Electro paramagnetic resonance and magnetization measurements of metal-substituted hydroxyapatites used in hyperthermia applications

  • Dr Hany Kamal Physics Department, Faculty of Science, Mansoura University, Mansoura 35516, Egypt
Keywords: hydroxyapatite, metal doped, EPR, magnetization, hyperthermia


Pure and metal doped hydroxyapatite samples nano-particles were prepared by the wet chemical method. Copper and cobalt is used in doping hydroxyapatite. Sample was prepared without change in the stoichiometric ratio of Ca/P and Ca+M/P inside the structure of HA (M;metal). Sample was characterized by electron paramagnetic resonance, magnetization, transmission electron microscope and electron diffraction. Samples posses the highest value of magnetic susceptibility was chosen for more study to test their ability for application in the field of hyperthermia treatment of bone tumors. Magnetization curves were obtained for samples to study their behavior under the effect of magnetic field. The sample doped with copper and cobalt exhibited hysteresis loops which are characteristic for the magnetic materials. The samples were classified to be ferromagnetic material. Sample prepared by mixing Cu and co had the highest values of saturation magnetization (MS), area (A) enclosed within the hysteresis loop and magnetic anisotropy which represent an indicator of the energy generated in the material under the effect of magnetic field, and hence the amount of heat produced by the sample.  TEM and EDP techniques were used to study the internal structure of these samples. The micrographs and the diffraction patterns showed and confirmed the presence of crystal structures within the samples. The particle size was calculated from the micrographs and found to be in the range of nanometer for all the selected samples.


Download data is not yet available.


1. Nandi, S., et al., Orthopaedic applications of bone graft & graft substitutes: a review. 2010.
2. Dubok, V.A., Bioceramics―yesterday, today, tomorrow. Powder Metallurgy and Metal Ceramics, 2000. 39(7): p. 381-394.
3. Raucci, M.G., D. Giugliano, and L. Ambrosio, Fundamental Properties of Bioceramics and Biocomposites. Handbook of Bioceramics and Biocomposites, 2014: p. 1-19.
4. Gao, C., et al., Current progress in bioactive ceramic scaffolds for bone repair and regeneration. International journal of molecular sciences, 2014. 15(3): p. 4714-4732.
5. Bose, S., D. Banerjee, and A. Bandyopadhyay, Introduction to Biomaterials and Devices for Bone Disorders. Materials and Devices for Bone Disorders, 2016: p. 1.
6. Dorozhkin, S.V., Calcium orthophosphate bioceramics. Ceramics International, 2015. 41(10): p. 13913-13966.
7. D'Amora, U., et al., Hybrid Nanocomposites with Magnetic Activation for Advanced Bone Tissue Engineering. Bio-Inspired Regenerative Medicine: Materials, Processes, and Clinical Applications, 2016: p. 179.
8. Bañobre-López, M., et al., Hyperthermia induced in magnetic scaffolds for bone tissue engineering. IEEE Transactions on Magnetics, 2014. 50(11): p. 1-7.
9. Hurley, K.R., et al., Characterization of magnetic nanoparticles in biological matrices. 2015, ACS Publications.
10. Dutz, S. and R. Hergt, Magnetic particle hyperthermia—a promising tumour therapy? Nanotechnology, 2014. 25(45): p. 452001.
11. Ramakrishna, S., et al., Biomaterials: a nano approach. 2016: CRC Press.
12. Liu, Y., K. Ai, and L. Lu, Polydopamine and its derivative materials: synthesis and promising applications in energy, environmental, and biomedical fields. Chemical reviews, 2014. 114(9): p. 5057-5115.
13. Sadat-Shojai, M., et al., Synthesis methods for nanosized hydroxyapatite with diverse structures. Acta biomaterialia, 2013. 9(8): p. 7591-7621.
14. Tas, A.C., Use of Biomineralization Media in Biomimetic Synthesis of Hard Tissue Substitutes. Advances in Bioceramics and Biotechnologies II: Ceramic Transactions, Volume 247, 2014: p. 91-104.
15. Brown, W.E., et al., Octacalcium phosphate and hydroxyapatite: crystallographic and chemical relations between octacalcium phosphate and hydroxyapatite. Nature, 1962. 196(4859): p. 1050-1055.
16. LeGeros, R.Z., Calcium phosphate-based osteoinductive materials. Chemical reviews, 2008. 108(11): p. 4742-4753.
17. Zreiqat, H., et al., The incorporation of strontium and zinc into a calcium–silicon ceramic for bone tissue engineering. Biomaterials, 2010. 31(12): p. 3175-3184.
18. O’Donnell, M., et al., Structural analysis of a series of strontium-substituted apatites. Acta Biomaterialia, 2008. 4(5): p. 1455-1464.
19. Bose, S. and S. Tarafder, Calcium phosphate ceramic systems in growth factor and drug delivery for bone tissue engineering: a review. Acta biomaterialia, 2012. 8(4): p. 1401-1421.
20. Boanini, E., M. Gazzano, and A. Bigi, Ionic substitutions in calcium phosphates synthesized at low temperature. Acta biomaterialia, 2010. 6(6): p. 1882-1894.
21. Theron, J., J. Walker, and T. Cloete, Nanotechnology and water treatment: applications and emerging opportunities. Critical reviews in microbiology, 2008. 34(1): p. 43-69.
22. DeNardo, S.J., et al., Development of tumor targeting bioprobes (111In-chimeric L6 monoclonal antibody nanoparticles) for alternating magnetic field cancer therapy. Clinical Cancer Research, 2005. 11(19): p. 7087s-7092s.
23. Shiba, H., Magnetic susceptibility at zero temperature for the one-dimensional Hubbard model. Physical Review B, 1972. 6(3): p. 930.
24. Stouff, P. and J. Boulègue, Geochemistry and crystallochemistry of oceanic hydrothermal manganese oxyhydroxides showing Mn-Cu association. Geochimica et Cosmochimica Acta, 1989. 53(4): p. 833-843.
25. Sutter, B., et al., Characterization of iron, manganese, and copper synthetic hydroxyapatites by electron paramagnetic resonance spectroscopy. Soil Science Society of America Journal, 2002. 66(4): p. 1359-1366.
26. Kostakis, G.E., et al., High-nuclearity cobalt coordination clusters: Synthetic, topological and magnetic aspects. Coordination Chemistry Reviews, 2012. 256(11): p. 1246-1278.
27. Schenck, J.F., The role of magnetic susceptibility in magnetic resonance imaging: MRI magnetic compatibility of the first and second kinds. Medical physics, 1996. 23(6): p. 815-850.
28. Sharifi, I., H. Shokrollahi, and S. Amiri, Ferrite-based magnetic nanofluids used in hyperthermia applications. Journal of Magnetism and Magnetic Materials, 2012. 324(6): p. 903-915.
29. Cullity, B.D. and C.D. Graham, Introduction to magnetic materials. 2011: John Wiley & Sons.
30. Goya, G., et al., Static and dynamic magnetic properties of spherical magnetite nanoparticles. Journal of Applied Physics, 2003. 94(5): p. 3520-3528.
31. Gould, C., et al., Tunneling anisotropic magnetoresistance: a spin-valve-like tunnel magnetoresistance using a single magnetic layer. Physical review letters, 2004. 93(11): p. 117203.
32. Chiba, D., et al., Magnetization vector manipulation by electric fields. Nature, 2008. 455(7212): p. 515.
33. Jacob, K., K. Fitzner, and C. Alcock, Activities in the spinel solid solution, phase equilibria and thermodynamic properties of ternary phases in the system Cu-Fe-0. Metallurgical and Materials Transactions B, 1977. 8(2): p. 451-460.