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.

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

The 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.

Removal of the herbicide 2,4-dichlorophenoxyacetate from water to zinc-aluminium-chloride layered double hydroxides.

Batch sorption studies were conducted to investigate the potential of [Zn-Al-Cl] layered double hydroxides (LDHs) for the removal of the herbicide 2,4-dichlorophenoxyacetate (2,4-D) from contaminated aqueous solutions. Experiments were performed at different pH values, initial pesticide concentration, solid/pesticide ratio and anion exchange capacity of LDHs. The LDH samples evaluated had very high retention capacity for 2,4-D whose removal was a rapid process, as a quasi-equilibrium state was reached after 1-h reaction time. The adsorption can be described by Langmuir-type isotherms, with an average affinity constant of 12.5 L mmol(-1). At initial 2,4-D concentrations between 0.08 and 4 m molL(-1), the solids removed up to 98% of the pesticide. Physicochemical characterization of the LDH solids, both fresh and after removal of 2,4-D, by X-ray diffraction, infrared spectroscopy and thermogravimetry, indicates that the retention of 2,4-D is done by adsorption on the surface of the solid for low 2,4-D concentrations. However, a combination of surface adsorption and interlayer ion exchange takes place when the 2,4-D concentration is high.