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First-principles electronic structure study of rhizoferrin and its Fe(III) complexes

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Abstract

We have determined the structure and coordination chemistry of rhizoferrin (Rf), which is a particular type of siderophore, and its Fe(III) complexes using density functional theory calculations. Our results show that the Fe(III) ion binds in an octahedral coordination, with a low-spin (S = 1/2) charge-neutral chiral complex having the largest binding energy of the investigated complexes. We have also calculated nuclear magnetic resonance parameters, such as chemical shifts for 1H and 13C, and indirect nuclear spin–spin couplings for 1H–1H and 13C–1H in free Rf and in a low-spin neutral Rf metal complex, as well as nuclear quadrupole interaction parameters, such as asymmetry parameter and nuclear quadrupole coupling constants for 14N. Our calculated values for the chemical shifts for free Rf are in excellent agreement with experimental data while the calculated NMR parameters for Fe(III) complexes are predictions for future experimental work.

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Acknowledgments

Argonne National Laboratory is a US DOE Science Laboratory operated under contract no. DE-AC02-06CH11357 by UChicago Argonne, LLC. The research was performed, in part, at Argonne National Laboratory as a research participant in the Visiting Faculty Program. The program is administered by Argonne’s Division of Communication, Education, and Public Affairs (CEPA) with funding provided by the U.S. Department of Energy. This work used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation grant number OCI-1053575. The authors acknowledge the University of Central Florida Stokes Advanced Research Computing Center for providing computational resources and support that have contributed to results reported herein. URL: http://webstokes.ist.ucf.edu.

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Authors and Affiliations

  1. Department of Physics and Astronomy, University of Central Florida, Orlando, FL, USA

    Archana Dubey

  2. Materials Science Division, Argonne National Laboratory, Chicago, IL, USA

    Olle Heinonen

  3. Department of Physics and Astronomy, Northwestern University, Chicago, IL, USA

    Olle Heinonen

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  1. Archana Dubey
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  2. Olle Heinonen
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Correspondence to Olle Heinonen.

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Dubey, A., Heinonen, O. First-principles electronic structure study of rhizoferrin and its Fe(III) complexes. Biometals 26, 1003–1012 (2013). https://doi.org/10.1007/s10534-013-9677-4

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  • DOI: https://doi.org/10.1007/s10534-013-9677-4

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