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A DFT, X- and W-band EPR and ENDOR Study of Nitrogen-Centered Species in (Nano)Hydroxyapatite

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Abstract

Incorporation of the nitrogen-containing impurities in hydroxyapatite (HAp) powders with the sizes of the crystallites of (20–50) nm was studied using first-principles modeling combined with the multi-frequency (9 and 94 GHz) electron paramagnetic resonance (EPR) methods. It is shown that the observed EPR spectra are undoubtedly due to the presence of the bulk radiation-induced NO3 2− radicals. This conclusion is based on spin-polarized density functional theory calculations of spectroscopic parameters within gauge-including projector augmented wave framework followed by the exact comparison of the simulated EPR and electron–nuclear double resonance spectra with the experimental findings. In addition, a comprehensive analysis of the simulated properties allows us to suggest that the paramagnetic centers preferably occupy PO4 3− sites in the HAp structure.

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Acknowledgments

This work was funded by the subsidy allocated to Kazan Federal University for the state assignment in the sphere of scientific activities. M.G. and T.B. acknowledge the subsidy of the Russian Government to support the Program of competitive Growth of Kazan Federal University among World’s Leading Academic Centers. The measurements were done on the equipment of the Centre of the Shared Facilities of Kazan Federal University.

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  1. Institute of Physics, Kazan Federal University, Kremlevskaya 18, 420008, Kazan, Russia

    Marat Gafurov, Timur Biktagirov, Georgy Mamin & Sergei Orlinskii

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  1. Marat Gafurov
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  2. Timur Biktagirov
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Correspondence to Timur Biktagirov.

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Gafurov, M., Biktagirov, T., Mamin, G. et al. A DFT, X- and W-band EPR and ENDOR Study of Nitrogen-Centered Species in (Nano)Hydroxyapatite. Appl Magn Reson 45, 1189–1203 (2014). https://doi.org/10.1007/s00723-014-0572-0

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