Mixed phase bioceramics in the CaMgSi2O6 – MoO3 system: Mechanical properties and in-vitro bioactivity

Mixed phase materials in the quasi binary diopside (CaMgSi₂O₆) – molybdite (MoO₃) system were synthesized by a precipitation method. Materials were fabricated with diopside to molybdite ratios of 1:0, 10:1, 5:1, 2:1 and 1:1. XRD, SEM and EDS results show that alongside the initial diopside phase, phases such as calcium molybdate CaMoO₄, rod-like enstatite MgSiO₃ and cristobalite SiO₂ formed as the molybdite content increased, and diopside was entirely absent at the highest molybdite content. At lower Mo content, mixed phase materials showed higher hardness and slower biodegradation in SBF relative to pristine diopside, while maintaining reasonable hydroxyapatite (HAp) formation capability. In contrast, materials with higher molybdite content exhibited lower hardness and bioactivity. The variation in the mechanical and bioactive performance could be attributed to the presence of bulk CaMoO₄, acting as a reinforcement, and rod-like MgSiO₃ with a highly porous and fragile structure. The trend of hardness is not consistent to the proportion of the component phases could be attributed to morphologies, interfaces, and densities of the samples. Both of secondary phases had poorer HAp deposition compared to pure diopside, indicating the MoO₃ addition lowered mixed phase CaMgSi₂O₆ – MoO₃ bioceramics’ ability to form Hap. The results suggest that moderate addition of molybdite to diopside would be an effective pathway towards crystalline bioceramics with enhanced performance.     

A novel fabrication procedure for producing high strength hydroxyapatite ceramic scaffolds with high porosity

Hydroxyapatite (HA) scaffolds were fabricated using the space holder method with a pressureless sintering process in a systematically developed manner at different fabrication stages to increase the strength of the scaffold at high porosity. Polyvinyl alcohol (PVA) and Polymethyl methacrylate (PMMA) were used as binders and space holder agents, respectively. The physical properties of the HA scaffolds were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), linear shrinkage test, and porosity measurements. The mechanical properties of the HA scaffolds were analyzed using compressive strength measurements. The results revealed that the HA scaffold met the expected quality requirements with a compressive strength of 2.2 MPa at a porosity of 65.6% with pore sizes distributed in the range of 126–385 μm. The shrinkage of the scaffold diameter occurred by 20.27%, this diameter shrinkage predominantly to the shrinkage of the HA scaffold caused by sintering. Besides, suspect that a higher PMMA concentration causes pore size shrinkage upon sintering. The formation of pore interconnections was evidenced by SEM observations and the ‘translucent light method’ developed in this study. The results of the scaffold phase test using XRD showed that the final scaffold consisted only of the HA phase, as the PVA and PMMA phases burned out during the sintering process.     

Nanocomposite powders of hydroxyapatite-graphene oxide for biological applications

The repair of bone fractures is a clinical challenge for patients with impaired healing, such as osteoporosis. Currently, different strategies have been developed to design new biomaterials, enhancing their interactions with biological systems and conducting the cellular behavior in the desired direction to help fracture healing. In the present work, hydroxyapatite-graphene oxide (HA-GO) nanocomposites were produced and the morphological and physicochemical influences of the addition of 0.5 wt%, 1.0 wt% and 1.5 wt% of GO to HA were observed. FEG-SEM and TEM analyses of HA-GO nanocomposites showed HA nanoparticles adhered to the surface of the GO sheets, suggesting an effective method to form nanostructured graphene-based biomaterials. As confirmation, physicochemical analyses by Raman, FTIR and TGA demonstrated a strong affinity between HA and GO, according to the increase of concentration from 0.5 wt% to 1.5 wt% GO in the HA-GO nanocomposites. Also, in order to evaluate the HA-GO nanocomposites behavior under biological microenvironment, in vitro bioactivity and indirect cytotoxicity tests were performed. FEG-SEM analyses confirmed the positive results for the bioactivity properties of HA-GO nanocomposite and indirect cytotoxicity demonstrated that even with a decrease in the hDPSCs viability and proliferation, when increasing to 1.5 wt% of GO concentration, high level of cell viability was exhibited by HA-GO nanocomposites. These biological results suggested the 0.5 wt% HA-GO nanocomposite as a potential bioactive bone graft and a promising biomaterial for bone tissue regeneration, when compared to the pure HA.     

Influence of iron doping towards the physicochemical and biological characteristics of hydroxyapatite

Hydroxyapatite (HAP) is the naturally occurring mineral form of calcium apatite and the most studied material as a bone substituent. Considering HAP's inherent properties, this study explored changes in HAP's characteristics from doping with other metals such as Fe. To form pure HAP and Fe-HAP with different amounts of Fe, we used the hydrothermal approach, and the composites that formed were thoroughly analyzed for their crystallinity, surface bonding, morphology, magnetic behavior, mechanical strength, biocompatibility, hemocompatibility, and in vitro cytotoxicity. The powder XRD studies confirmed the samples' crystallinity, and the lowest crystalline size was 19.7 nm in 10Fe-HAP. The FTIR analysis confirmed the formation of HAP by the hydroxyl, phosphate, and carbonate groups. The FESEM demonstrated that the morphology of the pure HAP was rod-shaped, which transformed into spheres after Fe doping. The EDS analysis confirmed the successful formation of HAP and Fe-HAP composites. The magnetic studies indicated the diamagnetic behavior of the pure HAP, while the Fe-doped HAPs had a superparamagnetic nature with saturation magnetizations (M_s) of 2Fe-HAP, 4Fe-HAP, and 10Fe-HAP at 0.0062, 0.0092, and 0.029 emu/g respectively. Assessment of the mechanical properties, biocompatibility, hemocompatibility, and cytotoxicity indicated that the Fe-doped HAPs were superior to the pure HAP, and among the Fe-HAPs, the 10Fe-HAP) had the highest amount of Fe and the best characteristics. The studies also indicated that Ca²⁺ interactions influenced the cells via HAP doping with that of Fe, equally increasing the physicochemical and biological properties.     

Synthesis of strontium (Sr) doped hydroxyapatite (HAp) nanorods for enhanced adsorption of Cr (VI) ions from wastewater

The development of high-efficiency adsorbents for heavy metal ion removal from wastewater is highly desirable and challenging due to their synthesis complexity and low adsorption capacities. Herein, we reported the synthesis of strontium (Sr) doped hydroxyapatite (HAp) for the increased Cr (VI) adsorption. The effects of pH, temperature, and time on adsorption performances were studied. As a result, the Sr-HAp nanorods can achieve a Cr (VI) adsorption capacity of 443 mg/g, which is significantly higher than that of HAp nanorods (318 mg/g). To better understand the adsorption mechanism, the Langmuir isotherm model was established. The modeling results indicated that Langmuir monolayer chemical adsorption contributed to the efficient Cr (VI) ion removal for Sr-HAp nanorods adsorbents. The surface area and surface functional groups (O–H) contributed to the different Cr (VI) adsorption capacities between HAp and Sr-HAp.     

Hydroxyapatite forming ability,ion release and antibacterial activity of the melt-derived SiO2–P2O5–Na2O–CaO–F glasses modified by replacing CaO with SrO and ZnO

Since the discovery of 1970s, bioactive glass has been a hot topic of research because of its excellent biological activity, which makes it a material that can repair and replace human bone tissue organs. In this work, the bioactive glasses in the system SiO₂–P₂O₅–Na₂O–CaO–F with different amounts of strontium oxide (SrO) and zinc oxide (ZnO) were prepared by the conventional melt quenching technology. The hydroxyapatite (HA) forming ability, ion release and antibacterial activity of these prepared glasses were investigated and the obtained results illustrated that SrO-doped samples had a better ability to form HA in modified simulated body fluid (MSBF) than ZnO-doped samples. As the immersion time of the sample in MSBF increased, the content of HA phase gradually increased. In the same immersion time, the formation ability of HA and the variation of SrO substitution amount showed a non-linear trend, which is mainly related to the influence of SrO content on the glass network structure. The results of ion concentration showed that the formation of HA was the result of the comprehensive action of various ions in the solution, especially the release rate of Si⁴⁺ ions, which had a direct impact on the formation ability of HA. The antibacterial test illustrated that the difference in antibacterial activity of bacteria solution at different sample concentrations may be related to the high pH environment and the osmotic effects caused by the non-physiological concentration of ions in the solution. The glass sample contained 4 wt% SrO showed the minimum bactericidal concentration at 64 mg/mL. The glass samples prepared in this experiment had good biological activity and antibacterial effect, making them suitable for using in dentistry and orthopedic applications, as well as providing a valuable composition reference for the preparation of bioactive glass with excellent comprehensive properties.     

Rare earth element cerium substituted Ca–Si–Mg system bioceramics: From mechanism to mechanical and degradation properties

Cerium (Ce)-substituted diopsides (CaMgSi₂O₆) with enhanced mechanical strength and bioactivity were fabricated by precipitation method, followed by annealing at 1000 °C for 4 h. The mineralogical, morphological, in vitro biomineralization, degradation, and mechanical properties were investigated in order to assess the factors and mechanisms affecting the resultant properties. The X-ray diffractometer results showed that the onset of substitutional solid solubility in 0.25 mol Ce would result in new phase formation (cerium dioxide [CeO₂], and magnesium silicate [MgSiO₃]) further causing lattice instability. With increasing Ce dopant levels to 1.00 mol, the initial CaMgSi₂O₆ phase was completely replaced by new phases. The field-emission scanning electron microscopy results indicated that the 0.25 mol Ce had the best biomineralization performance in vitro, while less hydroxyapatite precipitates were found with further increasing Ce dopant levels, suggesting the new phases led to the hindrance of precipitates. The weight loss values indicated that the high dissolution rate of ions in the matrix was observed in the pure sample, while the high readsorption rate of ions in the simulated body fluid (SBF) occurred with increasing Ce dopant levels. The pH value and the inductively coupled plasma-mass spectrometer results suggested that the release of Ca and Mg ions controlled the pH value. The mechanical strength of matrices before SBF immersion was related to the phase transformation, the elastic modulus of CeO₂ and CaMgSi₂O₆, and the release of Mg ions, while the mechanical strength of matrices after SBF immersion was dominated by the structure of matrices.     

A comprehensive review on the preparation and application of calcium hydroxyapatite: A special focus on atomic doping methods for bone tissue engineering

Hydroxyapatite (HAP) has been considered to be one of the most preferred scaffold materials among many in the last decade for the bone tissue engineering. Be it prosthetic implants, scaffolds or artificial bone cement, hydroxyapatite has received highest attraction among all due to its chemical and physical properties similar to that of human bone. Although it can be used in the bone tissue engineering as the original composition; for enhancing its different properties relevant to in vivo applications, the calcium in HAP may also be replaced by other atomic dopants depending on usage. Here, we review various HAP coating agents and methods, their merits and demerits. We also review various HAP doping materials, including both cationic as well as anionic materials. We discuss the effects and usage of substitution of hydroxyapatite and their subsequent usage in both bone tissue engineering and maxillofacial surgeries. We consider various research articles published in recent times to accomplish detailed discussion on the subject.     

Effect of Mn doping on hydrolysis of low-temperature synthesized metastable alpha-tricalcium phosphate

In the present work, effect of Mn doping on hydrolysis rate of low-temperature synthesized metastable α-tricalcium phosphate (α-TCP) was investigated. α-TCP powders containing different amount of Mn²⁺ ions (0, 0.5 and 1 mol%) were synthesized by wet co-precipitation process, followed by annealing and crystallization of as-precipitated amorphous calcium phosphate at 700 °C. It was demonstrated that the presence of Mn²⁺ ions significantly retards hydrolysis rate of α-TCP. While pristine α-TCP fully hydrolyzed with a conversion to calcium-deficient hydroxyapatite in 10 h, complete hydrolysis of α-TCP doped with 0.5 and 1 mol% of Mn occurred only after 20 and 35 h, respectively. Initial and final products were characterized by X-ray diffraction (XRD) analysis, infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). Chemical composition of starting and fully hydrolyzed α-TCP powders was determined by inductively coupled plasma optical emission spectrometry (ICP-OES).     

Effect of nanosilica addition on bioactivity and in vivo properties of calcium aluminate cement

This study aims at assessing the influence of nanosilica on the bioactivity and mechanical properties of calcium aluminate cement. For this purpose, nanosilica was applied as a replacement for calcium aluminate cement at 0, 2, 5 and 8 wt%. The main components were analyzed by scanning electron microscope coupled with surface imaging and elemental analysis, fourier transform infrared spectroscopy and X-ray diffraction analysis. To estimate the bioactivity of specimens, hydroxyapatite formation on the surface of cement paste was investigated in the simulated body fluid solution. In addition, in vivo evaluation of calcium aluminate cement was performed in subcutaneous tissue of rats. To investigate the mechanical properties, both compressive and flexural strengths were also measured. The results revealed that by increasing nanosilica up to 8 wt%, the strength enhanced. Moreover all cement paste samples with various amounts of nanosilica represented good bioactivity because of formation of bonelike apatite layer on the surface of specimens within 28 days after soaking in simulated body fluid. In vivo experiments indicated that the cement sample was absorbed by the tissue and there was no infection at the implant site. Based on the in vitro and in vivo results, the specimen with 2 wt% nanosilica represented the highest bioactivity.