Biocatalytic synthesis of polypyrrole powder, colloids, and films using horseradish peroxidase

Polypyrrole was synthesized in high yield by a biocatalytic method in mild aqueous media using hydrogen peroxide as oxidizer. A redox mediator, 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) diammonium salt, was used to oxidize the pyrrole. ABTS is a very effective peroxidase substrate, which was enzymatically oxidized to generate a radical cation that in turn was able to chemically oxidize pyrrole. This indirect biocatalytic method was implemented because pyrrole is not a substrate of horseradish peroxidase, however, the polymerization process was successfully optimized and later adapted to prepare also polypyrrole thin films and water dispersible polypyrrole colloids. The polypyrrole powder and colloids were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, electrical conductivity, and thermogravimetric analysis. In addition, the deposition of the polypyrrole thin film was monitored using a quartz-crystal microbalance and its morphology studied by optical and scanning electron microscopy. The biocatalytic polymerization of pyrrole results in a polymer spectroscopically very similar to chemically synthesized polypyrrole.     

Synthesis and evaluation of the potential deleterious effects of ZnO nanomaterials (nanoneedles and nanoflowers) on blood components,including albumin,erythrocytes and human isolated primary neutrophils

The application of zinc oxide (ZnO) nanoparticles in biomaterials has increased significantly in the recent years. Here, we aimed to study the potential deleterious effects of ZnO on blood components, including human serum albumin (HSA), erythrocytes and human isolated primary neutrophils. To test the influence of the morphology of the nanomaterials, ZnO nanoneedles (ZnO-nn) and nanoflowers (ZnO-nf) were synthesized. The zeta potential and mean size of ZnO-nf and ZnO-nn suspensions in phosphate-buffered saline were ?10.73 mV and 3.81 nm and ?5.27 mV and 18.26 nm, respectively. The incubation of ZnO with HSA did not cause its denaturation as verified by the absence of significant alterations in the intrinsic and extrinsic fluorescence and in the circular dichroism spectrum of the protein. The capacity of HSA as a drug carrier was not affected as verified by employing site I and II fluorescent markers. Neither type of ZnO was able to provoke the activation of neutrophils, as verified by lucigenin- and luminol-dependent chemiluminescence and by the extracellular release of hydrogen peroxide. ZnO-nf, but not ZnO-nn, induced the haemolysis of erythrocytes. In conclusion, our results reinforce the concept that ZnO nanomaterials are relatively safe for usage in biomaterials. A potential exception is the capacity of ZnO-nf to promote the lysis of erythrocytes, a discovery that shows the importance of the morphology in the toxicity of nanoparticles.     

Effect of EVA copolymer containing different VA content on the thermal and rheological properties of bio-based high-density polyethylene/ethylene vinyl acetate blends

The effect of ethylene vinyl acetate (EVA) concentration and vinyl acetate (VA) content of EVA on the mechanical, morphological, and rheological properties of bio-based high-density polyethylene (BioPE)/EVA blends was investigated. The blends were characterized by X-ray diffraction, differential scanning calorimetry, scanning electron microscopy, and rheological measurements under oscillatory shear flow. The degree of crystallinity of BioPE decreased with the increase in the EVA concentration and was unaffected with the increase in the VA content. DMTA results showed a decrease in the storage modulus (E′) with the increase in EVA content and that the BioPE/EVA19 blends showed higher E′ values than BioPE/EVA28 blend. The impact strength substantially increased with the addition of EVA concentration above 5 mass% and was higher for the blends containing the highest VA content. The blends containing a higher content of VA exhibited the higher EVA dispersed phase domain size, which increased with the increase in EVA concentration. The complex viscosity increased with the increase in the EVA content, being higher for the BioPE/EVA blends containing higher VA content. The storage modulus increased, at low frequencies, with the increase in the EVA content and can be ascribed to the increase in the EVA dispersed phase domain size.

     

Identification of the Active Principle Conferring Anti-Inflammatory and Antinociceptive Properties in Bamboo Plant

Early plants began colonizing earth about 450 million years ago. During the process of coevolution, their metabolic cellular pathways produced a myriad of natural chemicals, many of which remain uncharacterized biologically. Popular preparations containing some of these molecules have been used medicinally for thousands of years. In Brazilian folk medicine, plant extracts from the bamboo plant Guadua paniculata Munro have been used for the treatment of infections and pain. However, the chemical basis of these therapeutic effects has not yet been identified. Here, we performed protein biochemistry and downstream pharmacological assays to determine the mechanisms underlying the anti-inflammatory and antinociceptive effects of an aqueous extract of the G. paniculata rhizome, which we termed AqGP. The anti-inflammatory and antinociceptive effects of AqGP were assessed in mice. We identified and purified a protein (AgGP), with an amino acid sequence similar to that of thaumatins (~20 kDa), capable of repressing inflammation through downregulation of neutrophil recruitment and of decreasing hyperalgesia in mice. In conclusion, we have identified the molecule and the molecular mechanism responsible for the anti-inflammatory and antinociceptive properties of a plant commonly used in Brazilian folk medicine.     

Monitoring thermal,structural properties,methotrexate release and biological activity from biocompatible spray-dried microparticles

Boron phosphates (BPs) with different acidities were prepared by regulating the calcination temperatures for the reaction products of boric acid and phosphoric acid. The crystal structure, morphology, surface acidity, and thermal stability were characterized by X-ray diffraction, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), chemical absorbed apparatus, and thermogravimetric analysis (TG). The effects of BPs on the combustion behavior and catalyzing the carbonization of bisphenol-A epoxy resin (EP) were investigated by the limiting oxygen index (LOI) and cone calorimetry test. Upon loading 5 mass% BP prepared at 300 °C, the LOI value of the EP/BP composites increased to 29.6%, and moreover, the peak heat release rate and average specific extinction area decreased by 43 and 25%, respectively. A possible catalyzing carbonization mechanism was explored by TG coupled with Fourier transform infrared spectroscopy (TG–FTIR), TG, FTIR, SEM, Raman spectroscopy (Raman), and XPS. The results demonstrated that BP catalyzed EP to degrade at relatively low temperature, and the yield, compactness, and graphitization degree of the char residue were obviously enhanced with an increase in the ratio of Brønsted and Lewis acid sites (B/L value) and the total surface acid sites on the BP surface. Therefore, the catalyzing carbonization flame retardancy of the EP/BP composites can be improved through regulating the surface acidity of BP.     

Bidder's organ of Bufo ictericus: a light and electron microscopy analysis

Male toads of the Bufonidae Family have rudimentary ovaries designated Bidder's organs, and if the testes are removed this organ develops into a functional ovary, representing a morphological strategy for the reproduction of the species. The Bidder's organ of Bufo ictericus was examined using routine and histochemical techniques by light microscopy and transmission electron microscopy. Each Bidder's organ presented a typical ovarian morphology, being composed of a cortex and a medulla. Bidderian follicles in different stages of development were visualized in the cortex, where they are better developed. The germ cells exhibit a large oocyte with a round-shaped nucleus. The Bidderian follicles are supported by a loose net of reticular fibers. In the medullar region, collagen fibers were immersed in the matrix rich in blood vessels that also contained a small quantity of neutral glycoproteins rich in hexose and/or sialic acid and carboxylated polymers with a characteristic distribution of glycosaminoglycans. The oocyte and the follicular cells were separated by a narrow space containing microvilli. The oocyte exhibit a well developed smooth endoplasmic reticulum, a poorly developed Golgi apparatus, and occasional lysosomes. Concentric cisternal complexes are often visualized; however, their morphological significance remains unclear. The peroxisomes display a fine granular matrix without a crystalline core, with a weak 3,3′-diaminobenzidine-reaction. Intimate association between peroxisomes, peroxisomes and lipid inclusions was observed in the oocyte, suggesting its participation in yolk metabolism.     

Transport properties of a 2DEG in the presence of tilted magnetic field: the influence of a 1D modulation

The effect of 1D periodic modulation on the transport and thermodynamic properties of a non-interacting two-dimensional electron gas (2DEG) is investigated. The Hamiltonian used also includes a tilted magnetic field, Rashba, and Dresselhauss spin-orbit interactions. The 1D periodic modulation introduces non-quantized regions on Hall conductivity and a non-zero diffusive conductivity. A method to estimate the modulation periodicity is given using the periodicity of Weiss oscillations on the diffusive conductivity.     

A novel antinociceptive sulphated polysaccharide of the brown marine alga Spatoglossum schroederi

Sulfated polysaccharides (SP) of brown algae (Phaeophyta) are composed mainly of alpha- L-fucose, being classified as fucans, with recognized role in inflammation but not in nociception, which was already described for SP obtained from red algae. Here the SP of the brown marine alga S. schroederi (named Ss-SP) was isolated and assayed for the antinociceptive effect. Ss-SP was isolated by DEAE-cellulose, analyzed by agarose gel electrophoresis and evaluated in nociception models (Formalin, Hot plate, Von Frey) using Swiss mice (20-25g). Anion exchange chromatography provided four major fractions being F1 (Ss-SP) that of highest metachromatic activity and sugar content. Ss-SP inhibited both phases of the formalin test. In the first phase the paw licking (55.2 +/- 8.07s) was reduced by 45% (30.5 +/- 6.51s) and 40% (32.85 +/- 8.66s) at 0.1 and 1 mg/kg, respectively. In the second phase, Ss-SP was also inhibitory about 39%, but only at 1 mg/kg (83.0 +/- 15.70s) compared to formalin (136.8 +/- 10.27s). This inhibitory effect suggests a mixed mechanism similar to morphine, which was not confirmed in the hot plate test, a model of pain associated with central neurotransmission. However, Ss-SP reduced the animal reaction in response to stimulation withVon Frey filament at the 2nd and 3rd h (20.8 +/- 6.86% versus carrageenan: 47.9 +/- 5.83%; 33.3 +/- 7.71% versus carrageenan: 62.5 +/- 9.83%). Accordingly, the paw edema induced by carrageenan (0.08 +/- 0.01g) was potently reduced in 45.35% by Ss-SP pre-treatment (0.02 +/- 0.003g), corroborating the anti-inflammatory activity demonstrated for brown seaweed polysaccharides. In conclusion our data revealed for the first time the antinociceptive effect of Ss-SP which could be used as a new source of analgesic substances.     

Study of degradation kinetics of sunflower oil on H-Beta zeolite

In this study, were studied the degradation of pure sunflower oil and mixed with H-Beta zeolite. This zeolite was synthesized by the hydrothermal method, followed by calcination and ion exchanged. The characterization of the zeolite was performed by X-ray diffraction and nitrogen adsorption/desorption by the method of BET. The analysis showed that H-Beta zeolite presented a good crystallinity and the template was completely removed from the catalyst. The thermal and catalytic degradation study was carried out using the TG/DTG method in multiple heating rates of 5, 10, and 20 °C min⁻¹. The isoconversion method proposed by Vyazovkin was applied to determine the kinetic parameters for degradation of the sunflower oil. The activation energy for the degradation process of pure sunflower oil was 193 kJ mol⁻¹, while for sunflower oil mixed with 20% of H-Beta zeolite was equivalent to 88 kJ mol⁻¹. It was verified that for the degradation of 90% of the sunflower oil mixed with H-Beta, for a period of 1 h, a temperature of 356 °C was required, whereas for the pure vegetable oil, this value was of 387 °C, at the same time period, showing that the catalyst was effective for the degradation process of sunflower oil.     

The piecewise linear optimization polytope: new inequalities and intersection with semi-continuous constraints

We give new facets and valid inequalities for the separable piecewise linear optimization (SPLO) knapsack polytope. We also extend the inequalities to the case in which some of the variables are semi-continuous. Finally, we give computational results that demonstrate their efficiency in solving difficult instances of SPLO and SPLO with semi-continuous constraints.