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EPR Detection of Possible Superparamagnetic Polyiron Nanoparticles and Free Radicals in the Blood Serum of Patients with Homozygous β-Thalassemia

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Abstract

In homozygous β-thalassemia blood transfusions and chelating therapy cannot prevent completely hemochromatosis. Labile ‘free’ iron forms in blood serum and evolves into insoluble inorganic deposits in tissues. Using X-band EPR at 163 K, we detected a new species of polynuclear iron in serum of some thalassemic patients. It showed a broad g < 2 line and an unusually high dynamic magnetic susceptibility due to ordered magnetism, which was detected by a decreased Q factor of the resonant cavity at B = 0. To explain the ordered magnetism and large line, we postulated either ferri- or ferromagnetic nanocrystals with non-zero residual magnetization, or superparamagnetic nanoparticles with antiferromagnetic ordering and incomplete spin compensation—or maybe both. While the results were not sufficient to check the first hypothesis, they are fully consistent with the second. The new species is similar to, but distinct from, ferritin’s mineral core, as it does not correlate with the ferritin concentration. The spectra suggest particles of ~1.7–4.1 nm diameter, plausibly containing ~40–300 Fe(III) ions coupled by oxygen bridges, but further confirmation is needed. The nanoparticles apparently formed a hydrophilic colloidal dispersion, being probably decorated with hydrophilic small organic molecules. They are postulated to form by heterogeneous nucleation around the ‘free’ iron, then aggregate in chains and eventually precipitate in the tissues. Stable free radicals detected in serum were tentatively identified as the hydroxyperoxyl and monodehydroascorbate radicals forming adducts with Cu(II)-ceruloplasmin, and the Hb–porphyrin–Fe(IV)=O oxoferryl radical probably stabilized on haptoglobin. They are consistent with oxy-radicals promoted both by ‘free’ iron and by polyiron nanoparticles. Potential medical applications like early assessment of patient’s evolution trend toward hemochromatosis and monitoring of the transfusional suppression of endogenous erythrocyte synthesis are suggested.

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Notes

  1. This sample was not included in subgroup I because it showed ordered magnetism only after 2 years and not after 1 month like those of subgroup I.

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Acknowledgments

E.A.P. and G.S. express their compassionate feelings for the disappearance of Prof. D. Camillo Giori (Parma, Italy), departed before the preparation of this article. They thank Dr. Anna Butturini (Los Angeles, CA) and Prof. Giancarlo Izzi (Parma) for providing the blood samples, access to the clinical records of the patients under study, and useful discussions. E.A.P. acknowledges the pertinent suggestions from Prof. Octavian G. Duliu and Prof. I.N. Mihailescu (Bucharest). E.A.P. undertook the experimental part of this work with the support of ICTP Programme for Training and Research in Italian Laboratories (TRIL), Abdus Salam International Centre for Theoretical Physics, Trieste, Italy.

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  1. Department of Life and Environment Physics, Horia Hulubei National Institute of Physics and Nuclear Engineering (NIPNE-HH), P.O. Box MG-6, 077125, Bucharest-Magurele, Romania

    Eugen A. Preoteasa

  2. Istituto di Scienze Fisiche, Università di Parma, 43100, Parma, Italy

    Eugen A. Preoteasa, Giulio Schianchi & D. Camillo Giori

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Preoteasa, E.A., Schianchi, G. & Giori, D.C. EPR Detection of Possible Superparamagnetic Polyiron Nanoparticles and Free Radicals in the Blood Serum of Patients with Homozygous β-Thalassemia. Appl Magn Reson 45, 537–571 (2014). https://doi.org/10.1007/s00723-014-0540-8

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