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Amorphous calcium phosphate-based materials are of major interest in the field of bone substitution. Very recently, the low-temperature synthesis of a new family of amorphous calcium phosphate containing both orthophosphate and pyrophosphate ions in controlled proportions has been reported. Despite their interest, especially due to the biochemical role and the hydrolysis of pyrophosphate occurring in vivo , the behavior of such materials when interacting with aqueous media has never been described. Consequently, we herein report the in vitro acellular evolution of three compositions of mixed calcium ortho- and pyrophosphate amorphous materials including a different orthophosphate proportion. As a first step to assess the physicochemical reactivity of these amorphous materials, they were tested in two different media at 37 °C, acidified water and simulated body fluid solution, from 1 h up to 15 days. The results demonstrated that they were quite stable and that they progressively released part of their constitutive ions, highlighting their potential for controlled delivery of bioactive ions (calcium, orthophosphate, and pyrophosphate ions). In addition to these properties, we showed that the material with the highest ortho/(ortho + pyro) phosphate ratio started to crystallize into nanocrystalline apatite analogous to bone mineral within 2 days or 2 weeks depending on the medium. For the other material compositions, no layer of apatite was detected at their surface with SBF testing despite the favorable supersaturation indexes, crystallization being probably inhibited by pyrophosphate ions released in the medium. This varying apatite-forming ability emphasizes the key role of the ortho/(ortho + pyro) phosphate ratio of these materials in their in vitro reactivity and bioactivity, which paves the way for the development of this promising family of amorphous calcium phosphate materials with tunable physicochemical and biological properties.

Calcium is an essential component of osteogenesis and is often required for imparting significant bioactivity to synthetic bone substitutes and, in particular, silicate-based materials. However, the mechanism of calcium incorporation inside sol-gel silicates is poorly understood. In this work, we shed light on the determinant parameters for incorporation of calcium into acid-base-catalyzed sol-gel silicates at ambient temperature: increasing the pH above the isoelectric point of silicic acid and the nature of the calcium counterion in the calcium precursor are found to be the key. Based on our proposed reaction sequence, we were able to compare calcium precursors and select an ideal candidate compound for the synthesis of bioactive glasses (BG) and organic-inorganic hybrids at ambient temperature. Reproducible syntheses and gel times of SiO 2 -CaO BG were obtained using calcium hydroxide (CH), and we demonstrate its usability in the synthesis of promising BG-polycaprolactone hybrid scaffolds. BG and hybrids prepared with CH were able to form nanocrystalline nonstoichiometric apatite in simulated body fluid. The increased reliability of low-temperature syntheses associated with the use of a stable and inexpensive alkaline-earth precursor are major steps toward the translation of calcium silicate hybrids or other alkaline-earth silicates from bench to clinic.