Novel HDPE/ground tyre rubber composite materials obtained through in‐situ polymerization and polymerization filling technique

Novel hybrid materials composed by a high density polyethylene (HDPE) matrix and powdered rubber coming from scrap tyres (ground tyre rubber [GTR]) were prepared. Two methods were followed: ethylene was polymerized by a metallocene catalyst (Cp₂ZrCl₂/methylaluminoxane) in the presence of a toluene dispersion of the filler (in‐situ polymerization); and the ethylene was polymerized out after supporting the aluminum‐based co‐catalyst onto the rubber particles surface (polymerization filling technique). The experimental conditions were varied in order to achieve the best catalyst productivity. All the synthesized composites were characterized in order to investigate the occurrence and the extent of interactions between HDPE macromolecular chains and the GTR components and their effects onto the final properties, by comparison with a composite where GTR was included into the matrix through blending in the melt. Scanning electron microscopy, atomic force microscopy, and solvent extractions were performed to this aim. The amount of thermoplastic matrix bonded to the filler was determined, and the extracted polymer was characterized by size exclusion chromatography and differential scanning calorimetry. Finally, stress–strain behavior of the composites obtained, respectively, by catalytic polymerization and melt mixing was compared. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40313.     

Atomic‐Resolution Structure of a Class C β‐Lactamase and Its Complex with Avibactam

β‐Lactamases (BLs) are important antibiotic‐resistance determinants that significantly compromise the efficacy of valuable β‐lactam antibacterial drugs. Thus, combinations with BL inhibitor were developed. Avibactam is the first non‐β‐lactam BL inhibitor introduced into clinical practice. Ceftazidime–avibactam represents one of the few last‐resort antibiotics available for the treatment of infections caused by near‐pandrug‐resistant bacteria. TRU‐1 is a chromosomally encoded AmpC‐type BL of Aeromonas enteropelogenes, related to the FOX‐type BLs and constitutes a good model for class C BLs. TRU‐1 crystals provided ultrahigh‐resolution diffraction data for the native enzyme and for its complex with avibactam. A comparison of the native and avibactam‐bound structures revealed new details in the conformations of residues relevant for substrate and/or inhibitor binding. Furthermore, a comparison of the TRU‐1 and Pseudomonas aeruginosa AmpC avibactam‐bound structures revealed two inhibitor conformations that were likely to correspond to two different states occurring during inhibitor carbamylation/recyclization.     

Surface electrostatic potentials in carbon nanotubes and graphene membranes investigated with electron holography

We used low-voltage transmission electron holography to probe surface electrostatic potentials in graphene membranes and carbon nanotubes, as the number of graphenes varies. Further, we measured the phase shift induced by an individual graphene, and mapped the phase shift variation throughout a whole few-graphene-crystal as a function of the local number of layers. We found a size/surface effect as the ratio between the surface and the total number of atoms increases for an individual nanotube or graphene membrane. This surface phase term can be related to a fine electrostatic potentials redistributions occurring at the outer layers in carbon nanotubes and graphene membranes.     

Absorption and scattering properties of carbon nanohorn-based nanofluids for direct sunlight absorbers

Abstract  

In the present work, we investigated the scattering and spectrally resolved absorption properties of nanofluids consisting in aqueous and glycol suspensions of single-wall carbon nanohorns. The characteristics of these nanofluids were evaluated in view of their use as sunlight absorber fluids in a solar device. The observed nanoparticle-induced differences in optical properties appeared promising, leading to a considerably higher sunlight absorption with respect to the pure base fluids. Scattered light was found to be not more than about 5% with respect to the total attenuation of light. Both these effects, together with the possible chemical functionalization of carbon nanohorns, make this new kind of nanofluids very interesting for increasing the overall efficiency of the sunlight exploiting device.     

Poly(lactide-co-glycolide) nanoparticles embedded in a micropatterned collagen scaffold for neuronal tissue regeneration

Micropatterned collagen scaffold with axially oriented pores embedded with poly(lactide-co-glycolide) nanoparticles (PLGA NPs) was synthesized and characterized. Two different concentrations of PLGA nanoparticles have been tested and the experimental results indicate that the concentration affects the release kinetic, whereas the stiffness, the crosslink density, and the degradation rate of the collagen matrix are comparable to bare scaffold. Further, the proposed crosslinking procedure provides a resistance to thermal and enzymatic degradation, thereby promoting the persistence of scaffold for a period of time compatible with nerve regeneration.     

Antiproliferative,Antibacterial and Antifungal Activity of the Lichen Xanthoria parietina and Its Secondary Metabolite Parietin

Lichens are valuable natural resources used for centuries throughout the world as medicine, food, fodder, perfume, spices and dyes, as well as for other miscellaneous purposes. This study investigates the antiproliferative, antibacterial and antifungal activity of the acetone extract of the lichen Xanthoria parietina (Linnaeus) Theodor Fries and its major secondary metabolite, parietin. The extract and parietin were tested for antimicrobial activity against nine American Type Culture Collection standard and clinically isolated bacterial strains, and three fungal strains. Both showed strong antibacterial activity against all bacterial strains and matched clinical isolates, particularly against Staphylococcus aureus from standard and clinical sources. Among the fungi tested, Rhizoctonia solani was the most sensitive. The antiproliferative effects of the extract and parietin were also investigated in human breast cancer cells. The extract inhibited proliferation and induced apoptosis, both effects being accompanied by modulation of expression of cell cycle regulating genes such as p16, p27, cyclin D1 and cyclin A. It also mediated apoptosis by activating extrinsic and intrinsic cell death pathways, modulating Tumor Necrosis Factor-related apoptosis-inducing ligand (TRAIL) and B-cell lymphoma 2 (Bcl-2), and inducing Bcl-2-associated agonist of cell death (BAD) phosphorylation. Our results indicate that Xanthoria parietina is a major potential source of antimicrobial and anticancer substances.     

Two Subtle Amino Acid Changes in a Transaminase Substantially Enhance or Invert Enantiopreference in Cascade Syntheses

Amine transaminases (ATAs) are powerful enzymes for the stereospecific production of chiral amines. However, the synthesis of amines incorporating more than one stereocenter is still a challenge. We developed a cascade synthesis to access optically active 3‐alkyl‐substituted chiral amines by combining two asymmetric synthesis steps catalyzed by an enoate reductase and ATAs. The ATA wild type from Vibrio fluvialis showed only modest enantioselectivity (14 % de) in the amination of (S)‐3‐methylcyclohexanone, the product of the enoate‐reductase‐catalyzed reaction step. However, by protein engineering we created two variants with substantially improved diastereoselectivities: variant Leu56Val exhibited a higher R selectivity (66 % de) whereas the Leu56Ile substitution caused a switch in enantiopreference to furnish the S‐configured diastereomer (70 % de). Addition of 30 % DMSO further improved the selectivity and facilitated the synthesis of (1R,3S)‐1‐amino‐3‐methylcyclohexane with 89 % de at 87 % conversion.     

Optimization of Diarylthiazole B‐Raf Inhibitors: Identification of a Compound Endowed with High Oral Antitumor Activity,Mitigated hERG Inhibition,and Low Paradoxical Effect

Aberrant activation of the mitogen‐activated protein kinase (MAPK)‐mediated pathway components, RAF‐MEK‐ERK, is frequently observed in human cancers and clearly contributes to oncogenesis. As part of a project aimed at finding inhibitors of B‐Raf, a key player in the MAPK cascade, we originally identified a thiazole derivative endowed with high potency and selectivity, optimal in vitro ADME properties, and good pharmacokinetic profiles in rodents, but that suffers from elevated hERG inhibitory activity. An optimization program was thus undertaken, focused mainly on the elaboration of the R¹ and R² groups of the scaffold. This effort ultimately led to N‐(4‐{2‐(1‐cyclopropylpiperidin‐4‐yl)‐4‐[3‐(2,5‐difluorobenzenesulfonylamino)‐2‐fluorophenyl]thiazol‐5‐yl}‐pyridin‐2‐yl)acetamide ( 20 ), which maintains favorable in vitro and in vivo properties, but lacks hERG liability. Besides exhibiting potent antiproliferative activity against only cell lines bearing B‐Raf V600E or V600D mutations, compound 20 also intriguingly shows a weaker “paradoxical” activation of MEK in non‐mutant B‐Raf cells than other known B‐Raf inhibitors. It also demonstrates very good efficacy in vivo against the A375 xenograft melanoma model (tumor volume inhibition >90 % at 10 mg kg^?1); it is therefore a suitable candidate for preclinical development.     

Nuclear and Cytoplasmic Soluble Proteins Extraction from a Small Quantity of Drosophila’s Whole Larvae and Tissues

The identification and study of protein’s function in several model organisms is carried out using both nuclear and cytoplasmic extracts. For a long time, Drosophila’s embryos have represented the main source for protein extractions, although in the last year, the importance of collecting proteins extracts also from larval tissues has also been understood. Here we report a very simple protocol, improved by a previously developed method, to produce in a single extraction both highly stable nuclear and cytoplasmic protein extracts from a small quantity of whole Drosophila’s larvae or tissues, suitable for biochemical analyses like co-immunoprecipitation.     

Microcomposites of Poly(ε‐caprolactone) and Poly(methyl methacrylate) Prepared by Suspension Polymerization in the Presence of Poly(ε‐caprolactone) Macromonomer

Poly(methyl methacrylate)‐poly(ε‐caprolactone) (PMMA/PCL) microparticles were synthesized by suspension polymerization of methyl methacrylate in the presence of PCL. The incorporation of a small amount of a macromonomer, methacryloyl‐terminated PCL (M‐PCL), into the reaction mixture, led to the formation of grafted systems, namely PMMA‐g‐PCL/PCL. The synthesis of the macromonomer and its characterization by nuclear magnetic spectroscopy (¹H NMR) is described. The role of M‐PCL as an effective compatibilizing agent in the composite was investigated. PMMA/PCL and PMMA‐g‐PCL/PCL composites were fully characterized by ¹H NMR, gel permeation chromatography (GPC) and thermal analysis, including thermogravimetric analysis (TGA), conventional differential scanning calorimetry (DSC), modulated DSC (MDSC) and dynamic mechanical thermal analysis (DMTA). Finally, the morphology of the prepared systems was investigated by scanning electron microscopy (SEM). The addition of compatibilizing agent led the formation of a more homogeneous microcomposite with improved mechanical properties.

SEM picture of PMMA‐g‐PCL/PCL composite surface.