Synthesis and Hydrolysis of Brushite (DCPD): The Role of Ionic Substitution

Brushite (dicalcium phosphate dihydrate, DCPD) is considered one of the possible precursors of the apatitic phase that constitutes the mineral component of bones, and it is often utilized in the preparation of biomaterials for hard tissue repair. In this work, we investigated the influence of ionic substitution on the synthesis, structure, and morphology of this calcium phosphate, as well as on its hydrolysis process. The results of structural refinements indicate that the range of possible substitution can reach values up to about 38 atom % for the big Sr ion, whereas it is quite limited for Zn, Co, and Mn. In particular, DCPD cannot be obtained as a single phase in the presence of zinc ions in solution. The kind and amount of substituent ions significantly influence the morphology of DCPD, promoting aggregation and crystal shape modifications, as well as its hydrolysis in solution. The results provide useful information for the understanding of the mineralization processes and for the design of new biomaterials

Strontium-Substituted α-TCP: Structure, Stability, and Reactivity in Solution

& alpha;-Tricalcium phosphate (& alpha;-TCP) is widelyused as acomponent of bone cements, and many efforts have been made to dopeit with strontium ion (Sr), which is known for its beneficial rolein bone tissue. However, the range of possible substitution of strontiumfor calcium (Ca) into & alpha;-TCP, as well as its effect on the & alpha;-TCPstructure, has not been clarified yet. Herein, we investigate thissubstitution through the examination of & alpha;-TCP synthesized athigh temperatures in the presence of increasing amounts of strontiumaccording to two different routes: 1-step and 2-steps. The results show that Sr can enter into an & alpha;-TCPstructure up to about 10 atom % and substitutes for calcium mostlyat specific cation sites, namely, M(5), M(11), and M(17), characterizedby relatively low bond valence sums and long mean Ca-O distance.Strontium presence stabilizes & alpha;-TCP delaying its transformationinto octacalcium phosphate and hydroxyapatite in H3PO4, as well as in physiological solution. Although the two methodsof synthesis provide similar structural results, the products of 1-step synthesis display a slightly smaller crystallitesize and greater solubility and, as a consequence, a faster hydrolysisreaction.& alpha;-Tricalcium phosphatepreparation through the solid-statereaction is described following two different procedures. The investigationof the range of possible substitution of strontium for calcium into & alpha;-TCP as well as its effect on the & alpha;-TCP structure ispresented. Furthermore, it is shown that strontium presence stabilizes & alpha;-TCP and delays its hydrolysis reaction into octacalcium phosphateand hydroxyapatite

Anti-Oxidant Multi-Functionalized Materials: Strontium-Substituted Monetite and Brushite as Delivery Systems for Curcumin

Curcumin has numerous biological activities and pharmaceutical applications related to its ability to inhibit reactive oxygen species. Herein, strontium-substituted monetite (SrDCPA) and strontium-substituted brushite (SrDCPD) were synthesized and further functionalized with curcumin with the aim to develop materials that combine the anti-oxidant properties of the polyphenol, the beneficial role of strontium toward bone tissue, and the bioactivity of calcium phosphates. Adsorption from hydroalcoholic solution increases with time and curcumin concentration, up to about 5-6 wt%, without affecting the crystal structure, morphology, and mechanical response of the substrates. The multi-functionalized substrates exhibit a relevant radical scavenging activity and a sustained release in phosphate buffer. Cell viability, morphology, and expression of the most representative genes were tested for osteoclast seeded in direct contact with the materials and for osteoblast/osteoclast co-cultures. The materials at relatively low curcumin content (2-3 wt%) maintain inhibitory effects on osteoclasts and support the colonization and viability of osteoblasts. The expressions of Alkaline Phosphatase (ALPL), collagen type I alpha 1 chain (COL1A1), and osteocalcin (BGLAP) suggest that curcumin reduces the osteoblast differentiation state but yields encouraging osteoprotegerin/receptor activator for the NFkB factor ligand (OPG/RANKL) ratio

Quercetin loaded gelatin films with modulated release and tailored anti-oxidant, mechanical and swelling properties

Quercetin, a flavonoid widely diffused in fruits and vegetables, is known for its good pharmacological qualities, such as anti-oxidant and anti-inflammatory properties. In this work, we loaded quercetin on gelatin films with the aim to develop materials with tailored anti-oxidant, mechanical and stability properties. To this purpose, gelatin films at increasing flavonoid content were prepared using two different solvents, namely H2O/EtOH (EtOH films) and DMSO (DMSO films). Quercetin content increased up to about 3.8 and 1.8 wt% in DMSO and EtOH films, respectively. The use of DMSO as solvent prevents the partial regain of collagen triple helix structure during gelling of gelatin sols and results in remarkable extensibility of the films. At variance, EtOH films display X-ray diffraction patterns and DSC plots in agreement with the presence of triple helix structure, and exhibit reduced swelling and increasing mechanical properties on increasing quercetin content. Moreover, their values of denaturation enthalpy indicate the presence of chemical interaction between the flavonoid and gelatin, which can be responsible of their lower quercetin release in PBS in comparison to DMSO films. The flavonoid release is sustained for both series of films and occurs through anchorage to gelatin nanoparticles. Moreover, both DMSO and EtOH functionalized films exhibit relevant anti-oxidant properties, in agreement with their RSA levels, which are comparable to that of pure quercetin

Gold nanoparticles supported on functionalized silica as catalysts for alkyne hydroamination: A chemico-physical insight

Highly stable gold nanoparticles anchored on propynylcarbamate-functionalized silica (Au/SiO2@Yne) have been efficiently utilized for the heterogeneous hydroamination of phenylacetylene with aniline under different reaction conditions. In order to ascertain the eventual influence of surface silanol groups on the system activity and selectivity tailored modifications of Au/SiO2@Yne catalysts were pursued according to two different strategies, involving respectively functionalization with trimethylethoxysilane (Au/SiO2@Yne-TMS) or post-treatment with triethylamine (Au/SiO2@Yne-NEt3). The prepared materials were analysed by several complementary techniques such as Solid State NMR (SS NMR), Transmission Electron Microscopy (TEM), X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction (XRD). A comparison of the resulting catalytic activities with that of the pristine Au/SiO2@Yne revealed a significant improvement for Au/SiO2@Yne-NEt3 in terms of both conversion and selectivity. Recycling and stability studies showed a catalytic activity decrease after the first run, due to the formation of polyphenylacetylene (PPhA) oligomers shielding the active sites. PPhA removal by sonication in acetone fully restored the catalytic activity and empowered the system with a good operational stability, a very crucial issue in view of eventual practical applications

Propargyl carbamate-functionalized Cu(II)-metal organic framework after reaction with chloroauric acid: An x-ray photoelectron spectroscopy data record

A copper-containing metal organic framework was prepared using the new organic linker 5-(2-{[(prop-2-yn-1-yloxy)carbonyl]-amino} ethoxy)isophthalic acid [1,3-H2YBDC (where Y = alkYne and BDC = Benzene DiCarboxylate)] and functionalized with gold particles by reaction with HAuCl4 under thermal treatment in methanol. The resulting system was investigated by complementary techniques to obtain information on its structure and morphology. In the present work, x-ray photoelectron spectroscopy (XPS) was employed to analyze the chemical composition of a representative specimen. Besides wide scan spectra, data obtained by the analysis of the C 1s, O 1s, N 1s, Cu 2p, and Au 4f signals are presented and critically discussed. The results highlight the reduction of Au(III) to mostly Au(I) species. Overall, the data presented herein may act as useful guidelines for the eventual tailoring of material properties and their possible implementation toward functional applications in heterogeneous catalysis

Strontium substituted hydroxyapatite with β-lactam integrin agonists to enhance mesenchymal cells adhesion and to promote bone regeneration

Multi-functionalization of calcium phosphates to get delivery systems of therapeutic agents is gaining increasing relevance for the development of functional biomaterials aimed to solve problems related to disorders of the muscolo-skeletal system. In this regard, we functionalized Strontium substituted hydroxyapatite (SrHA) with some β-lactam integrin agonists to develop materials with enhanced properties in promoting cell adhesion and activation of intracellular signaling as well as in counteracting abnormal bone resorption. For this purpose, we selected two monocyclic β-lactams on the basis of their activities towards specific integrins on promoting cell adhesion and signalling. The amount of β-lactams loaded on SrHA could be modulated on changing the polarity of the loading solution, from 3.5–24 wt% for compound 1 and from 3.2–8.4 wt% for compound 2. Studies on the release of the β-lactams from the functionalized SrHA in aqueous medium showed an initial burst followed by a steady-release that ensures a small but constant amount of the compounds over time. The new composites were fully characterized. Co-culture of human primary mesenchymal stem cells (hMSC) and human primary osteoclast (OC) demonstrated that the presence of β-lactams on SrHA favors hMSC adhesion and viability, as well as differentiation towards osteoblastic lineage. Moreover, the β-lactams were found to enhance the inhibitory role of Strontium on osteoclast viability and differentiation