One of the Substrate Waters for O2 Formation in Photosystem II Is Provided by the Water-Splitting Mn4CaO5 Cluster’s Ca2+ Ion
Abstract
During the catalytic step immediately prior to O–O bond formation in Photosystem II, a water molecule deprotonates and moves next to the water-splitting Mn4CaO5 cluster’s O5 oxo bridge. Considerable evidence identifies O5 as one of the two substrate waters that ultimately form O2. The relocated oxygen, known as O6 or Ox, may be the second. It is currently debated whether O6 or Ox originates as the Mn-bound water denoted W2 or as the Ca2+-bound water denoted W3. To distinguish between these two possibilities, we analyzed the D–O–D bending mode of the water molecule that deprotonates/relocates to become O6/Ox. Here, we show that this D–O–D bending mode is not altered by the D1-S169A mutation. Previously, we showed that this D–O–D bending mode is altered substantially when Sr2+ is substituted for Ca2+. Because Sr2+/Ca2+ substitution alters this D–O–D bending mode but the D1-S169A mutation does not, we conclude that the water-derived oxygen that relocates and becomes O6/Ox derives from the Ca2+-bound W3. This conclusion provides an important constraint for proposed mechanisms of O–O bond formation in Photosystem II.
- Publication Date:
- Research Org.:
- Univ. of California, Riverside, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
- OSTI Identifier:
- 1785444
- Grant/Contract Number:
- SC0005291
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Biochemistry
- Additional Journal Information:
- Journal Volume: 58; Journal Issue: 29; Journal ID: ISSN 0006-2960
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 59 BASIC BIOLOGICAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Genetics; Molecules; Ions; Transition metals; Water
Citation Formats
Kim, Christopher J., and Debus, Richard J. One of the Substrate Waters for O2 Formation in Photosystem II Is Provided by the Water-Splitting Mn4CaO5 Cluster’s Ca2+ Ion. United States: N. p., 2019.
Web. doi:10.1021/acs.biochem.9b00418.
Kim, Christopher J., & Debus, Richard J. One of the Substrate Waters for O2 Formation in Photosystem II Is Provided by the Water-Splitting Mn4CaO5 Cluster’s Ca2+ Ion. United States. https://doi.org/10.1021/acs.biochem.9b00418
Kim, Christopher J., and Debus, Richard J. Fri .
"One of the Substrate Waters for O2 Formation in Photosystem II Is Provided by the Water-Splitting Mn4CaO5 Cluster’s Ca2+ Ion". United States. https://doi.org/10.1021/acs.biochem.9b00418. https://www.osti.gov/servlets/purl/1785444.
@article{osti_1785444,
title = {One of the Substrate Waters for O2 Formation in Photosystem II Is Provided by the Water-Splitting Mn4CaO5 Cluster’s Ca2+ Ion},
author = {Kim, Christopher J. and Debus, Richard J.},
abstractNote = {During the catalytic step immediately prior to O–O bond formation in Photosystem II, a water molecule deprotonates and moves next to the water-splitting Mn4CaO5 cluster’s O5 oxo bridge. Considerable evidence identifies O5 as one of the two substrate waters that ultimately form O2. The relocated oxygen, known as O6 or Ox, may be the second. It is currently debated whether O6 or Ox originates as the Mn-bound water denoted W2 or as the Ca2+-bound water denoted W3. To distinguish between these two possibilities, we analyzed the D–O–D bending mode of the water molecule that deprotonates/relocates to become O6/Ox. Here, we show that this D–O–D bending mode is not altered by the D1-S169A mutation. Previously, we showed that this D–O–D bending mode is altered substantially when Sr2+ is substituted for Ca2+. Because Sr2+/Ca2+ substitution alters this D–O–D bending mode but the D1-S169A mutation does not, we conclude that the water-derived oxygen that relocates and becomes O6/Ox derives from the Ca2+-bound W3. This conclusion provides an important constraint for proposed mechanisms of O–O bond formation in Photosystem II.},
doi = {10.1021/acs.biochem.9b00418},
journal = {Biochemistry},
number = 29,
volume = 58,
place = {United States},
year = {Fri Jul 05 00:00:00 EDT 2019},
month = {Fri Jul 05 00:00:00 EDT 2019}
}
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