Bone is a natural mineral-organic nanocomposite protecting internal organs and allowing mobility. Through the ages, numerous strategies have been developed for repairing bone defects and fixing fractures. Several generations of bone repair biomaterials have been proposed, either based on metals, ceramics, glasses, or polymers, depending on the clinical need, the maturity of technologies, and knowledge of the natural constitution of the bone tissue to be repaired. The global trend in bone implant research is shifting toward osteointegrative, bioactive and possibly stimuli-responsive biomaterials and, where possible, resorbable implants that actively promote the regeneration of natural bone tissue. In this mini-review, the fundamentals of bone healing materials and clinical challenges are summarized and commented on with regard to progressing scientific discoveries. The main types of bone-healing materials are then reviewed, and their specific relevance to the field is reminded, with the citation of reference works. In the final part, we highlight the promise of hybrid organic-inorganic bioactive materials and the ongoing research activities toward the development of multifunctional or stimuli-responsive implants. This contribution is expected to serve as a commented introduction to the ever-progressing field of bone regeneration and highlight trends of future-oriented research.

One major warning emerging during the first worldwide combat against healthcare-associated infections concerns the key role of the surface in the storage and transfer of the virus. Our study is based on the laser coating of surfaces with an inorganic/organic composite mixture of amorphous calcium phosphate–chitosan–tetracycline that is able to fight against infectious agents, but also capable of preserving its activity for a prolonged time, up to several days. The extended release in simulated fluids of the composite mixture containing the drug (tetracycline) was demonstrated by mass loss and UV–VIS investigations. The drug release profile from our composite coatings proceeds via two stages: an initial burst release (during the first hours), followed by a slower evolution active for the next 72 h, and probably more. Optimized coatings strongly inhibit the growth of tested bacteria (Enterococcus faecalis and Escherichia coli), while the drug incorporation has no impact on the in vitro composite’s cytotoxicity, the coatings proving an excellent biocompatibility sustaining the normal development of MG63 bone-like cells. One may, therefore, consider that the proposed coatings’ composition can open the prospective of a new generation of antimicrobial coatings for implants, but also for nosocomial and other large area contamination prevention.

A large amount of research in orthopedic and maxillofacial domains is dedicated to the development of bioactive 3D scaffolds. This includes the search for highly resorbable compounds, capable of triggering cell activity and favoring bone regeneration. Considering the phosphocalcic nature of bone mineral, these aims can be achieved by the choice of amorphous calcium phosphates (ACPs). Because of their metastable property, these compounds are however to-date seldom used in bulk form. In this work, we used a non-conventional “cold sintering” approach based on ultrafast low-pressure RT compaction to successfully consolidate ACP pellets while preserving their amorphous nature (XRD). Complementary spectroscopic analyses (FTIR, Raman, solid-state NMR) and thermal analyses showed that the starting powder underwent slight physicochemical modifications, with a partial loss of water and local change in the HPO₄^2- ion environment. The creation of an open porous structure, which is especially adapted for non-load bearing bone defects, was also observed. Moreover, the pellets obtained exhibited sufficient mechanical resistance allowing for manipulation, surgical placement and eventual cutting/reshaping in the operation room. Three-dimensional porous scaffolds of cold-sintered reactive ACP, fabricated through this low-energy, ultrafast consolidation process, show promise toward the development of highly bioactive and tailorable biomaterials for bone regeneration, also permitting combinations with various thermosensitive drugs.

This article reports the successful one-step synthesis of two micron-sized composite powders consisting of chitosan and amorphous calcium phosphate. These composite materials are prepared by spray drying of a solution containing chitosan and calcium phosphate precursors. The co-precipitation of chitosan and calcium phosphate precursors during the process induces a highly homogeneous distribution of the phases. The mineral phase identified as spherical nanoparticles dispersed in chitosan showed no chemical bonding with the polymer. As demonstrated by electron microscopy , small angle X-ray scattering and spectroscopies, variation in chitosan concentrations significantly influences the size and spatial distribution of the mineral phase. These results present a promising approach for the preparation of chitosan/amorphous calcium phosphate composite powders with controlled and tunable properties with potential applications in the field of biomaterial engineering such as bone substitutes.

Amorphous calcium phosphates (ACPs) represent a family of bioactive compounds particularly relevant to bone regeneration. However, due to their intrinsic metastability, their processing into 3D‐shaped materials cannot be undergone by conventional sintering methods and requires cold sintering approaches. Also, their microstructure and local compositional changes still have to be explored in detail. To this aim, spectroscopy techniques are particularly appealing to probe local chemical environments at the microscale. Concerning ACPs, one question regards the distribution of (hydrogenated) phosphate species, as they may lead to various evolutionary trends. In this contribution, we purposely exploited the laser–beam interaction through Raman mapping to trigger the in situ HPO₄²⁻‐to‐P₂O₇⁴⁻ transformation. Analysis by a multivariate approach allowed us to spot P₂O₇⁴⁻ clusters resulting from HPO₄²⁻‐rich initial domains. Moreover, a blue shift of the ν₁PO₄³⁻ band was noticed in the close vicinity of these clusters, thus evidencing a local evolution of the chemical composition of the ACP. These results, corroborated by differential thermal analysis, demonstrate the relevance of using the laser–sample interaction through local heating to probe the spatial evolution induced, in our case, by an ultrafast compaction process. Comparison of outcomes obtained using two different laser/power strategies finally evidenced the need to adapt the Raman analytical conditions to the behavior of the metastable material to analyze.

Ce mémoire porte sur l'élaboration et la caractérisation d'un matériau composite chitosane/phosphate de calcium destiné à une utilisation dans le domaine de la substitution osseuse. Le procédé d'atomisation-séchage a été choisi pour élaborer ce composite sous forme d'une poudre susceptible d'être transformée en revêtement ou objet 3D. Une étude préliminaire a permis d'appréhender les mécanismes de synthèse du phosphate de calcium, la phase minérale, par atomisation-séchage. Une suspension de particules d'hydroxyapatite stœchiométrique ou d'apatite biomimétique dispersées dans une solution acide mène systématiquement à l'apparition d'une phase amorphe. La proportion de cette phase amorphe dans la poudre atomisée-séchée est dépendante de la taille et de la cristallinité du matériau d'origine. L'atomisation séchage d'une solution acide contenant les ions précurseurs de calcium et phosphate mène à la formation d'une phase principalement amorphe. Cette poudre a pu être décrite à différentes échelles : à une échelle de l'ordre du nanomètre apparaissent des clusters, à une échelle de l'ordre de la centaine de nanomètres des agrégats sphériques de clusters organisés en chapelet tortueux et imbriqués sont identifiés et enfin à une échelle micrométrique des agglomérats de nanoparticules ont été mises en évidence. Le phosphate de calcium ainsi synthétisé possède un rapport molaire Ca/P proche de 1.3. Au-delà de ce rapport dans la solution à atomiser, de l'acétate de calcium (utilisé ici comme précurseur) recristallise dans la poudre. Pour élaborer la poudre composite, le polymère a été solubilisé et ajouté d'abord dans une suspension acide d'hydroxyapatite avant atomisation. Cette première stratégie mène à la formation d'un composite qui présente de fortes inhomogénéités de répartition des phases organiques et minérales. Pour limiter ce problème lié à la distribution de tailles de grains de la phase minérale, une seconde stratégie a été développée. Une solution de polymère contenant des précurseurs de phosphate de calcium a été préparée pour favoriser l'association à l'échelle nanométrique des deux phases. Après atomisation-séchage, un matériau composite présentant une très bonne dispersion de la phase minérale dans la matrice organique est synthétisé. La structuration de la phase minérale est modifiée par la présence du polymère. Cette modification se traduit par une diminution de la fraction volumique des clusters et, à l'échelle supérieure, la phase minérale n'est plus présente sous forme de chapelet mais en particules sphériques isolées. Par ailleurs, une interaction chimique est envisagée en raison des liaisons de type hydrogène, ioniques ou de coordinations possibles entre les deux phases. La présence du polymère inhibe également la formation de l'acétate de calcium cristallin en favorisant la formation d'un sel d'acétate de chitosane. Deux techniques de mises en forme ont été étudiées (MAPLE, pour l'élaboration de revêtements minces et l'impression 3D de pâte pour l'obtention d'objet massif) et ont permis de mettre en avant le potentiel de transformation de la poudre préparée par atomisation séchage. Les études biologiques faites sur le revêtement ont de plus permis de démontrer les propriétés antibactériennes du matériau utilisé.