Optical identification of the long-wavelength (700-1700 nm) electronic excitations of the native reaction centre, Mn4CaO5 cluster and cytochromes of photosystem II in plants and cyanobacteria

Jennifer Morton, Fusamichi Akita, Yoshiki Nakajima, Jian Ren Shen, Elmars Krausz

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5 Citations (Scopus)

Abstract

Visible/UV absorption in PS II core complexes is dominated by the chl-a absorptions, which extend to ~ 700 nm. A broad 700-730 nm PS II core complex absorption in spinach has been assigned [1] to a charge transfer excitation between ChlD1 and ChlD2. Emission from this state, which peaks at 780 nm, has been seen [2] for both plant and cyanobacterial samples. We show that Thermosynechococcus vulcanus PS II core complexes have parallel absorbance in the 700-730 nm region and similar photochemical behaviour to that seen in spinach. This establishes the low energy charge transfer state as intrinsic to the native PS II reaction centre. High-sensitivity MCD measurements made in the 700-1700 nm region reveal additional electronic excitations at ~ 770 nm and ~ 1550 nm. The temperature and field dependence of MCD spectra establish that the system peaking near 1550 nm is a heme-to-Fe(III) charge transfer excitation. These transitions have not previously been observed for cyt b559 or cyt c550. The distinctive characteristics of the MCD signals seen at 770 nm allow us to assign absorption in this region to a dz 2 → dx2 - y2 transition of Mn(III) in the Ca-Mn4O5 cluster of the oxygen evolving centre. Current measurements were performed in the S1 state. Detailed analyses of this spectral region, especially in higher S states, promise to provide a new window on models of water oxidation.

Original languageEnglish
Pages (from-to)153-161
Number of pages9
JournalBiochimica et Biophysica Acta - Bioenergetics
Volume1847
Issue number2
DOIs
Publication statusPublished - 2014

Fingerprint

Photosystem II Protein Complex
Cyanobacteria
Cytochromes
Charge transfer
Wavelength
Spinacia oleracea
Electric current measurement
Heme
Energy Transfer
Oxygen
Oxidation
Water
Temperature

Keywords

  • Charge-transfer
  • Circular dichroism
  • Magnetic circular dichroism
  • Oxygen evolving centre
  • Photosystem II
  • Reaction centre

ASJC Scopus subject areas

  • Biochemistry
  • Biophysics
  • Cell Biology
  • Medicine(all)

Cite this

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title = "Optical identification of the long-wavelength (700-1700 nm) electronic excitations of the native reaction centre, Mn4CaO5 cluster and cytochromes of photosystem II in plants and cyanobacteria",
abstract = "Visible/UV absorption in PS II core complexes is dominated by the chl-a absorptions, which extend to ~ 700 nm. A broad 700-730 nm PS II core complex absorption in spinach has been assigned [1] to a charge transfer excitation between ChlD1 and ChlD2. Emission from this state, which peaks at 780 nm, has been seen [2] for both plant and cyanobacterial samples. We show that Thermosynechococcus vulcanus PS II core complexes have parallel absorbance in the 700-730 nm region and similar photochemical behaviour to that seen in spinach. This establishes the low energy charge transfer state as intrinsic to the native PS II reaction centre. High-sensitivity MCD measurements made in the 700-1700 nm region reveal additional electronic excitations at ~ 770 nm and ~ 1550 nm. The temperature and field dependence of MCD spectra establish that the system peaking near 1550 nm is a heme-to-Fe(III) charge transfer excitation. These transitions have not previously been observed for cyt b559 or cyt c550. The distinctive characteristics of the MCD signals seen at 770 nm allow us to assign absorption in this region to a dz 2 → dx2 - y2 transition of Mn(III) in the Ca-Mn4O5 cluster of the oxygen evolving centre. Current measurements were performed in the S1 state. Detailed analyses of this spectral region, especially in higher S states, promise to provide a new window on models of water oxidation.",
keywords = "Charge-transfer, Circular dichroism, Magnetic circular dichroism, Oxygen evolving centre, Photosystem II, Reaction centre",
author = "Jennifer Morton and Fusamichi Akita and Yoshiki Nakajima and Shen, {Jian Ren} and Elmars Krausz",
year = "2014",
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language = "English",
volume = "1847",
pages = "153--161",
journal = "Biochimica et Biophysica Acta - Bioenergetics",
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T1 - Optical identification of the long-wavelength (700-1700 nm) electronic excitations of the native reaction centre, Mn4CaO5 cluster and cytochromes of photosystem II in plants and cyanobacteria

AU - Morton, Jennifer

AU - Akita, Fusamichi

AU - Nakajima, Yoshiki

AU - Shen, Jian Ren

AU - Krausz, Elmars

PY - 2014

Y1 - 2014

N2 - Visible/UV absorption in PS II core complexes is dominated by the chl-a absorptions, which extend to ~ 700 nm. A broad 700-730 nm PS II core complex absorption in spinach has been assigned [1] to a charge transfer excitation between ChlD1 and ChlD2. Emission from this state, which peaks at 780 nm, has been seen [2] for both plant and cyanobacterial samples. We show that Thermosynechococcus vulcanus PS II core complexes have parallel absorbance in the 700-730 nm region and similar photochemical behaviour to that seen in spinach. This establishes the low energy charge transfer state as intrinsic to the native PS II reaction centre. High-sensitivity MCD measurements made in the 700-1700 nm region reveal additional electronic excitations at ~ 770 nm and ~ 1550 nm. The temperature and field dependence of MCD spectra establish that the system peaking near 1550 nm is a heme-to-Fe(III) charge transfer excitation. These transitions have not previously been observed for cyt b559 or cyt c550. The distinctive characteristics of the MCD signals seen at 770 nm allow us to assign absorption in this region to a dz 2 → dx2 - y2 transition of Mn(III) in the Ca-Mn4O5 cluster of the oxygen evolving centre. Current measurements were performed in the S1 state. Detailed analyses of this spectral region, especially in higher S states, promise to provide a new window on models of water oxidation.

AB - Visible/UV absorption in PS II core complexes is dominated by the chl-a absorptions, which extend to ~ 700 nm. A broad 700-730 nm PS II core complex absorption in spinach has been assigned [1] to a charge transfer excitation between ChlD1 and ChlD2. Emission from this state, which peaks at 780 nm, has been seen [2] for both plant and cyanobacterial samples. We show that Thermosynechococcus vulcanus PS II core complexes have parallel absorbance in the 700-730 nm region and similar photochemical behaviour to that seen in spinach. This establishes the low energy charge transfer state as intrinsic to the native PS II reaction centre. High-sensitivity MCD measurements made in the 700-1700 nm region reveal additional electronic excitations at ~ 770 nm and ~ 1550 nm. The temperature and field dependence of MCD spectra establish that the system peaking near 1550 nm is a heme-to-Fe(III) charge transfer excitation. These transitions have not previously been observed for cyt b559 or cyt c550. The distinctive characteristics of the MCD signals seen at 770 nm allow us to assign absorption in this region to a dz 2 → dx2 - y2 transition of Mn(III) in the Ca-Mn4O5 cluster of the oxygen evolving centre. Current measurements were performed in the S1 state. Detailed analyses of this spectral region, especially in higher S states, promise to provide a new window on models of water oxidation.

KW - Charge-transfer

KW - Circular dichroism

KW - Magnetic circular dichroism

KW - Oxygen evolving centre

KW - Photosystem II

KW - Reaction centre

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U2 - 10.1016/j.bbabio.2014.11.003

DO - 10.1016/j.bbabio.2014.11.003

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JO - Biochimica et Biophysica Acta - Bioenergetics

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