Low-frequency resonance Raman characterization of the oxygen-evolving complex of photosystem II

Agnes Cua, David H. Stewart, Michael J. Reifler, Gary W Brudvig, David F. Bocian

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Abstract

The O2-evolving complex (OEC) of photosystem II (PSII) contains a tetramanganese (Mn4) cluster, a redox-active tyrosine, and Ca2+/CI- ions, but its molecular structure has not been determined. Vibrational spectroscopy has the potential of providing new structural information for the OEC, particularly the Mn4 cluster. Toward this goal, the vibrational characteristics of the OEC of PSII were examined using near-infrared (NIR) excitation Raman spectroscopy. NIR excitation decreases the background contribution from chlorophyll emission/Raman scattering and affords the opportunity of probing selectively low-energy electronic transitions of the Mn4 cluster. The primary emphasis of the Raman study was on the low- frequency range of the spectrum (220-620 cm-1) where Mn-ligand vibrational modes are expected to occur. The low-frequency region was examined for both the S1 and S2 oxidation states of the Mn4 cluster. A particular effort was made to probe a NIR transition of the S2 state that has been reported to mediate photoconversion from the multiline to the g = 4.1 form of the S2 state [Boussac et al. Biochemistry 1996, 35, 6984-6989]. The Raman studies revealed the following: (1) the Raman spectra of Mn-depleted PSII and PSII in the S2 state are nearly identical; (2) the Raman spectrum of PSII in the S1 state displays several unique low-frequency bands not present in the S2 state that can be assigned as Mn-ligand vibrational modes and appear to maximize in intensity at λ(ex) ~ 820 nm; and (3) several of the S1 state Raman bands are shifted bY D2O/H2O exchange. Collectively, these results indicate that the S1 state of the Mn4 cluster (1) has a NIR electronic transition from which resonance enhanced Raman scattering can be induced and (2) is coordinated by at least two H2O or OH- groups. The studies reported herein also demonstrate the potential of NIR-excitation Raman techniques for probing selectively the OEC in PSII and, in particular, for characterizing the coordination environment of the Mn4 cluster.

Original languageEnglish
Pages (from-to)2069-2077
Number of pages9
JournalJournal of the American Chemical Society
Volume122
Issue number9
DOIs
Publication statusPublished - Mar 8 2000

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Photosystem II Protein Complex
Raman scattering
Oxygen
Infrared radiation
Raman Spectrum Analysis
Ligands
Vibrational spectroscopy
Biochemistry
Chlorophyll
Molecular structure
Frequency bands
Raman spectroscopy
Molecular Structure
Oxidation-Reduction
Tyrosine
Spectrum Analysis
Oxidation
Ions

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Low-frequency resonance Raman characterization of the oxygen-evolving complex of photosystem II. / Cua, Agnes; Stewart, David H.; Reifler, Michael J.; Brudvig, Gary W; Bocian, David F.

In: Journal of the American Chemical Society, Vol. 122, No. 9, 08.03.2000, p. 2069-2077.

Research output: Contribution to journalArticle

Cua, Agnes ; Stewart, David H. ; Reifler, Michael J. ; Brudvig, Gary W ; Bocian, David F. / Low-frequency resonance Raman characterization of the oxygen-evolving complex of photosystem II. In: Journal of the American Chemical Society. 2000 ; Vol. 122, No. 9. pp. 2069-2077.
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AB - The O2-evolving complex (OEC) of photosystem II (PSII) contains a tetramanganese (Mn4) cluster, a redox-active tyrosine, and Ca2+/CI- ions, but its molecular structure has not been determined. Vibrational spectroscopy has the potential of providing new structural information for the OEC, particularly the Mn4 cluster. Toward this goal, the vibrational characteristics of the OEC of PSII were examined using near-infrared (NIR) excitation Raman spectroscopy. NIR excitation decreases the background contribution from chlorophyll emission/Raman scattering and affords the opportunity of probing selectively low-energy electronic transitions of the Mn4 cluster. The primary emphasis of the Raman study was on the low- frequency range of the spectrum (220-620 cm-1) where Mn-ligand vibrational modes are expected to occur. The low-frequency region was examined for both the S1 and S2 oxidation states of the Mn4 cluster. A particular effort was made to probe a NIR transition of the S2 state that has been reported to mediate photoconversion from the multiline to the g = 4.1 form of the S2 state [Boussac et al. Biochemistry 1996, 35, 6984-6989]. The Raman studies revealed the following: (1) the Raman spectra of Mn-depleted PSII and PSII in the S2 state are nearly identical; (2) the Raman spectrum of PSII in the S1 state displays several unique low-frequency bands not present in the S2 state that can be assigned as Mn-ligand vibrational modes and appear to maximize in intensity at λ(ex) ~ 820 nm; and (3) several of the S1 state Raman bands are shifted bY D2O/H2O exchange. Collectively, these results indicate that the S1 state of the Mn4 cluster (1) has a NIR electronic transition from which resonance enhanced Raman scattering can be induced and (2) is coordinated by at least two H2O or OH- groups. The studies reported herein also demonstrate the potential of NIR-excitation Raman techniques for probing selectively the OEC in PSII and, in particular, for characterizing the coordination environment of the Mn4 cluster.

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