Papers by Author: Christèle Combes

Abstract: This contribution gathers various examples illustrating the fact that nanocrystalline apatites represent a genuine multi-functionalizable platform for a wide range of biomedical applications. It is indeed possible to convey additional functionalities to the already appealing properties of biomimetic apatites, via appropriate ionic substitutions and/or through controlled molecular adsorptions. In link with bone regeneration, we depict here examples of enhanced osteoconduction/induction and of the addition of antibacterial features to bone implants. But we also point out the promise of apatite-based colloidal nanoparticles in other domains not related to bone, such as nanomedicine (cell diagnosis/therapy), which we address by conferring luminescence properties and by adding cell recognition abilities.

Abstract: The purpose of this study was to improve injectability and cohesiveness of original calcium carbonate-calcium phosphate mixed (CaCO3-CaP) self-setting paste for bone filling and repair. With this aim in view dry co-grinding was implemented on the solid phase (vaterite and dicalcium phosphate dihydrate) of this cement. A protocol designed to quantify paste injectability has been established and pointed out the synergistic positive effects of solid phase co-grinding treatment on injectability, cohesiveness and setting time of the paste. The improvement of these properties are related to close and homogeneous association of reactive powders and to the decrease of specific surface area favoring the powders hydration process enhancing setting reaction rate. In addition, the particle size decrease and morphology modification improved flowability of the paste which results in a low and constant (320 g) force level to extrude the paste.

Abstract: 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.

Abstract: 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.

Abstract: 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.

Abstract: The feasibility of calcium carbonate-based cements involving the re-crystallization of metastable calcium carbonate varieties has been demonstrated. Two cement compositions were obtained by mixing either calcium carbonate phases (cement A) or a calcium carbonate and a calcium phosphate phase (cement B) with an aqueous media. These cements set and hardened after 30 minutes and 90 minutes respectively. The final composition of cement A was calcite and aragonite whereas cement B lead to a carbonated apatite analogous to bone mineral. Despite poor mechanical properties the presence of a high carbonate content in the final phase might be of interest to increase the cement resorption rate and to favour its replacement by bone tissue. First assays of implantation performed on fresh anatomical pieces (fresh cadavers) at 37°C revealed important advantages of such cement compositions: easiness of use, rapid setting, good adhesion to bone, very good homogeneity and stability of the cement.

Abstract: 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 HPO4 2- ions by CO3 2- 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 HPO4 2- 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.