β-tricalcium phosphate (β-TCP) is one of the most common bioceramics, widely applied in bone cements and implants. Herein we synthesized β-TCP by solid state reaction in the presence of increasing amounts of two biologically active ions, namely strontium and zinc, in order to clarify the structural modifications induced by ionic substitution. The results of X-ray diffraction analysis indicate that zinc can substitute for calcium into a β-TCP structure up to about 10 at% inducing a reduction of the cell parameters, whereas the substitution occurs up to about 80 at% in the case of strontium, which provokes a linear increase of the lattice constants, and a slight modification into a more symmetric structure. Rietveld refinements and solid-state ³¹P NMR spectra demonstrate that the octahedral Ca(5) is the site of β-TCP preferred by the small zinc ion. ATR-FTIR results indicate that zinc substitution provokes a disorder of β-TCP structure. At variance with the behavior of zinc, strontium completely avoids Ca(5) site even at high concentration, whereas it exhibits a clear preference for Ca(4) site. The infrared absorption bands of β-TCP show a general shift towards lower wavenumbers on increasing strontium content. Particularly significant is the shift of the infrared symmetric stretching band at 943 cm⁻¹ due to P(1), that is the phosphate more involved in Ca(4) coordination, which further supports the occupancy preference of strontium.

Dicalcium phosphate dihydrate (DCPD) is one of the mineral phases indicated as possible precursors of biological apatites and it is widely employed in the preparation of calcium phosphate bone cements. Herein, we investigated the possibility to functionalize DCPD with aspartic acid (ASP) and poly-aspartic acid (PASP), as models of the acidic macromolecules of biomineralized tissues, and studied their influence on DCPD hydrolysis. To this aim, the synthesis of DCPD was performed in aqueous solution in the presence of increasing concentrations of PASP and ASP, whereas the hydrolysis reaction was carried out in physiological solution up to three days. The results indicate that it is possible to prepare DCPD functionalized with PASP up to a polyelectrolyte content of about 2.3 wt%. The increase of PASP content induces crystal aggregation, reduction of the yield of the reaction and of the thermal stability of the synthesized DCPD. Moreover, DCPD samples functionalized with PASP display a slower hydrolysis than pure DCPD. On the other hand, in the explored range of concentrations (up to 10 mM) ASP is not incorporated into DCPD and does not influence its crystallization nor its hydrolysis. At variance, when present in the hydrolysis solution, ASP, and even more PASP, delays the conversion into the more stable phases, octacalcium phosphate and/or hydroxyapatite. The greater influence of PASP on the synthesis and hydrolysis of DCPD can be ascribed to the cooperative action of the carboxylate groups and to its good fit with DCPD structure.

Monetite and brushite are regarded with increasing interest for the preparation of biomaterials for applications in the musculoskeletal system. Herein, we investigated the influence of strontium substitution in the structures of these two phosphates on bone cell response. To achieve this aim, co-cultures of human primary osteoclasts and human osteoblast-like MG63 cells were tested on strontium-substituted monetite and strontium-substituted brushite, as well as on monetite and brushite, as controls. In both structures, strontium substitution for calcium amounted to about 6 at% and provoked enlargement of the cell parameters and morphologic variations. Cumulative release in physiological solution increased linearly over time and was greater from brushite (up to about 160 and 560 mg/L at 14 days for Sr and Ca, respectively) than from monetite (up to about 90 and 250 mg/L at 14 days for Sr and Ca, respectively). The increasing viability of osteoblast-like cells over time, with the different expression level of some typical bone markers, indicates a more pronounced trigger toward osteoblast differentiation and osteoclast inhibition by brushite materials. In particular, the inhibition of cathepsin K and tartrate-resistant acid phosphatase at the gene and morphological levels suggests strontium-substituted brushite can be applied in diseases characterized by excessive bone resorption.

In this paper we used curcumin as a functionalizing agent of gelatin films with the aim to get antioxidant materials with modulated physico-chemical properties. To this aim, we prepared gelatin films at different contents of curcumin up to about 1.2 wt%. The as-prepared films, as well as glutaraldehyde crosslinked films, were submitted to several tests: swelling, water solubility, differential scanning calorimetry, X-ray diffraction, mechanical tests and curcumin release. The radical scavenging activity of the as-prepared films is similar to that of free curcumin, indicating remarkable antioxidant properties. All the other tested properties vary as a function of curcumin content and/or the presence of the crosslinking agent. In particular, the films exhibit sustained curcumin release in different solvents. Thanks to its biocompatibility, biodegradability and lack of antigenicity, gelatin uses span from food processing to packaging and biomaterials. It follows that the modulated properties exhibited by the functionalized materials developed in this work can be usefully employed in different application fields.

In this work we synthesized mesoporous bioactive glass nanospheres (nMBG) with the aim to utilize them as substrates for loading one of the most potent amino-bisphosphonates, alendronate (AL). The results of the chemical and structural characterization show that the nMBG display a relatively high surface area (528 m²/g) and a mean pore volume of 0.63 cm³/g, both of which decrease on increasing alendronate content. It is possible to modulate the amount of AL loaded into the nanospheres up to a maximum value of about 17 wt %. In vitro tests were performed using a human osteosarcoma cell line (MG63) and a murine monocyte/macrophage cell line as osteoclast model (RAW 264.7). The results indicate that even the lower concentration of alendronate provokes decreased tumor cell viability, and that osteoclast activity exhibits an alendronate dose-dependent inhibition. The data suggest that nMBG can act as a suitable support for the local delivery of alendronate, and that the antiresorptive and antitumor properties of the functionalized mesoporous nanospheres can be modulated by varying the amount of alendronate loading.