Search Results (86)

Endodontic irrigant solutions act as crucial pretreatment conditioning agents in dentin biomimetic remineralization, preparing the collagen scaffold for calcium phosphate infiltration and subsequent tooth structure reconstruction. In this study, root dentin discs were exposed for 10 min to five irrigant solutions: sodium hypochlorite (NaClO, 3%), EDTA (17%), citric acid (CA, 10%), chlorhexidine (CHX, 2%), and an innovative experimental formulation containing citric acid (7%) and surfactants. Samples were then aged in Hank’s Balanced Salt Solution (HBSS) at 37 °C for three months to simulate long-term clinical conditions. Physicochemical modifications of the collagen and apatite phases were assessed at each experimental stage using ATR-FTIR spectroscopy, with the A_CaP/A_{Amide I} and A₈₇₀/A_CaP absorbance ratios as markers of the degree of mineralization and apatite carbonate content, respectively. Results indicated that CHX- and EDTA-treated dentin exhibited the highest remineralization after ageing, while NaClO impeded remineralization due to collagen degradation. The experimental irrigant produced the most pronounced demineralization, followed by CA; however, it also facilitated significant remineralization, attributed to citrate–collagen binding and surfactant-enhanced apatite nucleation. NaClO selectively degraded collagen and increased apatite crystallinity; CA inhibited apatite nucleation through adsorbed citrate ions, and CHX and EDTA induced minimal alterations. These findings provide molecular-level evidence linking short-term irrigant effects to the long-term potential for dentin biomineralization, with direct implications for irrigant selection in regenerative endodontic protocols. It should be noted that this study was conducted on dentin discs obtained from a single tooth; all findings should therefore be regarded as preliminary and require confirmation in studies with larger, biologically independent sample sizes. Full article

The development of multifunctional biomaterials for bone repair requires precursors that combine bioactivity, moderate antimicrobial growth-inhibitory effect, and imaging. This study demonstrates the multifunctional versatility of a single family of rare-earth-doped β-tricalcium phosphates (β-TCPs), Ca₉Eu(PO₄)₇ and Ca₉Dy(PO₄)₇, across three distinct formats: bioactive thin films (for implant coatings), brushite cements (for injectable bone fillers), and radiopaque PMMA bone composites (for load-bearing applications). This work serves as a proof-of-concept that the same doped phosphate precursors can address different clinical needs while retaining bioactivity, antimicrobial properties, and radiopacity. The phosphate precursors were synthesized via solid-state reaction. Pulsed laser deposition (PLD) was used to form amorphous, dense, and crack-free coatings, which exhibited excellent in vitro bioactivity through the rapid dissolution–reprecipitation of a carbonated apatite layer in simulated body fluid. The brushite-based bone cements were produced from doped β-TCPs. These cements demonstrated high cytocompatibility with mesenchymal stromal cells (>89% viability) and significantly enhanced osteogenic differentiation with antimicrobial activity against common pathogens (S. aureus, E. coli, P. aeruginosa). Furthermore, incorporation of these phosphates as fillers into PMMA bone cement resulted in a homogeneous particle distribution with reduced agglomeration compared to undoped β-TCPs, achieving clinically relevant radiopacity values (913 ± 22.4 HU for Dy-doped sample). Post-mortem studies by the CT method were performed on the vertebrae with PMMA–phosphate composites and brushite cements. It was shown that brushite cement in ovine lumbar vertebrae defects exhibited the highest radiopacity (1450–1550 ± 25 HU). The findings establish rare-earth-doped β-TCP as a unified multifunctional precursor that imparts bioactivity, the ability to support in vitro mineralization, antimicrobial properties, and enhanced radiopacity to thin films, phosphate cements, and polymer composite materials. Full article

The aim of this in vitro study was to evaluate the ability of the new strontium-containing composite, Stela (SDI, Victoria, Australia), to induce hydroxyapatite formation and promote remineralization of demineralized dentin, compared to SDR Flow+ (York, PA, USA). Twenty-four dentin slices (1 mm thick) were obtained from extracted wisdom teeth using a microtome and demineralized with 17% EDTA for 2 h. A layer of either Stela or SDR Flow+ was applied to each slice, allowed to set, and preserved in 0.1% thymol solution. Samples were analyzed at 1, 7, 14 and 28 days (n = 3 per group and time). Measurements were taken at baseline, after demineralization, and after application. Apatite formation was assessed using Fourier-transform infrared spectroscopy (FTIR), while changes in the Calcium/Phosphate (Ca/P) ratio were evaluated by Energy Dispersive Spectroscopy (EDX). Statistical comparisons were performed using the Wilcoxon test (p < 0.05). Both materials promoted carbonated hydroxyapatite formation and increases in calcium and phosphate. Stela exhibited an apatite peak (1420 cm⁻¹) as early as 24 h and significant increases in calcium and phosphate from day 7. SDR Flow+ reached its peak at 14 days and showed significant increases in the Ca/P ratio. By 28 days, both materials achieved comparable remineralization, confirming their effectiveness in treating demineralized dentine. Full article

With increasing life expectancy and an aging global population, the demand for orthopedic and dental implants is increasing. Recently developed, citric-acid-based anodization processes facilitate the production of more bioactive oxide layers by incorporating important bone minerals such as Ca, P, and Mg and forming bone-like crystalline compounds such as carbonated apatite on titanium implant materials. The primary goal of the present study was to evaluate the applicability of these anodization processes to solid and 3D-printed titanium alloy substrates. The anodized oxides produced on each solid or 3D-printed lattice substrate revealed multi-scaled surface roughness profiles as evidenced by scanning electron microscopy, optical microscopy, and surface roughness analyses. Additionally, each oxide group was shown to incorporate substantial amounts of Ca, P, and Mg bone-mineral dopants and form AB-type carbonated apatite, as shown using a combination of energy-dispersive spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and attenuated total reflectance–Fourier transform infrared spectroscopy analyses. Finally, each oxide group showed sustained Ca, P, and Mg ion release during an inductively coupled plasma spectroscopy dissolution assessment, and demonstrated early apatite-forming ability during simulated body fluid bioactivity testing. The findings of this study show much promise for the applicability of these novel oxide coatings to a wide variety of future titanium implant applications. Full article

Phosphate is a crucial non-renewable mineral resource, mainly utilized in producing fertilizers that support global agriculture. As phosphorus is an indispensable nutrient for plant growth, phosphate holds a key position in ensuring food security. While deposits are distributed worldwide, the largest reserves are concentrated in Morocco. The Benguerir phosphate mining in Morocco generates heterogeneous waste (i.e., including overburden, tailings, and phosphogypsum) that complicates management and valorization, which is the beneficial reuse or value recovery from waste materials (e.g., use in cover systems, buffering, or other engineered applications). Therefore, it is essential to characterize their mineralogical properties to evaluate their environmental impact and possibilities for reuse or site revegetation. To do so, we integrate VNIR–SWIR reflectance spectroscopy with HandHeld X-ray fluorescence (HHXRF) to characterize phosphate waste rock and assess its reuse potential. For this purpose, field samples (n = 104) were collected, and their spectral reflectance was measured using an ASD FieldSpec 4 spectroradiometer (350–2500 nm) under standardized laboratory conditions. Spectra were processed (Savitzky–Golay smoothing, convex-hull continuum removal) and matched to ECOSTRESS library references; across the dataset, library matching achieved mean RMSE = 0.15 ± 0.053 (median 0.145; 0.085–0.350), median SAM = 0.134 rad, median SID = 0.029, and mean R² = 0.748 ± 0.170, with 84% of spectra yielding R² > 0.70. In parallel, HHXRF major and trace elements were measured on all samples to corroborate spectral interpretations. Together, these analyses resolve carbonate–clay–phosphate assemblages (dolomite commonly dominant, with illite/smectite–kaolinite, quartz, and residual carbonate-fluorapatite varying across samples). Elemental ratios (e.g., Mg/Ca distinguishing dolomite from calcite; K/Al indicating illite) reinforce spectral trends, and phosphate indicators delineate localized enrichment (P₂O₅ up to 23.86 wt % in apatite-rich samples). Overall, the combined workflow is rapid, low-impact, and reproducible, yielding coherent mineralogical patterns that align across spectroscopic and geochemical lines of evidence and providing actionable inputs for selective screening, targeted material reuse, and more sustainable mine reclamation planning. Full article

Bioactive glasses remain promising candidates for enhancing osseointegration on metallic implants. However, achieving a composition that combines controlled dissolution, cytocompatibility, and antimicrobial functionality remains an ongoing challenge. Building upon the prior structural and thermal characterization of boron-substituted 6P55 phosphosilicate glasses, this study investigates the biological consequences of incorporating 0, 5, 10, and 15 mol% B₂O₃ to determine their suitability as coatings for Ti6Al4V. Glass extracts were evaluated using L-929 fibroblast cultures (MTT assay and ImageJ-based cell counting), antimicrobial assays against Escherichia coli and Staphylococcus aureus using a semi-quantitative dilution-plating method, and SBF immersion studies to assess pH evolution, surface mineralization, and Ca/P ratio development. FTIR and SEM analyses revealed composition-dependent formation of phosphate-, carbonate-, and silicate-rich surface layers, with 5B exhibiting the most consistent early-stage hydroxyapatite-like signatures, supported by Ca/P ratios approaching the stoichiometric value. The pH measurements showed rapid alkalization for 5B and moderate buffering behavior at higher boron contents, consistent with boron-dependent modifications to network connectivity. Cytocompatibility studies demonstrated a dose- and time-dependent reduction in cell number at elevated B₂O₃ levels, whereas the 0B and 5B extracts maintained higher viability and preserved cell morphology. Antibacterial assays revealed strain-dependent and sub-lethal inhibitory effects, with E. coli exhibiting stronger sensitivity than S. aureus, likely due to differences in cell wall architecture and susceptibility to ionic osmotic microenvironment changes. When considered alongside previously published computational and physicochemical results, the biological data indicate that moderate boron incorporation (5 mol%) provides the most favorable balance between dissolution kinetics, apatite formation, cytocompatibility, and antimicrobial modulation. These findings identify the 5B composition as a strong candidate for further optimization toward bioactive glass coatings on Ti6Al4V implants. Full article

Titanium implants are widely used in medicine because of their favorable mechanical properties and biocompatibility; however, the rapidly forming titanium oxide coatings do not provide an ideal bioactive surface to stimulate osseointegration. This study aims to enhance titanium implant osseointegration through anodization processes designed to incorporate elements and compounds present within human bone into the surface oxides. Commercially pure titanium grade 4 (CPTi) discs were anodized in either oxalic, malic, or ascorbic acid-based electrolytes. Each resulting oxide exhibited complex surface topographies. EDS analyses revealed that Ca, P, and Mg bone chemistry dopant elements were incorporated into each of the oxide coatings. X-ray diffraction analyses revealed combinations of anatase and calcium titanate compounds present in each oxide. Additionally, two of the anodized oxides showed calcium oxide formation, and one oxide also revealed tricalcium phosphate (α-TCP) and hydroxyapatite (HA) formation. Subsequent FTIR spectroscopy analyses revealed carbonate substitution peaks to be present in two of the oxides. This finding indicated that the TCP and HA compounds shown in the XRD analyses of one oxide represented the formation of bone-like carbonated calcium phosphate compounds. A 21-day cell culture study showed favorable cell culture responses for each of the organic-acid-based anodized oxides. Moreover, two of the oxides showed good cytocompatibility and early osteogenic differentiation compared to non-anodized titanium controls. Thus, the organic acid anodization processes developed in this study show promise to enhance future titanium implant clinical outcomes. Full article

Skarn-type iron ore is economically significant, and numerous skarn ore deposits have been identified in the North China Craton. The newly discovered orbicular diorite in this region is distinguished from other analogous rocks due to the accumulation of large magnetite particles, which may shed new light on the genesis of this ore type. The magnetite in different parts of the orbicular structure exhibits distinct compositional differences. For example, magnetite at the edge has a small particle size (200 μm) and is associated with the minerals plagioclase and hornblende, indicating that it crystallized from normal diorite magma. By contrast, magnetite in the core has a relatively large particle size (>1000 μm), is associated with apatite and actinolite, and contains apatite inclusions as well as numerous pores. The size of magnetite in the mantle falls between that of the edge and the core. The syngenetic minerals of magnetite in the mantle include epidote and plagioclase. The magnetites in the cores of orbicules have a higher content of Ti, Al, Ni, Cr, Sc, Zn, Co, Ga, and Nb than those in the rim. The δ⁵⁶Fe value of the core magnetite (0.46‰–0.78‰) is much higher than that of the mantle and rim magnetite in orbicules. Moreover, the δ⁵⁶Fe value of magnetite increases as the V content of magnetite gradually decreases. This large iron isotope fractionation is likely driven by liquid immiscibility that forms iron-rich melts under high oxygen fugacity. The reaction between magma and carbonate xenoliths (Ca, Mg)CO₃ during magma migration generates abundant CO₂, which significantly increases the oxygen fugacity of the magmatic system. Under the action of CO₂ and other volatile components, liquid immiscibility occurs in the magma chamber, and Fe-rich oxide melts are formed by the melting of carbonate xenoliths. Iron oxides (Fe₃O₄/Fe₂O₃₎ will crystallize close to the liquidus due to high oxygen fugacity. These characteristics of magnetite in the Tanling orbicular diorite (Wuan, China) indicate that diorite magma reacts with carbonate xenoliths to form “Fe-rich melts”, and skarn iron deposits are probably formed by the reaction of intermediate-basic magma with carbonate rocks that generate such “Fe-rich melts”. A possible reaction is as follows: diorite magma + carbonate → (magnetite-actinolite-apatite) + garnet + epidote + feldspar + hornblende + CO₂↑. Full article

The Kızılcaören alkaline silicate–carbonatite complex, located in the Sivrihisar (Eskişehir, NW Anatolia) region, includes phonolite, trachyte, carbonatite, pyroclastics, and REE mineralization (bastnäsite as a critical REE mineral). The emplacement and origin of this complex are poorly constrained, as previous studies mostly concentrated on the petrology of the alkaline rocks, carbonatite, and REE-mineralization, and little attention has been paid to the texture, composition, and origin of the pyroclastic rocks. The pyroclastic rocks in the region contain both rounded and angular-shaped cognate and wall-rock xenoliths derived from syenitic/trachytic hypabyssal rocks and carbonatites, as well as juvenile components such as carbonatite droplets and pelletal lapilli. The syenitic/trachytic hypabyssal rock fragments contain sanidine with high BaO (up to 3.3 wt.%) contents, amphibole (magnesio-fluoro-arfvedsonite), and apatite. Some clasts seem to have reacted with carbonatitic material, including high-SrO (up to 0.6 wt.%) calcite, dolomite, baryte, benstonite, fluorapatite. The carbonatite rock fragments are composed of calcite, baryte, fluorite, and bastnäsite. The carbonatite droplets have a spinifex-like texture and contain rhombohedral Mg-Fe-Ca carbonate admixtures, baryte, potassic-richterite, and parisite embedded in larger crystals of high-SrO (up to 0.7 wt.%) calcite. The spherical–elliptical pelletal lapilli (2–3 mm) contain a lithic center mantled by flow-aligned prismatic sanidine (with BaO up to 3.5 wt.%) microphenocrysts settled in a high-SrO (up to 0.7 wt.%) cryptocrystalline CaCO₃ matrix. All these components are embedded in an ultra-fine-grained matrix. The EPMA results from the matrix reveal that, chemically, it consists largely of BaO-rich sanidine, with minor carbonate, baryte and Fe-Ti oxide. The presence of pelletal lapilli, which is one of the most common and characteristic features of diatreme fillings in alkaline silicate–carbonatite complexes, reveals that the pyroclastic rocks in the region represent a tuffisite formed by intrusive fragmentation and fluidization processes in the presence of excess volatile components consisting mainly of CO₂ and F. Full article

Enhancing osseointegration is a common goal for many titanium implant coatings, since the naturally forming oxides are often bioinert and exhibit less than ideal bone-to-implant contact. Oxide coating surface topographies, chemistries, and crystallinities are known to play key roles in enhancing bone–implant interactions. In the present study, two novel anodization processes were developed in electrolytes based on juiced navel oranges to create bioactive oxide coatings on commercially pure titanium (CPTi) surfaces. Both oxide groups revealed multi-scaled micro and nano surface topographies, significant Ca and P-dopant incorporation exhibiting Ca/P ratios similar to human bone (1.7 and 1.8), and physiologically relevant Mg uptake levels of <0.1% and 1.4 at%. XRD and FTIR analyses of each oxide revealed a combination of tricalcium phosphate and hydroxyapatite phases that showed carbonate substitutions indicative of bone-like apatite formation. Finally, VDI indentation testing revealed good adhesion strengths, minimal cracking, and no visible delamination for both oxides. In summary, the anodization processes in the present study were shown to produce carbonated tricalcium phosphate and apatite containing oxides with contrasting levels of Mg uptake that show much promise to improve future implant clinical outcomes. Full article

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

This study investigates the dynamic operation of a pilot-scale precipitation reactor designed to produce oxygenated phosphocalcium apatites with controlled composition and low crystallinity, closely mimicking the mineral phase of bone. Our approach is based on integrating kinetic monitoring and dynamic reactor control to direct the formation of apatites with tailored structural and chemical properties. Three synthesis routes were explored using CaCO₃, Ca(NO₃)₂, and CaCl₂ as calcium precursors, under optimized Ca/P molar ratios. The evolution of ionic concentrations (Ca²⁺, PO₄³⁻), peroxide and molecular oxygen incorporation, and carbonate content was monitored over a reaction time range of 2 min to 4 h. Characterization by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and chemical analysis revealed a time-dependent transformation of amorphous phases into poorly crystalline apatites with specific textures. After 60 min, the Ca/P atomic ratio stabilized at approximately 1.575, and the resulting apatites exhibited structural features comparable to those of human bone. This study highlights the influence of reactor operation time on precipitation kinetics and the properties of bioactive apatites in a scalable system. The results offer promising prospects for the large-scale production of bone-mimetic materials. However, the lack of biological validation remains a limitation. Future studies will assess the cytocompatibility and bioactivity of these materials to confirm their potential for biomedical applications. Full article

The paper reports the first findings of a series of alkali carbonate, chloride, and sulfate minerals among the usual groundmass kimberlite minerals, such as olivine, phlogopite, monticellite, calcite, spinel-group minerals, perovskite, ilmenite, rutile, and apatite. The sample was collected from an unserpentinized coherent kimberlite dyke that crosscuts earlier volcaniclastic kimberlite in the central part of the Udachnaya-East pipe. This rock can be described as primary/original kimberlite that did not interact with external/internal hydrothermal fluids either during its formation or after its crystallization. At least three alkali-rich carbonates have been found, a previously unknown (and perhaps, a new one) Na-, Ca-, K-, and S-rich carbonate with the calculated empirical formula (Na,K)₆Ca₄(CO₃,SO₄)₇, shortite Na₂Ca₂(CO₃)₃, and nyerereite (Na,K)₂Ca(CO₃)₂. Chlorides in this kimberlite are halite NaCl and sylvite KCl, and the sulfate is aphthitalite K₃Na(SO₄)₂. The content of the Na-Ca-K-S-rich carbonate in the rock is ~15 vol %, that of shortite and halite is ≤5 vol % each, and those of sylvite and aphthitalite are ≤1 vol %. All alkali-rich minerals are of late magmatic origin. This follows from that (i) the studied kimberlite does not contain any secondary water-rich minerals of hydrothermal transformation of the rocks, such as serpentine, chlorite or iowaite; and (ii) crystalline inclusions of such usual kimberlite minerals as olivine, phlogopite, monticellite, calcite, spinel, perovskite, and apatite were found within Na-Ca-K-S-rich carbonate and halite. This publication expands the list of minerals of magmatic origin identified in the groundmass of worldwide kimberlites by at least three minerals: Na-Ca-K-S-rich (new?) carbonate, sylvite, and aphthitalite. It is important to note that all alkali carbonates, chlorides, and sulfates are unstable during secondary hydrothermal alterations of kimberlites, and hence, these minerals cannot be found in serpentinized rocks. Full article

The increasing demand for titanium implants necessitates improved longevity. Plasma-sprayed hydroxyapatite coatings enhance implant osseointegration but are susceptible to delamination. Alternatively, anodized hydroxyapatite coatings have shown greater adhesion strengths. The present study aimed to develop anodized hydroxyapatite coatings on titanium using commercial calcium-fortified fruit juice as a calcium source. Varying the electrolyte compositions enabled the formation of four oxide groups with different predominate calcium compounds. Each oxide’s morphology, crystallinity, chemistry, molecular structure, and adhesion quality were compared and contrasted. Nanoscale SEM images revealed a progression from porous surface oxide to white surface deposits to petal-like hydroxyapatite structures with the changing anodization electrolytes. Oxide thickness evaluations showed progression from a single-layered oxide with low Ca-, P-, and Mg-dopant incorporations to bi-layered oxide structures with increased Ca-, P-, and Mg-dopant incorporation with changing electrolytes. The bi-layered oxide structures exhibited a titanium-dioxide-rich inner layer and calcium-compound-rich outer layers. Furthermore, indentation analyses confirmed good adhesion quality for three oxides. For the predominate hydroxyapatite oxides, FTIR analyses showed carbonate substitutions indicating the presence of bone-like apatite formation, and ICP-OES analyses revealed prolonged Ca and Mg release over 30 days. These Mg-enhanced carbonated apatite coatings show much promise to improve osseointegration and future implant lifetimes. Full article

Calcium phosphate (CaP)-based materials are largely explored in orthopedics, to increase osseointegration of the prostheses and specifically in spine surgery, to permit better fusion. To address these aims, nanostructured biogenic apatite coatings are emerging, since they better mimic the characteristics of the host tissue, thus potentially being better candidates compared to their synthetic counterpart. Here, we compare hydroxyapatite (HA) nanostructured coatings, obtained by ionized jet deposition, starting from synthetic and natural sources. The starting materials and the corresponding films are characterized and compared from a compositional and morphological point of view, then their stability is studied after post-treatment annealing. Although all the films are formed by globular aggregates and show morphological features at different scales (from nano to micro), significant differences are found in composition between the synthetic and naturally derived HA in terms of magnesium and sodium content, carbonate substitution and Ca/P ratio, while differences between the coatings obtained by the different natural HA sources are minor. In addition, the shape of the aggregates is also target-dependent. All coatings have a good stability after over 14 days of immersion in medium, with natural apatite coatings showing a better behavior, as no cracking and detachments are observed during immersion. Based on these results, both synthetic and naturally derived apatitic materials appear promising for applications in spine surgery, with coatings from natural sources possessing physiochemical properties more similar to the mineral phase of the human bone tissue. Full article