Search Results (46)

In this study, high-energy milled (HEM) samples of natural phosphorites from Estonian deposits were investigated. The activation was performed via planetary mill with Cr-Ni grinders with a diameter of 20 mm. This method is an ecological alternative, since it eliminates the disadvantages of conventional acid methods, namely the release of gaseous and solid technogenic products. The aim of the study is to determine the changes in the structure to follow the solid-state transitions and the isomorphic substitutions in the anionic sub-lattice in the structure of the main mineral apatite in the samples from Estonia, under the influence of HEM activation. It is also interesting to investigate the influence of HEM on structural-phase transformations on the structure of impurity minerals-free calcite/dolomite, pyrite, quartz, as well as to assess their influence on the thermal behavior of the main mineral apatite. The effect of HEM is monitored by using a complex of analytical methods, such as chemical analysis, powder X-ray diffraction (PXRD), wavelength-dispersive X-ray fluorescence (WD-XRF) analysis, and Fourier-transformed infrared (FTIR) analysis. The obtained results prove the correlation in the behavior of the studied samples with regard to their quartz content and bonded or non-bonded carbonate ions. After HEM activation of the raw samples, the following is established: (i) anionic isomorphism with formation of A and A-B type carbonate-apatites and hydroxyl-fluorapatite; (ii) solid-phase synthesis of calcium orthophosphate-CaHPO₄ (monetite) and dicalcium diphosphate-β-Ca₂P₂O₇; (iii) enhanced chemical reactivity by approximately three times by increasing the solubility via HEM activation. The dry milling method used is a suitable approach for solving technological projects to improve the composition and structure of soils, increasing soil fertility by introducing soluble forms of calcium phosphates. It provides a variety of application purposes depending on the composition, impurities, and processing as a soil improver, natural mineral fertilizer, or activator. Full article

To address the biological inertness of pure titanium implants, a composite coating with a strontium-doped hydroxyapatite (Sr-HA) phase and H₂Ti₅O₁₁·H₂O nanorods was engineered via ultrasonic-assisted micro-arc oxidation (UMAO) with hydrothermal treatment (HT). The ultrasonic field was applied to modulate the MAO discharge behavior, enhancing ion transport and coating formation. Structural characterization revealed that UMAO-HT coatings exhibited a lower anatase/rutile ratio and higher Sr-HA crystallinity, as compared to MAO-HT. In vitro simulated body immersion studies showed that UMAO-HT induced rapid apatite formation within 24 h, with a better apatite-inducing ability than the conventional MAO-HT. Density functional theory (DFT) simulations demonstrated that Sr substitution in HA lowered the (001) surface work function, enhancing Ca²⁺ adsorption energy and promoting apatite phase nucleation. This work reported the synergistic effects of ultrasonic-induced microstructure optimization and Sr-HA higher bioactivity, providing a mechanistic framework for designing next-generation bioactive coatings with enhanced osseointegration potential. Full article

Apatites are very important compounds of mineralogical and biological meaning. Apatites originated from the calcium hydroxy compound 3Ca₃(PO₄)₂·Ca(OH)₂ and potentially might form three series of isomorphic salts, derived from cationic substitutions in the positions of Ca(I) and Ca(II) ions in the core compound; anionic substitutions of phosphates; and substitutions of anions and very simple chemical entities instead of the hydroxyl group in channel locations. The energies coupled with the ion exchanges inside those three locations were studied using our original method resulting from the transformation of Braggs’ law. The energy changes resulting from the ion exchanges were studied in connection with either the ionic radii for the cations or ionic volumes for the anions. The same series were observed when the variabilities of energy were confronted with the variabilities in the sinus of diffraction angle Θ showing changes in momentum transfer. In particular, the relationships between the energy changes and the coupled changes in the universal crystallographic parameter d showed the surprising uniformity of all ion exchanges in the apatites. The incremental change in the Braggs’ d-parameter always demands the same change in the energy, with good approximation, independently of the location of the ion exchange. So, the isomorphism of the apatites is not triple but a uniform one at the energy level. Such an approach enables the estimation of the volume of the ion-□ (□-vacancies) agglomerates. The introduction of ions with greater volumes exerts the phenomenon of swelling of apatite cells, which can be quantitatively estimated. The dependence of diffraction spectra on the temperature allows for the determination of minimal values of crystallographic cell volumes and d parameters at the temperature of 0 K. In sum, the study of energies connected with the change of Bragg dimension d is a new and valuable method of insight into the behaviour of apatite crystals. Full article

Background/Objectives: A biocomposite based on magnesium-doped hydroxyapatite and enriched with amoxicillin (MgHApOx) was synthesized using the coprecipitation method and is presented here for the first time. Methods: The stability of MgHAp and MgHApOx suspensions was evaluated by ultrasound measurements. The structure of the synthesized MgHAp and MgHApOx was examined with X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The crystalline structure was determined by X-ray diffraction. The FTIR data were collected in the range of 4000–400 cm⁻¹. The morphology of the nanoparticles was evaluated by scanning electron microscopy (SEM). Furthermore, the biocompatible properties of MgHAp, MgHApOx and amoxicillin (Ox) suspensions were assessed using human fetal osteoblastic cells (hFOB 1.19 cell line). The antimicrobial properties of the MgHAp, MgHApOx and Ox suspension nanoparticles were assessed using the standard reference microbial strains Staphylococcus aureus ATCC 25923, Escherichia coli ATCC 25922 and Candida albicans ATCC 10231. Results: X-ray studies have shown that the biocomposite retains the characteristics of HAp and amoxicillin. The SEM assessment exhibited that the apatite contains particles at nanometric scale with acicular flakes morphology. The XRD and SEM results exhibited crystalline nanoparticles. The average crystallite size calculated from XRD analysis increased from 15.31 nm for MgHAp to 17.79 nm in the case of the MgHApOx sample. The energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) analysis highlighted the presence of the constituent elements of MgHAp and amoxicillin. Moreover, XPS confirmed the substitution of Ca²⁺ ions with Mg²⁺ and the presence of amoxicillin constituents in the MgHAp lattice. The results of the in vitro antimicrobial assay demonstrated that MgHAp, MgHApOx and Ox suspensions exhibited good antimicrobial activity against the tested microbial strains. The results showed that the antimicrobial activity of the samples was influenced by the presence of the antibiotic and also by the incubation time. Conclusions: The findings from the biological assays indicate that MgHAp and MgHApOx are promising candidates for the development of new biocompatible and antimicrobial agents for biomedical applications. Full article

Dicalcium phosphate anhydrous (DCPA, CaHPO₄) is regarded as an orthopedic material due to its ability to match the generation of new bone to the rate of implant resorption without considering the material’s mechanical stability. Additionally, magnesium (Mg) is widely recognized for its essential function in bone metabolism, especially during the initial phases of osteogenesis. Therefore, we explored the influences of Mg ions on DCPA powder, in biological responses, and on the enhancement of osteogenic properties. Mg-DCPA powders with varying substitution levels (0, 3, 5, and 7 mol%) were produced using the co-precipitation method. In the in vitro test, precipitates began to develop on the surface of the Mg-DCPA powders after 7 days. These results indicate that Mg ions in the DCPA powder could enhance the generation of a new apatite phase when subjected to physiological fluids on the surface of the powder. In addition, the osteogenic performance of the DCPA powder was improved by adding Mg ions. The most effective magnesium substitution content in the DCPA powder in order to improve its osteogenic potential was approximately 3 mol%. Consequently, this amount of magnesium in the DCPA powder could control the maintaining time in the implantation operation to produce a new apatite phase. Full article

Mesoporous bioactive glass nanoparticles (MBGNs) have attracted significant attention as multifunctional nanocarriers for various applications in both hard and soft tissue engineering. In this study, multifunctional strontium (Sr)- and zinc (Zn)-containing MBGNs were successfully synthesized via the microemulsion-assisted sol–gel method combined with a cationic surfactant (cetyltrimethylammonium bromide, CTAB). Sr-MBGNs, Zn-MBGNs, and Sr-Zn-MBGNs exhibited spherical shapes in the nanoscale range of 100 ± 20 nm with a mesoporous structure. Sr and Zn were co-substituted in MBGNs (60SiO₂-40CaO) to induce osteogenic potential and antibacterial properties without altering their size, morphology, negative surface charge, amorphous nature, mesoporous structure, and pore size. The synthesized MBGNs facilitated bioactivity by promoting the formation of an apatite-like layer on the surface of the particles after immersion in Simulated Body Fluid (SBF). The effect of the particles on the metabolic activity of human mesenchymal stem cells was concentration-dependent. The hMSCs exposed to Sr-MBGNs, Zn-MBGNs, and Sr-Zn-MBGNs at 200 μg/mL enhanced calcium deposition and osteogenic differentiation without osteogenic supplements. Moreover, the cellular uptake and internalization of Sr-MBGNs, Zn-MBGNs, and Sr-Zn-MBGNs in hMSCs were observed. These novel particles, which exhibited multiple functionalities, including promoting bone regeneration, delivering therapeutic ions intracellularly, and inhibiting the growth of Staphylococcus aureus and Escherichia coli, are potential nanocarriers for bone regeneration applications. Full article

In the biomedical field, nanocrystalline hydroxyapatite is still one of the most attractive candidates as a bone substitute material due to its analogies with native bone mineral features regarding chemical composition, bioactivity and osteoconductivity. Ion substitution and low crystallinity are also fundamental characteristics of bone apatite, making it metastable, bioresorbable and reactive. In the present work, biomimetic apatite and apatite/chitosan composites were produced by dissolution–precipitation synthesis, using mussel shells as a calcium biogenic source. With an eye on possible bone reconstruction and drug delivery applications, apatite/chitosan composites were loaded with strontium ranelate, an antiosteoporotic drug. Due to the metastability and temperature sensitivity of the produced composites, sintering could be carried out by conventional methods, and therefore, cold sintering was selected for the densification of the materials. The composites were consolidated up to ~90% relative density by applying a uniaxial pressure up to 1.5 GPa at room temperature for 10 min. Both the synthesised powders and cold-sintered samples were characterised from a physical and chemical point of view to demonstrate the effective production of biomimetic apatite/chitosan composites from mussel shells and exclude possible structural changes after sintering. Preliminary in vitro tests were also performed, which revealed a sustained release of strontium ranelate for about 19 days and no cytotoxicity towards human osteoblastic-like cells (MG63) exposed up to 72 h to the drug-containing composite extract. Full article

The matter constituting the enamels of four types of organisms was studied. The variability of the ions was presented in molar units. It was proven that the changes in water contents of the enamel are significantly positively related to changes in Mg; inversely, there is also a strong connection with changes in Ca and P, the main components of bioapatite. The variability in the organic matter has the same strong and positive characteristics and is also coupled with changes in Mg contents. Amelogenins in organic matter, which synthesize enamel rods, likely have a role in adjusting the amount of Mg, thus establishing the amount of organic matter and water in the whole enamel; this adjustment occurs through an unknown mechanism. Ca, P, Mg, and Cl ions, as well as organic matter and water, participate in the main circulation cycle of bioapatites. The selection of variations in the composition of bioapatite occurs only along particular trajectories, where the energy of transformation linearly depends on the following factors: changes in the crystallographic d parameter; the increase in the volume, V, of the crystallographic cell; the momentum transfer, which is indirectly expressed by ΔsinΘ value. To our knowledge, these findings are novel in the literature. The obtained results indicate the different chemical and crystallographic affinities of the enamels of selected animals to the human ones. This is essential when animal bioapatites are transformed into dentistic or medical substitutes for the hard tissues. Moreover, the role of Mg is shown to control the amount of water in the apatite and in detecting organic matter in the enamels. Full article

The environment model for the description of the location of carbonate ions in apatites predicts that approximately half of the carbonate occupies the apatite channel. This model relies on the influence of entities surrounding the carbonate on its IR spectrum and can be used to determine how various substituents affect the location and structure of that ion. Careful deconvolution (peak-fitting) of the asymmetric carbonate IR region was used to determine the percentage of A-type (channel) ions, A′-type (channel with either a Ca²⁺ vacancy or substitution of Na⁺ for Ca²⁺) ions, and B-type (substitution for phosphate) ions. In our previous applications of this model, we have looked at the effect of alkali metal ions, such as sodium, lithium, and potassium, the ammonium ion, and the rare earth europium ion. In the present work, we explore the incorporation of the first-row transition metal ions and find that they have little effect on the location of the carbonate ion. Like the un-substituted carbonated apatite, these apatites contain about half of the carbonate in the channel, at least in derivatives that contain up to half a mole of the metal ion per mole of apatite. Attempts to incorporate greater amounts of metal ions by aqueous ion-combination reactions generally lead to lower-resolution XRD patterns and IR spectra that produce greater uncertainties in the peak-fitting modeling. Full article

This paper presents the synthesis of the triple substituted carbonated hydroxyapatite with magnesium, strontium and zinc (Mg-Sr-Zn-CHAp), as well as its structural, morphological and compositional characterization. The analytical techniques used (WDXRF, XRD and FTIR) highlighted, on the one hand, the B form for the apatite structure, as well as the presence of the three metal ions in the apatite structure, on the other hand (small shifts of 1120–900 cm⁻¹ and 500–600 cm⁻¹ absorption peaks due to the metals incorporated into the CHAp structure). The ratio between the metallic ions that substitute calcium and Ca²⁺, and phosphorus is increased, the value being 2.11 in comparison with CHAp and pure hydroxyapatite. Also, by using imaging techniques such as optical microscopy and SEM, spherical nanometric particles (between 150 and 250 nm) with a large surface area and large pores (6 m²/g surface area, pores with 6.903 nm diameters and 0.01035 cm³/g medium volume, determined by nitrogen adsorption/desorption analysis) and a pronounced tendency of agglomeration was highlighted. Also, the triple substituted carbonated hydroxyapatite was tested as an inorganic consolidant by using stone specimens prepared in the laboratory. The efficiency of Mg-Sr-Zn-CHAp in the consolidation processes was demonstrated by specific tests in the field: water absorption, peeling, freeze–thaw behavior, chromatic parameters as well as mechanical strength. All these tests presented conclusive values for the use of this consolidant in the consolidation procedures of stone surfaces (lower water absorption, increased mechanical strength, higher consolidation percent, decreased degradation rate by freeze–thaw, no significant color changes). Full article

In this study, hydroxyapatite with the substitution of calcium cations by iron and phosphate by silicate groups was synthesized via a mechanochemical method. The as-prepared compounds have the general formula Ca_10−xFe_x(PO₄)_6−x(SiO₄)_x(OH)_2−xO_x/2 with x = 0–1.5. The thermal stability of the as-prepared compounds was studied by ex situ annealing of powders in a furnace. It has been established that, at 800 °C for x ≤ 0.5, a partial decomposition of the substituted apatites occurs with the formation of the β–Ca₃(PO₄)₂ phase. At high “x” values, the formation of this phase starts at the lower temperature of 700 °C, followed by the formation of Fe₂O₃ at 900 °C. The introduction of iron and silicate ions into the hydroxyapatite lattice was shown to decrease its thermal stability. Full article

In this review, the current status of the influence of added ions (i.e., SiO₄⁴⁻, CO₃²⁻, etc.) and surface states (i.e., hydrated and non-apatite layers) on the biocompatibility nature of hydroxyapatite (HA, Ca₁₀(PO₄)₆(OH)₂) is discussed. It is well known that HA is a type of calcium phosphate with high biocompatibility that is present in biological hard tissues such as bones and enamel. This biomedical material has been extensively studied due to its osteogenic properties. The chemical composition and crystalline structure of HA change depending on the synthetic method and the addition of other ions, thereby affecting the surface properties related to biocompatibility. This review illustrates the structural and surface properties of HA substituted with ions such as silicate, carbonate, and other elemental ions. The importance of the surface characteristics of HA and its components, the hydration layers, and the non-apatite layers for the effective control of biomedical function, as well as their relationship at the interface to improve biocompatibility, has been highlighted. Since the interfacial properties will affect protein adsorption and cell adhesion, the analysis of their properties may provide ideas for effective bone formation and regeneration mechanisms. Full article

Biomimetic nanocrystalline apatites analogous to bone mineral can be prepared using soft chemistry. Due to their high similarity to bone apatite, as opposed to stoichiometric hydroxyapatite for example, they now represent an appealing class of compounds to produce bioactive ceramics for which drug delivery and ion exchange abilities have been described extensively. However, immersion in aqueous media of dried non-carbonated biomimetic apatite crystals may generate an acidification event, which is often disregarded and not been clarified to-date. Yet, this acidification process could limit their further development if it is not understood and overcome if necessary. This may, for example, alter biological test outcomes, during their evaluation as bone repair materials, due to potentially deleterious effects of the acidic environment on cells, especially in in vitro static conditions. In this study, we explore the origins of this acidification phenomenon based on complementary experimental data and we point out the central role of the hydrated ionic layer present on apatite nanocrystals. We then propose a practical strategy to circumvent this acidification effect using an adequate post-precipitation equilibration step that was optimized. Using this enutralization protocol, we then showed the possibility of performing (micro)biological assessments on such compounds and provide an illustration with the examples of post-equilibrated Cu²⁺- and Ag⁺-doped nanocrystalline apatites. We demonstrate their non-cytotoxicity to osteoblast cells and their antibacterial features as tested versus five major pathogens involved in bone infections, therefore pointing to their relevance in the field of antibacterial bone substitutes. The preliminary in vivo implantation of a relevant sample in a rat’s calvarial defect confirmed its biocompatibility and the absence of adverse reaction. Understanding and eliminating this technical barrier should help promoting biomimetic apatites as a genuine new class of biomaterial-producing compounds for bone regeneration applications, e.g., with antibacterial features, far from being solely considered as “laboratory curiosities”. Full article

Biomimetic apatites exhibit a high reactivity allowing ion substitutions to modulate their in vivo response. We developed a novel approach combining several bioactive ions in a spatially controlled way in view of subsequent releases to address the sequence of events occurring after implantation, including potential microorganisms’ colonization. Innovative micron-sized core-shell particles were designed with an external shell enriched with an antibacterial ion and an internal core substituted with a pro-angiogenic or osteogenic ion. After developing the proof of concept, two ions were particularly considered, Ag⁺ in the outer shell and Cu²⁺ in the inner core. In vitro evaluations confirmed the cytocompatibility through Ag-/Cu-substituting and the antibacterial properties provided by Ag⁺. Then, these multifunctional “smart” particles were embedded in a polymeric matrix by freeze-casting to prepare 3D porous scaffolds for bone engineering. This approach envisions the development of a new generation of scaffolds with tailored sequential properties for optimal bone regeneration. Full article

Developments in the field of nanostructures open new ways for designing and manufacturing innovative materials. Here, we focused on new original ways of calculating energy changes during the substitution of foreign ions into the structure of apatites and bioapatites. Using these tools, the energetic costs of ion exchanges were calculated for the exemplary cases known from the literature. It was established that the most costly were ion exchanges of some cations inside apatites and of anions, and the least costly exchanges in tetrad channel positions. Real energy expenses for bioapatites are much smaller in comparison to mineral apatites due to the limited involvement of magnesium and carbonates in the structure of hard tissues. They are of the order of several electron volts per ion. The rigorous dependences of the energy changes and crystallographic cell volumes on the ionic radii of introduced cations were proved. The differentiation of the positioning of foreign ions in locations of Ca(I) and Ca(II) could be calculated in the case of a Ca-Pb reaction in hydroxyapatite. The energetic effects of tooth aging were indicated. The ability of energy change calculation during the ion exchange for isomorphic substances widens the advantages resulting from X-ray diffraction measurements. Full article