Carbonate-substituted Hydroxyapatite Research Articles

Fabrication of antibacterial bone scaffold based on carbonate-substituted hydroxyapatite containing magnesium from black sea urchin (Arbacia lixula) shells reinforced with polyvinyl alcohol and gelatin

Carbonate-substituted hydroxyapatite containing magnesium (Mg–C-HAp) was introduced through dissolution-precipitation treatment of hydroxyapatite containing magnesium (Mg-HAp) based on a black sea urchin (arbacia lixula) shells as novel biogenic materials. Based on chemical composition analysis, the Mg–C-HAp formed A- and B-type CHAp, which contained high carbonate ions. The Ca/P ratio of Mg–C-HAp was 1.707, very close to the biological bone apatite of 1.71. The Mg content in Mg–C-HAp was also relatively high, with the Mg/(Ca + Mg) ratio of 0.139, which is beneficial for antibacterial agents. The morphology of Mg–C-HAp showed particles with nanosize that provide a large surface area of ion promotion. The antibacterial test revealed that the Mg–C-HAp performed high antibacterial activity against Pseudomonas aeruginosa. The Mg–C-HAp-based porous scaffolds were then fabricated using the freeze-drying method with variations of polyvinyl alcohol (PVA) and gelatin fraction. According to the physicochemical analysis, the addition of PVA and gelatin in the scaffold structure decreased the crystallinity of the Mg–C-HAp/PVA/Gel scaffold. This lower crystallinity indicates high biodegradability, which is good for new bone growth. The macropores of the Mg–C-HAp/PVA/Gel scaffold were appropriate for new bone and blood vessel formation. The micropores of the Mg–C-HAp/PVA/Gel scaffold can be a medium for cells to grow. The microporosity of the Mg–C-HAp/PVA/Gel scaffold was also suitable for cell nutrient promotion. The compressive strength of the Mg–C-HAp/PVA/Gel scaffold was sufficient for bone regeneration. The Mg–C-HAp/PVA/Gel scaffold demonstrated high antibacterial activity against P. aeruginosa, so the Mg–C-HAp/PVA/Gel scaffold can maintain the role of Mg and carbonate content for antibacterial purposes. The good physicochemical, mechanical, and antibacterial properties of the Mg–C-HAp/PVA/Gel scaffold represented its suitable characteristics for antibacterial bone scaffolds.

Rapid Deposition of the Biomimetic Hydroxyapatite-Polydopamine-Amino Acid Composite Layers onto the Natural Enamel.

In this work, we developed a technology that enables rapid deposition of biomimetic composite films onto natural enamel slices (known as biotemplates). These films are composed of polydopamine (PDA) and nanocrystalline carbonate-substituted hydroxyapatite (nano-cHAp) that have been functionalized with amino acid l-Arginine. We utilized atomic force microscopy (AFM) and scattering scanning near-field optical microscopy (s-SNOM) combined with infrared (IR) synchrotron to achieve nanoscale spatial resolution for both IR absorption and topography analyses. This combined analytical modality allowed us to understand how morphology connects to local changes in the chemical environment on the biotemplate surface during the deposition of the bioinspired coating. Our findings revealed that when using the proposed technology and after the deposition of the first PDA layer, the film formed on the enamel surface nearly covers the entire surface of the specimen whose thickness is larger on the surface of the emerging enamel prisms. Calculation of the crystallinity index for the biomimetic layer showed a multiple increase compared with natural enamel. This indicates regular and dense aggregation of nano-cHAp into larger crystals, imitating the morphology of natural enamel rods. The microhardness of the formed PDA-based biomimetic layer mineralized with nano-cHAp functionalized with amino acid l-Arginine deposited on natural enamel was practically the same as that of natural enamel. The characterization of nano-cHAp-amino acid-PDA layers using IR and Raman microspectroscopy showed that l-arginine acts as a conjunction agent in the formation of mineralized biomimetic composite coatings. The uniformity of the mechanisms of PDA layer formation under different deposition conditions and substrate types allows for the formation of coatings regardless of the macro- and micromorphology of the template. Therefore, the results obtained in this work have a high potential for future clinical applications in dental practice.

Synthesis of a 3D Porous Multicomponent Bioceramic Scaffold

In this study, 3D porous multicomponent bioceramic scaffolds were fabricated. Hydroxyapatite (HA) and carbonate-substituted hydroxyapatite (CHA) synthesized from Asian moon scallop shell (Amusium pleuronectes) served as the bioceramics, whereas alginate and chitosan served as the polymeric components. The study was focused on determining whether the presence of polyvinyl alcohol (PVA) in the scaffold exerted an impact. When PVA was not included, the morphological examination revealed that the samples exhibited porous structures characterized by effective pore interconnectivity and a substantial pore size. X-ray diffraction and scanning electron microscopic analyses indicated that the inclusion of PVA led to a decrease in the crystallinity, pore size, and porosity of the scaffolds. Those containing PVA exhibited porosity levels in the range of 56%–60%, and pore sizes ranged from 42 to 90 µm. These properties may provide advantages for the scaffold with respect to the ability for cell migration and cell attachment, thus enhancing new bone formation. Moreover, the compositions of HA and chemically modified HA (CHA) within the scaffold influenced the crystallinity and uniformity of the scaffold morphology. This finding suggests the potential for crafting a customized porous bioceramic scaffold based on specific compositions.

Hydroxyapatite/poly(vinyl alcohol)/chitosan coating with gentamicin for orthopedic implants

Electrophoretic deposition (EPD) was employed to fabricate composite coatings aimed for orthopedic implants. Hydroxyapatite (HAP), poly(vinyl alcohol) (PVA) and chitosan (CS) coatings, with or without antibiotic gentamicin (Gent) were deposited in a single-step process from aqueous suspension, using EPD. Polymer/mineral composite coatings were formed with the aim to mimic the natural composition of bone tissue, along with improved coatings antibacterial properties, at the same time serving as a drug carrier, allowing local administration of antibiotic. Structural and morphological characterization of HAP/PVA/CS and HAP/PVA/CS/Gent coatings was investigated by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TG/DTG), and scanning electron microscopy (SEM) proving carbonate-substituted HAP. The presence of gentamicin contributed to the bactericidal activity of composite HAP/PVA/CS/Gent coating against Staphylococcus aureus and Escherichia coli. Cytotoxicity studies were performed towards human MRC-5 and mice L929 fibroblast cell lines, and both investigated samples (HAP/PVA/CS and HAP/PVA/CS/Gent) expressed good biocompatibility, without causing toxic effect on tested cells. Biomineralization potential was investigated by measuring the alkaline phosphatase activity, demonstrating high potential of HAP/PVA/CS/Gent to induce the growth of new HAP layer. Therefore, the present investigation proposes the production of composite coatings from non-toxic (aqueous) suspensions, consisting of biocompatible and bioactive components, along with antibiotic gentamicin, improving the antibacterial coatings' properties.

Functionalized cellulose nanofibrils in carbonate-substituted hydroxyapatite nanorod-based scaffold from long-spined sea urchin (Diadema setosum) shells reinforced with polyvinyl alcohol for alveolar bone tissue engineering.

In this study, carbonate-substituted hydroxyapatite (C-HAp) nanorods were synthesised using a dissolution-precipitation reaction on hydroxyapatite (HAp) nanorods based on long-spined sea urchin (Diadema setosum) shells. From the EDS analysis, the Ca/P molar ratio of C-HAp was 1.705, which was very close to the Ca/P of natural bone apatite of 1.71. The FTIR and XRD analyses revealed the AB-type CHAp of the C-HAp nanorods. The TEM showed the rod-like shape of nanosize C-HAp with a high aspect ratio. The antibacterial test against Pseudomonas aeruginosa and Staphylococcus aureus also showed that C-HAp had a high antibacterial activity. The C-HAp/PVA-based scaffolds were fabricated, using a freeze-drying method, for use in alveolar bone tissue engineering applications. There were various scaffolds, with no filler, with microcrystalline cellulose (MCC) filler, and with cellulose nanofibrils (CNF) filler. The physicochemical analysis showed that adding PVA and cellulose caused no chemical decomposition but decreased the scaffold crystallinity, and the lower crystallinity created more dislocations that can help cells proliferate well. The antibacterial activity showed that the CNF induced the higher antibacterial level of the scaffold. According to the SEM results, the micropores of the C-HAp/PVA/CNF can provide a place for cells to grow, and its porosity can promote cell nutrient supply. The macropores of the C-HAp/PVA/CNF were also suitable for cells and new blood vessels. Therefore, the C-HAp/PVA/CNF scaffold was examined for its cytocompatibility using the MTT assay against NIH/3T3 fibroblast cells with a 24 h incubation. The C-HAp/PVA/CNF scaffold showed a high cell viability of 90.36 ± 0.37% at a low scaffold dose of 31.25 μg mL-1. The scaffold could also facilitate NIH/3T3 cells to attach to its surface. The IC50 value had also been estimated to be 2732 μg mL-1.

Development of a Hybrid Biomimetic Enamel-Biocomposite Interface and a Study of Its Molecular Features Using Synchrotron Submicron ATR-FTIR Microspectroscopy and Multivariate Analysis Techniques.

Using a biomimetic strategy and bioinspired materials, our work proposed a new technological approach to create a hybrid transitional layer between enamel and dental biocomposite. For this purpose, an amino acid booster conditioner based on a set of polar amino acids (lysine, arginine, hyaluronic acid), calcium alkali, and a modified adhesive based on BisGMA and nanocrystalline carbonate-substituted hydroxyapatite are used during dental enamel restoration. The molecular properties of the hybrid interface formed using the proposed strategy were understood using methods of multivariate statistical analysis of spectral information collected using the technique of synchrotron infrared microspectroscopy. The results obtained indicate the possibility of forming a bonding that mimics the properties of natural tissue with controlled molecular properties in the hybrid layer. The diffusion of the amino acid booster conditioner component, the calcium alkali, and the modified adhesive with nanocrystalline carbonate-substituted hydroxyapatite in the hybrid interface region creates a structure that should stabilize the reconstituted crystalline enamel layer. The developed technology can form the basis for an individualized, personalized approach to dental enamel restorations.

Engineering of biomimetic mineralized layer formed on the surface of natural dental enamel

The problem of engineering a biomimetic mineralized layer on the surface of native dental tissue (bio-template) was considered in our work.The formation of the mineralized layer on a biotemplate is achieved with the use of nanocrystalline carbonate-substituted calcium hydroxyapatite (HAp), calcium alkali, and a complex of polyfunctional organic and polar amino acids.By applying the set of structural and spectroscopic methods of analysis we have confirmed the formation of a mineralized biomimetic HAp layer on the surface of bio-template with properties resembling those of natural hard tissue. The thickness of the biomimetic mineralized layer varies from 300 to 500 nm, while the direction of some ncHAp nanocrystals coincides with that of the apatite crystals in the enamel.We also demonstrated that the engineered mineralized HAp layer was characterized by homogeneous micromorphology and enhanced nanohardness in the region of the enamel rods exceeding those of native enamel.The development of a strategy for biomimetic engineering and a technique for enamel surface pre-treatment to enable tissue mineralization has huge potential in dental applications.

Biomimetic Mineralization of Tooth Enamel Using Nanocrystalline Hydroxyapatite under Various Dental Surface Pretreatment Conditions.

In this report, we demonstrated the formation of a biomimetic mineralizing layer obtained on the surface of dental enamel (biotemplate) using bioinspired nanocrystalline carbonate-substituted calcium hydroxyapatite (ncHAp), whose physical and chemical properties are closest to the natural apatite dental matrix, together with a complex of polyfunctional organic and polar amino acids. Using a set of structural, spectroscopy, and advanced microscopy techniques, we confirmed the formation of a nanosized ncHAp-based mineralized layer, as well as studying its chemical, substructural, and morphological features by means of various methods for the pretreatment of dental enamel. The pretreatment of a biotemplate in an alkaline solution of Ca(OH)2 and an amino acid booster, together with the executed subsequent mineralization with ncHAp, led to the formation of a mineralized layer with homogeneous micromorphology and the preferential orientation of the ncHAp nanocrystals. It was shown that the homogeneous crystallization of hydroxyapatite on the biotemplate surface and binding of individual nanocrystals and agglomerates into a single complex by an amino acid booster resulted in an increase (~15%) in the nanohardness value in the enamel rods area, compared to that of healthy natural enamel. Obtaining a similar hierarchy and cleavage characteristics as natural enamel in the mineralized layer, taking into account the micromorphological features of dental tissue, is an urgent problem for future research.

Chemically Bound Resorbable Ceramics as an Antibiotic Delivery System in the Treatment of Purulent–Septic Inflammation of Bone Tissue

Local drug delivery systems are an effective approach in the treatment of purulent–septic inflammation of bone tissue. Chemically bonded multiphase ceramics based on calcium-deficient carbonate-substituted hydroxyapatite combine resorbability, osteoconductivity, and the possibility of volumetric incorporation of antibiotics. Macroporosity is regulated by the concentration of polyethylene glycol granules introduced into the initial powder composition, followed by their extraction. The selected conditions for the consolidation of the ceramic matrix and the extraction of PEG granules retain the activity of vancomycin, which is confirmed by the results of microbiological studies. The concentration of vancomycin and the porosity affect the local concentration and release of the antibiotic. The incorporation method provides a prolonged release of the antibiotic for up to 31 days. In vivo experiments with bone implantation have shown that chemically bound macroporous ceramics with incorporated vancomycin are a therapeutically effective carrier of the substance during the healing of bone defects in conditions of surrounding purulent–septic inflammation, and can be considered as a carrier for local antibacterial therapy, at the site of implantation.

Investigating pair distribution function use in analysis of nanocrystalline hydroxyapatite and carbonate-substituted hydroxyapatite.

Hydroxyapatite (HA) is a complex material, which is often nanocrystalline when found within a biological setting. This work has directly compared the structural characteristics derived from data collected using a conventional laboratory-based X-ray diffractometer with those collected from a dedicated pair distribution function (PDF) beamline at Diamond Light Source. In particular, the application of PDF analysis methods to carbonated HA is evaluated. 20 synthetic samples were measured using both X-ray diffraction (XRD) and PDFs. Both Rietveld refinement (of laboratory XRD data) and real-space refinement (of PDF data) were used to analyse all samples. The results of Rietveld and real-space refinements were compared to evaluate their application to crystalline and nanocrystalline hydroxyapatite. Significant relationships were observed between real-space refinement parameters and increasing carbonate substitution. Understanding the local order of synthetic hydroxyapatite can benefit several fields, including both biomedical and clinical settings.

The Molecular and Mechanical Characteristics of Biomimetic Composite Dental Materials Composed of Nanocrystalline Hydroxyapatite and Light-Cured Adhesive.

The application of biomimetic strategies and nanotechnologies (nanodentology) has led to numerous innovations and provided a considerable impetus by creating a new class of modern adhesion restoration materials, including different nanofillers. An analysis of the molecular properties of biomimetic adhesives was performed in this work to find the optimal composition that provides high polymerisation and mechanical hardness. Nanocrystalline carbonate-substituted calcium hydroxyapatite (nano-cHAp) was used as the filler of the light-cured adhesive Bis-GMA (bisphenol A-glycidyl methacrylate). The characteristics of this substance correspond to the apatite of human enamel and dentin, as well as to the biogenic source of calcium: avian eggshells. The introduction and distribution of nano-cHAp fillers in the adhesive matrix resulted in changes in chemical bonding, which were observed using Fourier transform infrared (FTIR) spectroscopy. As a result of the chemical bonding, the Vickers hardness (VH) and the degree of conversion under photopolymerisation of the nano-cHAp/Bis-GMA adhesive increased for the specified concentration of nanofiller. This result could contribute to the application of the developed biomimetic adhesives and the clinical success of restorations.

Efficacy of HAF toothpastes in primary and permanent dentitions. A 2-years triple-blind RCT

ObjectivesThe aim of this RCT was to compare the caries preventive efficacy and the slowing down of previous caries lesions of toothpastes containing fluoride biomimetic hydroxyapatite (HA) complex compared to sodium monofluorophosphate fluoridated toothpastes in Italian schoolchildren. To validate this hypothesis a triple-blind randomized clinical trial was designed. MethodsIn total 610 children (4–5 and 6–7 years) were enrolled. Four toothpastes, two containing fluoride-substituted hydroxyapatite (HAF) (1000 and 1450 ppmF) and magnesium-, strontium-, carbonate-substituted hydroxyapatite, in a chitosan matrix and two Mono fluoridated toothpastes (1000 and 1450 ppmF) were randomly administered during 24 months to two groups with younger children (Gyoung) and to two groups with older children (Gold), those containing 1450 ppmF. ICDAS was used to score lesions as initial (up to score 2), moderate (scores 3–4) and severe (scores 5–6). The children were instructed to brush for two minutes three times/day. Caries examination was repeated at 12 and 24 months. The efficacy of the treatment was assessed by calculating the reduction in Risk Ratio (RR) and the number needed to treat (NNT). Results; Overall, 518 patients (Gyoung = 268; Gold = 250) concluded the trial. The drop-rate was 11.84% for Gyoung and 17.22% for Gold. The caries increment at 24-month evaluation was statistically lower in the primary dentition in the HAF arms compared to the traditional fluoridated arms (0.18 vs 0.27 p = 0.04 in Gyoung and 0.16 vs 0.30 p = 0.01 in Gold for severe lesions). In the permanent dentition (Gold), caries increase was also statistically lower in the HAF arm, both for initial and severe lesions (0.09 vs 0.17 p = 0.02 and 0.18 vs 0.28 p = 0.01, respectively). In primary dentition, children receiving HAF Toothpaste had a RR of 39% (Gyoung) and 38% (Gold), compared to children receiving traditional Toothpastes. The RR in the permanent dentition was 29% in children treated with HAF toothpaste. Conclusions; The use of toothpastes containing biomimetic hydroxyapatite and fluoride reduces caries increment in children over a period of 2 years more than traditional fluoridated toothpastes.

XANES investigation of the influence of a coordinating atomic environment in biomimetic composite materials

In our work, the influence of the coordination environment of the Ca atom states in biomimetic mineralizing composite dental materials integrated with dental tissue was investigated. Biomimetic composites as well as natural dental tissue samples were investigated using synchrotron X-ray absorption near edge structure (XANES) spectroscopy. Energy structure studies revealed a number of important features related to the different type of calcium atom environment. the surface of nanocrystalline calcium carbonate-substituted hydroxyapatite (nano-cHAp) crystals in natural enamel and dentin involved in the formation of bonds with the organic matrix is more characterized by the coordination environment of the calcium atom corresponding to its location in the CaI position, i.e. bound through common oxygen atoms with PO4 tetrahedrons. At the same time, on the surface of nano-cHAp crystals in bioinspired dental materials, the calcium atom is more characteristically located in the CaII position, bound to the hydroxyl OH group. The detected features in the coordination atomic environment in nano-cHAp play a fundamental role for engineering a biomimetic dental composite of the natural organomineral interaction in the mineralized tissue.

Biomimetic strategy of a hybrid biointerface creation between native human dental tissue and dental composite

The aim of the studyis the peculiarities of the molecular composition of the biointerface between the native human dental tissue and the dental composite, created in an alkaline environment, based on synchrotron chemical infrared micro-mapping. When creating a biomimetic interface under alkaline conditions, we used an original bioprimer, dentin conditioner, nanofilled universal adhesive, and a light-curing compomer based on BIS-GMA. Biointerface analysis was carried out on the basis of chemical infrared micro-mapping, implemented using the equipment of the Australian Synchrotron, and subsequent multivariate cluster analysis of the collected spectral data array. It was shown that the use of a primer modified with a set of polar amino acids additionally facilitated the opening of dentinal tubules and the penetration of the bioprimer components into the dentin with the formation of a deeper transitional hybrid layer. At the same time, modification of the Bis-GMA adhesive using nanocrystalline carbonate-substituted hydroxyapatite, which has a structural and morphological organization similar to natural dental tissue apatite, led to an increase in the degree of conversion of the used adhesive material during polymerization. Using a biomimetic strategy and nanocrystals of carbonate-substituted hydroxyapatite as a filler of a universal adhesive, the necessary conjugation at the interface with dentin can be achieved without disrupting the polymerization processes, as well as preserving the natural structural complexity of the intact tissue, which makes it possible to take into account the individual characteristics of the patient.

Investigation of the Effect of Nanocrystalline Calcium Carbonate-Substituted Hydroxyapatite and L-Lysine and L-Arginine Surface Interactions on the Molecular Properties of Dental Biomimetic Composites.

Differences in the surface interactions of non-stoichiometric nanocrystalline B-type carbonate-substituted hydroxyapatite (n-cHAp) with the amino acids L-Lysine hydrochloride (L-LysHCl) and L-Arginine hydrochloride (L-ArgHCl) in acidic and alkaline media were determined using structural and spectroscopic analysis methods. The obtained data confirm that hydroxyapatite synthesized using our technique, which was used to develop the n-cHAp/L-LysHCl and n-cHAp/L-ArgHCl composites, is nanocrystalline. Studies of molecular composition of the samples by Fourier transform infrared spectroscopy under the change in the charge state of L-Lysine in environments with different alkalinity are consistent with the results of X-ray diffraction analysis, as evidenced by the redistribution of the modes’ intensities in the spectra that is correlated with the side chains, i.e., amide and carboxyl groups, of the amino acid. During the formation of a biomimetic composite containing L-Lysine hydrochloride and n-cHAp, the interaction occurred through bonding of the L-Lysine side chain and the hydroxyl groups of hydroxyapatite, which created an anionic form of L-Lysine at pH ≤ 5. In contrast, in biocomposites based on L-Arginine and n-cHAp, the interaction only slightly depends on pH value, and it proceeds by molecular orientation mechanisms. The X-ray diffraction and infrared spectroscopy results confirm that changes in the molecular composition of n-cHAp/L-ArgHCl biomimetic composites are caused by the electrostatic interaction between the L-ArgHCl molecule and the carbonate-substituted calcium hydroxyapatite. In this case, the bond formation was detected by Fourier transform infrared (FTIR) spectroscopy; the vibrational modes attributed to the main carbon chain and the guanidine group of L-Arginine are shifted during the interaction. The discovered interaction mechanisms between nanocrystalline carbonate-substituted hydroxyapatite that has physicochemical properties characteristic of the apatite in human dental enamel and specific amino acids are important for selecting the formation conditions of biomimetic composites and their integration with the natural dental tissue.

Raman and XANES Spectroscopic Study of the Influence of Coordination Atomic and Molecular Environments in Biomimetic Composite Materials Integrated with Dental Tissue.

In this work, for the first time, the influence of the coordination environment as well as Ca and P atomic states on biomimetic composites integrated with dental tissue was investigated. Bioinspired dental composites were synthesised based on nanocrystalline calcium carbonate-substituted hydroxyapatite (nano-cHAp) obtained from a biogenic source and a set of polar amino acids that modelled the organic matrix. Biomimetic composites, as well as natural dental tissue samples, were investigated using Raman spectromicroscopy and synchrotron X-ray absorption near edge structure (XANES) spectroscopy. Molecular structure and energy structure studies revealed several important features related to the different calcium atomic environments. It was shown that biomimetic composites created in order to reproduce the physicochemical properties of dental tissue provide good imitation of molecular and electron energetic properties, including the carbonate anion CO32− and the atomic Ca/P ratio in nanocrystals. The features of the molecular structure of biomimetic composites are inherited from the nano-cHAp (to a greater extent) and the amino acid cocktail used for their creation, and are caused by the ratio between the mineral and organic components, which is similar to the composition of natural enamel and dentine. In this case, violation of the nano-cHAp stoichiometry, which is the mineral basis of the natural and bioinspired composites, as well as the inclusion of different molecular groups in the nano-cHAp lattice, do not affect the coordination environment of phosphorus atoms. The differences observed in the molecular and electron energetic structures of the natural enamel and dentine and the imitation of their properties by biomimetic materials are caused by rearrangement in the local environment of the calcium atoms in the HAp crystal lattice. The surface of the nano-cHAp crystals in the natural enamel and dentine involved in the formation of bonds with the organic matrix is characterised by the coordination environment of the calcium atom, corresponding to its location in the CaI position—that is, bound through common oxygen atoms with PO4 tetrahedrons. At the same time, on the surface of nano-cHAp crystals in bioinspired dental materials, the calcium atom is characteristically located in the CaII position, bound to the hydroxyl OH group. The features detected in the atomic and molecular coordination environment in nano-cHAp play a fundamental role in recreating a biomimetic dental composite of the natural organomineral interaction in mineralised tissue and will help to find an optimal way to integrate the dental biocomposite with natural tissue.

Measures of Bone Mineral Carbonate Content and Mineral Maturity/Crystallinity for FT-IR and Raman Spectroscopic Imaging Differentially Relate to Physical-Chemical Properties of Carbonate-Substituted Hydroxyapatite.

Bone mineral carbonate content assessed by vibrational spectroscopy relates to fracture incidence, and mineral maturity/ crystallinity (MMC) relates to tissue age. As FT-IR and Raman spectroscopy become more widely used to characterize the chemical composition of bone in pre-clinical and translational studies, their bone mineral outcomes require improved validation to inform interpretation of spectroscopic data. In this study, our objectives were (1) to relate Raman and FT-IR carbonate:phosphate ratios calculated through direct integration of peaks to gold-standard analytical measures of carbonate content and underlying subband ratios; (2) to relate Raman and FT-IR MMC measures to gold-standard analytical measures of crystal size in chemical standards and native bone powders. Raman and FT-IR direct integration carbonate:phosphate ratios increased with carbonate content (Raman: p < 0.01, R2 = 0.87; FT-IR: p < 0.01, R2 = 0.96) and Raman was more sensitive to carbonate content than the FT-IR (Raman slope + 95% vs FT-IR slope, p < 0.01). MMC increased with crystal size for both Raman and FT-IR (Raman: p < 0.01, R2 = 0.76; FT-IR p < 0.01, R2 = 0.73) and FT-IR was more sensitive to crystal size than Raman (c-axis length: slope FT-IR MMC + 111% vs Raman MMC, p < 0.01). Additionally, FT-IR but not Raman spectroscopy detected differences in the relationship between MMC and crystal size of carbonated hydroxyapatite (CHA) vs poorly crystalline hydroxyapatites (HA) (slope CHA + 87% vs HA, p < 0.01). Combined, these results contribute to the ability of future studies to elucidate the relationships between carbonate content and fracture and provide insight to the strengths and limitations of FT-IR and Raman spectroscopy of native bone mineral.

ВЛИЯНИЕ СОСТАВА КРИСТАЛЛОХИМИЧЕСКОЙ СТРУКТУРЫ КАЛЬЦИЙ-ФОСФАТНОГО НАНОКОМПОЗИТА НА ФОРМИРОВАНИЕ ЭЛЕКТРОПОВЕРХНОСТНЫХ И КИСЛОТНО-ОСНОВНЫХ СВОЙСТВ

The single-phase modified nanostructured hydroxyapatites and biomimetic calcium-phosphate nanocomposite (BMHAP) doped by silicate and carbonate anions are synthesized by chemical precipitation in aqueous solutions. The chemical composition of the obtained samples is studied by energy dispersive X-ray spectroscopy using a scanning electron microscope. It is shown that the obtained molar ratios are close to the design values in all samples. The influence of different modifying ions in the crystal-chemical structure of hydroxyapatite (HAp) on the electrosurface properties of the synthesized products has been studied. Unmodified hydroxyapatite, silicate-substituted hydroxyapatite, and BMHAP particles are found to carry a negative charge in an aqueous suspension at pH = 7, while carbonate-substituted HAp particles had a positive charge. It is revealed that the introduction of silicate and carbonate anions into the HAp structure is accompanied by an increase in negative values of the zeta-potential from -1.05 to -4.29 mV. The change in the distribution of active centers on the surface of modified nanostructured hydroxyapatites is studied by the adsorption of acid-base indicators method with pKax in the range from -0.3 to +12.8. In contrast to stoichiometric hydroxyapatite, in BMHAP the neutral Bronsted centers prevails, and their concentration is 48.38 mmol-eq/g

Effect of different CO32− to PO43− molar ratios on the properties, morphology, and Pb(II) removal performance of carbonated hydroxyapatite

Hydroxyapatite (HAP) and a series of carbonate-substituted hydroxyapatite (CHAP) materials were prepared using a facile hydrothermal method and characterized by powder X-ray diffractometer (XRD), nitrogen adsorption-desorption analyzer, transmission electron microscope (TEM), Fourier transform infrared spectrometer (FT-IR), and elemental analyzer. The effect of different CO32− to PO43- molar ratios on the properties, morphology, and Pb(II) removal performance of the synthesized materials was investigated. Varying the molar ratios of CO32− to PO43-, from 0:19 (HAP) to 5:14 (CHAP5), 10:9 (CHAP10), and 15:4 (CHAP15), resulted in smaller particle size, lower crystallinity, and higher surface area of materials with higher CO32− concentrations. Consequently, CHAP15 demonstrated significantly superior maximum adsorption capacity (1697 mg g-1) among all the synthesized materials. The isotherm and kinetics of Pb(II) adsorption by CHAP15 were satisfactorily described by the Langmuir isotherm model and the pseudo-first-order kinetic model, respectively. The dominant mechanism for Pb(II) removal by CHAP15 was the dissolution of adsorbent followed by the reaction of Pb(II) ions with phosphate ions and with carbonate ions to form poorly-soluble compounds: Pb10(PO4)6(OH)2 and Pb3(CO3)2(OH)2.

Mechanism of interaction among nanocrystalline carbonate-substituted hydroxyapatite and polar amino-acids for the biomimetic composite technology: Spectroscopic and structural study

This study investigated changes in the interaction of B-type non-stoichiometric nanocrystalline carbonate-substituted hydroxyapatite (nano-CHAP) with polar amino acids (AA) with respect to CHAP-AA linking. Molecular vibrational spectroscopy revealed for the first time that the surface interaction of polar amino acids with defective nano-CHAP is determined not only by the charge state of AA but can be mediated by a foreign ion conjugated with the lateral bonds of amino acids. Understanding this mechanism of CHAP-AA interaction is required for the development of the new generation of dental biomimetic materials based on HAP as well as for their qualitative integration with the amino acid matrix of the dental tissues.