Apatite Lattice Research Articles

The location of cationic substitutions in carbonated biomimetic apatites significantly affects crystal nanomechanics

Bone and teeth are comprised of carbonate-substituted apatites with cationic substitutions, like sodium and potassium. Cations substitute for calcium in the apatite lattice but it is unclear whether they substitute for Ca(1) or Ca(2). Additionally, although we know that anionic substitutions affect the mineral mechanics, it is unclear how cationic substitutions affect mineral stiffness. Here, a combined experimental and theoretical approach using in situ fluid-mediated hydrostatic loading with synchrotron Wide Angle X-ray Scattering (WAXS) and Density Functional Theory (DFT) is used to elucidate the role of CO32− and Na+ or K+ co-substitutions on the atomic structure and mechanics of biomimetic apatites. Comparison of WAXS and DFT results showed that preferential substitutions at the Ca(1) and Ca(2) sites depended on cationic type and concentration, with a preference for Ca(1) at higher levels of co-substitution. Substitution levels and location of the cationic substitution both significantly affected the modulus of the minerals. This presents a new paradigm for the development of biomimetic apatites with multi-property tunability by considering composition and atomic organization.

Mobilities of volatiles (H, F and C) in apatite at high temperatures

Apatite serves as a notable host for diverse volatiles, but experimental data concerning the mobilities of volatiles out of its lattice remains scarce. Despite several investigations elucidating the diffusivities of F, Cl, and OH, their interplay mechanism remains poorly understood. Herein, to unveil the mobilities of hydrogen, fluorine, and carbon out of the apatite lattice and their intricate interaction mechanisms during high temperature processes, we carry out annealing experiments at 900, 1000, and 1100 °C on two apatite samples with distinct fluorine contents. Our findings indicate that along the c-axis, hydrogen diffusion coefficients surpass those of fluorine by 2–3 orders of magnitude, with lower activation energies observed. Hydrogen diffusion shows strong anisotropy, with lager diffusivities and lower activation energies along the c-axis than the a-axis. For both hydrogen and fluorine, the Durango apatite shows smaller diffusivities along the c-axis than the Imilchil apatite. Contrarily, carbon diffusion is absent in both samples at these temperatures. These differences in diffusivity may suggest that hydrogen diffuses as OH− along the a-axis and as H+ along the c-axis, while fluorine diffusion relies on hydrogen diffusion along the c-axis. Based on these new data, the capacity of apatite to record volatiles can be evaluated. All volatiles, including hydrogen, is likely preserved within the core of apatite during thermal events from several days to years, such as rapid volcanic eruptions. However, for prolonged thermal events lasting hundreds of millions of years, apatite preserves volatiles for F, Cl and C, but not hydrogen.

Tuning Mg Doping and Features of Bone-like Apatite Nanoparticles Obtained via Hydrothermal Synthesis.

Nanocrystalline apatites have been intensively studied for decades, not only for their well-known mimesis of bone apatite but also for applicative purposes, whether as biomaterials for skeletal repair or more recently for a variety of nanomedical applications enabled by their peculiar surface characteristics. Particularly, ion-doped apatites are of great interest because the incorporation of foreign ions in the composition of apatite (nano)crystals alters the bulk and surface properties, modifying their ability to interact with the external environment. This is clearly seen in the physiology of bone tissue, whose mineral phase, a low crystallinity apatitic phase, can dynamically exchange ions with cells, thus driving bone metabolism. Taking bone mineral as a model, the present work describes the development of Mg-doped hydroxyapatite nanoparticles, exploiting hydrothermal synthesis to achieve extents of Mg2+ doping hardly achieved before and using citrate to develop stable apatite colloidal dispersions. Morphological and physicochemical analyses, associated with in-depth investigation of ions populating the apatitic lattice and the nonapatitic surface layer, concurred to demonstrate the cooperative presence of Mg2+ and citrate ions, affecting the dynamic ion retention/release mechanisms. Achieving high Mg2+ doping rates and understanding how Mg doping translates into surface activation of apatite-based nanoparticles is expected to foster the design of novel smart and tunable devices, to adsorb and release ionic species and cargo molecules, with potential innovations in the biomedical field or even beyond, as in catalysis or for environmental remediation.

Corrosion resistance studies of copper and magnesium-doped fluorohydroxyapatite coatings on titanium biomaterial

This study discusses the contribution of Cu2+ and Mg2+, two biologically important ions substituted into the structure of fluorohydroxyapatite. FHA, a partial substitution of fluorine ion in HA has received a great attention because it improves the corrosion resistance of orthopedic implants. Copper, Magnesium and copper-Magnesium doped fluorohydroxyapatite (FHA) coatings were electrochemical deposited on titanium (Ti) using a cyclic voltammetry technique. The coatings properties were identified by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The corrosion behavior of coated and uncoated samples, immersed for 7 days in aerated simulated body fluid (SBF) in a presence of 0.2 g/l human serum albumin (HAS) was investigated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The synergetic effect of albumin and doped elements on the degradation of Ti was studied. As a result of these investigations, it is revealed that: fluoride, copper and magnesium were successfully incorporated into apatite lattice structure. The additions of ions in FHA crystal matrix reduced the crystallite size, increased the crystallinity and changed the structure of F-hydroxyapatite. All the electrochemical techniques employed demonstrated that the coatings that were produced offered superior protection against corrosion for titanium when exposed to artificial body fluids. The nano-Mg-FHA coating improves effective protection to Ti and presents the highest corrosion resistance. The outcomes of this investigation were also compared with already published works to validate the research results.

High-resolution Raman spectroscopy reveals compositional differences between pigmented incisor enamel and unpigmented molar enamel in Rattus norvegicus

Dental enamel is a peculiar biological tissue devoid of any self-renewal capacity as opposed to bone. Thus, a thorough understanding of enamel composition is essential to develop novel strategies for dental enamel repair. While the mineral found in bone and dental enamel is generally viewed as the biologically-produced equivalent of hydroxy(l)apatite, the formation of these bioapatites is controlled by different organic matrix frameworks—mainly type-I collagen in bone and amelogenin in enamel. In lower vertebrates, such as rodents, two distinct types of enamel are produced. Iron-containing pigmented enamel protects the continuously growing incisor teeth while magnesium-rich unpigmented enamel covers the molar teeth. Using high-resolution Raman spectroscopy, scanning electron microscopy, and energy dispersive X-ray spectroscopy, this work explores the differences in acid phosphate (HPO42−), carbonate (CO32−), hydroxyl (OH−), iron, and magnesium content of pigmented incisor enamel and unpigmented molar enamel of Sprague Dawley rats. Bundles of hydroxy(l)apatite nanowires comprise the enamel prisms, where prisms in pigmented enamel are wider and longer than those in unpigmented molars. In contrast to magnesium-rich unpigmented enamel, higher mineral crystallinity, and higher HPO42− and OH− levels are hallmark features of iron-rich pigmented enamel. Furthermore, the apparent absence of iron oxides or oxy(hydroxides) indicates that iron is introduced into the apatite lattice at the expense of calcium, albeit in amounts that do not alter the Raman signatures of the PO43− internal modes. Compositional idiosyncrasies of iron-rich pigmented and nominally iron-free unpigmented enamel offer new insights into enamel biomineralisation supporting the notion that, in rodents, ameloblast function differs significantly between the incisors and the molars.

X-ray diffraction studies of a partially demineralized oriented cortical bone with the controlled depth of analysis

The in vitro demineralization of bone tissue is used for simulating the osteoporosis related bone loss. This way would be helpful in observations of bone apatite dissolution in microstructural level and may give significant input for understanding crystal-chemistry of bone resorption. In the case of cortical bone, demineralization occurs inhomogeneously, with the formation of a superficial demineralized layer and a transition zone with a gradient of concentration and structural characteristics perpendicular to the reaction advance front. Changes in the microstructural parameters of the bone mineral in this interface zone are of great interest for understanding the resorptive processes in the bone associated with osteoporosis. In this work, the SEM-EDX method was used to estimate the sizes of the demineralized and interface layers in the cortical bone during stepwise demineralization in HCl water solution; the general patterns of changes in the concentrations of Ca, P, and Cl in these layers were established. The calculations of the effective penetration depth of X-rays in diffraction mode for the intact and partially demineralized cortical bone were performed. It is shown that the use of CoKα radiation (instead of the usual CuKα) ensures the depth of probing within the interface zone, which allows to adequately assess the microstructural parameters (crystallite sizes and lattice microdeformations) of altered bioapatite in the zone of its interaction with an acid agent. A nonmonotonic change in the average size of crystallites and microdeformations of the apatite lattice was revealed during acid demineralization of the bone. Using asymmetric XRD geometry, the evidence was obtained that the affected mineral of the transition zone does not contain other crystalline phases except for weakly crystallized apatite. For the first time, the depth-controlled XRD analysis was applied to such a complex (surface-gradient) object as partially demineralized cortical bone. Additionally, we propose a rapid, averaging, and non-destructive method for estimating the depth of the reaction front dividing the demineralized and non-demineralized portions of the bone by XRD. The consistency of XRD and SEM-EDX data on the thickness values of the demineralized layer is shown.

Evaluation of antimicrobial property of thymoquinone synthesized with black cumin hydroxyapatite crystals against dental pathogens - An Invitro study

Introduction: Nigella sativa, also known as black seed, black cumin, and/or Habbatul Barakah, is a medicinal herbal plant. Thymoquinone (TQ), one of Nigella sativa's active ingredients, has been shown to be anticarcinogenic, anti-inflammatory, analgesic, and antimicrobial. Hydroxyapatite (HA) is an inorganic mineral with the apatite lattice structure (A10(BO4)6C2). The aim of the current study is to incorporate thymoquinone with blackcumin hydroxyapatite crystals to form a new nanoformulation and to find out its cytotoxicity and antimicrobial properties against dental pathogens. Materials and method: Streptococcus mutans, Staphylococcus aureus, Enterococcus faecalis, and Candida albicans were the species used. The antimicrobial efficacy of the nanoparticles was evaluated using the agar well diffusion method at different concentrations ranging from 25 micron litres to 100 micron litres. UV double beam spectrophotometers in the wavelength range of 250-750nm were used to characterise the synthesised nanoparticles. Results: The zone of inhibition against Staphylococcus mutans and Candida albicans was found to be highest at 100 L concentration. As the concentrations of new nano formulation solution increased, the mean zone of inhibition grew. Conclusion: The study showed that there is potential antimicrobial property of the new nano formulation against Streptococcus mutans and Staphylococcus aureus also there is antifungal activity against Candida albicans

Hydrothermal Synthesis of Fluorapatite Coatings over Titanium Implants for Enhanced Osseointegration-An In Vivo Study in the Rabbit.

This work aims at the development and characterization of fluorapatite coatings, innovatively prepared by the hydrothermal method, aiming for enhanced osseointegration of titanium implants. Fluoride-containing coatings were prepared and characterized by scanning and transmission electron microscopy, Fourier-transform infrared spectroscopy-attenuated total reflectance, and X-ray photoelectron spectroscopy. The biological response was characterized by microtomographic evaluation and histomorphometric analysis upon orthotopic implantation in a translational rabbit experimental model. Physic-chemical analysis revealed the inclusion of fluoride in the apatite lattice with fluorapatite formation, associated with the presence of citrate species. The in vivo biological assessment of coated implants revealed an enhanced bone formation process-with increased bone-to-implant contact and bone volume. The attained enhancement of the osteogenic process may be attributable to the conjoined modulatory activity of selected fluoride and citrate levels within the produced coatings. In this regard, the production of fluorapatite coatings with citrate, through the hydrothermal method, entails a promising approach for enhanced osseointegration in implant dentistry and orthopedic applications.

Essential processes involving REE-enrichment in biogenic apatite in deep-sea sediment decoded via multivariate statistical analyses

Deep-sea sediments highly enriched in rare-earth elements (REE), termed “REE-rich mud,” have recently attracted attention as a potential mineral resource for industrially critical metals. Biogenic apatite or fish teeth and bone debris comprises the mineral phase which primarily hosts REE in deep-sea sediments; thus, biogenic apatite is a key material to decipher the formation process of REE-rich mud. We investigated the key process(es) controlling REE-enrichment in biogenic apatite through a novel data-driven approach. We analyzed the in situ chemical composition of biogenic apatite grains collected from REE-rich mud in the western North Pacific Ocean. Subsequently, the dataset of 685 analytical points × 35 elements was statistically analyzed via independent component analysis. Our new approach extracted four independent components (ICs) as geochemically meaningful and statistically independent signatures: substitution of elements into apatite lattice (IC1), the relatively rapid adsorption process that occurred at the sediment-water interface (IC2), elemental transfer from volcanic materials during early diagenesis (IC3), and metalliferous or detrital impurities physically adhering to or infiltrating apatite grains (IC4). Data distributions within the real and IC spaces provide insights into physicochemical processes involving elemental incorporation into biogenic apatite. We argue that after settlement on the seafloor, the fish bones and dentine in teeth adsorb REE from the overlying seawater and REE-enriched porewater at the sediment-water interface, resulting in the preferential enrichment of light rare-earth elements into apatite from these solutions. Further, that REE adsorbed on the apatite crystal surface was incorporated into the crystal lattice via substitution. The IC2 signal was intensified in the layers of “extremely REE-rich mud”, suggesting that the REE adsorption process was facilitated during the formation of layers with remarkably high bulk-sediment REE contents. This may reflect an increased supply of REE-carrier substances such as organic matter, which degraded on the seafloor and released REE at the sediment-water interface, which is associated with changes in paleoceanographic conditions including ocean surface bioproductivity.

Ashing of bone: errors due to loss of CO2 and their correction.

Ashing is widely used to determine weight fraction of water-free bone that is mineral, but no standard procedure exists and the range of techniques used spans a range of temperatures and times over which the amount of weight loss is variable. We show that variability is largely due to progressive loss of CO2 from CO3 2- ions in the apatite crystal lattice, beginning at 600 ℃, typically used for ashing. We test the effect of varying temperature, time, and weight of sample and develop a reliable method, using small samples. Replicate samples of bovine cortical bone were tested at 500 ℃, 600 ℃, and 700 ℃ for times ranging up to 24h. We also tested samples of multiple humans at what we concluded to be the optimal conditions. Varying conditions of ashing resulted in variations in apparent ash weight % by up to 7%. Samples between 5 and 20mg heated to 600 ℃ for 1h gave results agreeing with generally accepted values, but with much smaller variability. Ash wt% values for multiple human bone samples differed by up to 4.8%, but replicate data for individuals agree to ± 1 wt%. In conclusion, a satisfactory method is given for ash weight determination using small samples, and yielding highly reproducible data. If accepted widely, ash weight values between laboratories could be used to study variations due to diet, age, drug treatment, and disease.

A computational study on strontium ion modified hydroxyapatite-fibronectin interactions.

Protein adsorption is the first key step in cell-material interactions. The initial phase of such an adsorption process can only be probed using modelling approaches like molecular dynamics (MD) simulations. Despite a large number of studies on the adsorption behaviour of proteins on different biomaterials including calcium phosphates (CaP), little attention has been paid towards the quantitative assessment of the effects of various physicochemical influencers like surface modification, pH, and ionic strength. In the case of doped CaPs, surface modification through isomorphic substitution of foreign ions inside the apatite structure is of particular interest in the context of protein-HA interactions, as it is widely used to tailor the biological response of HA. Given this background, we present here the molecular-level understanding of the fibronectin (FN) adsorption mechanism and kinetics on a Sr2+-doped hydroxyapatite, HA, (001) surface at 300 K by means of all-atom molecular dynamics simulations. Electrostatic interactions involved in the adsorption of FN on HA were found to be significantly modified due to Sr2+ doping into the apatite lattice. In harmony with the published experimental observations, the Sr-doped surfaces were found to better support FN adhesion compared to pure HA, with 10 mol% Sr-doped HA exhibiting the best FN adsorption. The observed altered adsorption behaviour of FN on Sr-doped HA was correlated with the Hofmeister effect. Moreover, the non-monotonous trend of the FN-material interaction energy can be attributed to the spatial rearrangement of the functional groups (PO43-, OH-) in the apatite crystal. Sr2+ ions also influence the stability of the secondary structure of FN, as observed from the root mean square deviation (RMSD) and root mean square fluctuation (RMSF) analysis. The presence of Sr2+ enhances the flexibility of specific residues (residue nos. 20-44, 74-88) of the FN module. Rupture forces to disentangle FN from the biomaterial surface, obtained from steered molecular dynamics (SMD) simulations, were found to corroborate well with the results of equilibrium MD simulations. One particular observation is that the availability of an RGD motif (Arginine-Glycine-aspartate sequence, which interacts with cell surface receptor integrin to form a focal adhesion complex) for the interaction with cell surface receptor integrin is not significantly influenced by Sr2+ substitution.

Synthesis and characterization of chlorinated hydroxyapatite as novel synthetic bone substitute with negative zeta potential

In the present work, chlorine doped hydroxyapatite (ClHA), with varying degrees of ion replacement was successfully synthesized by a simple ball milling technique. The resulting powders were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, Field emission scanning electron microscopy and particle size analyzer. The zeta potential of the powders was performed in physiological saline (0.154 M). The results confirmed the formation of apatite as the main phase in all chlorine substituted powders except for some incremental changes in the lattice parameter ‘a’ and unit cell volumes of the resultant powders. However, the crystallinity of the powders declined from 96% to 83%. Fourier transform infrared spectroscopy results confirmed the incorporation of Cl ions in the apatite lattice by the appearance of new bands at 677 cm-1. FESEM results revealed that the crystallites have grown into grains with no major agglomeration. Vicker hardness test results revealed a hardness value of 2.65 ± 0.258 GPa for ClHA4 dense bodies at a load of 200g. Zeta potential analysis of the powders suggested that ClHA nanopowders can prove to be a potential bone implant material.

Microcomputed tomography (laboratory and synchrotron) of intact archeological human second metacarpal bones and age at death

Laboratory microcomputed tomography (microCT) and synchrotron microCT imaged intact human second metacarpal bones (mc2) from two UK archeological sites: Ancaster (3rd to 4th century CE) and Wharram Percy (11th to 14th century CE). Two female mc2 were studied from each of three age at death cohorts (young, 18–29 years; middle, 30–49 years; old ≥50 years) along with a modern control mc2. The present investigation is complementary with an X-ray scattering study of the same mc2 where the authors found no age-at-death-related changes in carbonated apatite lattice parameters and found collagen D-period peaks in the small angle regime in a minority of the mc2. This led the present authors to ask whether microCT could assign mc2 to the age cohort estimated by dental wear and whether material between bioerosion porosity and apparently free of diagenetic changes correlated with presence of strong D period peaks. Lab-microCT derived values of bone volume fraction BV/TV (bone volume BV divided by total volume TV) for distal and proximal metaphyses provided age estimates that agree with those of dental wear. Cortical microstructure corroborated the BV/TV determination. Synchrotron microCT revealed significant diagenesis in all of the Wharram Percy and two of the Ancaster mc2; the resulting microstructural changes were attributed to microbial attack. The Ancaster mc2 whose microstructure matched that of the modern mc2 had D-period peaks with intensities matching the modern bone. MicroCT with different voxel sizes was shown, therefore, to be very useful in age determination and in the assessment of 3D diagenetic changes.

Selective Laser Melting of Hydroxyapatite: Perspectives for 3D Printing of Bioresorbable Ceramic Implants.

Hydroxyapatite, being the major mineral component of tooth enamel and natural bones, is a good candidate for bone tissue engineering applications. One of the promising approaches for manufacturing of three-dimensional objects is selective laser sintering/melting which enables the creation of a dense structure directly during 3D printing by adding material layer-by-layer. The effect of laser irradiation with a wavelength of 10.6 μm on the behavior of mechanochemically synthesized hydroxyapatite under different treatment conditions was studied for the first time in this work. It was shown that, in contrast to laser treatment, the congruent melting is impossible under conditions of a relatively slow rate of heating in a furnace. Depending on the mode of laser treatment, hydroxyapatite can be sintered or melted, or partially decomposed into the more resorbable calcium phosphates. It was found that the congruent selective laser melting of hydroxyapatite can be achieved by treating the dense powder layer with a 0.2 mm laser spot at a power of 4 W and at a scanning speed of 700 mm/s. Melting was shown to be accompanied by the crystallization of a dense monolayer of oxyhydroxyapatite while preserving the initial apatite crystal lattice. The thickness of the melted layer, the presence of micron-sized pores, and the phase composition can be controlled by varying the scanning speed and laser power. This set of parameters permits the use of selective laser melting technology for the production of oxyhydroxyapatite biodegradable implants with acceptable properties by 3D printing.

Review Article Recent Advances in Preventing Dental Erosion

Dental erosion is defined as an irreversible loss of dental hard tissue due to exposure to chelating agents or non-bacterial acids. The occurrence of this condition was noted and the incidence and prevalence of dental erosion has been increasingly documented.The Ant erosive agents such as Anacardic acid in which the key component is the cashewnut shell liquid is phenolic lipids. It is a mixture of molecules which are saturated and unsaturated. It is also considered to have an anti-microbial effect and has been studied for the treatment of cancer, oxidative damage, inflammation and obesity disorders. Other anti-erosive agent like Fluoride helps in tooth remineralization. Fluorapatite, rather than hydroxyapatite, forms during the process of remineralization when fluoride is found in oral fluids. In apatite crystal lattice formation, fluoride ions replace hydroxy ions. Fluorapatite, even under acidic conditions, is less soluble than hydroxyapatite, which helps to regenerate tooth enamel. Fluoride is therefore a stronger anti-erosive agent. Various Recent advances in anti-erosive agents are Calcium and phosphate, Casein phosphopeptide amorphous calcium phosphate (CPP-ACP), Protease inhibitors, Oils, Chitosan chitosan and Multivalent metal ions Various techniques to evaluate dental erosion are in vitro techniques and in vivo techniques. In vitro techniques are Scanning electron microscope, Surface Profilometry, Polarized Light Microscopyand Non-Contact Confocal Laser Scanning Microscopy (CLSM). And iv vivo techniques are Photographs Clinical review and indices. The most important point of treatment is identifying and removing the erosion factor, above all current materials and methods. Therefore, early identification of the lesions, evaluation and removal of the etiological variables are relevant topics.

Fabrication of silver-doped apatite powders from silver-substituted octacalcium phosphate powders via solid–solid phase-conversion process

The excellent biocompatibility of apatite (hydroxyapatite, HAp; carbonate apatite, CO3Ap) materials makes them suitable candidates as bone substitutes. However, they have no antibacterial ability. Meanwhile, silver (Ag) exhibits excellent antibacterial properties across a wide antibacterial spectrum. However, soluble Ag salts exhibit cytotoxicity and poor aesthetic properties. We dope Ag into an apatite unit lattice in order for the composite material to exhibit antibacterial contact abilities while simultaneously limiting the release of Ag+, which is the primary cause of the unwanted color changes and cytotoxicity. When a crystal structure in which silver ions are substituted for Ca in octacalcium phosphate (OCP) (Ag-OCP) is immersed in water and/or (NH4)2CO3-containing solutions, Ag-OCP is converted into an apatite containing Ag via a solid–solid phase-transformation process. The Ag contents of the apatite and precursor Ag-OCP are the same. The CO3 content of apatite samples depends on the (NH4)2CO3 concentration of the treated solutions. A single-pot, single-step treatment enables the synthesis of both Ag-containing HAp and CO3Ap. Further, these Ag-containing HAp and CO3Ap samples show little color change from that of the precursor Ag-OCP.

Beyond dissolution: Xerostomia rinses affect composition and structure of biomimetic dental mineral in vitro.

Xerostomia, known as dry mouth, is caused by decreased salivary flow. Treatment with lubricating oral rinses provides temporary relief of dry mouth discomfort; however, it remains unclear how their composition affects mineralized dental tissues. Therefore, the objective of this study was to analyze the effects of common components in xerostomia oral rinses on biomimetic apatite with varying carbonate contents. Carbonated apatite was synthesized and exposed to one of the following solutions for 72 hours at varying pHs: water-based, phosphorus-containing (PBS), mucin-like containing (MLC), or fluoride-containing (FC) solutions. Post-exposure results indicated that apatite mass decreased irrespective of pH and solution composition, while solution buffering was pH dependent. Raman and X-ray diffraction analysis showed that the addition of phosphorus, mucin-like molecules, and fluoride in solution decreases mineral carbonate levels and changed the lattice spacing and crystallinity of bioapatite, indicative of dissolution/recrystallization processes. The mineral recrystallized into a less-carbonated apatite in the PBS and MLC solutions, and into fluorapatite in FC. Tap water did not affect the apatite lattice structure suggesting formation of a labile carbonate surface layer on apatite. These results reveal that solution composition can have varied and complex effects on dental mineral beyond dissolution, which can have long term consequences on mineral solubility and mechanics. Therefore, clinicians should consider these factors when advising treatments for xerostomia patients.

Internalization of Fluoride in Hydroxyapatite Nanoparticles.

Hydroxyapatite (HAP) is a cost-effective material to remove excess levels of fluoride from water. Historically, HAP has been considered a fluoride adsorbent in the environmental engineering community. This paper substantiates an uptake paradigm that has recently gained disparate support: assimilation of fluoride to bulk apatite lattice sites in addition to surface lattice sites. Pellets of HAP nanoparticles (NPs) were packed into a fixed-bed media filter to treat solutions containing 30 mg-F/L (1.58 mM) at pH 8, yielding an uptake of 15.97 ± 0.03 mg-F/g-HAP after 864 h. Solid-state 19F and 13C magic-angle spinning nuclear magnetic resonance spectroscopy demonstrated that all removed fluoride is apatitic. A transmission electron microscopy analysis of particle size distribution, morphology, and crystal habit resulted in the development of a model to quantify adsorption and total fluoride capacity. Low- and high-estimate median adsorption capacities were 2.40 and 6.90 mg-F/g-HAP, respectively. Discrepancies between experimental uptake and adsorption capacity indicate the range of F- that internalizes to satisfy conservation of mass. The model was developed to demonstrate that F- internalization in HAP NPs occurs under environmentally relevant conditions and as a tool to understand the extent of F- internalization in HAP NPs of any kind.

Development of a new approach to diagnosis of the early fluorosis forms by means of FTIR and Raman microspectroscopy

This study is aimed at investigating the features of mineralization of the enamel apatite at initial stages of fluorosis development. Samples of teeth with intact and fluorotic enamel in an early stage of the disease development (Thylstrup–Fejerskov Index = 1–3) were studied by Raman scattering and FTIR using Infrared Microspectroscopy beamline at Australian Synchrotron equipment. Based on the data obtained by optical microspectroscopy and calculation of the coefficient R [A-type/B-type], which represents the ratio of carbonation fraction of CO32−, replacing phosphate or hydroxyl radicals in the enamel apatite lattice, the features of mineralization of enamel apatite in the initial stages of development of the pathology caused by an increased content of fluorine in the oral cavity were established. Statistical analysis of the data showed significant differences in the mean values of R [A-type/B-type] ratio between the control and experimental groups for surface layers (p < 0.01). The data obtained are potentially significant as benchmarks in the development of a new approach to preventive diagnostics of the development of initial and clinically unregistered stages of human teeth fluorosis, as well as personalized control of the use of fluoride-containing caries-preventive agents.

Low-Cost Deposition of Antibacterial Ion-Substituted Hydroxyapatite Coatings onto 316L Stainless Steel for Biomedical and Dental Applications

Substitutions of ions into an apatitic lattice may result in antibacterial properties. In this study, magnesium (Mg)-, zinc (Zn)-, and silicon (Si)-substituted hydroxyapatite (HA) were synthesized using a microwave irradiation technique. Polyvinyl alcohol (PVA) was added during the synthesis of the substituted HA as a binding agent. The synthesized Mg-, Zn-, and Si-substituted HAs were then coated onto a 316L-grade stainless-steel substrate using low-cost electrophoretic deposition (EPD), thereby avoiding exposure to high temperatures. The deposited layer thickness was measured and the structural, phase and morphological analysis were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and scanning electron microscope (SEM), respectively. The bacterial adhesion of Staphylococcus aureus was characterized at 30 min, 2 h and 6 h. The results showed homogeneous, uniform thickness (50–70 µm) of the substrate. FTIR and XRD showed the characteristic spectral peaks of HA, where the presence of Mg, Zn and Si changed the spectral peak intensities. The Mg–HA coating showed the least bacterial adhesion at 30 min and 2 h. In contrast, the Si–HA coating showed the least adhesion at 6 h. EPD showed an effective way to get a uniform coating on bio-grade metal implants, where ionic-substituted HA appeared as alternative coating material compared to conventional HA and showed the least bacterial adhesion.