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X-ray absorption near-edge structure micro-spectroscopy study of vanadium speciation in Phycomyces blakesleeanus mycelium

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Abstract

Vanadium speciation in the fungus Phycomyces blakesleeanus was examined by X-ray absorption near-edge structure (XANES) spectroscopy, enabling assessment of oxidation states and related molecular symmetries of this transition element in the fungus. The exposure of P. blakesleeanus to two physiologically important vanadium species (V5+ and V4+) resulted in the accumulation of this metal in central compartments of 24 h old mycelia, most probably in vacuoles. Tetrahedral V5+, octahedral V4+, and proposed intracellular complexes of V5+ were detected simultaneously after addition of a physiologically relevant concentration of V5+ to the mycelium. A substantial fraction of the externally added V4+ remained mostly in its original form. However, observable variations in the pre-edge-peak intensities in the XANES spectra indicated intracellular complexation and corresponding changes in the molecular coordination symmetry. Vanadate complexation was confirmed by 51V NMR and Raman spectroscopy, and potential binding compounds including cell-wall constituents (chitosan and/or chitin), (poly)phosphates, DNA, and proteins are proposed. The evidenced vanadate complexation and reduction could also explain the resistance of P. blakesleeanus to high extracellular concentrations of vanadium.

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Acknowledgments

We thank the Swiss Light Source (SLS) facility for beam time allocation (Proposal Id 20131280) and excellent working conditions. This work was supported by the Grants of Ministry of Education and Science of Republic of Serbia: OI-173040 and OI-173028 (in part). TD was founded by ALBA Ih-house research grant “X-ray imaging of the protein aggregates induced by nanoparticles in vitro”. The authors thank Dr Vesna Rakic for DSC measurements and Nenad Stevic for technical assistance during ICP–OES measurements.

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The authors declare no conflict of interest.

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    Authors and Affiliations

    1. Institute for Multidisciplinary Research, Department of Life Sciences, University of Belgrade, Kneza Višeslava 1, 11030, Belgrade, Serbia

      Milan Žižić, Miroslav Nikolic, Marina Stanić & Strahinja Križak

    2. CELLS – ALBA, Carretera BP 1413, de Cerdanyola del Vallès a Sant Cugat del Vallès, km. 3,3, 08290, Cerdanyola del Vallès, Barcelona, Spain

      Tanja Dučić

    3. Swiss Light Source, Paul Scherrer Institute, 5232, Villigen-PSI, Switzerland

      Daniel Grolimund

    4. Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, 11000, Belgrade, Serbia

      Danica Bajuk-Bogdanović

    5. Institute of General and Physical Chemistry, NMR Laboratory, Studentski trg 12-16, 11000, Belgrade, Serbia

      Joanna Zakrzewska

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    1. Milan Žižić
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    Correspondence to Milan Žižić.

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    Milan Žižić and Tanja Dučić contributed equally to this work.

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    Žižić, M., Dučić, T., Grolimund, D. et al. X-ray absorption near-edge structure micro-spectroscopy study of vanadium speciation in Phycomyces blakesleeanus mycelium. Anal Bioanal Chem 407, 7487–7496 (2015). https://doi.org/10.1007/s00216-015-8916-7

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