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Multifrequency cw-EPR investigation of the catalytic molybdenum cofactor of polysulfide reductase from Wolinella succinogenes

  • Thomas PrisnerEmail author
  • Sevdalina Lyubenova
  • Yener Atabay
  • Fraser MacMillan
  • Achim Kröger
  • Oliver Klimmek
Original Article

Abstract

Electron paramagnetic resonance (EPR) spectra of the molybdenum centre in polysulfide reductase (Psr) from Wolinella succinogenes with unusually high G-tensor values have been observed for the first time. Three different MoV states have been generated (by the addition of the substrate polysulfide and different redox agents) and analysed by their G- and hyperfine tensors using multifrequency (S-, X- and Q-band) cw-EPR spectroscopy. The unusually high G-tensor values are attributed to a large number of sulfur ligands. Four sulfur ligands are assumed to arise from two pterin cofactors; one additional sulfur ligand was identified from mutagenesis studies to be a cysteine residue of the protein backbone. One further sulfur ligand is proposed for two of the MoV states, based on the experimentally observed shift of the g av value. This sixth sulfur ligand is postulated to belong to the polysulfide substrate consumed within the catalytic reaction cycle of the enzyme. The influence of the co-protein sulfur transferase on the MoV G-tensor supports this assignment.

Keywords

Molybdoenzymes Molybdopterin G-tensor Q-band EPR S-band EPR 

Notes

Acknowledgements

This work was supported by the Sonderforschungsbereich "Molecular Bioenergetics" of the Deutsche Forschungsgemeinschaft (DFG, Sfb 472). Axel Weber is thanked for performing the S-band cw-EPR measurements and the EPR division of Bruker, Rheinstetten, for the possibility to perform the Q-band EPR measurements.

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Copyright information

© SBIC 2003

Authors and Affiliations

  • Thomas Prisner
    • 1
    Email author
  • Sevdalina Lyubenova
    • 1
  • Yener Atabay
    • 1
  • Fraser MacMillan
    • 1
  • Achim Kröger
    • 2
  • Oliver Klimmek
    • 2
  1. 1.Institute of Physical and Theoretical ChemistryJohann Wolfgang Goethe-University FrankfurtFrankfurt am MainGermany
  2. 2.Institute of MicrobiologyJohann Wolfgang Goethe-University FrankfurtFrankfurt am MainGermany

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