Synthesis and properties of branched polyethylene/high-density polyethylene blends using a homogeneous binary catalyst system composed of early and late transition metal complexes

Branched polyethylene/high-density polyethylene blends (BPE/HDPE) with a wide range of molecular weights, melt flow indexes (MFI), and intrinsic viscosity were prepared using the homogeneous binary catalyst system composed by Ni(alpha-diimine)Cl-2 (1) (alpha-diimine = 1,4-bis(2,6-diisopropylphenyl)-acenaphthenediimine) and {Tp(Ms*)} TiCl3 (2) (Tp(Ms*)=hydridobis(3-mesitylpyrazol-1-yl)(5-mesityl-pyrazol-1-yl)) activated with MAO and/or TIBA in hexane at two different polymerization temperatures (30 and 55 degreesC) and by varying the nickel loading molar fraction (x(Ni)). At all Temperatures, a non-linear correlation between the x(Ni) and the productivity was observed, suggesting the occurrence of a synergistic effect between the nickel and the titanium catalyst precursors, which is more pronounced at 55 degreesC. The molecular weight of the BPE/HDPE blends considerably decreases with increasing Al/M molar ratio. The melt flow indexes (MFI) and intrinsic viscosities (eta) are strongly affected by x(Ni), but the melting temperatures are nearly constant, 132 +/- 3 degreesC. Dynamic mechanical thermal analysis (DMTA) shows the formation of different polymeric materials where the stiffness vanes according, to the x(Ni) and temperature used in the polymerization reaction. The surface morphology of the BPE/HDPE blends studied by scanning electron microscopy (SEM) revealed a low miscibility between the PE phases resulting in the formation of a sandwich structure after etching with o-xylene.

Polymer light emitting devices with Langmuir Blodgett (LB) films of a polyfluorene derivative

Polyfluorenes are promising materials for the emitting layer of polymer light emitting devices (PLEDs) with blue emission. In this work, we report on PLEDs fabricated with Langmuir-Blodgett (LB) films of a polyfluorene derivative, namely poly(9,9-di-hexylfluorenediyl vinylene-alt-1,4-phenylenevinylene) (PDHF-PV). Y-type LB films were transferred onto ITO substrates at a surface pressure of 35 mN m-1 and with dipping speed of 3 mm min -1. A thin aluminum layer was evaporated on top of the LB film, thus yielding a sandwich structure (ITO/PDHF-PV(LB)/Al). Current-voltage (I vs V) measurements indicate that the device displays a classical behavior of a rectifying diode. The threshold value is approximately 5 V, and the onset for visible light emission occurs at ca. 10 V. From the a.c. electrical responses we infer that the active layer has a typical behavior of PLEDs where the real component of ac conductivity obeys a power-law with the frequency. Cole-Cole plots (Im(Z) vs. Re(Z)) for the device exhibit a series of semicircles, the diameter of which decreases with increasing forward bias. This PLED structure is modeled by a parallel resistance and capacitance combination, representing the dominant mechanisms of charge transport and polarization in the organic layer, in series with a resistance representing the ITO contact. Overall, the results presented here demonstrate the feasibility of LEDs made with LB films of PDHF-PV.

Estudo das propriedades elétro-óptica de dispositivos eletroluminescentes confeccionados com um compósito híbrido

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

SeP hole injection layer for devices based on organic materials

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Avaliação do efeito ambiental nas propriedades mecânicas e viscoelásticas de compósitos híbridos de titânio/fibra de carbono/resina epóxi

Hybrid composites combining metal plates and laminates with continuous fiber reinforced polymer, called fiber-metal (CHMF), have been particularly attractive for aerospace applications, due mainly to their high mechanical strength and stiffness associated with low density. These laminates (CHMF) consist of a sandwich structure consisting of layers of polymer composites and metal plates, stacked alternately. This setting allows you to combine the best mechanical performance of polymer composites reinforced with long fibers, to the high toughness of metals. Environmental effects should always be considered in the design of structural components, because these materials in applications are submitted to the effects of moisture in the atmosphere, the large cyclical variations of temperature around 82 ° C to -56 ° C, and high effort mechanical. The specimens of fibermetal composite were prepared at EMBRAER with titanium plates and laminates of carbon fiber/epoxy resin. This study aims to evaluate the effect of different environmental conditions (water immersion, hygrothermal chamber and thermal shock) of laminate hybrid titanium/carbon fiber/epoxy resin. The effects of conditioning were evaluated by interlaminar shear tests - ILSS, tensile, and vibration free

Structure of chorismate synthase from Mycobacterium tuberculosis

In bacteria, fungi, plants, and apicomplexan parasites, the aromatics compounds, such as aromatics amino acids, are synthesized through seven enzymes from the shikimate pathway, which are absent in mammals. The absence of this pathway in mammals make them potential targets for development of new therapy against infectious diseases, such as tuberculosis, which is the world's second commonest cause of death from infectious disease. The last enzyme of shikimate pathway is the chorismate synthase (CS), which is responsible for conversion of the 5-enolpyruvylshikimate-3-phosphate to chorismate. Here, we report the crystallographic structure of CS from Mycobacterium tuberculosis (MtCS) at 2.65 angstrom resolution. The MtCS structure is similar to other CS structures, presenting beta-alpha-beta sandwich structural topology, in which each monomer of MtCS consists of a central helical core. The MtCS can be described as a tetramer formed by a dimer of dimers. However, analytical ultracentrifugation studies suggest the MtCS is a dimer with a more asymmetric shape than observed on the crystallographic dimer and the existence of a low equilibrium between dimer and tetramer. Our results suggest that the MtCS oligomerization is concentration dependent and some conformational changes must be involved on that event. (c) 2005 Elsevier B.V. All rights reserved.

The X-ray crystallographic structure of Escherichia coli branching enzyme

Branching enzyme catalyzes the formation of alpha-1,6 branch points in either glycogen or starch. We report the 2.3-Angstrom crystal structure of glycogen branching enzyme from Escherichia coli. The enzyme consists of three major domains, an NH2-terminal seven-stranded beta-sandwich domain, a COOH-terminal domain, and a central alpha/beta-barrel domain containing the enzyme active site. While the central domain is similar to that of all the other amylase family enzymes, branching enzyme shares the structure of all three domains only with isoamylase. Oligosaccharide binding was modeled or branching enzyme using the enzyme-oligosaccharide complex structures of various alpha-amylases and cyclodextrin glucanotransferase and residues were implicated in oligosaccharide binding. While most of the oligosaccharides modeled well in the branching enzyme structure, an approximate 50degrees rotation between two of the glucose units was required to avoid steric clashes with Trp(298) of branching enzyme. A similar rotation was observed in the mammalian alpha-amylase structure caused by an equivalent tryptophan residue in this structure. It appears that there are two binding modes for oligosaccharides in these structures depending on the identity and location of this aromatic residue.

Electrochemical genosensors for the detection of Bonamia parasite. Selection of single strand-DNA (ssDNA) probes by simulation of the secondary structure folding

A post-PCR nucleic acid work by comparing experimental data, from electrochemical genosensors, and bioinformatics data, derived from the simulation of the secondary structure folding and prediction of hybridisation reaction, was carried out in order to rationalize the selection of ssDNA probes for the detection of two Bonamia species, B. exitiosa and B. ostreae, parasites of Ostrea edulis.Six ssDNA probes (from 11 to 25 bases in length, 2 thiolated and 4 biotinylated) were selected within different regions of B. ostreae and B. exitiosa PCR amplicons (300 and 304 bases, respectively) with the aim to discriminate between these parasite species. ssDNA amplicons and probes were analyzed separately using the "Mfold Web Server" simulating the secondary structure folding behaviour. The hybridisation of amplicon-probe was predicted by means of "Dinamelt Web Server". The results were evaluated considering the number of hydrogen bonds broken and formed in the simulated folding and hybridisation process, variance in gaps for each sequence and number of available bases. In the experimental part, thermally denatured PCR products were captured at the sensor interface via sandwich hybridisation with surface-tethered probes (thiolated probes) and biotinylated signalling probes. A convergence between analytical signals and simulated results was observed, indicating the possibility to use bioinformatic data for ssDNA probes selection to be incorporated in genosensors. (C) 2011 Elsevier B.V. All rights reserved.