Assessing the biocompatibility of NiTi shape memory alloys used for medical applications

The present paper reviews aspects related to the biocompatibility of NiTi shape memory alloys used for medical applications. These smart metallic materials, which are characterised by outstanding mechanical properties, have been gaining increasing importance over the last two decades in many minimal invasive surgery and diagnostic applications, as well as for other uses, such as in orthodontic appliances. Due to the presence of high amounts of Ni, the cytotoxicity of such alloys is under scrutiny. In this review paper we analyse work published on the biocompatibility of NiTi alloys, considering aspects related to: (1) corrosion properties and the different methods used to test them, as well as specimen surface states; (2) biocompatibility tests in vitro and in vivo; (3) the release of Ni ions. It is shown that NiTi shape memory alloys are generally characterised by good corrosion properties, in most cases superior to those of conventional stainless steel or Co–Cr–Mo-based biomedical materials. The majority of biocompatibility studies suggest that these alloys have low cytotoxicity (both in vitro and in vivo) as well as low genotoxicity. The release of Ni ions depends on the surface state and the surface chemistry. Smooth surfaces with well-controlled structures and chemistries of the outermost protective TiO₂ layer lead to negligible release of Ni ions, with concentrations below the normal human daily intake.     

Metal-directed assembly of chiral bis-Zn(II) Schiff base structures

Tetra-Schiff bases derived from (chiral) bis-salphen ligand scaffolds furnish, upon metalation with appropriate metal reagents, their multinuclear structures with associated Zn(OAc)(2) or Zn(OH)(2) fragments. The tendency of retaining these salts was investigated using four different (chiral) bis-salphen scaffolds. The presence of the additional Zn ions was supported by NMR studies, mass determinations and X-ray crystallography showing in two cases the possible mode of coordination within these multinuclear structures. In one case, dimerization of the Zn(3) complex leads to a unique hexanuclear Zn(6) complex being a mixture of diastereoisomeric complexes as revealed by NMR spectroscopy.     

Phenolic Acids and Flavonoids in Acetonic Extract from Quince (Cydonia oblonga Mill.): Nutraceuticals with Antioxidant and Anti-Inflammatory Potential

Quince (Cydonia oblonga Mill.) is a potential source of polyphenolic compounds related with beneficial biological processes. In this study polyphenols from quince fruit were extracted with aqueous acetone at different ratios. A polyphenol profile was identified and quantified by LC-ESI-QqQ. The antioxidant capacity (ORAC and DPPH) and anti-inflammatory effect (inhibition of COX-2 cyclooxygenase) were evaluated in vitro. The results indicated an effect of the aqueous acetone ratio on the extraction of polyphenolic compounds. The higher extraction yields of polyphenolic compounds were attained with 60–75% aqueous acetone. However, extracts obtained with 85% aqueous acetone promoted higher antioxidant and anti-inflammatory effects. Optimal scaling analysis indicated that hydroxycinnamic acids (quinic and chlorogenic), hydroxybenzoic acids (vanillic and syringic), flavonoids (quercetin and kaempferol), dihydrochalcones (neohesperidin) and flavones (acacetin) are related to the antioxidant activity of quince. While phenolic acids, flavonols (kaempferol-3-O-glucoside and rutin) and flavanols (epicatechin) generated the anti-inflammatory effect by inhibiting 52.3% of the COX-2 enzyme. Therefore, a selective extraction of phenolic mix can reduce oxidative stress or inflammatory processes. This suggests the use of quince as a natural source with significant nutraceutical potential.     

Linear and non-linear nature of the flow of polypropylene filled with ferrite particles: from low to concentrated composites

The flow behavior of a filled suspension consisting of ferrite particles suspended in a polypropylene matrix with and without the addition of a commercial dispersant (Solplus DP310) was studied. The composites were filled with 10, 20, 30, and 40 vol.%. Both capillary and parallel disk rotational flows were employed. On the one hand, dynamic results confirm general trends found for highly concentrated systems. The higher is the filler level, the lower is the linear viscoelastic domain. When adding the dispersant agent, it was shown a larger linear viscoelastic domain, lower moduli values and thus, lower viscosity. Also, the critical strain, G′ and G′′ showed a power law dependency on the volume fraction. On the other hand, the capillary results showed no dependency of the flow properties on the die. Thus, no slip of the suspension at the wall was observed. Actually, this experimental finding elucidated that the significant decrease on viscosity produced by the addition of the dispersant agent at 40 vol.% is principally due to lubricant effects and not at all to slip contributions. The results also reveal three distinct flow regimes. Low, moderate, and high shear rates lead to different microstructure under flow.     

The ferrocene--lithium cation complex in the gas phase.

The stable isomers of the ferrocene--lithium cation gas-phase ion complex have been studied with the hybrid density functional theory. The method of calculation chosen has been tested checking its performance for the more studied protonated ferrocene species. Our calculations demonstrate that the procedure used is reliable. We have found two isomers of the ferrocene--lithium cation complex separated by a barrier of 25.6 kcal/mol. The most stable isomer of this complex has Li(+) on-top of one of the cyclopentadienyls, while in the least stable isomer Li(+) binds the central iron metal. The latter isomer has been characterized as a planetary system in the sense that Li(+) has one thermally accessible planar orbit around the central ferrocene moiety. Our calculations lead to a value of ferrocene's gas-phase lithium cation basicity of 37.4 kcal/mol for the on-top complex and 29.4 kcal/mol for the metal-bound complex.     

Elucidating a particulate matter deposition episode by combining scanning electron microscopy and X-ray fluorescence spectrometry.

Multielemental composition and morphology of particulate matter samples were examined to detect the presence of two potential responsible pollutant emitters at four sites impacted during a pollution episode in the City of Campana, Argentina. Coke and smoke black are the main constituents associated to the industrial plants that were considered, a priori, as responsible pollutant emitters. Wavelength dispersive X-ray fluorescence (WDXRF) was employed for the analysis of metals in samples coming from both, suspected sources and four sites. On the basis of multielemental composition profiles, a screening analysis was undertaken for exploring similarities among sources and sample sites adopting the average concentration profile of the crustal rock as soil surrogate. Particle morphology was studied by scanning electron microscopy (SEM) in source samples and in those environmental samples selected through the screening analysis. Two types of collected samples were analyzed: 1) those with composition profiles closer to the potential sources and 2) those closer to the cluster rock. This strategy was adequate to identify the responsible source of the contamination episode.     

New bicyclic phosphorous ligands: synthesis, structure and catalytic applications in ionic liquids

New azadioxaphosphabicyclo[3.3.0]octane ligands showing a trans arrangement with regard to the two five-membered heterocycles, were obtained as a mixture of three conformers, in agreement with molecular modelling studies. The stability of oxaphosphane ligands was studied under basic catalytic conditions, monitored by NMR spectroscopy. Palladium catalytic systems containing these ligands were active in Suzuki C-C cross-coupling reactions between phenylboronic acid and aryl halides (bromide and chloride derivatives) bearing electron-donor or electron-withdrawing substituents, in both organic and ionic liquid solvents. The catalytic systems showed a high stability even under the most severe reaction conditions used in this work. The ionic liquid catalytic phase could be recycled up to ten times without significant activity loss.