Exchange reactions at calcium phosphates surface and applications to biomaterials

The interaction of calcium phosphates with biological molecules under controlled conditions permits the formulation of meaningful conclusions concerning the driving forces. The uptake and release at the material-solution interface is the result of the various interactions between and within the system components which include the solid surface, the adsorbate, the solvent and other solutes present. The understanding of adsorption and desorption mechanisms with respect to active molecules can be exploited for the development of drug delivery applications

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

Evaluation of the kinetic and relaxation time of gentamicin sulfate released from hybrid biomaterial Bioglass-chitosan scaffolds

International audienceChitosan scaffolds, combined with bioactive glass 46S6, were prepared to serve as gentamicin sulfate delivery in situ systems for bone biomaterials. This work presents a study about the effect of the ratio chitosan/bioactive glass (CH/BG) on the release of gentamicin sulfate and on the bioactivity during in vitro experiments. SEM observations allowed understanding the bond between the glass grains and the chitosan matrix. In vitro results showed that scaffolds form a hydroxyapatite (HA) Ca10(PO4)6(OH)2 after 15 days of immersion in a simulated body fluid (SBF).The interest of this study is to see that the increase of the content of bioactive glass in the chitosan matrix slows the release of gentamicin sulfate in the liquid medium. Starting concentration of gentamicin sulfate has an influence on the relaxation time of the scaffolds. Indeed, an increasing concentration delays the return to a new equilibrium. Contents of chitosan and bioactive glass do not affect the relaxation time. Synthesized scaffolds could be adapted to a clinical situation: severity and type of infection, weight and age of the patient

Injectability, microstructure and release properties of sodium fusidate-loaded apatitic cement as a local drug-delivery system

The introduction of an antibiotic, sodiumfusidate (SF), into the liquid phase of calcium carbonate–calcium phosphate(CaCO3–CaP) bone cement was evaluated, considering the effect of the liquid to powder ratio (L/P) on the composition and microstructure of the set cement and the injectability of the paste. In all cases, we obtained set cements composed mainly of biomimetic carbonated apatite analogous to bone mineral. With this study,we evidenced a synergistic effect of the L/P ratio and SF presence on the injectability (i.e., the filter-pressing phenomenon was suppressed) and the setting time of the SF-loaded cement paste compared to reference cement(without SF). In addition, the in vitro study of SF release, according to the European Pharmacopoeia recommendations, showed that, regardless of the L/P ratio, the cement allowed a sustained release of the antibiotic over 1 month in sodiumchloride isotonic solution at 37 °C and pH 7.4; this release is discussed considering the microstructure characteristics of SF-loaded cements (i.e., porosity, pore-size distribution) before and after the release test. Finally, modelling antibiotic release kinetics with severalmodels indicated that the SF releasewas controlled by a diffusion mechanism

Adsorption on apatitic calcium phosphates for drug delivery: interaction with bisphosphonate molecules

Bisphosphonates (BPs) are well established as an important class of drugs for the treatment and prevention of several bone disorders including osteoporosis. This work investigated the interaction of two bisphosphonates, risedronate and tiludronate, with several apatitic supports, a well-crystallised hydroxyapatite (HA) and nanocrystalline apatites with varying maturation times, chemical composition and surface characteristics. The purpose was to fully understand the adsorption mechanism and desorption process, by the evaluation of the effect of several physicochemical parameters (temperature, pH and concentration of calcium and phosphate ions). Whatever the nature of the BP and the structure and composition of the apatite, the adsorption of such anti-resorptive agents can be well described as an ion exchange-reaction between phosphates species on the apatitic surface and BP molecules in solution. However, the parameters of adsorption can vary depending on the physicochemical conditions of the adsorption reaction. In addition, the structure and composition of the apatitic surface also influence the adsorption properties. Finally, BPs molecules are slowly released from apatitic supports, because most of the adsorbed molecules are irreversibly bound and not spontaneously released by dilution or simple washing. Moreover, similar to their adsorption, the release of bisphosphonates is strongly affected not only by the chemical properties of the molecule, but also by the chemical and structural characteristics of the apatitic substrates. The understanding of the adsorption and release processes provides fundamental tools for the development of drug delivery systems using apatite materials

Risedronate adsorption on bioactive glass surface for applications as bone biomaterial

International audienceThe aim of the current work is to study the physicochemical interactions between bisphosphonates molecules, risedronate (RIS) and bioactive glass (46S6) after their association by adsorption phenomenon. To more understand the interaction processes of RIS with the 46S6 surface we have used complementary physicochemical techniques such as Infrared (FTIR), RAMAN and nuclear magnetic resonance (NMR) spectroscopy. The obtained results suggest that risedronate adsorption corresponds to an ion substitution reaction with silicon ions occurring at the bioactive glass surface. Thus, a pure bioactive glass was synthesized and fully characterized comparing the solids after adsorption (46S6-XRIS obtained after the interaction of 46S6 and X% risedronate). Therefore, based on the spectroscopic results FTIR, RMAN and MAS-NMR, it can be concluded that strong interactions have been established between RIS ions and 46S6 surface. In fact, FTIR and RAMAN spectroscopy illustrate the fixation of risedronate on the bioactive glass surface by the appearance of several bands characterizing risedrontre. The 31P MAS-NMR of the composite 46S6-XRIS show the presence of two species at a chemical shift of 15 and 19 ppm demonstrating thus the fixation of the RIS on 46S6 surface

Propriétés de surface des apatites et adsorption de protéines

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Phosphorylated oil-filled microcapsules for anticorrosion self-healing coating

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Nanocrystalline apatites in biological systems: characterisation, structure and properties.

Nanocrystalline apatitic calcium phosphates play a crucial role in calcified tissues and biomaterials. One of the most interesting characteristics of biomimetic apatite nanocrystals is the existence of a surface hydrated layer essentially related to their formation process in solution. This hydrated layer shows specific spectroscopic characteristics. It seems to exist in its nascent state only in wet samples and is altered on drying. This surface-hydrated layer progressively disappears as the stable apatite domains develop. The surface ions can be rapidly and reversibly exchanged in solution, mainly with selected bivalent species. The exchange reactions clearly reveal the existence of two domains: the relatively inert apatite core and the very reactive surface-hydrated domains. The structure of the hydrated layer has been shown to be reversibly affected by the constituting ions. Such a surface layer in bone apatite nanocrystals could participate actively in homeostasis and probably other regulation processes. The specificity of biomimetic apatite nanocrystals also opens interesting possibilities in materials science. The mobility of the mineral ions on the crystal surface, for example, allows strong bonding and interactions either with other crystals or with different substrates. Inter-crystalline interactions have been described as a “crystal fusion” process in vivo and they could be involved in the setting reaction of biomimetic calcium phosphate cements. Ceramic-like materials using the surface interaction capabilities of the nanocrystals can be produced at very low temperature (below 200 C). The surface-hydrated layer could also be involved in interactions with macromolecules and polymeric materials or in the coating of implants. The ion exchange and adsorption capabilities of the nanocrystals could probably be used for drug release, offering a range of possible behaviours

Infrared, Raman and NMR investigations of risedronate adsorption on nanocrystalline apatites

International audienceThe aim of the current work was to study the physico-chemical interactions of a bisphosphonate molecule, risedronate, with a well-characterised synthetic nanocrystalline apatite (NCA) as a model bone mineral. We adopted a global approach, using complementary physico-chemical techniques such as FTIR,RAMAN and NMR spectroscopies in order to learn more about the interaction process of risedronate with the apatitic surface. The results obtained suggest that risedronate adsorption corresponds to an ion substitution reaction with phosphate ions occurring at the crystal surface. This mechanism explains the greater amount adsorbed (N) for NCA, compared to well crystallised stoichiometric hydroxyapatite, attributable to the well-developed hydrated layer at the surface of the nanocrystals. However, most calcium ions remain attached to the solid phase and the formation of insoluble risedronate calcium salts must also be considered as a competitive reaction to the adsorption. Thus a calcium risedronate salt was synthesised and fully characterised for comparison to the solids after adsorption. Following spectroscopic results, it can be concluded that a strong interaction was established between risedronate ions and calcium ions at the apatitic surface. However, under these experimental conditions there is no nucleation of a distinct calcium risedronate salt and the apatite crystals retain their integrity