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The iron–sulfur core in Rieske proteins is not symmetric

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Abstract

At variance with ferredoxins, Rieske-type proteins contain a chemically asymmetric iron–sulfur cluster. Nevertheless, X-ray crystallography apparently finds their [2Fe–2S] cores to be structurally symmetric or very close to symmetric (i.e. the four iron–sulfur bonds in the [2Fe–2S] core are equidistant). Using a combination of advanced density-based approaches, including finite-temperature molecular dynamics to access thermal fluctuations and free-energy profiles, in conjunction with correlated wavefunction-based methods we clearly predict an asymmetric core structure. This reveals a fundamental and intrinsic difference within the iron–sulfur clusters hosted by Rieske proteins and ferredoxins and thus opens up a new dimension for the ongoing efforts in understanding the role of Rieske-type [2Fe–2S] cluster in electron transfer processes that occur in almost all biological systems.

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Acknowledgments

We thank Professor Hofmann (Bochum) for his help in assessing X-ray crystallographic data. Md. E. Ali is grateful to support by the Alexander von Humboldt-Foundation via his Humboldt Postdoctoral Fellowship and D.M. acknowledges partial financial support from DFG. The calculations have been carried out using resources from NIC (Jülich), RV-NRW and SNIC-NSC(Linköping).

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Authors and Affiliations

  1. Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, 44780, Bochum, Germany

    Md. Ehesan Ali, Volker Staemmler & Dominik Marx

  2. Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016, India

    Nisanth N. Nair

  3. Max-Planck-Institut für Chemische Energiekonversion, Stiftstrasse 34–36, 45470, Mülheim an der Ruhr, Germany

    Marius Retegan & Frank Neese

Authors
  1. Md. Ehesan Ali
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  2. Nisanth N. Nair
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  3. Marius Retegan
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  4. Frank Neese
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  5. Volker Staemmler
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  6. Dominik Marx
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Correspondence to Md. Ehesan Ali.

Electronic supplementary material

Computational model and details of RR calculations and vibrational mode assignment; comparison of structural parameters of Rieske cores obtained from different methodologies.

Supplementary material 1 (pdf 5716 KB)

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Ali, M.E., Nair, N.N., Retegan, M. et al. The iron–sulfur core in Rieske proteins is not symmetric. J Biol Inorg Chem 19, 1287–1293 (2014). https://doi.org/10.1007/s00775-014-1185-7

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  • DOI: https://doi.org/10.1007/s00775-014-1185-7

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