Showing papers by "Florence Babonneau published in 2019"
TL;DR: The mineral-mineral and mineral-biomolecule interfaces in bone tissue must be driven by metastable hydrated amorphous environments rich in HPO42− ions rather than by stable crystalline environments of hydroxyapatite structure.
Abstract: Some compositional and structural features of mature bone mineral particles remain unclear. They have been described as calcium-deficient and hydroxyl-deficient carbonated hydroxyapatite particles in which a fraction of the PO43− lattice sites are occupied by HPO42− ions. The time has come to revise this description since it has now been proven that the surface of mature bone mineral particles is not in the form of hydroxyapatite but rather in the form of hydrated amorphous calcium phosphate. Using a combination of dedicated solid-state nuclear magnetic resonance techniques, the hydrogen-bearing species present in bone mineral and especially the HPO42− ions were closely scrutinized. We show that these HPO42− ions are concentrated at the surface of bone mineral particles in the so-called amorphous surface layer whose thickness was estimated here to be about 0.8 nm for a 4-nm thick particle. We also show that their molar proportion is much higher than previously estimated since they stand for about half of the overall amount of inorganic phosphate ions that compose bone mineral. As such, the mineral-mineral and mineral-biomolecule interfaces in bone tissue must be driven by metastable hydrated amorphous environments rich in HPO42− ions rather than by stable crystalline environments of hydroxyapatite structure.
148 citations
TL;DR: In this article, a series of polyaluminosilazanes were synthesized by reaction of dimethylethylamine alane complex with polysilazanes, and detailed information on the polymer structures were obtained by FTIR and multinuclear solid state NMR spectroscopies.
Abstract: A series of polyaluminosilazanes was synthesized by reaction of dimethylethylamine alane complex with polysilazanes. Starting from different dichlorosilanes, polysilazanes were obtained by means of ammonolysis. The latter reacted with the alane complex and led to solid polyalumino(carbo)silazanes that can be described as "custom-made" polymers since all the steps were monitored and controlled (from the choice of the molecular precursor to the polymerization and the functionalization with aluminum) in order to study the effect of the introduction of Al on the different reactive sites of the Si- backbone in the polysilazanes. Detailed information on the polymer structures were obtained by FTIR and multinuclear solid state NMR spectroscopies. The transition from the polymeric state to the ceramic inorganic state was investigated by means of solid-state NMR spectroscopy and finally the structural evolution of the final ceramics by high angle XRD, Raman spectroscopy and TEM imaging. It is noted that the polymer-derived SiAlCN ceramics are X-ray amorphous even at high temperature under nitrogen with some local crystallization. Upon further heating these materials tend to further crystallize into thermodynamically stable phases at a given chemical composition, such as SiC, Si3N4, free C, or AlN. Finally, the present study shows that the amorphous-to-crystalline transition is closely related to the nature and structure of the preceramic polymer.
11 citations