Development of a gel spinning process for high‐strength poly(ethylene oxide) fibers

This article describes a new gel‐spinning process for making high‐strength poly(ethylene oxide) (PEO) fibers. The PEO gel‐spinning process was enabled through an oligomer/polymer blend in place of conventional organic solvents, and the gelation and solvent‐like properties were investigated. A 92/8 wt% poly(ethylene glycol)/PEO gel exhibited a melting temperature around 45°C and was highly stretchable at room temperature. Some salient features of a gel‐spun PEO fiber with a draw ratio of 60 are tensile strength at break = 0.66 ± 0.04 GPa, Young's modulus = 4.3 ± 0.1 GPa, and a toughness corresponding to 117 MJ/m³. These numbers are significantly higher than those previously reported. Wide‐angle x‐ray diffraction of the high‐strength fibers showed good molecular orientation along the fiber direction. The results also demonstrate the potential of further improvement of mechanical properties. POLYM. ENG. SCI., 54:2839–2847, 2014. © 2014 Society of Plastics Engineers     

Evaluation of the Interaction between Phosphohistidine Analogues and Phosphotyrosine Binding Domains

We have investigated the interaction of peptides containing phosphohistidine analogues and their homologues with the prototypical phosphotyrosine binding SH2 domain from the eukaryotic cell signalling protein Grb2 by using a combination of isothermal titration calorimetry and a fluorescence anisotropy competition assay. These investigations demonstrated that the triazole class of phosphohistidine analogues are capable of binding too, suggesting that phosphohistidine could potentially be detected by this class of proteins in vivo.     

Separation of Xenon and Krypton in the Metal–Organic Frameworks M2(m-dobdc) (M=Co,Ni)

The separation of Xe and Kr from air is challenging owing both to the very low atmospheric concentrations of these gases and the need for their distillation at cryogenic temperatures. Alternatively, separation processes based on adsorption could provide a less energy-intensive route to the isolation of these gases. Here, we demonstrate that the metal–organic frameworks M₂(m-dobdc) (M=Co, Ni; m-dobdc⁴⁻=4,6-dioxido-1,3-benzenedicarboxylate) effectively separate Xe and Kr at ambient temperatures based on the different adsorption enthalpies of each gas at the coordinatively-unsaturated M²⁺ sites in each material. In situ Xe- and Kr-dosed powder X-ray diffraction studies further reveal key differences in the binding of Xe and Kr within the materials. In particular, while both gases adsorb near the framework open metal sites at 200 K, much higher Xe occupancies are observed at these sites relative to Kr, corroborating a stronger interaction of the polarizing M²⁺ cations with Xe. Further, while krypton is only found located above the open metal sites, two additional adsorption sites are observed for xenon, correlating with the stronger adsorption of Xe over Kr in these materials. These results suggest the possible utility of employing M₂(m-dobdc) materials in the adsorptive separation of Xe and Kr.     

Effect of combining ethylene/methyl acrylate/glycidyl methacrylate terpolymer and an organoclay on the toughening of poly(lactic acid)

Blends of poly(lactic acid) (PLA) and ethylene/methyl acrylate/glycidyl methacrylate terpolymer (EMA‐GMA) with and without the addition of an organoclay were prepared by melt mixing in a twin screw extruder. Mechanical, morphological, structural, and rheological properties of the systems have been investigated as function of its compositions. The impact strength (IS) of PLA increased with the addition of EMA‐GMA. Furthermore, the addition of 2.5 wt% of organoclay to the PLA/EMA‐GMA blend promoted improvements in the mechanical properties, such as IS, tensile strength, and strain‐at‐break. Further addition of organoclay, 5 wt%, led to a formation of a double percolated network, where the clay particles form bridges across EMA‐GMA droplets and glue them together, however, without coalescence. In addition, morphological and wide‐angle X‐ray scattering analyses evidenced that the clay presents a partially exfoliated structure and that remains inside the EMA‐GMA droplets, probably as a consequence of the approach used to produce the systems. POLYM. ENG. SCI., 54:1922–1930, 2014. © 2013 Society of Plastics Engineers     

Specificity of Lipoprotein Chaperones for the Characteristic Lipidated Structural Motifs of their Cognate Lipoproteins

Lipoprotein‐binding chaperones mediate intracellular transport of lipidated proteins and determine their proper localisation and functioning. Understanding of the exact structural parameters that determine recognition and transport by different chaperones is of major interest. We have synthesised several lipid‐modified peptides, representative of different lipoprotein classes, and have investigated their binding to the relevant chaperones PDEδ, UNC119a, UNC119b, and galectins‐1 and ‐3. Our results demonstrate that PDEδ recognises S‐isoprenylated C‐terminal peptidic structures but not N‐myristoylated peptides. In contrast, UNC119 proteins bind only mono‐N‐myristoylated, but do not recognise doubly lipidated and S‐isoprenylated peptides at the C terminus. For galectins‐1 and ‐3, neither binding to N‐acylated, nor to C‐terminally prenylated peptides could be determined. These results shed light on the specificity of the chaperone‐mediated cellular lipoprotein transport systems.     

Preparation and characterization of EVA/clay Nanocomposites with improved barrier performance

Poly (ethylene‐co‐vinyl acetate) (EVA)/clay nanocomposites containing two different organoclays with different clay loadings were prepared. The transport of gases (oxygen and nitrogen) through the composite membranes was investigated and the results were compared. These studies revealed that the incorporation of nanoclays in the polymer increased the efficiency of the membranes toward barrier properties. It was also found that the barrier properties of the membranes decreased with clay loadings. This is mainly due to the aggregation of clay at higher loadings. The morphology of the nanocomposites was studied by scanning electron microscopy, transmission electron microscopy and X‐ray scattering. Small angle X‐ray scattering results showed significant intercalation of the polymer chains between the organo‐modified silicate layers in all cases. Better dispersed silicate layer stacking and more homogeneous membranes were obtained for Cloisite® 25A based nanocomposites compared with Cloisite® 20A samples. Microscopic observations (SEM and TEM) were coherent with those results. The dispersion of clay platelets seemed to be maximized for 3 wt % of clay and agglomeration increased with higher clay loading. Wide angle X‐ray scattering results showed no significant modifications in the crystalline structure of the EVA matrix because of the presence of the clays. The effect of free volume on the transport behavior was studied using positron annihilation spectroscopy. The permeability results have been correlated with various permeation models. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of pure aragonite by sonochemical mineral carbonation

The objective of this work was to promote the formation of the aragonite polymorph of calcium carbonate, which has some valuable applications in industry, via the mineral carbonation route. The combination of ultrasound with magnesium ions promoted the formation of pure aragonite crystals at optimum conditions. It was possible to synthesize high purity aragonite precipitates at temperatures ranging from 24 °C to 70 °C, with the resulting powders possessing varying particle size distributions (from sub-micron up to 20 μm) and crystal morphologies (from acicular needles to novel hubbard squash-like particles). Several process parameters were found to influence the produced calcium carbonate polymorph ratios (aragonite over calcite). Higher values of magnesium-to-calcium ratio, intermediate ultrasound amplitude (60%), continuous ultrasound application (100% cycle), introduction of ultrasound pre-breakage, lowering of the CO₂ flow rate, and increase in the relative concentration (g/L Ca(OH)₂), all promoted aragonite formation. A potential route for industrial production of this material has been identified via a fed-batch process, which effectively reutilizes magnesium chloride while maintaining high aragonite yield. The results presented herein are significantly superior to aragonite formation using only single promoting techniques, typically found in literature, and go beyond by focusing on pure (>99%) aragonite formation.     

Comparative behavior of glucose oxidase and oxalate oxidase immobilized in mucin/chitosan hydrogels for biosensors applications

The analytical response of amperometric glucose electrodes was explained in the framework of the properties of hydrogels with different muc/chit ratio at pH = 7.00 used as immobilization matrix for glucose oxidase. The continuous increase in the sensitivity of the electrodes with the amount of chitosan was attributed to a more efficient crosslinking without affecting the enzyme activity. The results were compared with those obtained using the same matrices to immobilize Oxalate Oxidase at pH = 2.85 where it has the highest activity. A maximum sensitivity at muc/chit 70/30 ratio for these oxalate electrodes was observed. Decrease in permeability of negatively charged oxalate with the chitosan content in the matrices, in spite of the high partition coefficient, explains the analytical differences with glucose electrodes. Swelling and viscoelasticity of the hydrogels allowed to asses the importance of a hydrophilic environment for the enzyme in both cases.     

Polylactide latex/nanofibrillated cellulose bionanocomposites of high nanofibrillated cellulose content and nanopaper network structure prepared by a papermaking route

Previous attempts to use polylactide (PLA) latex particles and nanofibrillated cellulose (NFC) in papermaking processing have been limited to low NFC content. In the present study, a bionanocomposite material was successfully produced using a PLA latex and NFC. The components were mixed using a wet mixing method and bionanocomposite films were made by filtration followed by hot pressing. In composite materials, the dispersion of the reinforcing component in the matrix is critical for the material properties. Biopolymers such as PLA are non-polar and soluble only in organic solvents; NFC is, however, highly hydrophilic. By utilizing latex, i.e., an aqueous dispersion of biopolymer micro-particles, wet mixing is possible and the problem of aggregation of the hydrophilic nanocellulose in organic solvent is avoided. The properties of the resulting NFC/PLA latex bionanocomposite films were analyzed. Thorough blending resulted in good dispersion of the reinforcing component within the matrix. Adding increasing amounts of NFC improved the Young's modulus, tensile strength, and strain at break of the bionanocomposite material. The increase in the tensile properties was linear with increasing NFC content as a result of the good dispersion. The NFC also improved the thermal stability of the bionanocomposite material. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012