The acute inflammatory response to copper(II)-doped biphasic calcium phosphates.

Infection and inflammation are two key features to consider to avoid septic or aseptic loosening of bone-implanted biomaterials. In this context, various approaches to fine-tune the biomaterial's properties have been studied in order to modulate the crosstalk between immune and skeletal cells. Cation-doping strategies for tuning of calcium phosphates properties has been evidenced as a promising way to control the biomaterial-induced inflammatory process, and thus improving their osteoimmunomodulatory properties. Copper(II) ions are recognized for their antibacterial potential, but the literature on their impact on particulate material-induced acute inflammation is scarce. We synthesized copper(II) ions-doped biphasic calcium phosphate (BCP), intended to exhibit osteoimmunomodulatory properties. We addressed in vitro, for the first time, the inflammatory response of human primary polymorphonuclear neutrophils (PMNs) to copper(II) ions-doped or undoped (BCP) powders, synthesized by an original and robust wet method, in the presence or absence of LPS as a costimulant to mimic an infectious environment. ELISA and zymography allowed us to evidence, in vitro, a specific increase in IL-8 and GRO-α secretion but not MIP-1ß, TNF-α, or MMP-9, by PMNs. To assess in vivo relevance of these findings, we used a mouse air pouch model. Thanks to flow cytometry analysis, we highlighted an increased PMN recruitment with the copper(II) ions-doped samples compared to undoped samples. The immunomodulatory effect of copper(II) ions-doped BCP powders and the consequent induced moderate level of inflammation may promote bacterial clearance by PMNs in addition to the antimicrobial potential of the material. Copper(II) doping provides new insights into calcium phosphate (CaP)-based biomaterials for prosthesis coating or bone reconstruction by effectively modulating the inflammatory environment.

Intercalation and grafting of benzene derivatives into zinc-aluminum and copper-chromium layered double hydroxide hosts: an XPS monitoring study.

We report an original strategy to describe, via X-ray photoelectron spectroscopy (XPS) measurements, the interactions between the organic and the mineral sub-systems within a multifunctional hybrid material. A tunable layered double hydroxide (LDH) host system, either a Zn(2)Al- or Cu(2)Cr-hydrotalcite like compound, is modified with the insertion of the organic guest entities, 4-phenol-sulfonate (HBS) or -carboxylate (HBC). The resulting interactions are studied at two levels: after the organic molecules' insertion in the host LDH (ionic exchange between the LDH counter-ions and the organic anions) and after the condensation (grafting) of the organic species onto the mineral layers when thermally treated. For the inserted material, the main XPS results show a stabilization of the organic molecules within the mineral sheets via H bonding as found elsewhere with FTIR study, the mineral matrix being unchanged. The XPS signal of the organic molecules slightly changes with a widening of core peaks, attesting to some local surrounding modifications. When heating up the Zn(2)Al hybrid material, stronger interactions between organic and inorganic systems appeared from around 80 °C with some obvious electronic changes as monitored with the XPS S2p signal of the HBS guest molecules. At the same time, the PXRD pattern clearly shows a decrease of the basal spacing according to a two step contraction process which could be interpreted as a progressive organic molecule condensation onto the inorganic layers via iono-covalent bonds. A copper-chromium LDH is also studied to probe the same kind of interactions with the HBS molecules. The ability of distortion of such mineral material involves a peculiar process of contraction from 40 °C with the immediate and effective anchorage of organic molecules.

Synergetic effect of temperature and pressure on energetic and structural characteristics of {ZIF-8 + water} molecular spring.

Metal-organic frameworks (MOFs) and particularly their subclass - Zeolite Imidazolate Frameworks (ZIFs) - are used for a variety of applications including particularly energy storage. Highly porous MOFs mixed with non-wetting liquids can be used to form molecular springs (MS) for efficient mechanical and thermal energy storage/transformation. In this paper by means of high-pressure calorimetry the energetic characteristics of {ZIF-8 + water} MS were investigated in wide temperature and pressure ranges. Unexpectedly XRD measurements show that the concomitant effects of temperature and pressure on {ZIF-8 + water} MS leads to an irreversible change of the ZIF-8 structure, transforming its symmetry from cubic to orthorhombic. Whereas, previous studies have demonstrated the stability of ZIF-8 under either high pressure or high temperature.

Thorough analysis of silicon substitution in biphasic calcium phosphate bioceramics: a multi-technique study.

Four samples of composition Ca(10)(PO(4))(6-x)(SiO(4))(x)(OH)(2-x), with x=0.0, 0.1, 0.2 and 0.5, were prepared and characterized using powder X-ray and neutron powder diffraction, and (1)H, (31)P and (29)Si nuclear magnetic resonance (NMR) spectroscopy. The composition of the Si-substituted HAp phases was determined by joint Rietveld refinements from powder X-ray and powder neutron diffraction data. Taking into account electroneutrality, a chemical formula for the Si-substituted HAp phases with indication of the incorporated silicate amount is proposed. Solid-state (29)Si NMR confirms the presence of only Q(0) species, in good agreement with the presence of substituted HAp and beta-TCP phases only. Thanks to NMR spectroscopy, two types of protons in the Si-substituted HAp phase were identified, the new site corresponding to species engaged in hydrogen bonding with silicate anions. This allowed further refinement of the formulae for these phases with very good quantitative agreement for populations derived from the refinement and integration of NMR data.

Structural characterization and biological fluid interaction of Sol-Gel-derived Mg-substituted biphasic calcium phosphate ceramics.

Sol-Gel chemistry has been used to prepare undoped and Mg-substituted biphasic calcium phosphate (BCP) ceramics composed of hydroxyapatite (HAp) and whitlockite (beta-TCP) phases. Different series of samples have been synthesized with different Mg-doping levels (from 0 to 5 atomic % of Ca atoms substituted) and different temperatures of calcination (from 500 to 1100 degrees C). All of the powdered samples were systematically treated by Rietveld refinement to extract the quantitative phase analysis and the structural and microstructural parameters, to locate the Mg crystallographic sites, and to refine the composition of the Mg-substituted phases. The temperature dependence of the weight amount ratio between HAp and beta-TCP is not monotonic because of the formation of minor phases such as Ca(2)P(2)O(7), CaO, MgO, and CaCO(3) and certainly an amorphous phase. On the other hand, the Mg stabilizing feature on the beta-TCP phase has been evidenced and explained. The mechanism of stabilization by small Mg(2+) is different from that by large Sr(2+). Nevertheless, in both cases, the beta-TCP stabilization is realized by an improvement of the environment of the Ca4 site unusually face-coordinated to a PO(4) tetrahedron. The substitution of a Mg atom in the Ca5 site allows considerable improvement of the bond valence sum of the unusual Ca4 polyhedron. The temperatures of calcination combined with the amount of Mg atoms introduced allow monitoring of the phase composition of the BCP ceramics as well as their microstructural properties. The bioactivity properties of the BCP samples are improved by the presence of Mg atoms in the structure of the beta-TCP phase. The mechanism of improvement is mainly attributed to an accelerated kinetic of precipitation of a calcium phosphate layer at the surface comprising HAp and/or beta-TCP phases.

A new route for local probing of inner interactions within a layered double hydroxide/benzene derivative hybrid material.

This paper presents the preparation and characterization of hybrid hydrotalcite-type layered double hydroxides (Zn1-xAlx(OH)2HBSx.nH2O, with x=0.33) where HBS is the 4-phenol sulfonate, with a detailed analysis of the grafting process of this organic entity onto the host lattice. As a set of the usual techniques (XRD, TG-DT/MS, FTIR and 27Al MAS NMR) was used to characterize the hybrid materials, this work focuses on a joint study by X-ray photoelectron spectroscopy and some quantum-calculation modeling in order to highlight the nature of the interactions between the organic and the mineral sub-systems. For the as-prepared hybrid material, the main results lead to a quasi-vertical orientation of the organic molecules within the mineral sheets via H-bond stabilization. By heating the hybrid material up to 200 degrees C, the structure shrinks with the condensation of the organics; the different theoretical modeling done gives an energy-stable situation when a direct attachment of the HBS sulfonate group sets up with the mineral layers, in agreement with the recorded XPS experimental data.

Hydrogenation-induced insulating state in the intermetallic compound LaMg2Ni.

Hydrogenation-induced metal-semiconductor transitions usually occur in simple systems based on rare earths and/or magnesium, accompanied by major reconstructions of the metal host (atom shifts >2 A). We report on the first such transition in a quaternary system based on a transition element. Metallic LaMg2Ni absorbs hydrogen near ambient conditions, forming the nonmetallic hydride LaMg2NiH7 which has a nearly unchanged metal host structure (atom shifts <0.7 A). The transition is induced by a charge transfer of conduction electrons into tetrahedral [NiH4]4- complexes having closed-shell electron configurations.