Formation and evolution of hydrated surface layers of apatites

Nanocrystalline apatites exhibit a very fragile structured hydrated surface layer which is only observed in aqueous media. This surface layer contains mobile ionic species which can be easily exchanged with ions from the surrounding fluids. Although the precise structure of this surface layer is still unknown, it presents very specific spectroscopic characteristics. The structure of the hydrated surface layer depends on the constitutive mineral ions: ion exchanges of HPO42- ions by CO32- ions or of Ca2+ by Mg2+ ions result in a de-structuration of the hydrated layer and modifies its spectroscopic characteristics. However, the original structure can be retrieved by reverse exchange reaction. These alterations do not seem to affect the apatitic lattice. Stoichiometric apatite also shows HPO42- on their surface due to a surface hydrolysis after contact with aqueous solutions. Ion exchange is also observed and the environments of the surface carbonate ions seem analogous to that observed in nanocrystalline apatites. The formation of a hydrated layer in aqueous media appears to be a property common to apatites which has to be taken into account in their reactivity and biological behavior

Chemical Diversity of Apatites

Apatites can accommodate a large number of vacancies and afford multiple ionic substitutions determining their reactivity and biological properties. Unlike other biominerals they offer a unique adaptability to various biological functions. The diversity of apatites is essentially related to their structure and to their mode of formation. Special charge compensation mechanisms allow molecular insertions and ion substitutions and determine to some extent their solubility behaviour. Apatite formation at physiological pH involves a structured surface hydrated layer nourishing the development of apatite domains. This surface layer contains relatively mobile and exchangeable ions, and is mainly responsible for the surface properties of apatite crystals from a chemical (dissolution properties, ion exchange ability, ion insertions, molecule adsorption and insertions) and a physical (surface charge, interfacial energy) point of view. These characteristics are used by living organisms and can also be exploited in material science

Bone mineral: update on chemical composition and structure

Bone mineral: update on chemical composition and structur

Physico-chemical properties of nanocrystalline apatites: Implications for biominerals and biomaterials

Nanocrystalline apatites play an important role in biomineralisation and they are used as bioactive biominerals for orthopaedic applications. One of the most interesting characteristics of the nanocrystals, evidenced by spectroscopic methods, is the existence of a structured surface hydrated layer, well developed in freshly formed precipitates, which becomes progressively transformed into the more stable apatitic lattice upon ageing in aqueous media. The hydrated layer is very fragile and irreversibly altered upon drying. Several routes leading to different apatite compositions are found in biological systems. The loosely bound ions of the hydrated layer can be easily and reversibly substituted by other ions in fast aqueous ion exchange reactions. These ions can either be included in the growing stable apatite lattice during the ageing process or remain in the hydrated layer. The adsorption properties of nanocrystals appear to be strongly dependent on the composition of the hydrated layer and on ageing. The surface reactivity of the apatite nanocrystals can play a part in different biomaterials and could explain the setting reactions of biomimetic calcium phosphate cements and the possibility of obtaining adherent nanocrystalline coatings on different substrates

Biomimetic apatite-based biomaterials: on the critical impact of synthesis and post-synthesis parameters

Nanocrystalline apatites are major constituents of hard tissues, and attempts are made worldwide to prepare synthetic analogs. However the impact of synthesis/ postsynthesis parameters is often disregarded. Based on an updated knowledge on such compounds, we inspected the effects of synthesis parameters (maturation time, temperature,pH, nature of counter-ions) and post-treatments (re-immersion in aqueous media, thermal treatment) on physicochemical characteristics. Great modifications were noticed during the 3 first days of maturation, where a progressive evolution of the apatite phase (localized in the core of the nanocrystals) toward stoichiometry was observed at the expense of the non-apatitic surface layer which progressively disappears. Similar trends were also evidenced for maturation run under increasing temperatures, studied here in the range 20–100 °C. pH impacted more specifically the chemical composition. The nature of the counter-ion in the starting phosphate salt influenced composition and nonstoichiometry, depending on its (in)ability to be incorporated in the lattice. Freeze-drying allowed to preserve a high surface reactivity, although further evolutions were noticed after re-immersion. Effects of a thermal treatment of dried samples were unveiled, suggesting a denaturation of the hydrated layer on the nanocrystals. This work underlines the necessity of a good control of synthesis/postsynthesis parameters for the production of biomimetic apatites

Impact of Calcium Phosphate Particle Morphology on Osteoconduction: an in vivo study

Apatite/β−TCP particles exhibiting non-conventional urchin-like morphology were prepared by hydrothermal synthesis. Their implantation in the rat calvarium was followed during 60 days. A total absence of osteoconduction was observed despite a favorable chemical composition, stressing the fundamental role of particle morphology on bone regeneration. Results are discussed in relation with other literature data. Possible explanations include the disfavored accumulation of biological mediators due to the acicular shape of the particles and/or a limited accessibility for cells

Bioceramics: spark plasma sintering (SPS) of calcium phosphates

Calcium phosphates (Ca-P) are major constituents of calcified tissues, and are also extensively used for the elaboration of biomaterials. However, the usual high-temperature sintering processes generally lead to strong alterations of their chemical, physical and biological properties. Spark plasma sintering (SPS) is a non-conventional sintering technique based on the use of pulsed current, enabling fast heating and cooling rates, and lower sintering temperatures are often observed. The sintering of several orthophosphates (DCPD, amorphous TCP, beta-TCP, OCP, HA and biomimetic nanocrystalline apatites) by SPS was investigated in order to track potential advantages of this technique over usual Ca-P sintering methods. Special attention was given to the SPS consolidation of highly bioactive nanocrystalline apatites

Production, by co-grinding in a media mill, of porous biodegradable polylactic acid-apatite composite materials for bone tissue engineering

This paper presents the results of a study of the production of porous biodegradable composite materials by co-grinding, followed by scaffolding. Dry powders of polylactic acid and nanocrystalline carbonated apatite, analogous to bone mineral were co-ground in a tumbling ball mill in order to disperse the mineral filler within the polymer. Porous scaffolds were then made by hot moulding the mixture of the two components along with a pore-forming agent which was subsequently eliminated by washing. The mechanical resistance of the scaffolds was evaluated in order to determine the best operating conditions to produce implants offering optimised properties for use as bone substitutes. It was shown that 30 wt.% of filler and 70 wt.% of pore-forming agent produce scaffolds which are sufficiently porous and resistan

Peroxide-doped apatites: Preparation and effect of synthesis parameters

This contribution focused on the preparation of peroxide-doped calciumphosphate apatites—in viewof potential uses as bioactive bioceramics with antimicrobial functions, and on their main physico-chemical characteristics. Two synthesis routeswere investigated. First, the hydrolysis of β-TCP in the presence ofH2O2 was followed. However, only elevated concentrations inH2O2 in themediumor temperatures around 150 °C allowed us to reach the complete β-TCP-to-apatite hydrolysis process, and the obtained samples exhibited a high crystallinity state with no non-apatitic chemical environments. The second protocol tested consisted in the direct apatite precipitation in the presence of H2O2 in themedium (at room temperature). This protocol led to single-phased nanocrystalline apatites, and our data indicate that part of the apatitic OH− ions were substituted by oxygenated species, and typically by peroxide ions (quantified). Physico-chemical modifications in the form of an improvement in crystallinity state, an increase in unit cell volume, and the presence of additional Raman bands were noticed and discussed