Bioactive sphene-based ceramic coatings on cpTi substrates for dental implants: An in vitro study

Titanium implant surface modifications have been widely investigated to favor the process of osseointegration. The present work aimed to evaluate the effect of sphene (CaTiSiO5) biocoating, on titanium substrates, on the in vitro osteogenic differentiation of Human Adipose-Derived Stem Cells (hADSCs). Sphene bioceramic coatings were prepared using preceramic polymers and nano-sized active fillers and deposited by spray coating. Scanning Electron Microscopy (SEM) analysis, surface roughness measurements and X-ray diffraction analysis were performed. The chemical stability of the coatings in Tris-HCl solution was investigated. In vitro studies were performed by means of proliferation test of hADSCs seeded on coated and uncoated samples after 21 days. Methyl Thiazolyl-Tetrazolium (MTT) test and immunofluorescent staining with phalloidin confirmed the in vitro biocompatibility of both substrates. In vitro osteogenic differentiation of the cells was evaluated using Alizarin Red S staining and quantification assay and real-time PCR (Polymerase Chain Reaction). When hADSCs were cultured in the presence of Osteogenic Differentiation Medium, a significantly higher accumulation of calcium deposits onto the sphene-coated surfaces than on uncoated controls was detected. Osteogenic differentiation on both samples was confirmed by PCR. The proposed coating seems to be promising for dental and orthopedic implants, in terms of composition and deposition technology

Eu( iii )-doped calcium molybdate nano- and microstructures: microfluidic synthesis and morphology tuning via solvent dielectric constant and viscosity control

A novel and green microfluidic approach was employed for the synthesis of undoped and Eu(III)-doped calcium molybdate at room and low temperatures. The controlled formation of nano- and microstructures was successfully achieved by tuning the nucleation and growth stages of particle formation through a systematic variation of the viscosity and dielectric constant of the reaction medium, i.e. water and ethanol in different weight ratios and at different temperatures. Thanks to the inherent advantages of the microfluidic approach in terms of mass transport, mixing and heat exchange, it was possible to carry out the reaction at low temperature (-4 degrees C) in an effective manner and to further control the reaction conditions to achieve the formation of small and monodisperse nanoparticles. The synthesised nano- and microstructures, displaying different morphologies depending on reaction conditions, were investigated from a structural (XRD), dimensional and morphological (TEM, SEM), compositional (ICP-MS), and functional (photoluminescence) point of view. The remarkable photoluminescence properties of pure and Eu(III)-doped calcium molybdate structures proved that they are promising materials to be employed as phosphors

Copper(II) Lysinate and Pseudoproline Assistance in the Convergent Synthesis of the GLP-1 Receptor Agonists Liraglutide and Semaglutide

A growing interest in peptides as active pharmaceutical ingredients (APIs) requires the development of efficient strategies for their preparation. This is particularly challenging in the case of long peptides with a strong tendency for aggregation and folding. Here, we describe the pseudoproline-assisted convergent synthesis of GLP-1 receptor agonist lipopeptides liraglutide and semaglutide, which involves the stepwise condensation of three fragments in the solid phase. The insertion of a pseudoproline residue at the site of fragment coupling prevents aggregation and allows obtaining these peptides with excellent purity and high yield. In addition, for the synthesis of lipidated side chains, we developed a novel approach that involves copper(II) lysinate intermediates and can be particularly suitable for the industrial preparation of both liraglutide and semaglutide and other peptides with a similar branched structure.A growing interest in peptides as active pharmaceutical ingredients (APIs) requires the development of efficient strategies for their preparation. This is particularly challenging in the case of long peptides with a strong tendency for aggregation and folding. Here, we describe the pseudoproline-assisted convergent synthesis of GLP-1 receptor agonist lipopeptides liraglutide and semaglutide, which involves the stepwise condensation of three fragments in the solid phase. The insertion of a pseudoproline residue at the site of fragment coupling prevents aggregation and allows obtaining these peptides with excellent purity and high yield. In addition, for the synthesis of lipidated side chains, we developed a novel approach that involves copper(II) lysinate intermediates and can be particularly suitable for the industrial preparation of both liraglutide and semaglutide and other peptides with a similar branched structure

Study and development of a fluorescence based sensor system for monitoring oxygen in wine production: The WOW project

The importance of oxygen in the winemaking process is widely known, as it affects the chemical aspects and therefore the organoleptic characteristics of the final product. Hence, it is evident the usefulness of a continuous and real-time measurements of the levels of oxygen in the various stages of the winemaking process, both for monitoring and for control. The WOW project (Deployment of WSAN technology for monitoring Oxygen in Wine products) has focused on the design and the development of an innovative device for monitoring the oxygen levels in wine. This system is based on the use of an optical fiber to measure the luminescent lifetime variation of a reference metal/porphyrin complex, which decays in presence of oxygen. The developed technology results in a high sensitivity and low cost sensor head that can be employed for measuring the dissolved oxygen levels at several points inside a wine fermentation or aging tank. This system can be complemented with dynamic modeling techniques to provide predictive behavior of the nutrient evolution in space and time given few sampled measuring points, for both process monitoring and control purposes. The experimental validation of the technology has been first performed in a controlled laboratory setup to attain calibration and study sensitivity with respect to different photo-luminescent compounds and alcoholic or non-alcoholic solutions, and then in an actual case study during a measurement campaign at a renown Italian winery

Formation of metal-organic ligand complexes affects solubility of metals in airborne particles at an urban site in the Po valley

Abstract Metals in atmospheric aerosols play potentially an important role in human health and ocean primary productivity. However, the lack of knowledge about solubility and speciation of metal ions in the particles or after solubilisation in aqueous media (sea or surface waters, cloud or rain droplets, biological fluids) limits our understanding of the underlying physico-chemical processes. In this work, a wide range of metals, their soluble fractions, and inorganic/organic compounds contained in urban particulate matter (PM) from Padua (Italy) were determined. Metal solubility tests have been performed by dissolving the PM in water and in solutions simulating rain droplet composition. The water-soluble fractions of the metal ions and of the organic compounds having ligand properties have been subjected to a multivariate statistical procedure, in order to elucidate associations among the aqueous concentrations of these PM components in simulated rain droplets. In parallel, a multi-dimensional speciation calculation has been performed to identify the stoichiometry and the amount of metal-ligand complexes theoretically expected in aqueous solutions. Both approaches showed that the solubility and the aqueous speciation of metal ions were differently affected by the presence of inorganic and organic ligands in the PM. The solubility of Al, Cr, and Fe was strongly correlated to the concentrations of oxalic acid, as their oxalate complexes represented the expected dominant species in aqueous solutions. Oxalates of Al represented ∼98% of soluble Al, while oxalates of Cu represented 34–75% of the soluble Cu, and oxalates of Fe represented 76% of soluble Fe. The oxidation state of Fe can strongly impact the speciation picture. If Fe is present as Fe(II) rather than Fe(III), the amount of Cr and Cu complexed with diacids can increase from 75% to 94%, and from 32% to 53%, respectively. For other metals, the solubility depended on the formation of soluble aquo-complexes, hence with a scarce effect of the organic ligands. An iron-oxalate complex was also directly detected in aerosol sample extracts

In vitro evaluation of granules obtained from 3D sphene scaffolds and bovine bone grafts: chemical and biological assays

Sphene is an innovative bone graft material. The aim of this study was to investigate and compare the physicochemical and biological properties of Bio-Oss® (BO) and in-lab synthesized and processed sphene granules. BO granules of 1000-2000 μm (BO-L), 250-1000 μm (BO-S) and 100-200 μm (BO-p) for derived granules, and corresponding groups of sphene granules obtained from 3D printed blocks (SB-L, SB-S, SB-p) and foams (SF-L, SF-S and SF-p) were investigated. The following analyses were conducted: morphological analysis, specific surface area and porosity, inductively coupled plasma mass spectrometry (ICP-MS), cytotoxicity assay, Alizarin staining, bone-related gene expression, osteoblast migration and proliferation assays. All pulverized granules exhibited a similar morphology and SF-S resembled natural bone. Sphene-derived granules showed absence of micro- and mesopores and a low specific surface area. ICP-MS revealed a tendency for absorption of Ca and P for all BO samples, while sphene granules demonstrated a release of Ca. No cellular cytotoxicity was detected and osteoblastic phenotype in primary cells was observed, with significantly increased values for SF-L, SF-S, BO-L and BO-p. Further investigations are needed before clinical use can be considered

Postsynthetic Metalated MOFs as Atomically Dispersed Catalysts for Hydroformylation Reactions

A manganese-based metal-organic framework with dipyrazole ligands has been metalated with atomically dispersed Rh and Co species and used as a catalyst for the hydroformylation of styrene. The Rh-based materials exhibited excellent conversion at 80 °C with complete chemoselectivity, high selectivity for the branched aldehyde, high recyclability, and negligible metal leaching

metal ion release from fine particulate matter sampled in the po valley to an aqueous solution mimicking fog water kinetics and solubility

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Sustainability of using vineyard pruning residues as an energy source: Combustion performances and environmental impact

Open burning of agricultural waste is still a common practice as it is a rapid method for waste disposal, although natural biomass, including agriculture residues, can be exploited as a renewable energy source. We assessed the viability and sustainability of using vineyard pruning residues, as wood chips, for energy conversion. Wood chips, obtained from vineyards in the Prosecco DOCG region (Italy), were characterized in terms of chemical composition, calorific value, ash content and humidity. Combustion tests were performed in a medium-size biomass boiler (maximum power 500 kW) to assess the viability of the approach in terms of sustainable steady-state combustion. Primary emissions of both macro- and micro-pollutants were measured to assess the environmental impact. An analytical method was purposely developed for the determination of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) and in three matrices: fly ashes, condensate and gas. The results showed that vineyard pruning residues can be used for energy conversion in medium- and large-scale biomass boilers. Primary emissions of measured pollutants were all below limit values set by current European legislation except for particulate matter, for which current available abatement technologies are required to contain emissions, abatement technologies are required to contain emissions, thus making the use of vineyard pruning residues unsuitable for combustion in domestic appliances where such technologies are not installed. Bottom ashes produced during combustion were also characterized to assess whether they can be recycled in the vineyard as soil amendments/fertilizer. Copper content in combustion ashes exceeded limit values for ashes to be used as fertilizers in agricultural fields for some European countries but not for others, indicating that ashes may need to be disposed as waste

Synergistic Effect of Sn and Fe in Fe-Nx Site Formation and Activity in Fe-N-C Catalyst for ORR

Iron-nitrogen-carbon (Fe-N-C) materials emerged as one of the best non-platinum group material (non-PGM) alternatives to Pt/C catalysts for the electrochemical reduction of O2 in fuel cells. Co-doping with a secondary metal center is a possible choice to further enhance the activity toward oxygen reduction reaction (ORR). Here, classical Fe-N-C materials were co-doped with Sn as a secondary metal center. Sn-N-C according to the literature shows excellent activity, in particular in the fuel cell setup; here, the same catalyst shows a non-negligible activity in 0.5 M H2SO4 electrolyte but not as high as expected, meaning the different and uncertain nature of active sites. On the other hand, in mixed Fe, Sn-N-C catalysts, the presence of Sn improves the catalytic activity that is linked to a higher Fe-N4 site density, whereas the possible synergistic interaction of Fe-N4 and Sn-Nx found no confirmation. The presence of Fe-N4 and Sn-Nx was thoroughly determined by extended X-ray absorption fine structure and NO stripping technique; furthermore, besides the typical voltammetric technique, the catalytic activity of Fe-N-C catalyst was determined and also compared with that of the gas diffusion electrode (GDE), which allows a fast and reliable screening for possible implementation in a full cell. This paper therefore explores the effect of Sn on the formation, activity, and selectivity of Fe-N-C catalysts in both acid and alkaline media by tuning the Sn/Fe ratio in the synthetic procedure, with the ratio 1/2 showing the best activity, even higher than that of the iron-only containing sample (jk = 2.11 vs 1.83 A g-1). Pt-free materials are also tested for ORR in GDE setup in both performance and durability tests