Search Results (16)

This work aims to evaluate the potential use of natural wastes (in particular, clam shells) to synthesize one of the most well-known and versatile materials from the phosphate mineral group, hydroxyapatite (HAP). The obtained material was characterized in terms of morphology and composition using several analytical methods (scanning electron microscopy—SEM, X-ray diffraction—XRD, X-ray fluorescence—XRF, Fourier transform infrared spectroscopy—FTIR, thermal analysis—TGA, and evaluation of the porosity and specific surface characteristics by the Brunauer–Emmett–Teller—BET method) in order to confirm the successful synthesis of the material and to evaluate the presence of potential secondary phases. The developed material was further doped with iron oxide (HAP-Fe) using a microwave-assisted method, and both materials were evaluated in terms of photocatalytic activity determined by the photodecomposition of methylene blue (MB) which served as a contaminant model. The best results (approx. 33% MB degradation efficiency, after 120 min. of exposure) were obtained for the hydroxyapatite material, superior to the HAP-Fe composite (approx. 27%). The utilization of hydroxyapatite obtained from clam shells underscores the importance of sustainable and eco-friendly practices in materials syntheses. By repurposing waste materials from the seafood industry, we not only reduce environmental impact, but also create a valuable resource with diverse applications, contributing to advancements in both healthcare and environmental protection. Full article

Pd nanoparticles (PdNPs) were successfully deposited on the surface of Fe(III)-modified hydroxyapatite (HAp), which was subsequently used as a photocatalyst for simultaneous photocatalytic H₂ evolution and xylose conversion. The structural phase and morphology of the pristine HAp, FeHAp, and Pd@FeHAp were examined using XRD, SEM, and TEM instruments. At 20 °C, Pd@FeHAp provided a greater xylose conversion than pristine HAp and FeHAp, about 2.15 times and 1.41 times, respectively. In addition, lactic acid and formic acid production was increased by using Pd@FeHAp. The optimal condition was further investigated using Pd@FeHAp, which demonstrated around 70% xylose conversion within 60 min at 30 °C. Moreover, only Pd@FeHAp produced H₂ under light irradiation. To clarify the impact of Fe(III) doping in FeHAp and heterojunction between PdNPs and FeHAp in the composite relative to pure Hap, the optical and physicochemical properties of Pd@FeHAp samples were analyzed, which revealed the extraordinary ability of the material to separate and transport photogenerated electron-hole pairs, as demonstrated by a substantial reduction in photoluminescence intensity when compared to Hp and FeHAp. In addition, a decrease in electron trap density in the Pd@FeHAp composite using reversed double-beam photoacoustic spectroscopy was attributed to the higher photocatalytic activity rate. Furthermore, the development of new electronic levels by the addition of Fe(III) to the structure of HAp in FeHAp may improve the ability to absorb light by lessening the energy band gap. The photocatalytic performance of the Pd@FeHAp composite was improved by lowering charge recombination and narrowing the energy band gap. As a result, a newly developed Pd@FeHAp composite might be employed as a photocatalyst to generate both alternative H₂ energy and high-value chemicals. Full article

Recently, there has been increasing interest in developing biocompatible inhalable nanoparticle formulations, as they have enormous potential for treating and diagnosing lung disease. In this respect, here, we have studied superparamagnetic iron-doped calcium phosphate (in the form of hydroxyapatite) nanoparticles (FeCaP NPs) which were previously proved to be excellent materials for magnetic resonance imaging, drug delivery and hyperthermia-related applications. We have established that FeCaP NPs are not cytotoxic towards human lung alveolar epithelial type 1 (AT1) cells even at high doses, thus proving their safety for inhalation administration. Then, D-mannitol spray-dried microparticles embedding FeCaP NPs have been formulated, obtaining respirable dry powders. These microparticles were designed to achieve the best aerodynamic particle size distribution which is a critical condition for successful inhalation and deposition. The nanoparticle-in-microparticle approach resulted in the protection of FeCaP NPs, allowing their release upon microparticle dissolution, with dimensions and surface charge close to the original values. This work demonstrates the use of spray drying to provide an inhalable dry powder platform for the lung delivery of safe FeCaP NPs for magnetically driven applications. Full article

Among the several possible uses of nanoparticulated systems in biomedicine, their potential as theragnostic agents has received significant interest in recent times. In this work, we have taken advantage of the medical applications of Gadolinium as a contrast agent with the versatility and huge array of possibilities that microfluidics can help to create doped Hydroxyapatite nanoparticles with magnetic properties in an efficient and functional way. First, with the help of Computational Fluid Dynamics (CFD), we performed a complete and precise study of all the elements and phases of our device to guarantee that our microfluidic system worked in the laminar regime and was not affected by the presence of nanoparticles through the flow requisite that is essential to guarantee homogeneous diffusion between the elements or phases in play. Then the obtained biomaterials were physiochemically characterized by means of XRD, FE-SEM, EDX, confocal Raman microscopy, and FT-IR, confirming the successful incorporation of the lanthanide element Gadolinium in part of the Ca (II) binding sites. Finally, the magnetic characterization confirmed the paramagnetic behaviour of the nanoparticles, demonstrating that, with a simple and automatized system, it is possible to obtain advanced nanomaterials that can offer a promising and innovative solution in theragnostic applications. Full article

Synthesized hydroxyapatite (sHA)—calcium phosphate (CaP) based biomaterials play a vital role and have been widely used in the process of bone regeneration for bone defect repair, due to their similarities to the inorganic components of human bones. However, for bone tissue engineering purpose, the composite components, physical and biological properties, efficacy and safety of sHA still need further improvements. In this work, we synthesized inhomogeneous hydroxyapatite based on biomimetic trace elements (Mg, Fe, Zn, Mn, Cu, Ni, Mo, Sr, Co, BO₃³⁻, and CO₃²⁻) co-doped into HA (THA) (Ca_10−δM_δ(PO₄)_5.5(CO₃)_0.5(OH)₂, M = trace elements) via co-precipitation from an ionic solution. The physical properties, their bioactivities using in vitro osteoblast cells, and in vivo cytotoxicity using zebrafish were studied. By introducing biomimetic trace elements, the as-prepared THA samples showed nanorod (needle-like) structures, having a positively charged surface (6.49 meV), and showing paramagnetic behavior. The bioactivity studies demonstrated that the THA substrate can induce apatite particles to cover its surface and be in contact with surrounding simulated body fluid (SBF). In vitro biological assays revealed that the osteoblast-like UMR-106 cells were well-attached with growth and proliferation on the substrate’s surface. Upon differentiation, enhanced ALP (alkaline phosphatase) activity was observed for bone cells on the surface of the THA compared with that on the control substrates (sHA). The in vivo performance in embryonic zebrafish studies showed that the synthesized THA particles are nontoxic based on the measurements of essential parameters such as survivability, hatching rate, and the morphology of the embryo. The mechanism of the ions release profile using digital conductivity measurement revealed that sustained controlled release was successfully achieved. These preliminary results indicated that the synthesized THA could be a promising material for potential practical applications in bone tissue engineering. Full article

Hydroxyapatite (HA) is a calcium phosphate used in many fields, including biomedical applications. In particular, ion-doped HA nanomaterials (nHA) are developed for their increased bioactivity, particularly in the fields of regenerative medicine and nanomedicine. In this study, we assessed the ecotoxicological impact of five nHA materials: a synthesized calcium hydroxyapatite (CaP-HA), superparamagnetic iron-doped hydroxyapatite (Fe-HA), titanium-doped hydroxyapatite (Ti-HA), alginate/titanium-doped hydroxyapatite hybrid composite (Ti-HA-Alg), and a commercial HA. The soil ecotoxicology model species Folsomia candida (Collembola) was used, and besides the standard reproduction test (28 days), an extension to the standard for one more generation was performed (56 days). Assessed endpoints included the standard survival and reproduction, and additionally, growth. Exposure via the standard (28 days) did not cause toxicity, but reproduction increased in commercial HA (significantly at 320 mg HA/kg) whereas via the extension (56 days) it decreased in all tested concentrations. Juveniles’ size (56 days) was reduced in all tested nHA materials, except commercial HA. nHA materials seem to trigger a compromise between reproduction and growth. Long-term effects could not be predicted based on the standard shorter exposure; hence, the testing of at least two generations (56 days) is recommended to assess the toxicity of nanomaterials, particularly in F. candida. Further, we found that the inclusion of size as additional endpoint is highly relevant. Full article

Hydroxyapatite (HAp) is a calcium phosphate-based inorganic constitute in bones and teeth. The synthesis of nanostructured rods that mimic the natural bone apatite has attracted significant attention. Unfortunately, pristine HAp is unsuitable for clinical translation due to its brittleness, limited strength, uncontrolled leaching, and poor surface properties. These limitations necessitate size reduction, surface modification, and ion incorporation to expand their scope in bone reconstruction. Herein, iron-reinforced hydroxyapatite nanorods (Fe-HAp) were used as an inorganic component, and catechol-modified gelatin methacryloyl was employed as a surface functional modifier agent. Our study highlighted that Fe-doped HAp nanomaterials are more promising for developing bioactive surfaces than other ion-incorporated nanomaterials due to their metal-catechol network (MCN) surface engineering. Nanostructural, surface chemistries, cytocompatibility, and matrix mineralization characteristics of Fe-HAp and Fe-HAp/MCN nanorods have been comparatively studied. The results support that MCN-coated nanorod surfaces improved HAp cytocompatibility, bioactivity, and phase compatibility between organic/inorganic nanomaterials, which could be crucial for bone reconstruction. Full article

Iron-doped hydroxyapatite (Fe-HAp) is regarded as a promising magnetic material with innate biocompatibility. Despite the many studies reported in the literature, a detailed theoretical description of Fe inclusions is still missing. There is even no consensual view on what kind of Fe defects take place in Fe-HAp—iron interstitial or calcium substitutions? In order to address these questions, we employ modern first-principles methodologies, including hybrid density functional theory, to find the geometry, electronic, magnetic and thermodynamic properties of iron impurities in Fe-HAp. We consider a total of 26 defect configurations, including substitutional (phosphorus and calcium sites) and interstitial defects. Formation energies are estimated considering the boundaries of chemical potentials in stable hydroxyapatite. We show that the most probable defect configurations are: Fe${}^{3+}$ and Fe${}^{2+}$ substitutions of Ca(I) and Ca(II) sites under Ca-poor conditions. Conversely, Fe interstitials near the edge of the hydroxyl channel are favored in Ca-rich material. Substitutional Fe on the P site is also a probable defect, and unlike the other forms of Fe, it adopts a low-spin state. The analysis of Fe K-XANES spectra available in the literature shows that Fe-HAp usually contains iron in different configurations. Full article

Hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂, HAp) doped with various transition metals has generated great interest in view of its potential application in a wide variety of fields, including in catalysis as a support with a series of attractive properties. Despite a large number of experimental works devoted to the synthesis and application of iron-substituted hydroxyapatites, problems concerning the location, introduced defects, and charge compensation schemes for Fe²⁺ and/or Fe³⁺ cations in the crystal structure of HAp remain unclear. This paper is devoted to the comprehensive analysis of iron (II) and (III) introduction into the HAp lattice by density functional theory (DFT) calculations. We show that the inclusion of Fe²⁺ in the Ca(1) and Ca(2) positions of HAp is energetically comparable. For the Fe³⁺, there is a clear preference to be included in the Ca(2) position. The inclusion of iron results in cell contraction, which is more pronounced in the case of Fe³⁺. In addition, Fe³⁺ may form a shorter linkage to oxygen atoms. The incorporation of both Fe²⁺ and Fe³⁺ leads to notable local reorganization in the HAp cell. Full article

The material for bone scaffold replacement should be biocompatible and antibacterial to prevent scaffold-associated infection. We biofunctionalized the hydroxyapatite (HA) properties by doping it with lithium (Li). The HA and 4 Li-doped HA (0.5, 1.0, 2.0, 4.0 wt.%) samples were investigated to find the most suitable Li content for both aspects. The synthesized nanoparticles, by the mechanical alloying method, were cold-pressed uniaxially and then sintered for 2 h at 1250 °C. Characterization using field-emission scanning electron microscopy (FE-SEM) revealed particle sizes in the range of 60 to 120 nm. The XRD analysis proved the formation of HA and Li-doped HA nanoparticles with crystal sizes ranging from 59 to 89 nm. The bioactivity of samples was investigated in simulated body fluid (SBF), and the growth of apatite formed on surfaces was evaluated using SEM and EDS. Cellular behavior was estimated by MG63 osteoblast-like cells. The results of apatite growth and cell analysis showed that 1.0 wt.% Li doping was optimal to maximize the bioactivity of HA. Antibacterial characteristics against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were performed by colony-forming unit (CFU) tests. The results showed that Li in the structure of HA increases its antibacterial properties. HA biofunctionalized by Li doping can be considered a suitable option for the fabrication of bone scaffolds due to its antibacterial and unique bioactivity properties. Full article

Mesoporous hydroxyapatite (HA) and iron(III)-doped HA (Fe-HA) are attractive materials for biomedical, catalytic, and environmental applications. In the present study, the nanopowders of HA and Fe-HA with a specific surface area up to 194.5 m²/g were synthesized by a simple precipitation route using iron oxalate as a source of Fe³⁺ cations. The influence of Fe³⁺ amount on the phase composition, powders morphology, Brunauer–Emmett–Teller (BET) specific surface area (S), and pore size distribution were investigated, as well as electron paramagnetic resonance and Mössbauer spectroscopy analysis were performed. According to obtained data, the Fe³⁺ ions were incorporated in the HA lattice, and also amorphous Fe oxides were formed contributed to the gradual increase in the S and pore volume of the powders. The Density Functional Theory calculations supported these findings and revealed Fe³⁺ inclusion in the crystalline region with the hybridization among Fe-3d and O-2p orbitals and a partly covalent bond formation, whilst the inclusion of Fe oxides assumed crystallinity damage and rather occurred in amorphous regions of HA nanomaterial. In vitro tests based on the MG-63 cell line demonstrated that the introduction of Fe³⁺ does not cause cytotoxicity and led to the enhanced cytocompatibility of HA. Full article

It is known that iron is found as a trace element in bone tissue, the main inorganic constituent of which is hydroxyapatite. Therefore, iron-doped hydroxyapatite (HApFe) materials could be new alternatives for many biomedical applications. A facile dip coating process was used to elaborate the iron-doped hydroxyapatite (HApFe) nanocomposite coatings. The HApFe suspension used to prepare the coatings was achieved using a co-precipitation method, which was adapted in the laboratory. The quality of the HApFe suspension was assessed through dynamic light scattering (DLS), ultrasonic measurements, and zeta potential values. The hydroxyapatite XRD patterns were observed in the HApFe nanocomposite with no significant shifting of peak positions, thus suggesting that the incorporation of iron did not significantly modify the hydroxyapatite structure. The morphology of the HApFe nanoparticles was evaluated using transmission electron microscopy (TEM). Scanning electron microscopy (SEM) was used in order to investigate the morphologies of HApFe particles and coatings, while their chemical compositions were assessed using energy-dispersive X-ray spectroscopy (EDS). The SEM results suggested that the HApFe consists mainly of spherical nanometric particles and that the surfaces of the coatings are continuous and homogeneous. Additionally, the EDS spectra highlighted the purity of the samples and confirmed the presence of calcium, phosphorous, and iron in the analyzed sample. The in vitro cytotoxicity of the HApFe suspensions and coatings was evidenced using osteoblast cells. The MTT assay showed that both the HApFe suspensions and coatings exhibited biocompatible properties. Full article

Iron is one of the trace elements required by human body, and its deficiency can lead to abnormal bone metabolism. In this study, the effect of iron ions on the properties of tricalcium silicate bone cement (Fe/C₃Ss) was investigated. It effectively solved the problems of high pH value and low biological activity of calcium silicate bone cement. The mechanical properties, in vitro mineralization ability and biocompatibility of the materials were systematically characterized. The results indicate that tricalcium silicate bone cement containing 5 mol% iron displayed good self-setting ability, mechanical properties and biodegradation performance in vitro. Compared with pure calcium silicate bone cement (C₃Ss), Fe/C₃Ss showed lower pH value (8.80) and higher porosity (45%), which was suitable for subsequent cell growth. Immersion test in vitro also confirmed its good ability to induce hydroxyapatite formation. Furthermore, cell culture experiments performed with Fe/C₃Ss ion extracts clearly stated that the material had excellent cell proliferation abilities compared to C₃Ss and low toxicity. The findings reveal that iron-doped tricalcium silicate bone cement is a promising bioactive material in bone repair applications. Full article

This work reports on the synthesis, with the thermally induced phase separation (TIPS) technique, of poly (l-lactide) (PLLA) scaffolds containing Fe-doped hydroxyapatite (FeHA) particles for bone regeneration. Magnetization curves and X-ray diffraction indicate two magnetic particle phases: FeHA and magnetite Fe₃O₄. Magnetic nanoparticles (MNPs) are approximately 30 ± 5 nm in width and 125 ± 25 nm in length, and show typical ferromagnetic properties, including coercivity and rapid saturation magnetization. Scanning electron microscopy (SEM) images of the magnetic scaffolds reveal their complex morphology changes with MNP concentration. Similarly, at compositions of approximately 20% MNPs, the phase separation changes, passing from solid–liquid to liquid–liquid as revealed by the hill-like structures, with low peaks that give the walls in the SEM images a surface pattern of micro-ruggedness typical of nucleation mechanisms and growth. In vitro degradation experiments, carried out for more than 28 weeks, demonstrated that the MNPs delay the scaffold degradation process. Cytotoxicity is appreciated for FeHA content above 20%. Full article

Pathologic calcification leads to structural deterioration of implant materials via stiffening, stress cracking, and other structural disintegration mechanisms, and the effect can be critical for implants intended for long-term or permanent implantation. This study demonstrates the potential of using specific metal ions (MI)s for inhibiting pathological calcification in polyurethane (PU) implants. The hypothesis of using MIs as anti-calcification agents was based on the natural calcium-antagonist role of Mg²⁺ ions in human body, and the anti-calcification effect of Fe³⁺ ions in bio-prosthetic heart valves has previously been confirmed. In vitro calcification results indicated that a protective covering mesh of MI-doped PU can prevent calcification by preventing hydroxyapatite crystal growth. However, microstructure and mechanical characterisation revealed oxidative degradation effects from Fe³⁺ ions on the mechanical properties of the PU matrix. Therefore, from both a mechanical and anti-calcification effects point of view, Mg²⁺ ions are more promising candidates than Fe³⁺ ions. The in vitro MI release experiments demonstrated that PU microphase separation and the structural design of PU-MI matrices were important determinants of release kinetics. Increased phase separation in doped PU assisted in consistent long-term release of dissolved MIs from both hard and soft segments of the PU. The use of a composite-sandwich mesh design prevented an initial burst release which improved the late (>20 days) release rate of MIs from the matrix. Full article