Synthesis,characterization, and adsorption behavior of aminophosphinic grafted on poly(styrene‐Co‐divinylbenzene) for divalent metal ions in aqueous solutions

In the present work, two novel aminophosphinic acid ligands grafted on poly(styrene‐1%divinylbenzene) (St‐1%DVB) have been synthesized by reacting polymer precursors bearing primary amino groups with benzaldehyde (or propionaldehyde) and phenylphosphinic acid by the “one‐pot” Kabatachnik‐Fields reaction. The resins functionalized with aminophosphinic pendant groups were characterized by means of Fourier transform infrared spectroscopy (FTIR), thermal analysis, energy dispersive X‐ray microanalysis (EDX), and Scanning electron microscopy (SEM) imaging. Its adsorption capacity for divalent metal ions such as Cu(II) and Ni(II) were investigated. The adsorption procedure of Cu(II) and Ni(II) ions on polymer‐grafted aminophosphinic acid ligands was carried out by batch experiments. The result also shows that the adsorption process was best described by a pseudo‐second‐order kinetic equation and by the Langmuir adsorption isotherm. The best maximum adsorption capacity was obtained for resin with aminobenzylphosphinic acid groups [1.46 mg Cu(II)/g and 1.36 mg Ni(II)/g]. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Wetting properties of glycerol on silicon,native SiO2, and bulk SiO2 by scanning polarization force microscopy

Scanning polarization force microscopy, a relatively new non-contact scanning probe microscopy technique, was applied in order to investigate the properties of liquid surfaces (droplets), such as: topography, microscopic contact angle θ, surface potential energy P(e), spreading coefficient S, and disjoining pressure П. Investigations were carried out on glycerol droplets deposited on surfaces of bare silicon, silicon covered with native oxide, and bulk silicon oxide. Contact angle values were determined from directly measured topography profiles of micro- and nanodroplets. Values of surface potential energy, spreading coefficient, and disjoining pressure were calculated based on a model of the dependence of contact angle on droplet height. The results of these experiments offer valuable insights into the mechanisms of wetting phenomena at the microscopic scale.     

Engineering preliminaries to obtain reproducible mixtures of atelocollagen and polysaccharides

The critical stage in producing blends of biomacromolecules consists in the mixing of component solutions to generate homogenous diluted colloidal systems. Simple experimental investigations allow the establishment of the design rules of recipes and the procedures for preparing homogenous and compositionally reproducible mixtures. Starting from purified solutions of atelocollagen, hyaluronan and native gellan, having as low as possible inorganic salts content, initial binary and ternary mixtures can be prepared up to a total dry matter content of 0.150 g/dL, in no co-precipitating conditions. Two pH manipulation ways are feasible for homogenous mixing: (i) unbuffered prior correction at pH 5.5, and (ii) “rigid” buffering at pH 9.0, using organic species. Atelocollagen including co-precipitates can be obtained in the presence of one or both polysaccharides, preferably in pH domains far from the isoelectric point of scleroprotein. A critical behavior has been observed in mixtures containing gellan, due to its macromolecular dissimilarities compared with atelocollagen. In optimal binary mixtures, the coordinates of threshold points on the phase diagrams are 0.028% w/w atelocollagen/0.025% w/w hyaluronan, and 0.022% w/w atelocollagen/0.020% w/w gellan. Uni- or bi-phasic ternary systems having equilibrated ratios of co-precipitated components can be prepared starting from initial mixtures containing up to 0.032 g/dL atelocollagen, associated with, for example, 0.040 g/dL hyaluronan and 0.008 g/dL gellan, following the first pH manipulation way.     

Superior neuroprotective effects of cerebrolysin in heat stroke following chronic intoxication of Cu or Ag engineered nanoparticles. A comparative study with other neuroprotective agents using biochemical and morphological approaches in the rat

The possibility that cerebrolysin, a mixture of several active fragments of neurotrophic factors and peptides induces neuroprotection following nanoparticles induced exacerbation of brain damage in heat stroke was examined in a rat model. For this purpose, the therapeutic efficacy of Cerebrolysin (2.5 or 5 ml/kg) recommended for stroke treatment was used in comparison with other drugs in standard doses recommended for such therapy in clinical situations e.g., levetiracetam (44 mg/kg), pregabalin (200 mg/kg), topiramate (40 mg/kg,i.p.) and valproate (400 mg/kg). Rats subjected to 4 h heat stress in a biological oxygen demand (BOD) incubator at 38 degrees C (Rel Humid 45-47%; Wind vel 22.4 to 25.6 cm/sec) developed profound behavioral symptoms of heat stroke e.g., hyperthermia, profuse salivation, prostration and gastric ulcerations in the stomach. These rats also exhibited marked brain pathology at this time. Thus, breakdown of the blood-brain barrier (BBB) to proteins associated with brain edema formation could be seen in these heat stressed rats as compared to control groups. The edematous brain areas showed profound neuronal damage and/or distortion in large areas of the neuropil. These pathological symptoms were further exacerbated in Cu or Ag nanoparticles treated group (50-60 nm particle size, 50 mg/kg, i.p./day for 7 days) after identical heat stress on the 8th day. Pretreatment with cerebrolysin (2.5 ml/kg, i.v.) daily for 3 days in normal rats before heat stress significantly reduced the behavioral stress symptoms and the breakdown of the BBB function, edema formation and neuronal injuries. However, the magnitude and intensity of these neuroprotective effects were much less intense in all other drug treated rats after similar heat stress. On the other hand, almost double dose of cerebrolysin (5 ml/kg) was needed to achieve comparable neuroprotection in nanoparticles treated animals after heat stress. Whereas, double dose of all other compounds was much less effective in inducing neuroprotection in nanoparticles treated heat-exposed animals. These observations are the first to show that cerebrolysin exerts the most superior neuroprotective effects in heat stress as compared to other neuroprotective agents on brain pathology in normal and in nanoparticles treated group. Furthermore, cerebrolysin in double dose was the most effective in inducing neuroprotection in nanoparticles treated heat exposed rats on brain pathology as compared to double doses of other drugs. Taken together, our results show that cerebrolysin has the most superior neuroprotective effects on brain pathology in heat stroke in both normal and nanoparticles treated rats as compared to other contemporary neuroprotective agents, not reported earlier.     

An MRI-compatible robotic system with hybrid tracking for MRI-guided prostate intervention

This paper reports the development, evaluation, and first clinical trials of the access to the prostate tissue (APT) II system-a scanner independent system for magnetic resonance imaging (MRI)-guided transrectal prostate interventions. The system utilizes novel manipulator mechanics employing a steerable needle channel and a novel six degree-of-freedom hybrid tracking method, comprising passive fiducial tracking for initial registration and subsequent incremental motion measurements. Targeting accuracy of the system in prostate phantom experiments and two clinical human-subject procedures is shown to compare favorably with existing systems using passive and active tracking methods. The portable design of the APT II system, using only standard MRI image sequences and minimal custom scanner interfacing, allows the system to be easily used on different MRI scanners.     

Electrochemical deposition of bioactive coatings on Ti and Ti-6Al-4V surfaces

Passivating coatings of brushite (CaHPO₄·2H₂O) were obtained on Ti and Ti-6Al-4V ELI alloy substrates by cathodic polarization. After soaking in Ringer's solution for 48 h brushite was transformed to hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂) as confirmed by XRD, FT-IR and Raman spectroscopy. Electrochemical cyclic polarization curves of the coated biomaterials obtained in Ringer's solution at pH values of 7.1 and 8.91 as well as in Hank's Balanced Salt Solution (HBSS) at pH value of 7.4 show a nobler behavior than of the uncoated biomaterials. The coated biomaterials had lower corrosion rates than the uncoated biomaterials suggesting a protective character of the hydroxyapatite coating. Electrochemical impedance spectra (EIS) revealed capacitive behavior, owing to the protective, very resistant layer, the thickness of which increased with soaking time. The coated biomaterials presented higher electropositive open circuit potentials compared to the uncoated biomaterials as result of the protective effect of the coating. The morphology of the coatings changed with soaking time as the coatings became denser, smoother and better adhering. Hence such coatings may provide favorable structure for cell adhesion and proliferation.     

Properties of nanocomposite film combining hard TiN matrix with embedded fullerene-like WS2 nanoclusters

We have developed hard self-lubricant coatings combining a hard matrix (TiN) and a self-lubricant phase in the form of inorganic-like WS₂ fullerene. The nanoparticles were injected from the preparation chamber directly to the sample surface during reactive sputtering from a Ti target in Ar/N₂ atmosphere. The injection of the particles led to the local oxidation of the matrix due to the flow of residual oxygen from the preparation chamber; therefore, the final composite was TiN/Ti-O-WS₂. The observation of the composite film by scanning and transmission electron microscopies showed the incorporation of the WS₂ nanoparticles; however, their bonding with the matrix was weak. The analysis of the wear tracks did not show any presence of WS₂ in the contact.     

Exploring forces between individual colloidal particles with the atomic force microscope

Forces between individual colloidal particles can be measured with the atomic force microscope (AFM), and this technique permits the study of interactions between surfaces across aqueous solutions in great detail. The most relevant forces are described by the Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory, and they include electrostatic double-layer and van der Waals forces. In symmetric systems, the electrostatic forces are repulsive and depend strongly on the type and concentration of the salts present, while van der Waals forces are always attractive. In asymmetric systems, the electrostatic force can become attractive as well, even when involving neutral surfaces, while in rare situations van der Waals forces can become repulsive too. The enormous sensitivity of the double layer forces on additives present is illustrated with oppositely charged polyelectrolytes, which may induce attractions or repulsions depending on their concentrations.     

Long-term assessment of the implant titanium material—artificial saliva interface

This paper studies the long-term (20,000 exposure hours) behavior of titanium and Ti–5Al–4V alloy—Carter–Brugirard saliva interface and the short-term (500 exposure hours) resistance of titanium and Ti–5Al–4V alloy—Tani&Zucchi saliva interface. Potentiodynamic polarization method was applied for the determination of the main electrochemical parameters. Linear polarization measurements for to obtain the corrosion rates were used. Monitoring of the open circuit potentials (E _oc) for long-term have permitted to calculate the potential gradients due to the pH, ΔE _oc(pH) and to the saliva composition ΔE _oc(c) changes which can appear “in vivo” conditions and can generate local corrosion. Atomic force microscopy (AFM) has analyzed the surface roughness. Ion release was studied by atomic absorption spectroscopy (AAS). In Carter–Brugirard saliva both titanium and Ti–5Al–4V alloy present very stable passive films, long-term stability, “very good” resistance, low values of the open circuit potential gradients, which cannot generate local corrosion. In Tani&Zucchi artificial saliva, pitting corrosion and noble pitting protection potentials (which cannot be reached in oral cavity) were registered; titanium ion release is very low; surface roughness increase in time and in the presence of the fluoride ions, denoting some increase in the anodic activity.     

Improving chill control in iron powder treated slightly hypereutectic grey cast irons

Recent studies revealed that in eutectic to slightly hypereutectic grey irons (CE = 4.3%-4.5%) the presence of austenite dendrites provides an opportunity to improve the cast iron properties, as a high number of eutectic cells are "reinforced" by austenite dendrites. An iron powder addition proved to be important by promoting dendritic austenite in hypereutectic irons, but was accompanied by adverse effect on the characteristics of potential nuclei for graphite. The purpose of the present paper is to investigate the solidification pattern of these irons. Chill wedges with different cooling moduli (CM = 0.11 - 0.43 cm) were poured in resin bonded sand and metal moulds.Relative clear / mottled / total chill measurement criteria were applied. Iron powder additions led to a higher chill tendency, while single inoculation showed the strongest graphitizing effect. The various double treatments show an intermediate position, but the inoculant added after iron powder appears to be the most effective in reducing base iron chill tendency, for all cooling moduli and chill evaluation parameters. This performance reflects the improved properties of (Mn,X)S polygonal compounds as nucleation sites for graphite, especially in resin bonded sand mould castings. Both austenite and graphite nucleation benefit from a double addition of iron powder + inoculant,with positive effect on the final structure and chill tendency.