On arginine-based polyurethane-blends specific to vascular prostheses

Polymer blends based on Tecoflex™ and an experimental aliphatic polyurethane (HMDI-PCL-arginine stands for 4,4 (metylene-biscyclohexyl) isocyanate - poly (ε caprolactone) diol, SPUUR stands for segmented poly(urea)urethanes using amino acid of L-Arginine as chain extender) were obtained by solvent casting, and further studied by fourier transform infrared (FTIR) and Raman spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis, and X-ray diffraction (XRD). Their biological performances were assessed in terms of hemocompatibility and Human umbilical vein endothelial cell (HUVEC) cytotoxicity. Tensile properties of dumbbell specimens were compared to longitudinal and circumferential tensile properties of tubular vascular graft. FTIR showed that as the SPUUR content increased in the blend, absorptions at 2860 cm⁻¹ increased, carbonyl absorptions at 1724 cm⁻¹ broaden and the small peak at 2796 cm⁻¹, typical of Tecoflex™ disappeared. Raman spectroscopy showed that the low intensity carbonyl absorption at 1724 cm⁻¹ also increased with SPUUR content. DSC allowed detection of PCL soft segment melting (T_m = 50°C) in agreement with X-ray reflections at 21.3° and 23.6°, assigned to SPUUR. However, no improvements in thermal stability were detected by TGA by blending. The addition of SPUUR to Tecoflex™ improved hemocompatibility and HUVEC cytotoxicity. The vascular grafts performance showed that 40% SPUUR blends exhibited the highest force in the longitudinal test whereas 50% SPUUR blends showed the highest circumferential force. Pressure burst strength was higher than 1000 mmHg for all blends. Overall, these blends can be used for high caliber vascular grafts.     

Azoic dyes derived from 1-aryl-5-methyl-3-hydroxypyrazoles

The potentialities for 1-aryl-5-methyl-3-hydroxypyrazoles as intermediates in the field of dyes have been analysed. Some azoic derivatives have been synthesized and both electronic spectra and tinctorial properties on various substrates (wool, nylon, polyester, plasticized PVC) examined. The effect of substituents on the position of the long wavelength absorption maxima is discussed in terms of Hammett σ constants and interesting relationships are obtained. For each application the most important technical properties are assessed and significant fastness to various agents is evaluated.Finally a comparison with properties of similar pyrazol-5-one derivatives is made.     

Self‐Immobilizing Precatalysts: Norbornene‐Bridged Zirconium ansa‐Metallocenes

We report here the synthesis of new tethered biscyclopentadienyl and bisindenyl zirconocenes, bearing one unsaturation on the interannular bridge, and their use as self‐immobilizing catalysts. They proved to be active catalysts towards ethylene polymerization in solution, with activities comparable to those displayed by commercial rac‐Et(Ind)₂ZrCl₂. When tested as self‐polymerization catalysts under suitable experimental conditions, they gave colored precipitates that, once reactivated with MAO, were significantly active in ethylene polymerization, although lower than those of the corresponding catalytic systems in solution. The molecular weights of the produced polymers were similar to those obtained with the same catalysts in solution, but their distribution resulted to be broader, with values typical of heterogeneous catalytic systems. From ¹³C NMR studies we had the first spectroscopic evidence of the actual incorporation of a metallocene of this type into a polymeric chain.     

Use of Lactobacillus plantarum fermentation products in bread-making to prevent Bacillus subtilis ropy spoilage

Four fermentation products (FPs) of the lactic acid bacterium Lactobacillus plantarum ITM21B were screened for their anti-Bacillus activity in vitro and in bread-making trials. Results of the storage tests performed with loaves prepared with an FP or calcium propionate demonstrated that after 3 days at 30 degrees C, gross spoilage was evident in only the control loaves, which contained Bacillus subtilis at numbers of about 10(9) cfu/g. The highest inhibitory activity was shown by DM-FP obtained by growing L. plantarum in a defined medium (DM). Significantly, this medium contained an amino acceptor of the aminoacid transamination, namely alpha-ketoglutaric acid, and an aminoacid pool. With loaves prepared using the DM-acid mixture which simulated the DM-FP composition, the same reduction of ropy spoilage as with DM-FP was obtained after 3 days, while the efficacy of the mixture decreased after 7 days. This result suggests the potential involvement of some unknown metabolites in the inhibitory activity of DM-FP. In baked products made with flour based media (M1-FP, M2-FP, M3-FP), no ropy symptoms were noticeable after 3 days storage although a considerable Bacillus count was detected. DM-FP was as effective as calcium propionate (0.3% w/w, based on flour mass) in prolonging the Bacillus free-shelf life of yeast-leavened bread for 7 days.     

Solvent Extraction of Copper from Sulfate–Chloride Solutions Using LIX 84-IC and LIX 860-IC

ABSTRACT

The effect of chloride ions on the copper extraction equilibria, the rate of extraction, copper/iron selectivity, and chloride extraction was studied for organic phases containing pure ketoxime (LIX 84-IC) and pure nonylaldoxime (LIX 860N-IC). In these systems, the used aqueous phase contained total chloride concentrations from 0 to 110 g/l. It was determined that the chloride ions in the aqueous solution had a large negative effect on the extraction equilibria for LIX 84-IC and a small effect for LIX 860N-IC. This deleterious effect is attributed to an increase in the hydrogen ion activity coefficient in the presence of chloride ions. The chloride accelerated the rate of copper extraction even though the reaction was fast in all the tested conditions. An increase in the temperature from 25°C to 35°C affected positively the extraction equilibria for LIX 84-IC.     

Evidence for the Band‐Edge Exciton of CuInS2 Nanocrystals Enables Record Efficient Large‐Area Luminescent Solar Concentrators

Ternary I‐III‐VI₂ nanocrystals (NCs), such as CuInS₂, are receiving attention as heavy‐metals‐free materials for solar cells, luminescent solar concentrators (LSCs), LEDs, and bio‐imaging. The origin of the optical properties of CuInS₂ NCs are however not fully understood. A recent theoretical model suggests that their characteristic Stokes‐shifted and long‐lived luminescence arises from the structure of the valence band (VB) and predicts distinctive optical behaviours in defect‐free NCs: the quadratic dependence of the radiative decay rate and the Stokes shift on the NC radius. If confirmed, this would have crucial implications for LSCs as the solar spectral coverage ensured by low‐bandgap NCs would be accompanied by increased re‐absorption losses. Here, by studying stoichiometric CuInS₂ NCs, it is revealed for the first time the spectroscopic signatures predicted for the free band‐edge exciton, thus supporting the VB‐structure model. At very low temperatures, the NCs also show dark‐state emission likely originating from enhanced electron‐hole spin interaction. The impact of the observed optical behaviours on LSCs is evaluated by Monte Carlo ray‐tracing simulations. Based on the emerging device design guidelines, optical‐grade large‐area (30×30 cm²) LSCs with optical power efficiency (OPE) as high as 6.8% are fabricated, corresponding to the highest value reported to date for large‐area devices.     

Molecular mechanisms driving <Emphasis Type="Italic">Streptococcus mitis</Emphasis> entry into human gingival fibroblasts in presence of chitlac-nAg and saliva

The molecular mechanisms leading to Streptococcus mitis capability of entering oral cells were investigated in a co-culture of S. mitis and Human Gingival Fibroblasts (HGFs) in the presence of saliva. An innovative colloidal solution based on silver nanoparticles (Chitlac-nAg), a promising device for daily oral care, was added to the experimental system in order to study the effects of silver on the bacterial overgrowth and ability to enter non-phagocytic eukaryotic cells. The entry of bacteria into the eukaryotic cells is mediated by a signalling pathway involving FAK, integrin β1, and the two cytoskeleton proteins vinculin and F-actin, and down-regulated by the presence of saliva both at 3 and 48?h of culture, whereas Chitlac-n Ag exposure seems to influence, by incrementing it, the number of bacteria entering the fibroblasts only at 48?h. The formation of fibrillary extrusion from HGFs and the co-localization of bacteria and silver nanoparticles within the fibroblast vacuoles were also recorded. After longer experimental times (72 and 96?h), the number of S. mitis chains inside gingival cells is reduced, mainly in presence of saliva. The results suggest an escape of bacteria from fibroblasts to restore the microbial balance of the oral cavity.

Open image in new window

     

The catalytic activity of FeOx/ZrO2 for the abatement of NO with propene in the presence of O2

FeO_x/ZrO₂ samples, prepared by impregnation with Fe(NO₃)₃, were characterised by means of DRS, XRD, FTIR, redox cycles and volumetric CO adsorption. Volumetric CO adsorption, combined with FTIR, showed that 45% of iron in the sample containing 2.8 Fe atoms nm⁻² was capable of forming iron carbonyls. DRS evidenced Fe₂O₃ on samples with Fe-content≥2.8 atoms nm⁻². The selective catalytic reduction of NO with C₃H₆ in the presence of O₂ was studied with a reactant mixture containing NO=4000 ppm, C₃H₆=4000 ppm, O₂=2%. The dependence on iron-content suggests that only isolated iron, prevailing in dilute FeO_x/ZrO₂, is active for NO reduction, whereas iron on the surface of small oxide particles, prevailing in concentrated FeO_x/ZrO₂, is active for C₃H₆ combustion.