(+)/3585(-) cm-1 in the weakly hydrogen bonded OH stretching region. These peaks downshifted by 11-12 cm-1 upon H218O substitution and almost disappeared upon H/D exchange, and hence, they were definitely assigned to the water OH vibrations. Small intramolecular couplings of 3-6 cm-1 estimated from the OH frequencies of residual HOD species in a deuterated film indicate that these OH signals arise from two different water molecules that have significantly asymmetric hydrogen bond structures. Similar OH signals were observed in PSII-enriched membranes from spinach, suggesting that two water molecules commonly exist near YD irr...Continue Reading

Citations

Jun 11, 2009·Photosynthesis Research·Catherine Berthomieu, Rainer Hienerwadel
Jul 10, 2009·Journal of the American Chemical Society·David L Jenson, Bridgette A Barry
May 6, 2011·Proceedings of the National Academy of Sciences of the United States of America·Amandine Maréchal, Peter R Rich
Apr 20, 2013·Proceedings of the National Academy of Sciences of the United States of America·Keisuke SaitoHiroshi Ishikita
Nov 29, 2013·Journal of the Royal Society, Interface·Hiroshi Ishikita, Keisuke Saito
Apr 15, 2010·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Sven KessenRobert Bittl
May 3, 2008·Biochimica Et Biophysica Acta·Rainer HienerwadelCatherine Berthomieu
Apr 2, 2014·Chemical Reviews·Agostino MiglioreDavid N Beratan
Sep 3, 2014·Biochemistry·Johannes SjöholmStenbjörn Styring

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