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Title: D1-S169A Substitution of Photosystem II Perturbs Water Oxidation

Abstract

In photosystem II (PSII), photosynthetic water oxidation occurs at the tetramanganese–calcium cluster that cycles through light-induced intermediates (S0–S4) to produce oxygen from two substrate waters. The surrounding hydrogen-bonded amino acid residues and waters form channels that facilitate proton transfer and substrate water delivery, thereby ensuring efficient water oxidation. The residue D1-S169 lies in the “narrow” channel and forms hydrogen bonds with the Mn4CaO5 cluster via waters W1 and Wx. To probe the role of the narrow channel in substrate-water binding, we studied the D1-S169A mutation. PSII core complexes isolated from mutant cells exhibit inefficient S-state cycling and delayed oxygen evolution. The S2-state multiline EPR spectrum of D1-S169A PSII core complexes differed significantly from that of wild-type, and FTIR difference spectra showed that the mutation strongly perturbs the extensive network of hydrogen bonds that extends at least from D1-Y161 (YZ) to D1-D61. Finally, these results imply a possible role of D1-S169 in proton egress or substrate water delivery.

Authors:
 [1];  [1];  [2];  [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Yale Univ., New Haven, CT (United States). Dept. of Chemistry
  2. Univ. of California, Riverside, CA (United States). Dept. of Biochemistry
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1530435
Grant/Contract Number:  
FG02-05ER15646; SC0005291; SC0001423
Resource Type:
Accepted Manuscript
Journal Name:
Biochemistry
Additional Journal Information:
Journal Volume: 58; Journal Issue: 10; Journal ID: ISSN 0006-2960
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; cyanobacteria; mutation; oxygen evolution; photosystem II; structure; substrate water

Citation Formats

Ghosh, Ipsita, Banerjee, Gourab, Kim, Christopher J., Reiss, Krystle, Batista, Victor S., Debus, Richard J., and Brudvig, Gary W. D1-S169A Substitution of Photosystem II Perturbs Water Oxidation. United States: N. p., 2019. Web. doi:10.1021/acs.biochem.8b01184.
Ghosh, Ipsita, Banerjee, Gourab, Kim, Christopher J., Reiss, Krystle, Batista, Victor S., Debus, Richard J., & Brudvig, Gary W. D1-S169A Substitution of Photosystem II Perturbs Water Oxidation. United States. https://doi.org/10.1021/acs.biochem.8b01184
Ghosh, Ipsita, Banerjee, Gourab, Kim, Christopher J., Reiss, Krystle, Batista, Victor S., Debus, Richard J., and Brudvig, Gary W. Fri . "D1-S169A Substitution of Photosystem II Perturbs Water Oxidation". United States. https://doi.org/10.1021/acs.biochem.8b01184. https://www.osti.gov/servlets/purl/1530435.
@article{osti_1530435,
title = {D1-S169A Substitution of Photosystem II Perturbs Water Oxidation},
author = {Ghosh, Ipsita and Banerjee, Gourab and Kim, Christopher J. and Reiss, Krystle and Batista, Victor S. and Debus, Richard J. and Brudvig, Gary W.},
abstractNote = {In photosystem II (PSII), photosynthetic water oxidation occurs at the tetramanganese–calcium cluster that cycles through light-induced intermediates (S0–S4) to produce oxygen from two substrate waters. The surrounding hydrogen-bonded amino acid residues and waters form channels that facilitate proton transfer and substrate water delivery, thereby ensuring efficient water oxidation. The residue D1-S169 lies in the “narrow” channel and forms hydrogen bonds with the Mn4CaO5 cluster via waters W1 and Wx. To probe the role of the narrow channel in substrate-water binding, we studied the D1-S169A mutation. PSII core complexes isolated from mutant cells exhibit inefficient S-state cycling and delayed oxygen evolution. The S2-state multiline EPR spectrum of D1-S169A PSII core complexes differed significantly from that of wild-type, and FTIR difference spectra showed that the mutation strongly perturbs the extensive network of hydrogen bonds that extends at least from D1-Y161 (YZ) to D1-D61. Finally, these results imply a possible role of D1-S169 in proton egress or substrate water delivery.},
doi = {10.1021/acs.biochem.8b01184},
journal = {Biochemistry},
number = 10,
volume = 58,
place = {United States},
year = {Fri Feb 01 00:00:00 EST 2019},
month = {Fri Feb 01 00:00:00 EST 2019}
}

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