Novel hybrid magnetoactive composite scaffolds based on poly(3-hydroxybutyrate) (PHB), gelatin, and magnetite (Fe3O4) were fabricated by electrospinning. The morphology, structure, phase composition, and magnetic properties of composite scaffolds were studied. Fabrication procedures of PHB/gelatin and PHB/gelatin/Fe3O4 scaffolds resulted in the formation of both core-shell and ribbon-shaped structure of the fibers. In case of hybrid PHB/gelatin/Fe3O4 scaffolds submicron-sized Fe3O4 particles were observed in the surface layers of the fibers. The X-ray photoelectron spectroscopy results allowed the presence of gelatin on the fiber surface (N/C ratio–0.11) to be revealed. Incubation of the composite scaffolds in saline for 3 h decreased the amount of gelatin on the surface by more than ~75%. The differential scanning calorimetry results obtained for pure PHB scaffolds revealed a characteristic melting peak at 177.5 °C. The presence of gelatin in PHB/gelatin and PHB/gelatin/Fe3O4 scaffolds resulted in the decrease in melting temperature to 168–169 °C in comparison with pure PHB scaffolds due to the core-shell structure of the fibers. Hybrid scaffolds also demonstrated a decrease in crystallinity from 52.3% (PHB) to 16.9% (PHB/gelatin) and 9.2% (PHB/gelatin/Fe3O4). All the prepared scaffolds were non-toxic and saturation magnetization of the composite scaffolds with magnetite was 3.27 ± 0.22 emu/g, which makes them prospective candidates for usage in biomedical applications.
10 February 2022 in Nano-Structures & Nano-Objects
One-dimensional anisotropic nanoparticles are of great research interest across a wide range of biomedical applications due to their specific physicochemical and magnetic properties in comparison with isotropic magnetic nanoparticles. In this work, the formation of iron oxides and oxyhydroxide anisotropic nanoparticles (ANPs) obtained by the co-precipitation method in the presence of urea was studied. Reaction pathways of iron oxide and oxyhydroxide ANPs formation are described based on of X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and pulse magnetometry studies. It is shown that a nonmonotonic change in the Fe3O4 content occurs during synthesis. The maximum content of the Fe3O4 phase of 47.4% was obtained at 12 h of the synthesis. At the same time, the reaction products contain ANPs of α-FeOOH and submicron isotropic particles of Fe3O4, the latter formation can occur due to the oxidation of Fe2+ ions by air-oxygen and Ostwald ripening processes. A subsequent increase in the synthesis time leads to the predominant formation of an α-FeOOH phase due to the oxidation of Fe3O4. As a result of the work, a methodological scheme for the analysis of iron oxide and oxyhydroxide ANPs was developed.
This study considers a fabrication of magnetoactive scaffolds based on a copolymer of vinylidene fluoride and trifluoroethylene (P(VDF-TrFE)) and 5, 10, and 15 wt.% of magnetite (Fe3O4) nanoparticles modified with citric (CA) and oleic (OA) acids by solution electrospinning. The synthesized Fe3O4-CA and Fe3O4-OA nanoparticles are similar in particle size and phase composition, but differ in zeta potential values and magnetic properties. Pure P(VDF-TrFE) scaffolds as well as composites with Fe3O4-CA and Fe3O4-OA nanoparticles demonstrate beads-free 1 μm fibers. According to scanning electron (SEM) and transmission electron (TEM) microscopy, fabricated P(VDF-TrFE) scaffolds filled with CA-modified Fe3O4 nanoparticles have a more homogeneous distribution of magnetic filler due to both the high stabilization ability of CA molecules and the affinity of Fe3O4-CA nanoparticles to the solvent used and P(VDF-TrFE) functional groups. The phase composition of pure and composite scaffolds includes a predominant piezoelectric β-phase, and a γ-phase, to a lesser extent. When adding Fe3O4-CA and Fe3O4-OA nanoparticles, there was no significant decrease in the degree of crystallinity of the P(VDF-TrFE), which, on the contrary, increased up to 76% in the case of composite scaffolds loaded with 15 wt.% of the magnetic fillers. Magnetic properties, mainly saturation magnetization (Ms), are in a good agreement with the content of Fe3O4 nanoparticles and show, among the known magnetoactive PVDF or P(VDF-TrFE) scaffolds, the highest Ms value, equal to 10.0 emu/g in the case of P(VDF-TrFE) composite with 15 wt.% of Fe3O4-CA nanoparticles.