Effective production of multifunctional magnetic-sensitive biomaterial by an extrusion-based additive manufacturing technique.

A calcium phosphate (CaP)-based scaffold used as synthetic bone grafts, which smartly combines precise dimensions, controlled porosity and therapeutic functions, presents benefits beyond those offered by conventional practices, although its fabrication is still a challenge. The sintering step normally required to improve the strength of the ceramic scaffolds precludes the addition of any biomolecules or functional particles before this stage. This study presents a proof of concept of multifunctional CaP-based scaffolds, fabricated by additive manufacturing from an innovative ink composition, with potential for bone regeneration, cancer treatment by local magnetic hyperthermia and drug delivery platforms. Highly loaded inks comprising iron-doped hydroxyapatite and ß-tricalcium phosphate powders suspended in a chitosan-based solution, in the presence of levofloxacin (LEV) as model drug and magnetic nanoparticles (MNP), were developed. The sintering step was removed from the production process, and the integrity of the printed scaffolds was assured by the polymerization capacity of the ink composite, using genipin as a crosslinking agent. The effects of MNP and LEV on the inks' rheological properties, as well as on the mechanical and structural behaviour of non-doped and iron-doped scaffolds, were evaluated. Magnetic and magneto-thermal response, drug delivery and biological performance, such as cell proliferation in the absence and presence of an applied magnetic field, were also assessed. The addition of a constant amount of MNP in the iron-doped and non-doped CaP-based inks enhances their magnetic response and induction heating, with these effects more pronounced for the iron-doped CaP-based ink. These results suggest a synergistic effect between the iron-doped CaP-based powders and the MNP due to ferro/ferrimagnetic interactions. Furthermore, the iron presence enhances human mesenchymal stem cell metabolic activity and proliferation.

Smallest Bimetallic CoPt3 Superparamagnetic Nanoparticles.

We present for the first time a nonaqueous sol-gel route to produce ultrasmall (<2 nm) magnetic bimetallic CoPt3 nanoparticles (NPs). The one-pot procedure is carried out at low temperature (180 °C) using benzyl alcohol, acting as both reducing agent and solvent. The highly monodisperse CoPt3 NPs were investigated with innovative advanced X-ray methods (whole powder pattern modeling), HR-STEM, XPS, and SQUID magnetometry. XPS showed Co was mostly in metallic form, but with a very small amount of CoO on the NP surface. The spherical NPs had an ultrasmall diameter of 1.6 nm and could self-assemble in aligned linear chains, or nanobelts, of single NPs. They are superparamagnetic, with blocking temperature of ∼20 K and coercivity at 10 K of 27.9 kA m-1 (∼350 Oe). However, there is evidence of a second magnetic phase (probably CoO) in the ZFC magnetization curve, which enhances their magnetization values, without significantly affecting their superparamagnetism.

Peculiar Magnetoelectric Coupling in BaTiO3:Fe113 ppm Nanoscopic Segregations.

We report polycrystalline BaTiO3 with cooperative magnetization behavior associated with the scarce presence of about 113 atomic ppm of Fe ions, clearly displaying magnetoelectric coupling with significant changes in magnetization (up to ΔM/M ≈ 32%) at the ferroelectric transitions. We find that Fe ions are segregated mostly at the interfaces between grain boundaries and an Fe-rich phase, forming a self-composite with high magnetoelectric coupling above room temperature. We compare our results with ab initio calculations and other experimental results found in the literature, proposing mechanisms that could be behind the magnetoelectric coupling within the ferroelectric matrix. These findings open the way for further strategies to optimize interfacial magnetoelectric couplings.

Superferromagnetism in mechanically alloyed fcc Fe(23)Cu(77) with bimodal cluster size distribution.

Magnetic measurements, x-ray diffraction and Mössbauer spectroscopy were used to characterize a nanostructured fcc Fe(23)Cu(77) at.% alloy prepared by high-energy ball-milling, addressing in particular the effect of clustering on the nature of the interacting magnetic entities. The interpretation of magnetization measurements leads to the conclusion that grains, whose mean size is ∼16 nm, contain two populations of magnetic Fe-rich nanoclusters with a bimodal size distribution. These two sets of clusters contain about 14 and 400 Fe atoms and have magnetic moments of 30 µ(B) and 860 µ(B), respectively. The inter-cluster ferromagnetic interactions that lead to superferromagnetism with a Curie temperature T(C)∼220 K can be described by a mean field determined by the smaller clusters only, which account for 90% of the magnetization.