Influence of the molecular weight in mechanical properties and degradation kinetics of chitosan inverted colloidal crystals

Tissue engineering arises from the need to regenerate organs and tissues, requiring the development of scaffolds, which can provide an optimum environment for tissue growth. In this work, chitosan with different molecular weights was used to develop biodegradable 3D inverted colloidal crystals (ICC) structures for bone regeneration, exhibiting uniform pore size and interconnected network. Moreover, in vitro tests were conducted by studying the influence of the molecular weight in the degradation kinetics and mechanical properties. The production of ICC included four major stages: fabrication of microspheres; assembly into a cohesive structure, polymeric solution infiltration and microsphere removal. Chitosan’s degree of deacetylation was determined by infrared spectroscopy and molecular weight was obtained via capillary viscometry. In order to understand the effect of the molecular weight in ICC structures, the mass loss and mechanical properties were analyzed after degradation with lysozyme. Structure morphology observation before and after degradation was performed by scanning electron microscopy. Cellular adhesion and proliferation tests were carried out to evaluate ICC in vitro response. Overall, medium molecular weight ICC revealed the best balance in terms of mechanical properties, degradation rate, morphology and biological behaviour.

Tailoring microstructure and physical properties of poly(vinylidene fluoride–hexafluoropropylene) porous films

This paper presents a systematic study for the production of poly(vinylidene fluoride-hexafluoropropylene), P(VDF-HFP), porous films using solvent evaporation (SE) and non-solvent induced phase separation (NIPS) techniques. Parameters such as volume fraction of the copolymer solution, film thickness, time exposure to air, non-solvent and temperature of the coagulation bath were investigated on the morphology, crystallization and mechanical properties of the samples. Films with different porous morphologies including homogeneous pore sizes, macrovoids and spherulites were obtained depending on the processing conditions, which in turn affect the wettability and mechanical properties of the material. Knowing that the phase content of the films also depends on the processing conditions, this paper shows that P(VDF-HFP) films with tailored porous morphology, electroactive phase content, hydrophobicity, cristallinity and mechanical properties can be achieved for a specific application using the adequate SE and NIPS techniques conditions.

Poly(vinylidene fluoride-trifluoroethylene) porous films: tailoring microstructure and physical properties by solvent casting strategies

A systematic study for the production of porous poly(vinylidene fluoride-trifluoroethylene), P(VDF-TrFE), films using solvent evaporation and non-solvent induced phase separation techniques is presented. Processing parameters such as copolymer volume fraction, solvent, preset exposure time to air before immersion, and non-solvent and temperature of the coagulation bath were varied and the corresponding sample morphology, hydrophobicity, thermal and mechanical properties were determined. Film morphologies including homogeneous pore distributions, micropores, microvoids, spherulites and non-porous films were obtained. The morphology variations strongly influence sample hydrophobicity and mechanical properties. All samples crystallize in the electroactive β-phase with a degree of crystallinity around 30 %.

In vitro mechanical fatigue behavior of poly-ε-caprolactone macroporous scaffolds for cartilage tissue engineering: Influence of pore filling by a poly(vinyl alcohol) gel

Polymeric scaffolds used in regenerative therapies are implanted in the damaged tissue and subjected to repeated loading cycles. In the case of articular cartilage engineering, an implanted scaffold is typically subjected to long term dynamic compression. The evolution of the mechanical properties of the scaffold during bioresorption has been deeply studied in the past, but the possibility of failure due to mechanical fatigue has not been properly addressed. Nevertheless, the macroporous scaffold is susceptible to failure after repeated loading-unloading cycles. In this work fatigue studies of polycaprolactone scaffolds were carried by subjecting the scaffold to repeated compression cycles in conditions simulating the scaffold implanted in the articular cartilage. The behaviour of the polycaprolactone sponge with the pores filled with a poly(vinyl alcohol) gel simulating the new formed tissue within the pores was compared with that of the material immersed in water. Results were analyzed with Morrow’s criteria for failure and accurate fittings are obtained just up to 200 loading cycles. It is also shown that the presence of poly(vinyl alcohol) increases the elastic modulus of the scaffolds, the effect being more pronounced with increasing the number of freeze/thawing cycles.

Ureasilicate hybrid coatings for corrosion protection of galvanized steel in chloride-contaminated simulated concrete pore solution

Organic-inorganic hybrid (OIH) sol-gel coatings based on ureasilicates (U(X)) have promising properties for use as eco-friendly coatings on hot dip galvanized steel (HDGS) and may be considered potential substitutes for pre-treatment systems containing Cr(VI). These OIH coatings reduce corrosion activity during the initial stages of contact of the HDGS samples with highly alkaline environments (cementitious media) and allow the mitigation of harmful effects of an initial excessive reaction between cement pastes and the zinc layer. However, the behavior of HDGS coated with U(X) in the presence of chloride ions has never been reported. In this paper, the performance of HDGS coated with five different U(X) coatings was assessed by electrochemical measurements in chloride-contaminated simulated concrete pore solution (SCPS). U(X) sol-gel coatings were produced and deposited on HDGS by a dip coating method. The coatings performance was evaluated by electrochemical impedance spectroscopy, potentiodynamic polarization curves measurements, macrocell current density and polarization resistance in contact with chloride-contaminated SCPS. The SEM/EDS analyses of the coatings before and after the tests were also performed. The results showed that the HDGS samples coated with the OIH coatings exhibited enhanced corrosion resistance to chloride ions when compared to uncoated galvanized steel.

Poly(ester-urethane) scaffolds: effect of structure on properties and osteogenic activity of stem cells

The present study aimed to investigate the effect of structure (design and porosity) on the matrix stiffness and osteogenic activity of stem cells cultured on poly(ester-urethane) (PEU) scaffolds. Different three-dimensional (3D) forms of scaffold were prepared from lysine-based PEU using traditional salt-leaching and advanced bioplotting techniques. The resulting scaffolds were characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), mercury porosimetry and mechanical testing. The scaffolds had various pore sizes with different designs, and all were thermally stable up to 300â °C. In vitrotests, carried out using rat bone marrow stem cells (BMSCs) for bone tissue engineering, demonstrated better viability and higher cell proliferation on bioplotted scaffolds compared to salt-leached ones, most probably due to their larger and interconnected pores and stiffer nature, as shown by higher compressive moduli, which were measured by compression testing. Similarly, SEM, von Kossa staining and EDX analyses indicated higher amounts of calcium deposition on bioplotted scaffolds during cell culture. It was concluded that the design with larger interconnected porosity and stiffness has an effect on the osteogenic activity of the stem cells.

Permeability properties of ENaC selectivity filter mutants.

The epithelial Na(+) channel (ENaC), located in the apical membrane of tight epithelia, allows vectorial Na(+) absorption. The amiloride-sensitive ENaC is highly selective for Na(+) and Li(+) ions. There is growing evidence that the short stretch of amino acid residues (preM2) preceding the putative second transmembrane domain M2 forms the outer channel pore with the amiloride binding site and the narrow ion-selective region of the pore. We have shown previously that mutations of the alphaS589 residue in the preM2 segment change the ion selectivity, making the channel permeant to K(+) ions. To understand the molecular basis of this important change in ionic selectivity, we have substituted alphaS589 with amino acids of different sizes and physicochemical properties. Here, we show that the molecular cutoff of the channel pore for inorganic and organic cations increases with the size of the amino acid residue at position alpha589, indicating that alphaS589 mutations enlarge the pore at the selectivity filter. Mutants with an increased permeability to large cations show a decrease in the ENaC unitary conductance of small cations such as Na(+) and Li(+). These findings demonstrate the critical role of the pore size at the alphaS589 residue for the selectivity properties of ENaC. Our data are consistent with the main chain carbonyl oxygens of the alphaS589 residues lining the channel pore at the selectivity filter with their side chain pointing away from the pore lumen. We propose that the alphaS589 side chain is oriented toward the subunit-subunit interface and that substitution of alphaS589 by larger residues increases the pore diameter by adding extra volume at the subunit-subunit interface.

On the cellular site of two-pore channel TPC1 action in the Poaceae.

The slow vacuolar (SV) channel has been characterized in different dicots by patch-clamp recordings. This channel represents the major cation conductance of the largest organelle in most plant cells. Studies with the tpc1-2 mutant of the model dicot plant Arabidopsis thaliana identified the SV channel as the product of the TPC1 gene. By contrast, research on rice and wheat TPC1 suggested that the monocot gene encodes a plasma membrane calcium-permeable channel. To explore the site of action of grass TPC1 channels, we expressed OsTPC1 from rice (Oryza sativa) and TaTPC1 from wheat (Triticum aestivum) in the background of the Arabidopsis tpc1-2 mutant. Cross-species tpc1 complementation and patch-clamping of vacuoles using Arabidopsis and rice tpc1 null mutants documented that both monocot TPC1 genes were capable of rescuing the SV channel deficit. Vacuoles from wild-type rice but not the tpc1 loss-of-function mutant harbor SV channels exhibiting the hallmark properties of dicot TPC1/SV channels. When expressed in human embryonic kidney (HEK293) cells OsTPC1 was targeted to Lysotracker-Red-positive organelles. The finding that the rice TPC1, just like those from the model plant Arabidopsis and even animal cells, is localized and active in lyso-vacuolar membranes associates this cation channel species with endomembrane function.

Numerical simulation of ambient seismic wavefield modification caused by pore-fluid effects in an oil reservoir

We have modeled numerically the seismic response of a poroelastic inclusion with properties applicable to an oil reservoir that interacts with an ambient wavefield. The model includes wave-induced fluid flow caused by pressure differences between mesoscopic-scale (i.e., in the order of centimeters to meters) heterogeneities. We used a viscoelastic approximation on the macroscopic scale to implement the attenuation and dispersion resulting from this mesoscopic-scale theory in numerical simulations of wave propagation on the kilometer scale. This upscaling method includes finite-element modeling of wave-induced fluid flow to determine effective seismic properties of the poroelastic media, such as attenuation of P- and S-waves. The fitted, equivalent, viscoelastic behavior is implemented in finite-difference wave propagation simulations. With this two-stage process, we model numerically the quasi-poroelastic wave-propagation on the kilometer scale and study the impact of fluid properties and fluid saturation on the modeled seismic amplitudes. In particular, we addressed the question of whether poroelastic effects within an oil reservoir may be a plausible explanation for low-frequency ambient wavefield modifications observed at oil fields in recent years. Our results indicate that ambient wavefield modification is expected to occur for oil reservoirs exhibiting high attenuation. Whether or not such modifications can be detected in surface recordings, however, will depend on acquisition design and noise mitigation processing as well as site-specific conditions, such as the geologic complexity of the subsurface, the nature of the ambient wavefield, and the amount of surface noise.

Short and long-term effects of tillage systems and nutrient sources on soil physical properties of a Southern Brazilian Hapludox

Soil tillage promotes changes in soil structure. The magnitude of the changes varies with the nature of the soil, tillage system and soil water content and decreases over time after tillage. The objective of this study was to evaluate short-term (one year period) and long-term (nine year period) effects of soil tillage and nutrient sources on some physical properties of a very clayey Hapludox. Five tillage systems were evaluated: no-till (NT), chisel plow + one secondary disking (CP), primary + two (secondary) diskings (CT), CT with burning of crop residues (CTb), and CT with removal of crop residues from the field (CTr), in combination with five nutrient sources: control without nutrient application (C); mineral fertilizers, according to technical recommendations for each crop (MF); 5 Mg ha-1 yr-1 of poultry litter (wetmatter) (PL); 60 m³ ha-1 yr-1 of cattle slurry (CS) and; 40 m³ ha-1 yr-1 of swine slurry (SS). Bulk density (BD), total porosity (TP), and parameters related to the water retention curve (macroporosity, mesoporosity and microporosity) were determined after nine years and at five sampling dates during the tenth year of the experiment. Soil physical properties were tillage and time-dependent. Tilled treatments increased total porosity and macroporosity, and reduced bulk density in the surface layer (0.00-0.05 m), but this effect decreased over time after tillage operations due to natural soil reconsolidation, since no external stress was applied in this period. Changes in pore size distribution were more pronounced in larger and medium pore diameter classes. The bulk density was greatest in intermediate layers in all tillage treatments (0.05-0.10 and 0.12-0.17 m) and decreased down to the deepest layer (0.27-0.32 m), indicating a more compacted layer around 0.05-0.20 m. Nutrient sources did not significantly affect soil physical and hydraulic properties studied.

Physical properties of a rhodic haplustox under two sugarcane harvesting systems

This study had the purpose of evaluating the effects of two management types of sugarcane: harvesting of burnt cane (BCH) and mechanized harvesting of unburnt green cane (MCH), on some soil physical properties of a dystrophic Rhodic Haplustox. The data were then compared with results for the same soil type under native forest. A completely randomized design was used, with three treatments and 20 replications. The following characteristics were determined: organic matter, aggregate stability, soil bulk density, and porosity at depths of 0-0.20 m and soil penetration resistance. After 15 years of cultivation, there were some alterations in the soil under cane burnt before harvesting, evidenced by a drop in the weighted average diameter of stable aggregates in water and increased soil bulk density. Significant changes were also detected in total porosity and pore distribution under both harvesting systems. Critical values for penetration resistance were observed in the area under mechanized sugar cane harvesting, with a value of 4.5 MPa in the 40-55 cm layer. This value is considered high and could indicate compaction and restriction of root growth. Soil properties under the green cane (unburned) management system were closest to those of the soil under native forest.

Uncertainties in the prediction of spatial variability of soil CO2 emissions and related properties

The soil CO2 emission has high spatial variability because it depends strongly on soil properties. The purpose of this study was to (i) characterize the spatial variability of soil respiration and related properties, (ii) evaluate the accuracy of results of the ordinary kriging method and sequential Gaussian simulation, and (iii) evaluate the uncertainty in predicting the spatial variability of soil CO2 emission and other properties using sequential Gaussian simulations. The study was conducted in a sugarcane area, using a regular sampling grid with 141 points, where soil CO2 emission, soil temperature, air-filled pore space, soil organic matter and soil bulk density were evaluated. All variables showed spatial dependence structure. The soil CO2 emission was positively correlated with organic matter (r = 0.25, p < 0.05) and air-filled pore space (r = 0.27, p < 0.01) and negatively with soil bulk density (r = -0.41, p < 0.01). However, when the estimated spatial values were considered, the air-filled pore space was the variable mainly responsible for the spatial characteristics of soil respiration, with a correlation of 0.26 (p < 0.01). For all variables, individual simulations represented the cumulative distribution functions and variograms better than ordinary kriging and E-type estimates. The greatest uncertainties in predicting soil CO2 emission were associated with areas with the highest estimated values, which produced estimates from 0.18 to 1.85 t CO2 ha-1, according to the different scenarios considered. The knowledge of the uncertainties generated by the different scenarios can be used in inventories of greenhouse gases, to provide conservative estimates of the potential emission of these gases.

Physical properties of a Red-Yellow Latosol and productivity of a signalgrass pasture fertilized with increasing nitrogen doses

The physical properties and fertility of the soil are important factors in the formation and establishment of pasture. Changes in physical properties affect the movement of water, air, nutrients and roots, which, in turn, affect the productivity and longevity of pastures. The objective of this study was to evaluate the physical properties of the soil and the dry matter yield of a pasture with signalgrass cv. Basilisk (Brachiaria decumbens cv. Basilisk), fertilized with increasing nitrogen doses (N), on a dystrophic Red-Yellow Latosol. The experiment was conducted on the Fazenda Rio Manso of the Universidade Federal dos Vales do Jequitinhonha e Mucuri, in Couto de Magalhães de Minas, State of Minas Gerais, Brazil. To evaluate the annual forage yield, a split plot scheme in a randomized block design with four replications was used, with N doses (0, 50, 100, 150, and 200 kg/ha/year) in the plots and growing seasons (first and second) in the subplots. For soil evaluation, a split plot scheme was used with N doses (0, 25, 50, 75 and 100 kg/ha/cut) in the plots and three sampling times (prior to the experiment, at the end of the first growing season and at the end of the second growing season) in the subplots in a randomized block design with four replications. This analysis was performed separately at two soil depths (0-3 and 10-13 cm). Forage samples were analyzed for the annual dry matter yield (DMY), and soil samples were analyzed for pre-consolidation pressure (σp), initial soil bulk density (Bd), total pore volume (TPV) and void index (Vd). Higher nitrogen doses increased the dry matter yield of signalgrass pasture and the pre-consolidation pressure of the soil. The total pore volume and void index decreased, and the initial soil bulk density increased, though without promoting soil compaction.

Stabilization of soil hydraulic properties under a long term no-till system

The area under the no-tillage system (NT) has been increasing over the last few years. Some authors indicate that stabilization of soil physical properties is reached after some years under NT while other authors debate this. The objective of this study was to determine the effect of the last crop in the rotation sequence (1st year: maize, 2nd year: soybean, 3rd year: wheat/soybean) on soil pore configuration and hydraulic properties in two different soils (site 1: loam, site 2: sandy loam) from the Argentinean Pampas region under long-term NT treatments in order to determine if stabilization of soil physical properties is reached apart from a specific time in the crop sequence. In addition, we compared two procedures for evaluating water-conducting macroporosities, and evaluated the efficiency of the pedotransfer function ROSETTA in estimating the parameters of the van Genuchten-Mualem (VGM) model in these soils. Soil pore configuration and hydraulic properties were not stable and changed according to the crop sequence and the last crop grown in both sites. For both sites, saturated hydraulic conductivity, K0, water-conducting macroporosity, εma, and flow-weighted mean pore radius, R0ma, increased from the 1st to the 2nd year of the crop sequence, and this was attributed to the creation of water-conducting macropores by the maize roots. The VGM model adequately described the water retention curve (WRC) for these soils, but not the hydraulic conductivity (K) vs tension (h) curve. The ROSETTA function failed in the estimation of these parameters. In summary, mean values of K0 ranged from 0.74 to 3.88 cm h-1. In studies on NT effects on soil physical properties, the crop effect must be considered.

EFFECTS OF COMPACTION DUE TO MACHINERY TRAFFIC ON SOIL PORE CONFIGURATION

Soil compaction has been recognized as a severe problem in mechanized agriculture and has an influence on many soil properties and processes. Yet, there are few studies on the long-term effects of soil compaction, and the development of soil compaction has been shown through a limited number of soil parameters. The objectives of this study were to evaluate the persistence of soil compaction effects (three traffic treatments: T0, without traffic; T3, three tractor passes; and T5, five tractor passes) on pore system configuration, through static and dynamic determinations; and to determine changes in soil pore orientation due to soil compaction through measurement of hydraulic conductivity of saturated soil in samples taken vertically and horizontally. Traffic led to persistent changes in all the dynamic indicators studied (saturated hydraulic conductivity, K0; effective macro- and mesoporosity, εma and εme), with significantly lower values of K0, εma, and εme in the T5 treatment. The static indicators of bulk density (BD), derived total porosity (TP), and total macroporosity (θma) did not vary significantly among the treatments. This means that machine traffic did not produce persistent changes on these variables after two years. However, the orientation of the soil pore system was modified by traffic. Even in T0, there were greater changes in K0 measured in the samples taken vertically than horizontally, which was more related to the presence of vertical biopores, and to isotropy of K0 in the treatments with machine traffic. Overall, the results showed that dynamic indicators are more sensitive to the effects of compaction and that, in the future, static indicators should not be used as compaction indicators without being complemented by dynamic indicators.