Structural Dynamics of the Oxygen-Evolving Complex of Photosystem II in Water-Splitting Action

Andrew J. Wilson, Prashant Jain

Research output: Contribution to journalArticle

Abstract

Oxygenic photosynthesis in nature occurs via water splitting catalyzed by the oxygen-evolving complex (OEC) of photosystem II. To split water, the OEC cycles through a sequence of oxidation states (Si, i = 0-4), the structural mechanism of which is not fully understood under physiological conditions. We monitored the OEC in visible-light-driven water-splitting action by using in situ, aqueous-environment surface-enhanced Raman scattering (SERS). In the unexplored low-frequency region of SERS, we found dynamic vibrational signatures of water binding and splitting. Specific snapshots in the dynamic SERS correspond to intermediate states in the catalytic cycle, as determined by density functional theory and isotopologue comparisons. We assign the previously ambiguous protonation configuration of the S0-S3 states and propose a structural mechanism of the OEC's catalytic cycle. The findings address unresolved questions about photosynthetic water splitting and introduce spatially resolved, low-frequency SERS as a chemically sensitive tool for interrogating homogeneous catalysis in operando.

Original languageEnglish (US)
Pages (from-to)5853-5859
Number of pages7
JournalJournal of the American Chemical Society
Volume140
Issue number17
DOIs
StatePublished - May 2 2018

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Photosystem II Protein Complex
Structural dynamics
Raman Spectrum Analysis
Raman scattering
Oxygen
oxygen
scattering
Water
water
Photosynthesis
Protonation
catalysis
Catalysis
Density functional theory
photosynthesis
Light
oxidation
Oxidation

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Structural Dynamics of the Oxygen-Evolving Complex of Photosystem II in Water-Splitting Action. / Wilson, Andrew J.; Jain, Prashant.

In: Journal of the American Chemical Society, Vol. 140, No. 17, 02.05.2018, p. 5853-5859.

Research output: Contribution to journalArticle

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