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Biodegradable magnesium (Mg) and its alloy show huge potential as temporary bone substitute due to the favorable biocompatibility and mechanical compatibility. However, one issue deserves attention is the too fast degradation. In this work, mesoporous bioglass (MBG) with high pore volume (0.59 cc/g) and huge specific surface area (110.78 m2/g) was synthesized using improved sol-gel method, and introduced into Mg-based composite via laser additive manufacturing. Immersion tests showed that the incorporated MBG served as powerful adsorption sites, which promoted the in-situ deposition of apatite by successively adsorbing Ca2+ and HPO42−. Such dense apatite film acted as an efficient protection layer and enhanced the corrosion resistance of Mg matrix, which was proved by the electrochemical impedance spectroscopy measurements. Thereby, Mg based composite showed a significantly decreased degradation rate of 0.31 mm/year. Furthermore, MBG also improved the mechanical properties as well as cell behavior. This work highlighted the advantages of MBG in the fabrication of Mg-based implant with enhanced overall performance for orthopedic application.

In this work it is demonstrated the capacity of the sol–gel process to obtain materials with different phases, using the same chemical composition, and modifying only the conditions of hydrolysis and condensation. This method combined with the polymer sponge replica technique allowed to obtain a porous and three-dimensional scaffold, called core, consisting mainly of calcium phosphates. Additionally, due to the versatility of the sol–gel process, this core was coated with additional phases, constituted by silicon and magnesium, obtaining multilayer scaffolds. The scaffolds were physically and chemically characterized and the in vitro bioactivity was evaluated by immersion in simulated body fluid. The results of in vitro bioactivity showed that the core revealed a lamellar microstructure with some apatite precipitates after 14 days, while the multilayer scaffolds presented precipitates over the whole surface in only 3 days. The accelerated bioactivity and the general properties of the multiphase and multilayer scaffolds show the potential of this material in the area of tissue engineering.

Polyalkenoate cement (PAC) is a promising material for regenerative hard tissue therapy. The ionically rich glass component of PAC encourages bioactive interaction via. the release of essential ions. However, PAC bioactivity is restricted owing to (i) structurally inherent cationic network formers and (ii) surface bacterial biofilm formation. These two factors cause a deficiency in ion release, further complicated by secondary infections and premature therapeutic failure. Here, a multivalent zwitterionic network modifier (mZM) is presented for upregulation of ionic exchange and bioactivity enhancement. By introducing a non-zero charged mZM into PACs, an increase in the proportion of non-bridging oxygen occurs. The network modification promotes ion channel formation, causing a multiple-fold increase in ion release and surface deposition of hydroxy-carbonate apatite (ca. 74%). Experiments ex vivo and animal models also demonstrate the efficient remineralization ability of the mZM. Furthermore, divalent cationic interaction results in bacterial biofilm reduction (ca. 68%) while also influencing a shift in the biofilm species composition, which favors commensal growth. Therefore, PAC modification with mZM offers a promising solution for upregulation of bioactivity, even aiding in customization by targeting site-specific regenerative therapy in future applications.

This investigation aims to study a novel biologically derived coating applied on Ti alloy substrates. Obtained from a low-cost fish bone resource, a nanocrystalline hydroxyapatite has been synthesized and converted to an organic suspension. Coating was then manufactured by a high-velocity suspension flame spray process. The microstructure, phase composition, coating thickness, and roughness of hydroxyapatite (HA)-coated samples were studied. The results indicated the presence of both hydroxyapatite and β-tricalcium phosphate phases and the final coating layer was uniform and dense. In vitro bioactivity and biodegradability of the HA/Ti composite samples were estimated by immersion in simulated body fluid. Remarkable reductions in Ca2+ and PO43- ion concentrations were observed as well as low weight loss percentage and a slight variation in the pH value, indicating the generation of an apatite layer on the surface of all studied samples. Scanning electron microscopy, energy-dispersive x-ray analysis, and inductively coupled plasma–optical emission spectrometry confirm these results. Thus biological derived HA coatings are a promising candidate to enhance bioactivity and biodegradability of bone implants. To demonstrate feasibility on commercial medical components, a medical screw was coated and evaluated., Science & Technology Development Fund (STDF), Projekt DEAL

In this report, we have systematically evaluated the role of boron in regulating the degradation, apatite formation and antibacterial properties of bioactive glasses by substituting SiO2 with B2O3 in S53P4 based glass composition. The structural analysis of the glasses has been carried out using neutron diffraction and Raman spectroscopic techniques. The structural analysis of S53P4 base glass has revealed the presence of silicate and phosphate units in the form of Q2Si, Q3Si and isolated Q0P units. With the increasing replacement of SiO2 with B2O3, Raman spectroscopy revealed the formation of non-ring metaborate units and borate rings consisting of both BO3 and BO4 units at the expense of Q2Si and Q3Si units. Furthermore, DSC, HSM and dilatometry results confirmed that the sinterability parameter (Sc) and fragility index (m) values of borosilicate bioactive glasses help in achieving superior sintering and thermal processing without devitrification. Additionally, in vitro SBF immersion studies revealed an accelerated release of Si4+ and Ca2+ ions from the borosilicate glasses. In vitro antibacterial assays against E.coli bacterial inoculum illustrate the critical role of B2O3 in the bioactive glass composition.

Late Cretaceous felsic volcanism erupted as calderas in the terminal stage of the massive Cretaceous volcanism in SE China. This paper reports comprehensive geochemical and isotopic data for high-silica rhyolites from the Shiniushan and Xiaoxiong calderas in eastern Fujian–Zhejiang provinces, SE China. Zircon U-Pb dating constrains these rhyolites eruptions to 94–92 Ma and 93–89 Ma in the sites of the two calderas. All the samples possess high-silica contents with peraluminous characteristics and are enriched in light rare earth elements (LREEs), Rb, and Th-U and depleted in Ba, Nb-Ta, Sr and Eu. These samples have high whole-rock F (114–596 ppm) but low Cl (3.3–54.8 ppm) contents. Apatite minerals separated from the high-silica rhyolites are classified as fluorapatite and show F-rich (F > 3.56 wt%), Cl-poor (Cl

The compositional record of accessory minerals can provide insights into the character and petrogenesis of the parental magma. We demonstrate apatite’s applicability to petrogenetic studies through in situ trace element analysis of apatite in 60 granitoid plutons from the eastern Central Asian Orogenic Belt (CAOB). Rare earth element (REE) patterns of apatites usually mimic the trend of the host rock but are slightly enriched in MREE (middle REE), which is predominantly controlled by parental melt composition and REE partitioning. However, the REE patterns of apatites that are decoupled from those of host rocks, such as the depletions of LREE (light REE) and MREE, as well as the HREE (heavy REE) enrichment, result from the early crystallization of other REE-bearing minerals and late-stage metamorphism. Our data displays no significant relationship between apatite trace elements and highly fractionated granitoids in the eastern CAOB, highlighting the limitation of assessing the degree of magma differentiation through apatite geochemistry. More significantly, the variation of Sr in apatite shows a close correlation with the early crystallization of plagioclase, and the linear correlations of SrPl-SrWR, SrPl-SrAp, and SrAp-SrWR imply constant Sr partition coefficients of plagioclase and apatite. Furthermore, a partition coefficient of Sr between apatite and bulk rock is proposed ( D Apatite / b u l k r o c k Sr = 0.69 ). Our results also imply that apatite crystallizing from adakites inherits the typical trace element signatures of the adakitic melt and is characterized by high Sr, low HREY (Gd∼Lu+Y) contents and lack of Eu anomaly. In conclusion, apatite provides a vital bond to understand the petrogenesis of granitoids and shows the potential to track granitic sources in detrital grains.

The long setting time and insufficient strength of tricalcium silicate (TCS)-based cements are a main disadvantage for their clinical use. Therefore, the aim of this study was to develop an advanced TCS cement by incorporating polydopamine (PDA) nanoparticles. The setting time and compressive strength of TCS cement with incorporated PDA nanoparticles were evaluated. Furthermore, the effect of PDA nanoparticles on the apatite formation and the cytotoxicity of hydrated cements was investigated. The results show that the initial and final setting time of the cements were reduced by 63.9% and 46.7%, respectively, by adding 4 wt% PDA nanoparticles. The compressive strength of the cements reached 39.6 MPa by the addition of 4 wt% PDA and was thus 37.5% higher than that of pure TCS. Furthermore, the apatite-forming ability was also improved with the incorporation of 4 wt% PDA and the good biocompatibility was readily confirmed by using a fibroblast cell line. Our results showed that a TCS cement reinforced with PDA nanoparticles could be a promising dental restorative material.

In order to protect carbon fibers (CF) from oxidation damage during sintering process, rod-like Mg-doped nano-hydroxyapatite (Mg-nHA) with an increased thermal decomposition temperature and reduced sintering temperature was synthesized by hydrothermal method. The synthesized bone-like Mg-nHA with similar composition and morphology to bone apatite was used as the matrix to prepare CF reinforced Mg-nHA composites (CF/Mg-nHA) at a low temperature of 700 °C by pressureless sintering. The increase of temperature slightly influenced the growth of Mg-nHA prepared by hydrothermal method from 160 °C to 200 °C. The Mg-nHA were short and rod-like in structure with a length of approximate 100 nm. When doping 1% magnesium, the decomposition temperature of Mg-nHA increased by 100 °C compared with that of nHA. This can protect CF from oxidation damage which is often encountered when sintering CF reinforced hydroxyapatite composites at high temperature and enhance reinforcing effects of CF. The bending strength of CF/Mg-nHA with 1 wt% CF was 8.51 MPa, which increased by 19.5% compared with Mg-nHA. Alternatively, the rod-like Mg-nHA was prepared on the surface of CF by electrochemical deposition and Mg-nHA coated CF was used to reinforce Mg-nHA, the coefficient of thermal expansion mismatch between CF and HA matrix could be mitigated. The compressive strength of Mg-nHA coated CF reinforced Mg-nHA (CF/Mg-nHA/Mg-nHA) composites with 0.5% CF sintered at 800 °C were 41.3 ± 1.56 MPa, which was attributed to the improved strengthening effect of CF and the good interface between CF and Mg-nHA matrix.

Hydroxyapatite (HAP) is the major mineral phase in bone and teeth. The interaction of individual amino acids and citrate ions with different crystallographic HAP surfaces has remained uncertain for decades, creating a knowledge gap to rationally design interactions with peptides, proteins, and drugs. In this contribution, we quantify the binding mechanisms and binding free energies of the 20 end-capped natural amino acids and citrate ions on the basal (0 0 1) and prismatic (0 1 0)/(0 2 0) planes of hydroxyapatite at pH values of 7 and 5 for the first time at the molecular scale. We utilized over 1500 steered molecular dynamics simulations with highly accurate potentials that reproduce surface and hydration energies of (hkl) hydroxyapatite surfaces at different pH values. Charged residues demonstrate a much higher affinity to HAP than charge-neutral species due to the formation of superficial ion pairs and ease of penetration into layers of water molecules on the mineral surface. Binding free energies range from 0 to −60 kJ/mol and were determined with ∼ 10% uncertainty. The highest affinity was found for citrate, followed by Asp(-) and Glu(-), and followed after a gap by Arg(+), Lys(+), as well as by His(+) at pH 5. The (hkl)-specific area density of calcium ions, the protonation state of phosphate ions, and subsurface directional order of the ions in HAP lead to surface-specific binding patterns. Amino acids without ionic side groups exhibit weak binding, between −3 and 0 kJ/mol, due to difficulties to penetrate the first layer of water molecules on the apatite surfaces. We explain recognition processes that remained elusive in experiments, in prior simulations, discuss agreement with available data, and reconcile conflicting interpretations. The findings can serve as useful input for the design of peptides, proteins, and drug molecules for the modification of bone and teeth-related materials, as well as control of apatite mineralization.

Objective This study investigated the chemical and structural changes in the mineral phase and collagen of dentin during application of a mild universal adhesive. Particular attention was paid to the role of isopropanol and changes in water molecules. Methods In vitro application of the mild universal adhesive on dentin with two established etching modes (self-etch and etch-and-rinse) was studied using solid state nuclear magnetic resonance spectroscopy. Results It was evidenced that the etch-and-rinse mode leads to a decrease of the inorganic apatite and a reorganization of the residual mineral phase with a low amount of adhesive phosphate monoesters calcium salt formed, compared to the self-etch mode. In contrast, the adhesive interacts very similarly to the level of dentin collagen in both protocols, with a strong decrease in the amount of the free water molecules induced by the presence of isopropanol as the adhesive solvent, but without significant changes in the initial collagen structure. For both modes, the adhesive acrylates monomers remain mobile and can infiltrate the collagen. Significance Understanding the molecular interactions between dentin and adhesive solutions is a major challenge for designing products that lead to the formation of ideal dentin resin hybrid layer. Notably, one point considered essential is the presence of unbound water which, over time, is associated with a hydrolytic degradation of the organic matrix. Isopropanol, as an adhesive solvent, leads to a decrease in the amount of the less stable water molecules while the water molecules strongly attached to the collagen are retained, thus preserving the collagen structure.

This work is devoted to the study of the features of ismorphism in compounds of the Ca-Na-Bi-P-O-F system, which have a crystalline structure of the mineral apatite, as well as its effect on the biocompatibility of substances in relation to human cells in an in vitro model. The Ca10-2xBixNax(PO4)6F2 system (x = 0,1,2,3,4,5) is characterized by continuous isomorphism, which follows from the minimum deviations of the unit cell parameters from the Vegard and Rotgers rules. The refinement of the crystal structure showed that the cations are unevenly distributed between the 4f and 6h positions of the crystal structure of apatite: bismuth ions are predominantly localized in the 6h position, while sodium ions are concentrated in the 4f position. The standard MTT test showed the biocompatibility of compounds with x = 1,2,3,4, and at x = 1 an anomaly was found in the form of an increased relative cell growth rate. The paper discusses the possible crystal-chemical and morphological reasons for this phenomenon.

The lack of the required mechanical strength and adequate biodegradation rate of calcium phosphate materials constitutes the most relevant drawback prohibiting their use for orthopaedic applications. One of the promising strategies to overcome this intrinsic limitation is the functionalization of these materials through the combination with specific functional groups. In this study, we investigated APTES (3-aminopropyl-triethoxy-silane) functionalization of a poorly crystalline apatite (PCA) and its further combination for the first time to chitosan (CS) to elaborate PCA-APTES-CS functionalized composite material. XRD patterns of the elaborated materials exhibit broad peaks typical of poorly crystalline apatite. FTIR spectroscopy showed, in addition to the PCA characteristic bands, bands assigned to silane alkyl groups and evidenced the success of functionalization process. The TGA analysis confirmed the attachment of 8 wt% of APTES and 3 wt% of chitosan within the composite. SEM microscopy and EDX silicon mapping demonstrated a homogeneous silane presence on functionalized apatite surface and showed that chitosan enveloped the functionalized apatite particles surface. The elaborated PCA-APTES-CS functionalized composites exhibited compressive strength similar to the spongy bone. The functionalized biocomposite will be investigated as potential biomaterial for orthopedic application.

The effect of swift heavy silicon ion irradiation on hydroxyapatite prepared by hydrothermal technique was analyzed. The physical and biological properties were studied using G1XRD, Micro-Raman, photoluminescence, AFM, SEM, EDX, in vitro bioactivity, antimicrobial activity and drug release. When compared with pristine the crystallinity increases with an increase in fluence. Slight reduction in crystallinity was noted for irradiated samples at higher fluence (1×1013 and 1×1014 ions/cm2) than lower fluence (1×1012 ions/cm2). After irradiation the υ4 O-P-O asymmetric bending mode peak at 583 cm−1 disappeared. The PL intensity increases with an increase in fluence and it had become narrow and showed red shift. This suggests the material could find application as phosphors. The enhancement in band gap was attained for irradiated samples than Hpris (5.38–5.5 eV). AFM studies revealed the enhancement of roughness, particle size and pores on irradiation. SEM exposed the creation of pores along with an increase in porosity (2 µm to 30 µm). Formation of platy crystals was noted for 1×1013 ions/cm2 sample. In vitro bioactivity results with the formation of spherical (2 µm) apatite deposition along with the presence of interconnected pores (2–10 µm) which could enhance osteointegration and osteoconduction. In addition, Ca/P ratio was found to increase after soaking in SBF. Initial burst release followed by sustained release was obtained upto 45 h. Therefore it could assist in the treatment of bone and joint infection. Hence, SHI had improved the material to be used in biomedical field as an implant due to its enhanced properties such as crystallinity, pore size, surface roughness, PL intensity, antimicrobial activity, drug release and bioactivity.

Identifying magma fertility is an important task in ore genesis research. In this paper, we use apatite chemistry and Sr-Nd isotopes for such a study. The apatite crystals are from four Cretaceous coeval granodiorite intrusions with different styles of hydrothermal mineralization in the Tongling ore district, South China. The selected intrusions are Hucun, Dongguashan, and Xinwuli, which host both porphyry and skarn Cu deposits, and the Chaoshan, which hosts a skarn Au deposit. The abundances of apatite major and trace elements, such as Mn, V, Ce, S, F, Cl, and Cu, together with the whole-rock compositions, are used to decipher the oxidation states, volatile compositions, and Cu fertility of the parental magmas. The apatite Sr-Nd isotope compositions are used as tracers for the magma sources. The results show that: (1) the parental magma of the Au-mineralized intrusion is less oxidized and has higher S-Cl contents than those of the Cu-mineralized intrusions, and (2) the proportion of mantle-derived melt is much higher in the former than in the latter. The results also reveal that the Cumineralized intrusions have highly variable apatite Cu-Cl-S compositions. Specifically, the Xinwuli intrusion has much higher Cu but lower Cl-S contents in apatite than the other two intrusions, indicating that a Cu-rich magma is not universally required for the formation of hydrothermal Cu deposits. This study demonstrates that apatite is a robust petrogenetic and metallogenic indicator for porphyry and skarn-type Cu-Au ore deposits.

Aims The aim of this study was to develop and characterize a temporary restorative material based on a zinc oxide matrix containing niobophosphate bioactive glass (NbG) for the caries-affected dentin treatment. Material and methods NbG was added to a ZnO2 matrix in different concentrations (wt%). EDS-SEM, ATR-FTIR and XRD analyses were performed to characterize the cement. Calcium release was evaluated in TRIS solution after 1, 7 and 14 days by colorimetric method (A650). Compressive strengths and setting times were performed to analyze mechanical properties. Results EDS spectra confirmed the presence of Ca, P and Nb in the groups containing NbG. EDS mapping exhibit the ZnO2 homogeneous distribution, and NbG immersed in this matrix. Peaks suggesting interaction between matrix and NbG were not detected in Ftir spectra. Calcium releasing showed to be time-dependent for experimental groups containing 10, 20, 30 and 40%. The NbG incorporation progressively increased the compressive strength values in the experimental groups. NbG incorporation seemed to influence the ZnO2 matrix early setting reaction. No statistical difference was observed in the final setting time. Conclusion The addition of NbG particles into zinc oxide matrix could work as a mechanical reinforcement. It is suggested that the calcium released by the cement containing at least 10% NbG could induce apatite formation.

This study revealed activation mechanisms of apatite by polyacrylamide (PAM) during flotation of rare earth minerals in Bayan Obo Ore. This activation leads to high phosphorus content in rare earth concentrate. Ultraviolet (UV) absorption measurements show that adsorption of PAM on the surfaces of apatite and rare earths follows a pseudo-second-order reaction kinetic model. The isothermal adsorption process follows the Freundlich adsorption model, indicating that the adsorption of PAM on apatite is a multi-layer, non-uniform process, that is, physical and chemical adsorption occurs simultaneously. The measured zeta potential shows that under weakly alkaline conditions, amide groups with a negative charge are adsorbed on the surface of apatite, increasing the electronegativity, so that the potential is shifted negatively; however, the negative shift of the potential on the surface of rare earths is insignificant. Fourier transform infrared (FT-IR) test and X-ray photoelectron spectroscopy (XPS) results imply that PAM is chemically adsorbed on the surface of apatite, while 506E undergoes stronger chemical adsorption than PAM on the surface of rare earth minerals. It is found that multi-layer, non-uniform adsorption of PAM combining physical and chemical adsorption occurs on the surface of apatite and the process is dominated by physical adsorption: the adsorption of PAM on surfaces of apatite is stronger than that on the surface of rare earth minerals. Such adsorption activates the apatite, causing it to float during the flotation of rare earths, which is the reason for the high phosphorus content in the rare earth concentrate.

The ability of the Nagelschmidtite (Nagel) phase to promote osteogenesis, cementogenesis, and angiogenesis increased the interest in using this calcium silicophosphate bioceramic for tissue regeneration and vascularization applications. Nagel phase is a solid solution with the general formula Ca7-xNax(PO4)2+x(SiO4)2-x, which allows several substitutions being Ca7(PO4)2(SiO4)2 the most reported stoichiometry. Inspired by the well-known 45S5 bioactive glass chemical composition, we developed a synthesis route to obtain a Na-rich Nagel single phase. The effect of this bioceramic chemical and structural properties on apatite formation and crystallization mechanism is reported. The structural aspects at the nano and microscale of the mechanism of apatite growth and crystallization from the Nagel phase were compared to the formation process of Extra-Cellular Matrix (ECM) deposits in biological systems, revealing a biomimetic behavior during the apatite biomineralization process from the bioceramic.

Osteoclast-mediated bioresorption can be an efficient means of incorporating the dissolution of biomaterials in the bone remodeling process. Because of the compositionally and structurally close resemblance of biomaterials with the natural mineral phases of the bone matrix, synthetic carbonate-substituted apatite (CA) is considered as an ideal biomaterial for clinical use. The present study therefore investigated the effects of electrical polarization on the surface characteristics and interactions with human osteoclasts of hydroxyapatite (HA) and CA. Electrical polarization was found to improve the surface wettability of these materials by increasing the surface free energy, and this effect was maintained for 1 month. Analyses of human osteoclast cultures established that CA subjected to a polarization treatment enhanced osteoclast resorption but did not affect the early differentiation phase or the adherent morphology of the osteoclasts as evaluated by staining. These data suggest that the surface characteristics of the CA promoted osteoclast resorption. The results of this work are expected to contribute to the future design of cell-mediated bioresorbable biomaterials capable of resorption by osteoclasts and of serving as a scaffold for bone regeneration.

Surface modification of Zirconium (Zr) with Zirconia (ZrO2) nanotubes (NTs) was performed using a two-step electrochemical anodization to investigate the role of such a modified surface in apatite formation and the inhibition of bacterial growth on Zr implants. Pore size at the surface of the NT arrays was controlled, along with the NT length, by varying the 2nd-step anodizing time duration. Nearly four-fold changes in the pore size were achieved by varying the anodization at the second anodizing step. The apatite formation on the implant surfaces plays an important role in the osteointegration process, which can be greatly influenced by the morphology and crystalline structure of the surface. XRD analysis of the anodized surfaces identified a mixed phase of monoclinic and tetragonal ZrO2 NTs with the crystallite size decreasing with increased 2nd anodizing time duration. Surface roughness of the ZrO2 NTs decreased with an increase in anodizing time duration. The ZrO2 NTs with the largest pore sizes, and the smallest crystallite sizes (ZrO2-15 m) favoured the deposition of a Ca-rich compound on their surfaces following 24 days of soaking in SBF, and showed the highest apatite-forming ability among all studied samples. Antibacterial tests showed that the ZrO2-15 m sample exhibited antibacterial properties with 1log10 CFU/mL reduction of S. aureus and E. coli incubated in a buffer solution for 4 h. Loading the NT layer with antibacterial drug led to a complete inhibition of both bacterial species. The rate of drug release was slowed down by dip coating the drug loaded NTs in a PLGA solution. A higher number of dip-coating steps not only slowed down the release of the drug, it also led to a higher suppression of growth in both bacteria. Longer antibiotic exposure and optimized dosage of the drug released from ZrO2 NTs can therefore be managed by modifying the NT morphology and the number of PLGA dip-coating steps.

Bone apatite is not hydroxyapatite (HAp), it is carbonate apatite (CO3Ap), which contains 6–9 mass% carbonate in an apatitic structure. The CO3Ap block cannot be fabricated by sintering because of its thermal decomposition at the sintering temperature. Chemically pure (100%) CO3Ap artificial bone was recently fabricated through a dissolution–precipitation reaction in an aqueous solution using a precursor, such as a calcium carbonate block. In this paper, methods of fabricating CO3Ap artificial bone are reviewed along with their clinical and animal results. CO3Ap artificial bone is resorbed by osteoclasts and upregulates the differentiation of osteoblasts. As a result, CO3Ap demonstrates much higher osteoconductivity than HAp and is replaced by new bone via bone remodeling. Granular-type CO3Ap artificial bone was approved for clinical use in Japan in 2017. Honeycomb-type CO3Ap artificial bone is fabricated using an extruder and a CaCO3 honeycomb block as a precursor. Honeycomb CO3Ap artificial bone allows vertical bone augmentation. A CO3Ap-coated titanium plate has also been fabricated using a CaCO3-coated titanium plate as a precursor. The adhesive strength is as high as 76.8 MPa, with excellent tissue response and high osteoconductivity., Graphical abstract

Phosphorus is an indispensable element, while the existing phosphate rock resources are not enough to maintain the long-term demand of modern agricultural development. To ensure the sustainability of economic and social, it is necessary and urgent to seek the alternative phosphorus source of phosphate rock. In this study, calcined clam shell powder (CSP) was firstly used as a modifier and mixed with sewage sludge (SS) for co-pyrolysis to obtain sludge-derived pyrochars containing a large amount of bioavailable phosphorus. The effect of different temperatures (500, 600, 700, 800 °C) and dosages (0%, 10%, 20%, 30%) on the change in the form of phosphorus during the pyrolysis process were investigated. With the increase of temperature and the addition of CSP, the orthophosphate (Ortho-P) increased from 63.69% in the original SS to nearly 100%. Furthermore, the main phase of inorganic phosphorus (IP) changed, mainly in the form of apatite phosphorus (hydroxyapatite increased from 8.88% to 35.97%), and the concentration of easy-to-lose phosphorus reduced to 0.11 mg/g. After co-pyrolysis of SS with CSP, the passivation situation of heavy metals (HMs), such as Zn, Mn, Cr, Cu, Cd and Pb was significantly improved, thus reducing the potential environmental risk. The planting experiment proved that the sludge-derived pyrochars obtained by adding 20% CSP at 800 °C promoted the germination of seeds and the growth of seedlings. Consequently, the product of SS co-pyrolysis with CSP could be used as an excellently bioavailable and environmentally friendly phosphate fertilizer for agricultural production.

This study aimed to examine the in vitro elution profiles of echinocandins, micafungin and caspofungin, obtained from antibiotic-loaded bone cement (ALBC) comprising apatite (BIOPEX-R Excellent [BP-EX ®], HOYA Corporation, Tokyo, Japan) or polymethylmethacrylate (PMMA). ALBC containing micafungin or caspofungin in BP-EX® or PMMA were submerged in 10 mL/g of sterile phosphate buffer solution (PBS) and placed in an incubator shaker at 37 °C for 7 days. At predetermined time intervals (1, 2, 3, 6, and 7 days), all PBS was removed and replaced with fresh PBS. High-performance liquid chromatography was used to determine the amounts of antifungal compounds present in the collected PBS. The surface structures of ALBC comprising BP-EX ® and PMMA were observed using scanning electron microscopy (SEM). The amount of micafungin released from BP-EX® was significantly higher than that from PMMA (p = 0.007). Significantly less amounts of caspofungin than those of micafungin were released (p

The effect of CaCO3, Na2CO3, and CaF2 on the reduction roasting and magnetic separation of high-phosphorus iron ore containing phosphorus in the form of Fe3PO7 and apatite was investigated. The results revealed that Na2CO3 had the most significant effect on iron recovery and dephosphorization, followed by CaCO3, the effect of CaF2 was negligible. The mechanisms of CaCO3, Na2CO3, and CaF2 were investigated using X-ray diffraction (XRD), scanning electron microscopy and energy dispersive spectrometry (SEM-EDS). Without additives, Fe3PO7 was reduced to elemental phosphorus and formed an iron-phosphorus alloy with metallic iron. The addition of CaCO3 reacted with Fe3PO7 to generate an enormous amount of Ca3(PO4)2 and promoted the reduction of iron oxides. However, the growth of iron particles was inhibited. With the addition of Na2CO3, the phosphorus in Fe3PO7 migrated to nepheline and Na2CO3 improved the reduction of iron oxides and growth of iron particles. Therefore, the recovery of iron and the separation of iron and phosphorus were the best. In contrast, CaF2 reacted with Fe3PO7 to form fine Ca3(PO4)2 particles scattered around the iron particles, making the separation of iron and phosphorus difficult.

Porphyry deposits are the main source for global Cu and Mo production. The generation of hydrous silicate magmas and subsequent separation of volatile-rich magmatic fluids with hydrothermal alteration are significant processes leading to the formation of porphyry deposits. However, a specific understanding of these processes has been limited by a lack of direct mineralogical records in the evolving magmatic-hydrothermal system. In this paper, we present an integrated textural and geochemical investigation on apatite from the giant Daheishan porphyry Mo deposit in NE China, illustrating that apatite can be a potential recorder of the magmatic-hydrothermal evolution of porphyry systems. Apatite from the ore-forming porphyry displays distinctive core-rim textures, with melt inclusions in the resorption cores (Type-A1) and co-existing of melt and fluid inclusions in the euhedral rims (Type-A2), indicating a magmatic-hydrothermal origin of apatite. This is also supported by both chemical and isotopic compositions obtained by in situ analyses using laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) and LA-multi collector-ICP-MS. The late Type-A2 apatite is relatively enriched in incompatible elements, such as rare earth elements (REE) and Th, but slightly depleted in fluid-mobile elements such as Na and S, compared to the early Type-A1 apatite. Relatively homogeneous (87Sr/86Sr)i ratios (0.70436–0.70504) of the Type-A1 and Type-A2 apatites indicate that they were formed in a relatively closed system without detectable contamination. Meanwhile, some apatite in the wall rock (biotite granodiorite) shows characteristics of secondary altered textures, resulting from the intensive alteration by hydrothermal fluids exsolved from the porphyry system. Apatite trapped in mineral phenocrysts of the wall rock is usually unaltered (Type-B1 apatite), with clear oscillatory growth zones in cathodoluminescence (CL) images. In contrast, the intergranular apatite is commonly altered (Type-B2 apatite), with chaotic zoning in CL images, abundant micro-fractures and secondary fluid inclusions. Compositionally, the Type-B2 apatite shows notable tetrad REE patterns, relatively lower light-REE and S contents, and elevated 147Sm/144Nd ratios compared to the Type-B1 apatite. LA-ICP-MS U-Pb dating yields a lower intercept age of 171.4 ± 2.3 Ma for Type-B2, which is consistent with the age of 171.5 ± 2.4 Ma for Type-A2, but is notably younger than the Type-B1 apatite (175.5 ± 1.3 Ma). It is suggested that the Type-B2 apatite has been significantly reset by hydrothermal fluids exsolved from the porphyry system. Therefore, we conclude that the textures and geochemistry of apatite in porphyry systems can be used as a potential proxy for recording fluid exsolution and hydrothermal alteration processes.

Phosphatic clays, one type of phosphorite industry wastes, could induce environmental issues and geological disasters when they are piled in the open air. Previous research demonstrated that phosphatic clays usually exhibit poor performance in heavy metal immobilization mostly due to low phosphate content. Thus, phosphatic clays could not be applied in practical heavy metal remediation without pretreatment. If the adsorption performance of phosphatic clays could be improved, employing phosphatic clays for heavy metal immobilization may act as an eco-friendly, economic way to not only reutilize phosphorite industry wastes but also remedy environmental heavy metal pollution at the same time. In this study, we propose an argon plasma treatment approach to remarkably improve the effectiveness of phosphatic clay performances in heavy metal immobilization. The optimal Pb(II) sorption capacity of 66.7 mg g-1 can be obtained at pH 6 and 25°C by using 15-min argon plasma treated phosphatic clays, which is two times as large as those of the untreated phosphatic clays and almost reaches those of raw apatite minerals. Moreover, the Pb(II) desorption ratios of Pb(II)-adsorbed phosphatic clays are also reduced by 30%-60% at different pH conditions. Therefore, applying argon-plasma technique to transform waste phosphatic clays into efficient heavy-metal sorbents is a promising road to phosphorite waste reclamation and environmental remediation.

Dentin hypersensitivity (DH) is characterized by short or transient sharp pain arising from exposed dentin in response to thermal, physical, osmotic, or chemical elements (Holland et al., 1997, West et al., 2011). According to the hydrodynamic theory, hypersensitivity results from the rapid movement of the fluid within the dentinal tubules (Brannstrom et al., 1968). It is imperative to the efficacy of the DH treatment to address the etiological factors of the condition (Femiano et al., 2017). Desensitizing therapies consist of the use of chemical substances, laser irradiation, restorative treatments, periodontal surgeries which aim basically to control the hydrodynamic mechanisms of pain. However, these treatments do not achieve predictable results in all patients and may lose their effect over time (Cartwright, 2014, Zhu et al., 2015, Sole-Magdalena et al., 2017). Bioactive glass materials have been proposed for the treatment of DH (David, 2010, Curtis et al., 2010, Barry et al., 2011, Sauro et al., 2011, Cartwright, 2014, Hall et al., 2017, Bansal and Mahajan, 2017). The mechanism of action of bioactive glass starts when the material is exposed to an aqueous environment. The sodium ions (Na+) in the particles immediately are switched with hydrogen cations (H+ or H3O+). This rapid release of ions allows the calcium ions (Ca+2) in the particle structure, as well as the phosphate ions (PO4-3), to be released from the glass particles. The initial reactions occur in seconds of exposure and the release of the Ca+2 and PO4-3 ions continues as long as the particles are exposed to an aqueous environment. A localized and transient increase in pH occurs during the initial material exposure due to the release of Na+. This increase in pH helps to precipitate the Ca+2 and PO4-3 ions of the particle to form a layer of calcium phosphate Ca(PO4)2. As particle reactions and the deposition of calcium and phosphorus complexes are maintened, the layer crystallizes into hydroxycarbonate apatite which is chemically and structurally equal to biological apatite. The combination of residual particles and the newly formed apatite layer lead to physically occluding the dentin tubules, resulting in remission or pain reduction (Zhong et al., 2002, Zanotto et al., 2004, Hench, 2006). The maintenance of this layer on the dentin surface is a major challenge for the materials existing in the market, besides knowing the effectiveness of them for the treatment of DH. Studies have shown the absence of parameters such as: patient follow-up time, control groups, assessment scale for degree of pain, DH diagnostic methods and form of application of the product (Matranga et al., 2017, Hannigan and Lynch, 2013, Kim et al., 2011, Pandis et al., 2011, Fleming et al., 2013). The use of bioactive materials is a promising proposal for DH due to the the neoformation of a bioactive barrier on dentin surface (Bansal and Mahajan, 2017). They showed the ability to occlude the dentinal tubules and form a mechanically strong layer of hydroxyapatite on the dentin surface, which can resist degradation by repeated acid challenges (Du et al., 2008). Thus, the aim of this systematic review was to assess randomized controlled trials (RCT) carried out in the permanent teeth of adult patients in the DH treatment with bioactive dentrifices, either at-home or in-office.

The sintering behaviour and microstructural evolution of two batches of a commercial calcium-deficient hydroxyapatite powder were investigated. First, the sintered density as a function of the starting particle size distribution was studied, and the minimum particle size to get the desired target density was determined. Then, as the two batches were characterized by a slight difference in Ca/P ratio, the role of such ratio on phase and microstructural evolutions during sintering, as well as on mechanical and biological properties was investigated. It was observed that the powder with lower Ca/P ratio underwent significant hydroxyapatite (HA) to β-tricalcium phosphate (β-TCP) decomposition, with a simultaneous formation of tetracalcium phosphate (TTCP). The microstructure of sintered gelcast samples evolved during isothermal sintering at 1300 °C, moving from a starting homogeneous and narrow grain size distribution to a bimodal distribution after 3 h sintering. In fact, over time, large grains decomposed into smaller ones, finally providing a microstructure composed of coarse grains surrounded by plenty of ultra-fine grains. On the contrary, the powder with the higher Ca/P ratio provided a limited HA to β-TCP transformation, and normal grain growth by increasing the sintering time. Such differences lead to different mechanical properties for gelcast samples produced by the two powder batches, as the material with the lower Ca/P ratio affected by lower mechanical strength. Finally, sintered samples from both powders showed in-vitro bioactivity, with a larger surface coverage observed for the lower Ca/P ratio material. The morphology of the apatite layer seemed to be affected by the material composition, too, showing flake-like and needle-like morphologies depending on the Ca/P ratio of the starting powder.

Significant progress has been made on understanding the critical role of organic components in directing the collagen mineralization. We hypothesize that the inorganic trace elements might also play important role in the mineralization of collagenous matrix. To this aim, we systematically compared the in-vitro biomineralization behaviors of gelatin, gelatin-HA and gelatin-SiHA electrospun membranes. The results indicated that the presence of Si ions played a striking influence on the nucleation behaviors and mineralized structures. The gelatin-SiHA samples demonstrated more homogeneous nucleation within the gelatin fiber and growth along the fiber direction, in comparison with the heterogeneous nucleation and growth of spherulitic clusters on top of the nanofiber surface, i.e. extrafibrillar mineralization. The likely shift of the nucleation mode to the intrafibrillar mineralization in the presence of Si ions led to good alignment of apatite c-axis with the long axis of the nanofiber, resulting in a mineralization process and microstructure that were closer to those in natural bone. Cellular response analysis indicated that Si incorporation improved the MSC attachment and cytoskeleton organization. Such findings might have important implication in both understanding the complex mechanisms involved in collagen mineralization and optimal designing of advanced bio-inspired materials with potential superior mechanical and biological properties.

Disadvantages of conventional drug delivery systems (DDS), such as systemic circulation, interaction with physiochemical factors, reduced bioavailability, and insufficient drug concentration at bone defect site, have underlined the importance of developing efficacious local drug delivery systems. Octacalcium phosphate (OCP) is presumed to be the precursor of biologically formed apatite, owing to its similarity to hydroxyapatite (HAp) and readiness to convert to it. Specific crystal structure of OCP is constructed of compiled apatite layers and water layers, which make possible the incorporation of various ions in its structure, making it feasible to alter the overall effect OCP has in the system. Next to that intrinsic property, characteristics as high solubility, biodegradability and osteoconductivity have made it indispensable to tailor OCP as a carrier material. In this review, we present the main characteristics and progress done on utilizing OCP as an innovative vehicle and provide suggestions for possible research pathways and advantages for local drug delivery in bone tissue engineering. STATEMENT OF SIGNIFICANCE: Octacalcium phosphate (OCP), being a precursor to biologically formed apatite, has many assets when compared to other calcium phosphates. Owing to its highly pertinent structure, it is being used as a vehicle for biologically active substances or ions for bone regeneration. However, orchestrating drug delivery systems with OCP, in order to achieve the best possible outcome, is still a pioneering concept, and the all-encompassing data is still scarce. Although several articles have been published on this matter, to this date there is no systematic overview pointing out the benefits that OCP can bring in the field of drug delivery. Here we offer a comprehensive overview, starting from the OCP synthesis to its structure, morphology, and the biological significance OCP has.

Globally, significant examples of hydrothermal Cu-Co mineralization are rare within Archean greenstone belts, especially relative to the endowment of these terranes with other world-class hydrothermal ore deposits, particularly Au deposits. Using U-Pb geochronology of hydrothermal apatite, this study provides the first absolute age constraints on the timing of mineralization for the Carlow Castle Cu-Co-Au deposit. Carlow Castle is a complex, shear zone-hosted, veined Cu-Co-Au mineral system situated within the Paleo-Mesoarchean Roebourne greenstone belt of the Pilbara craton of northwestern Western Australia. Although U-Pb geochronology of this deposit is challenging due to low levels of radiogenic Pb in synmineralization apatite, mineralization is best estimated at 2957 ± 67 Ma (n = 61). Additionally, analysis of alteration phases associated with Carlow Castle mineralization suggests that it is dominated by a propylitic assemblage that is characteristic of alkaline fluid chemistry and peak temperatures >300°C. Within proximal portions of the northwest Pilbara craton, the period of Carlow Castle’s formation constrained here is associated with significant base-metal volcanogenic massive sulfide mineralization and magmatic activity related to back-arc rifting. This rifting and associated magmatic activity are the most likely source of Carlow Castle’s unique Cu-Co-Au mineralization. Carlow Castle’s Mesoarchean mineralization age makes it among the oldest discovered Cu-Co-Au deposits globally, and unique in the broader context of hydrothermal Cu-Co-Au deposits. Globally, hydrothermal Cu-Co mineralization occurs almost exclusively as Proterozoic and Phanerozoic stratiform sediment-hosted Cu-Co deposits due to the necessity of meteorically derived oxidized ore fluids in their formation. This research therefore has implications for exploration for atypical Cu-Co deposits and Cu-Co metallogenesis through recognition of comparably uncommon magmatic-hydrothermal Cu-Co-Au ore-forming processes and, consequently, the potential for analogous Cu-Co-Au mineralization in other Archean greenstone belts.

Experimental investigations of Yb2Si2O7 pellet exposed to Calcium-Ferrum-Alumina-Silicate (CFAS) at 1400 °C in ambient air were carried out to reveal corrosion reaction between molten silicate deposit and Yb2Si2O7. Phase transformation, microstructure evolution and reaction mechanism were evaluated. Results indicated that the corrosion process was accompanied by the infiltration of CFAS melt, the dissolution of Yb2Si2O7 and the reprecipitation of Yb2Si2O7 and Ca2Yb8(SiO4)6O2 apatite as reaction product. The formation of apatite decreased the concentration of Ca2+ in the melt. After CFAS exposure at 1400 °C for 30 h, the thickness of the apatite layer stopped increasing due to insufficient Ca2+ content, and remained at about 115.4 μm. However, the infiltration depth of CFAS melt increased with the extending corrosion duration and increasing deposit content. And the infiltration rate was preliminarily found to first decrease and then increase with time. Most of the residual CFAS were crystallized into garnet (Ca3Fe2(SiO4)3 and Yb3Fe5O12) and mayerite (Ca12Al14O33), while a small volume of amorphous glass was dispersed among the garnet and mayerite grains.

Four types of zinc (Zn)-doped hydroxyapatite (Zn-HAp) nanoparticles were prepared using calcium nitrate tetrahydrate as an anti-sintering agent during calcination at 600°C for 1 hr, to prevent calcination-induced aggregation. The Zn content of the nanopowders was determined at 0, 4.3, 9.2, and 14.7% [Zn/(Ca + Zn) × 100] using inductively coupled plasma atomic emission spectroscopic analysis. Based on X-ray diffraction analysis, the products were shown to possess an apatite structure without other crystalline impurities. The cell parameters of Zn-HAp nanoparticles decreased with increasing of Zn content in the HAp structures. This tendency implies that Zn ions substituted for Ca sites in the HAp crystal lattices. To investigate the biological effects of Zn-HAp nanoparticles, cell proliferation activity of MC3T3-E1 osteoblasts and antibacterial activity against Escherichia coli were evaluated in vitro. According to the results obtained, Zn-HAp nanoparticles containing of 14.7% Zn ions was noticeable shown shareability of the conflicting activities at 0.1 mg/mL.

In this study, mineralization during brick preparation was performed with ureolytic bacterium, Lysinibacillus fusiformis that use urine as a substrate, omitting the heat that is normally required. Artificial urine for reasons of standardization was used to grow the bacterium for bio-bricks made of clay and cement, but their mineralization was enabled by biological activity instead of by heat. Scanning electron microscopy and energy dispersion X-ray spectroscopy were conducted to analyse the microstructures formed by L. fusiformis that precipitated various minerals in synthetic urine. The brick specimens were tested for compressive strength that was 59% more than control ones, whereas porosity of bio-bricks was 13% compared to 22% of control specimens. The minerals formed in the bio-bricks confirmed as struvite, apatite and calcite by Fourier-transform infrared spectroscopy and X-ray diffraction spectra, were responsible for improved strength and reduced porosity. The research provided evidence in utilizing ureolytic bacteria as a mode to mineralize clay in brick production with the use of (artificial) urine as a substrate.

The paper describes methods for the preparation of compounds with an apatite structure containing only iodine atoms in the “halogen” position. The crystal structure of the compounds was refined by the Rietveld method. The resulting apatites have a structure with a space group P63/m and have the following unit cell parameters: Ba4 f 1.78(2)Ba6 h 2.75(2)(PO4)3I0.04(2) (a = 10.18609(34) Å, c = 7.71113(30) Å, V = 692.889(54) Å3, R = 5.448 %), Pb4 f 1.82(2)Pb6 h 2.75(2)(PO4)3I0.13(2) (a = 9.87882(18) Å, c = 7.43222(16) Å, V = 628.144(26) Å3, R = 8.533 %), Pb4 f 1.90(2)Pb6 h 2.68(2)(PO4)3I0.16(2) (a = 9.87058(48) Å, c = 7.41255(46) Å, V = 625.437(72) Å3, R = 5.433 %). The study of the crystal structure showed a relatively low efficiency of the binding of iodine in the apatite matrix.

Fluid flux through Earth’s surface and its interior causes geochemical cycling of elements in the Earth. Quantification of such process needs accurate knowledge about the composition and properties of the fluids. Knowledge about the fluids in Earth’s interior is scarce due to limitations in both experimental methods and thermodynamic modeling in high/ultrahigh pressure–temperature conditions. In this study, we present halogen (Cl, F) measurements in apatite grains from the mafic (metagabbro), and felsic (two-pyroxene granulite, charnockite, hornblende-biotite gneiss) rocks preserved in the Nilgiri Block, southern India. Previous experiments show that it is difficult to incorporate Cl in apatite compared to F at high pressure and temperature conditions. Based on regional trends in Cl and F content in apatite (with highest Cl content 2.95 wt%), we suggest the presence of acidic C–O–H fluids in the lower crust (~20–40 km deep) during the high-grade metamorphism of these rocks. These fluids are capable of causing extreme chemical alterations of minerals, especially refractory ones. They also have significant potential for mass transfer, causing extensive geochemical variations on a regional scale and altering the chemical and isotope records of rocks formed in the early Earth. Our findings have important relevance in understanding speciation triggered by acidic fluids in the lower crust, as well as the role of fluids in deep Earth processes.

Osteoinductivity is a crucial factor to determine the success and efficiency of posterolateral spinal fusion (PLF) by employing calcium phosphate (Ca-P) bioceramics. In this study, three kinds of Ca-P ceramics with microscale to nanoscale gain size (BCP-control, BCP-micro and BCP-nano) were prepared and their physicochemical properties were characterized. BCP-nano had the spherical shape and nanoscale gain size, BCP-micro had the spherical shape and microscale gain size, and BCP-control (BAM®) had the irregular shape and microscale gain size. The obtained BCP-nano with specific nanotopography could well regulate in vitro protein adsorption and osteogenic differentiation of MC3T3 cells. In vivo rabbit PLF procedures further confirmed that nanotopography of BCP-nano might be responsible for the stronger bone regenerative ability comparing with BCP-micro and BCP-control. Collectedly, due to nanocrystal similarity with natural bone apatite, BCP-nano has excellent efficacy in guiding bone regeneration of PLF, and holds great potentials to become an alternative to standard bone grafts for future clinical applications., Graphical abstract Image 1, Highlights • The nanocrystal of porous BCP ceramic spheres is similar to natural bone apatite. • BCP nanoceramics is conducive to protein adsorption and osteogenic differentiation of MC3T3 cells. • Osteoindutivity of BCP ceramics is a crucial factor to determine the sucess and efficiency of PLF. • BCP ceramic spheres with nanotopography hold great potential in clinical PLF applications.

By using apatite-type Ln10Si6O27 (Ln = La, Sm, Gd) solids with oxide-ion-conduction properties, the effect of conductivity on the catalytic activity of 1 wt% Pt/Ln10Si6O27 for toluene combustion was clarified. With increasing Ln3+ ion size, the lattice volume of Ln10Si6O27 increased, resulting in the enhancement of the conductivity, likely due to the expansion of the oxide-ion-conducting pathway; that is, the conductivity increased in the order Gd10Si6O27 < Sm10Si6O27 < La10Si6O27. The conductivity of the Ln10Si6O27 promoter affected the oxygen release ability of 1 wt% Pt/Ln10Si6O27, which led to the oxidation of Pt0 to Pt2+/4+. Correspondingly, the Pt/Ln10Si6O27 catalyst facilitated toluene combustion, and the catalytic activity increased in the order 1 wt% Pt/Gd10Si6O27

Application of apatite (U-Th)/He thermochronology has been hindered by incomplete understanding of diffusion systematics that leads to the single-grain age dispersion often displayed by samples, particularly those from older, slowly cooled settings. We applied the continuous ramped heating (CRH) method to an apatite suite from Cathedral Rocks in the Transantarctic Mountains (TAM) that have high age dispersion in order to explain processes that complicate 4He diffusion in apatite. Examining 132 apatite grains from a total of six samples, we confirmed earlier apatite (U-Th)/He results showing that measured AHe ages have at least three-fold intra-sample dispersion with no obvious relationships between ages and effective uranium concentration (eU) or grain size. CRH results on these apatites yielded two groups. Those with younger ages, characterized by unimodal incremental 4He gas-release curves, displayed simple volume diffusion behavior. In contrast, grains with older ages generally show complex gas release in the form of sharp spikes and/or extended gas-release at high temperatures (i.e., ≥800 °C). Simply-behaved apatites still show considerable age dispersion that exceeds what grain size, radiation damage, and analytical uncertainty can explain, but this dispersion appears to be related to variations in 4He diffusion kinetics. The screened AHe ages from simply-behaved younger apatite grains together with kinetic information from these grains suggest that the sampled region experienced slow cooling prior to rapid cooling (rock exhumation) beginning ca. 35 Ma. This interpretation is consistent with other studies indicative of an increase in exhumation rates at this time, possibly related to the initiation of glaciation at the Eocene-Oligocene climate transition. An attempt to correct older apatite ages by simply removing extraneous gas-release components yielded some ages that are too young for the samples’ geologic setting, suggesting that the factors that lead to complex laboratory release behavior can impact both the expected radiogenic component as well as those that are apparently extraneous. From our observations, we infer that many apatite grains contain imperfections of varying kinds that contribute significantly to kinetic variability beyond that associated with radiation damage and conclude that: (1) CRH analysis can serve as a routine screening tool for AHe dating and offers opportunities to reveal first-order kinetic variations; (2) model-dependent age correction may be possible but would require some means of estimating the broad proportions of 4He components incorporated into grains before and after closure to diffusion, and (3) interpretation of highly dispersed AHe ages requires assessment of individual-grain diffusion kinetics beyond that predicted by radiation-damage models.

Synthetic biphasic bioceramics composed of hydroxyapatite (HA) and other calcium phosphates (CPs) can provide promising efficiency in the treatment of bone defects based on the rapid dissolution of the CPs, to allow its replacement by freshly formed bone, along with the slow resorption of the HA, to preserve the volume of the grafted area. For this purpose, the present study was conducted to prepare nanosized biphasic calcium phosphate (n-BCP) using a facile mechanochemical process. The experimental outputs were also compared to the commercial-grade HA in terms of physicochemical features. The Rietveld refinement was utilized to calculate the phase contents and crystal structures of the composites, including crystallite size, lattice parameters, and unit cell volume. Besides, the atomic arrangement of Ca1, Ca2, PO43−, and OH− groups in the hexagonal crystal structure of HA and triclinic structure of anhydrous dicalcium phosphate (DCPA) was determined. The phase fraction, crystallite size, and the powder density of the biphasic structures, which were derived by Rietveld refinement, were found to be affected by ball-milling. In addition to biphasic structures, a monolithic hexagonal HA with an isotropic crystal growth was formed after 7 h of ball-milling under an argon atmosphere. The in vitro test in a simulated body fluid (SBF) confirmed the bioactivity of the biphasic structure through the formation of a bone-like apatite layer after one week.

Mixing of cogenetic magmas represents an important process in granite petrogenesis but is difficult to identify and is consequently often overlooked due to the absence of obvious isotopic distinctions between the mixed melts. We have conducted in situ elemental and O isotope analyses on apatite from Cretaceous Zhangzhou calc-alkaline granite in southeast China. We integrated these data with micro-analyses on other minerals (plagioclase, zircon, and titanite) as well as whole-rock geochemistry to decipher the mixing history of this granitic complex. The apatite occurs as an early crystallizing phase forming inclusions in biotite, plagioclase, and titanite, and is characterized by core-rim zonation textures with a dark core and bright rims in backscattered images. The core domains have remarkably higher SO3 and Li concentrations but much lower SiO2, REE, and Y concentrations than the rim domains. However, both the cores and rims show geochemical compositions similar to that from typical I-type granite and also have mantle-like O isotope compositions (the core has δ18O = 5.3–6.8‰ and the rim has δ18O = 5.2–6.4‰, respectively), indicating crystallization from granitic melts derived from newly accreted crust. The combined major and trace element and O isotope compositions of apatite and whole-rock geochemistry suggest that compositional evolution of the Zhangzhou granite involved mixing between two cogenetic magma batches, with variable degrees of subsequent differentiation. Batch I magma was a low-SiO2 and high-SO3 melt, whereas Batch II magma was a high-SiO2 and low-SO3 melt that experienced devolatilization. The high-S content in apatite cores further suggests the parental magma of the Zhangzhou granite likely originated from a sulfur-rich source comprising mainly newly accreted arc crust in response to subduction of the paleo-Pacific Ocean. The geochemical records of these magmatic processes are rarely observed in coeval zircon, titanite, and plagioclase. Our study, therefore, demonstrates that apatite geochemistry is potentially a more suitable monitor of complex magmatic evolution, including devolatilization and mixing of isotopically indistinguishable magmas.

AIM To fabricate and characterize nano-hydroxyapatite (nHA) grafted and non-grafted glass fibre-based endodontic posts. METHODOLOGY Experimental glass fibre posts were fabricated using silanized nHA grafted (ex-HA) and non-grafted glass fibre (ex-P) reinforced resins. The structural analysis and morphological patterns were analysed with Fourier transform infrared spectroscopy and scanning electron microscopy, respectively. EverStick® glass fibre posts (eS) were used as a control group. The degree of conversion, flexural strength, and flexural modulus was investigated and the fractured structure was evaluated with a scanning electron microscope. Root canals were prepared in human extracted teeth restored with experimental and control posts. The push-out bond strength was evaluated with radicular dentine at days 7, 30, and 90, and the presence of voids at the interface were measured at day 1, 7, 30, and 90 with micro-computed tomography. The Shapiro-Wilk test and one-way ANOVA post-hoc Tukey's test were performed. The level of significance was set at 0.05. RESULTS The SEM and FTIR confirmed the presence of a silane-coupling agent on the glass fibres. The ex-HA post had a significantly lower degree of conversion compared to the ex-P post (p = .0008), but a significantly higher conversion than the eS post (p = .0014). The maximum flexural strength value was obtained with the ex-HA post with an insignificant difference (p = .366) compared to ex-P post and a significant difference (p = .029) compared to the eS post. The flexural modulus of ex-HA, ex-P, and eS posts were significantly different (p = .037). Similarly, the ex-HA post had a significantly higher push-out bond strength at days 7 and 30 (p = .037) compared to the ex-P and eS posts. The volume of voids had a nonlinear behaviour amongst the groups with no significant difference between the posts. CONCLUSION The fabrication of the experimental posts was successful and the ex-HA post had greater flexural strength and push-out bond strength compared to the ex-P post. The degree of conversion of the ex-HA post was lower than the ex-P and eS posts. The volume of voids of ex-HA and ex-P posts was lower than that of eS posts.

The relevance of the research. In the Tomsk region, the weathering crusts are very widespread, their gold content has been established, but a detailed study of the mineral composition has not previously been carried out. The relevance of the research is caused by the need to identify the conditions for formation of weathering crusts and to establish the patterns of accumulation of a wide range of minerals in them. The main aim of the research is to study the morphological and chemical features, paragenetic associations and distribution of minerals of the phosphate group, division into primary, transformed, and newly formed, the use of phosphates as minerals-indicators of the conditions for the formation of weathering crusts and their relationship with the distribution of gold. The object: residual and redeposited weathering crusts of the Tomsk region and the minerals of the phosphate group contained in them. Methods. The crystal morphological features of minerals of the phosphate group, their paragenetic associations were studied microscopically using an OLYMPUS SZX10 stereomicroscope, the chemical composition of minerals was determined using a HORIBA Scientific XGT-7200 X-ray fluorescence microscope and a TESCAN VEGA 3 SBU X-50 X-50 EDS Max OXFORD scanning electron microscope. Results. In the weathering crusts of the Tomsk region, phosphates of the apatite group, rare earth elements, and aluminophosphates of the crandallite group have been found. Phosphate minerals are divided into groups: primary terrigenous phosphates, stable in weathering crusts and released during the destruction of bedrock (monazite, xenotime, apatite), hypergene-transformed, altered during weathering (monazite), and secondary (monazite, cularite, flitorensite, crandallite, goyacite, gorseixite, plumbogumite). Established in different zones of the weathering crust, phosphate associations for the most part represent links in the successive transformation of minerals from calcium and rare-earth phosphates to aluminum, indicating an increase in the acidity of the mineral formation environment. In the upper part of the hydrolysis zone of the residual weathering crust, the greatest accumulation of gold is noted.

A simple low-temperature method for the deposition of apatite on porous charcoal from rice husk is proposed. The deposition was carried out by impregnation and subsequent treatment of porous charco...

Hydroxyapatite (HA) is similar to the inorganic component of human bone and teeth. Because of its excellent biocompatibility, bioactivity, and osteoconductivity, HA is widely used as a biomedical material. However, its biodegradability is poor. Oyster shells are mainly composed of CaCO3 and other trace elements, such as Mg, Sr, K, and Na. As a raw material for synthesizing HA, oyster shells not only serve as biowaste for efficient utilization but also contain various trace elements that are beneficial to the growth of bone tissue; they can thus enhance the overall biological performance of the bioceramic. In this study, microrod HA bundles were successfully synthesized using microwave irradiation with the aid of ethylene diamine tetra-acetic acid disodium salt (Na2EDTA) as a chelating agent. The formation of microrod HA bundles was expected to promote the material’s biodegradability, and the bundles could have potential in the field of bone tissue repair. The optimal parameters for synthesis of microrod HA bundles were a Na2EDTA-to-oyster-shell-powder ratio of 2/2 and a microwave power of 700 W. The microrod HA bundles degraded more easily than did the irregular HA aggregates, indicating that the morphology of the microrod bundles resulted in a higher HA degradation rate. Bioactivity tests revealed that numerous spherical apatite particles formed on the surface of the microrod HA bundles, indicating that they had excellent bioactivity. Finally, the microrod HA bundles had high protein adsorption capability, which facilitates the control of cell attachment and proliferation and is thus beneficial to tissue regeneration.

The behavior of hydroxyapatite containing zinc and silicate ions during selective laser melting under irradiation at 10.6 µm was studied for the first time. For comparison, the behavior of the material heated in a high-temperature furnace was investigated. It was found that, in contrast to the slow heating in the furnace, heating of the mechanochemically synthesized material with the degree of substitution x = 0.2 by scanning the laser spot enables its recrystallization with retention of substituent ions in the apatite structure. At high degrees of substitution (x = 1, 2), hydroxyapatites are unstable under both heating regimes. Different heating conditions lead to the formation of different impurity phases.