RESUMO

The design of hydrogels based on natural polymers that have modulation of antibacterial capacity, ideal performance in release capacity of encapsulated drugs, and desired bioactivity for applications in wound healing represents a modern trend in biomaterials. In this work, novel hydrogels of semi-interpenetrating polymeric networks based on collagen and xanthan gum (XG) were investigated. The linear chains of XG can semi-interpenetrate inside to matrix of crosslinked collagen with polyurethane under physiological conditions, generating amorphous surfaces with fibrillar-granular reliefs that have accelerated gelation time (about 15 min), super water absorption (up to 3100%) and high inhibition capacity of pathogenic bacteria such asEscherichia coli(up to 100% compared to amoxicillin at 20 ppm). The increment of XG in the hydrogel (up to 20 wt.%) allows for improvement in the storage module, resistance to thermal degradation, slow the rate of hydrolytic and proteolytic degradation, allowing to encapsulate and controlled release of molecules such as ketorolac and methylene blue; besides, it shows to keep the metabolic activity of fibroblasts and monocytes at 48 h of evaluation, without observing cytotoxic effects. The bioactivity of these hydrogels is improved since they have excellent hemocompatibility and enhanced cell proliferation. Specifically, the hydrogel with 20 wt.% of XG shows to decrease the production of tumor necrosis factor-αand CCL-2 cytokines, increasing the production of transforming growth factor-ßin human monocytes, which could be used to modulate inflammation and regenerative capacity in wound healing strategies.

Assuntos

RESUMO

The preparation of hydrogels based on biopolymers like collagen and gum arabic gives a chance to provide novel options that can be used in biomedical field. Through a polymeric semi-interpenetration technique, collagen-based polymeric matrices can be associated with gum arabic while controlling its physicochemical and biological properties. To create novel hydrogels with their potential use in the treatment of wounds, the semi-interpenetration process, altering the concentration (0-40% by wt) of gum arabic in a collagen matrix is explored. The ability of gum arabic to create intermolecular hydrogen bonds in the collagen matrix enables the development of semi-interpenetrating polymeric networks (semi-IPN)-based hydrogels with a faster gelation time and higher crosslinking. Amorphous granular surfaces with linked porosity are present in matrices with 30% (by wt) of gum arabic, enhancing the storage modulus and thermal degradation resistance. The hydrogels swell to very high extent in hydrolytic and proteolytic environments, good hemocompatibility, and suppression of growth of pathogens like E. coli, and all it is enhanced by gum arabic included them, in addition to enabling the controlled release of ketorolac. The chemical composition of theses semi-IPN matrices have no deleterious effects on monocytes or fibroblasts, promoting their proliferation, and lowering alpha tumor necrosis factor (α-TNF) secretion in human monocytes.

RESUMO

The interest in the Coordinative Chain Transfer Polymerization (CCTP) of a family of naturally occurring hydrocarbon monomers, namely terpenes, for the production of high-performance rubbers is increasing year by year. In this work, the synthesis of poly(ß-myrcene) via CCTP is introduced, using neodymium versatate (NdV3), diisobutylaluminum hydrade (DIBAH) as the catalytic system and dimethyldichlorosilane (Me2SiCl2) as the activator. A bimodal distribution in the GPC signal reveals the presence of two populations at low conversions, attributable to dormants (arising from reversible chain transfer reactions) and dead chains (arising from termination and irreversible chain transfer reactions); a unimodal distribution is generated at medium and high conversions, corresponding to the dominant species, the dormant chains. Additionally, a mathematical kinetic model was developed based on the Method of Moments to study a set of selected experiments: ([ß-myrcene]0:[NdV3]0:[DIBAH]0:[Me2SiCl2]0 = 660:1:2:1, 885:1:2:1, and 533:1:2:1). In order to estimate the kinetic rate constant of the systems, a minimization of the sum of squared errors (SSE) between the model predicted values and the experimental measurements was carried out, resulting in an excellent fit. A set of the Arrhenius parameters were estimated for the ratio [ß-myrcene]0:[NdV3]0:[DIBAH]0:[Me2SiCl2]0 = 660:1:2:1 in a temperature range between 50 to 70 °C. While the end-group functionality (EGF) was predominantly preserved as the ratio [ß-myrcene]0:[NdV3]0 was decreased, higher catalytic activity was obtained with a high ratio.

RESUMO

Use of multi-wall carbon nanotubes (MWCNTs) in external layers (A-layers) of ABA-trilayer polypropylene films was investigated, with the purpose of determining intrinsic and extrinsic factors that could lead to antistatic behavior of transparent films. The incorporation of 0.01, 0.1, and 1 wt % of MWCTNs in the A-layers was done by dilution through the masterbatch method. Masterbatches were fabricated using isotactic polypropylene (iPP) with different melt flow indexes 2.5, 34, and 1200 g/10 min, and using different ultrasound assist methods. It was found that films containing MWCNTs show surface electrical resistivity of 1012 and 1016 Ω/sq, regardless of the iPP melt flow index (MFI) and masterbatch fabrication method. However, electrostatic charge was found to depend upon the iPP MFI, the ultrasound assist method and MWCNT concentration. A percolation electron transport mechanism was determined most likely responsible for this behavior. Optical properties for films containing MWCNTs do not show significant differences compared to the reference film at MWCNT concentrations below 0.1 wt %. However, an enhancement in brightness was observed, and it was attributed to ordered iPP molecules wrapping the MWCNTs. Bright transparent films with low electrostatic charge were obtained even for MWCNTs concentrations as low as 0.01 wt %.

RESUMO

Metamaterial behavior of polymer nanocomposites (NCs) based on isotactic polypropylene (iPP) and multi-walled carbon nanotubes (MWCNTs) was investigated based on the observation of a negative dielectric constant (ε'). It is demonstrated that as the dielectric constant switches from negative to positive, the plasma frequency (ωp) depends strongly on the ultrasound-assisted fabrication method, as well as on the melt flow index of the iPP. NCs were fabricated using ultrasound-assisted extrusion methods with 10 wt % loadings of MWCNTs in iPPs with different melt flow indices (MFI). AC electrical conductivity (σ(AC)) as a function of frequency was determined to complement the electrical classification of the NCs, which were previously designated as insulating (I), static-dissipative (SD), and conductive (C) materials. It was found that the SD and C materials can also be classified as metamaterials (M). This type of behavior emerges from the negative dielectric constant observed at low frequencies although, at certain frequencies, the dielectric constant becomes positive. Our method of fabrication allows for the preparation of metamaterials with tunable ωp. iPP pure samples show only positive dielectric constants. Electrical conductivity increases in all cases with the addition of MWCNTs with the largest increases observed for samples with the highest MFI. A relationship between MFI and the fabrication method, with respect to electrical properties, is reported.

RESUMO

Miniemulsion polymerization was used as the synthetic method to produce clay/poly(methyl methacrylate) nanocomposites. Two kinds of interfacial interactions clay-polymer particle were observed by electron microscopy, one where the polymer particles are adhered on the surface of the larger fragments of clay, and another where nanometric fragments of clay are encapsulated by polymer particles. Variations in the glass transition temperature (T(g)) and thermomechanical properties of the matrix, as function of clay content, were observed. In particular, at the highest clay loading (1.0 wt%) depression of T(g) and thermomechanical properties were observed. The increased clay-polymer matrix interfacial area appears to be the conditioning factor that determines such behavior.

Assuntos