Fe-Doping-Induced Magnetism in Nano-Hydroxyapatites

Doping of biocompatible nanomaterials with magnetic phases is currently one of the most promising strategies for the development of advanced magnetic biomaterials. However, especially in the case of iron-doped magnetic hydroxyapatites, it is not clear if the magnetic features come merely from the magnetic phases/ions used as dopants or from complex mechanisms involving interactions at the nanoscale. Here, we report an extensive chemical-physical and magnetic investigation of three hydroxyapatite nanocrystals doped with different iron species and containing small or no amounts of maghemite as a secondary phase. The association of several investigation techniques such as X-ray absorption spectroscopy, Mössbauer, magnetometry, and TEM allowed us to determine that the unusual magnetic properties of Fe^2+/3+-doped hydroxyapatites (FeHA) occur by a synergy of two different phenomena: i.e., (i) interacting superparamagnetism due to the interplay between iron-doped apatite and iron oxide nanoparticles as well as to the occurrence of dipolar interactions and (ii) interacting paramagnetism due to Fe³⁺ ions present in the superficial hydrated layer of the apatite nanophase and, to a lesser extent, paramagnetism due to isolated Fe³⁺ ions in the apatite lattice. We also show that a major player in the activation of the above phenomena is the oxidation of Fe²⁺ into Fe³⁺, as induced by the synthesis process, and their consequent specific positioning in the FeHA structure.