Effect of the degree of porosity on the performance of poly(vinylidene fluoride-trifluoroethylene)/poly(ethylene oxide) blend membranes for lithium-ion battery separators

Porous polymer membranes based on poly(vinylidene fluoride-trifluoroethylene)/poly(ethylene oxide) copolymers, P(VDF-TrFE)/PEO, are prepared through the, from partial to total, elimination of PEO, leading to interconnected micropores in the polymer blends. Electrolyte uptake, thermal and mechanical properties depend on the amount of PEO present in the polymer blend. Further, the degree of crystallinity of PEO and the elastic modulus (E´) of the polymer blend decrease with increasing PEO removal. Electrical properties of the polymer blend membranes are influenced by the porosity and are dominated by diffusion. The temperature dependence of ionic conductivity follows the Arrhenius behavior. It is the highest for the membranes with a volume fraction of pores of 44% (i.e, 90% PEO removal), reaching a value of 0.54 mS.cm-1 at room temperature. Battery performance was determined by assembling Li/C-LiFePO4 swagelok cells. The polymer blends with 90% PEO removal exhibit rate (124 mAhg-1 at C/5 and 47 mAhg-1 at 2C) and cycling capabilities suitable for lithium ion battery applications.

Modulation of the secretome of hBMSCs by tailoring the macromolecular gradient in hydrogels to generate tissue-to-tissue interfaces

Tissue-to-tissue interfaces are commonly present in all tissues exhibiting structural, biological and chemical gradients serving a wide range of physiological functions. These interfaces are responsible for mediation of load transfer between two adjacent tissues. They are also important structures in sustaining the cellular communications to retain tissueâ s functional integration and homeostasis. [1] All cells have the capacity to sense and respond to physical and chemical stimulus and when cultured in three-dimensional (3D) environments they tend to perform their function better than in two-dimensional (2D) environments. Spatial and temporal 3D gradient hydrogels better resemble the natural environment of cells in mimicking their extracellular matrix. [2] In this study we hypothesize that differential functional properties can be engineered by modulation of macromolecule gradients in a cell seeded threedimensional hydrogel system. Specifically, differential paracrine secretory profiles can be engineered using human Bone Marrow Stem Cells (hBMSCâ s). Hence, the specific objectives of this study are to: assemble the macromolecular gradient hydrogels to evaluate the suitablity for hBMSCâ s encapsulation by cellular viability and biofunctionality by assessing the paracrine secretion of hBMSCâ s over time. The gradient hydrogels solutions were prepared by blend of macromolecules in one solution such as hyaluronic (HA) acid and collagen (Col) at different ratios. The gradient hydrogels were fabricated into cylindrical silicon moulds with higher ratio solutions assembled at the bottom of the mould and adding the two solutions consecutively on top of each other. The labelling of the macromolecules was performed to confirm the gradient through fluorescence microscopy. Additionally, AFM was conducted to assess the gradient hydrogels stiffness. Gradient hydrogels characterization was performed by HA and Col degradation assay, degree of crosslinking and stability. hBMSCâ s at P3 were encapsulated into each batch solution at 106 cells/ml solution and gradient hydrogels were produced as previously described. The hBMSCâ s were observed under confocal microscopy to assess viability by Live/Dead® staining. Cellular behaviour concerning proliferation and matrix deposition was also performed. Secretory cytokine measurement for pro-inflammatory and angiogenesis factors was carried out using ELISA. At genomic level, qPCR was carried out. The 3D gradient hydrogels platform made of different macromolecules showed to be a suitable environment for hBMSCâ s. The hBMSCâ s gradient hydrogels supported high cell survival and exhibited biofunctionality. Besides, the 3D gradient hydrogels demonstrated differentially secretion of pro-inflammatory and angiogenic factors by the encapsulated hBMSCâ s. References: 1. Mikos, AG. et al., Engineering complex tissues. Tissue Engineering 12,3307, 2006 2. Phillips, JE. et al., Proc Natl Acad Sci USA, 26:12170-5, 2008

Measurement of Spin Correlation in Top-Antitop Quark Events and Search for Top Squark Pair Production in pp Collisions at s√=8 TeV Using the ATLAS Detector

A measurement of spin correlation in tt¯ production is presented using data collected with the ATLAS detector at the Large Hadron Collider in proton-proton collisions at a center-of-mass energy of 8 TeV, corresponding to an integrated luminosity of 20.3 fb−1. The correlation between the top and antitop quark spins is extracted from dilepton tt¯ events by using the difference in azimuthal angle between the two charged leptons in the laboratory frame. In the helicity basis the measured degree of correlation corresponds to Ahelicity=0.38±0.04, in agreement with the Standard Model prediction. A search is performed for pair production of top squarks with masses close to the top quark mass decaying to predominantly right-handed top quarks and a light neutralino, the lightest supersymmetric particle. Top squarks with masses between the top quark mass and 191 GeV are excluded at the 95% confidence level.

Cross-language influences on new second language vocabulary acquisition: the effect of learning method

Dissertação de mestrado integrado em Psicologia

The role of deviant-letter position in cognate word processing

Dissertação de mestrado integrado em Psicologia

Bimodal information increases spontaneous interpersonal synchronization of goal directed upper limb movements

When interacting with each other, people often synchronize spontaneously their movements, e.g. during pendulum swinging, chair rocking[5], walking [4][7], and when executing periodic forearm movements[3].Although the spatiotemporal information that establishes the coupling, leading to synchronization, might be provided by several perceptual systems, the systematic study of different sensory modalities contribution is widely neglected. Considering a) differences in the sensory dominance on the spatial and temporal dimension[5] , b) different cue combination and integration strategies [1][2], and c) that sensory information might provide different aspects of the same event, synchronization should be moderated by the type of sensory modality. Here, 9 naïve participants placed a bottle periodically between two target zones, 40 times, in 12 conditions while sitting in front of a confederate executing the same task. The participant could a) see and hear, b) see , c) hear the confederate, d) or audiovisual information about the movements of the confederate was absent. The couple started in 3 different relative positions (i.e., in-phase, anti-phase, out of phase). A retro-reflective marker was attached to the top of the bottles. Bottle displacement was captured by a motion capture system. We analyzed the variability of the continuous relative phase reflecting the degree of synchronization. Results indicate the emergence of spontaneous synchronization, an increase with bimodal information, and an influence of the initial phase relation on the particular synchronization pattern. Results have theoretical implication for studying cue combination in interpersonal coordination and are consistent with coupled oscillator models.

Thermal characterization of polyhydroxyalkanoates and poly(lactic acid) blends obtained by injection molding

In this work we present the thermal characterization of the full scope of polyhydroxyalcanoate and poly(lactic acid) blends obtain by injection molding. Blends of polyhydroxyalcanoate and poly(lactic acid) (PHA/PLA) were prepared in different compositions ranging from 0–100% in steps of 10%. The blends were injection molded and then characterized by differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and wide angle X-ray diffraction (WAXD). The increment of PHA fraction increased the degree of crystallinity of the blend and the miscibility of the base polymers as verified by the Fox model. The WAXD analysis indicates that the presence of PHA hindered the PLA crystallization. The crystallization evolution trough PHA weight fraction (wf) shows a phase inversion around 50-60%. SEM analyses confirmed that the miscibility of PHA/PLA blends increased with the incorporation of PHA and became total for values of PHA higher that 50%.

Nonsolvent induced phase separation preparation of poly(vinylidene fluoride-co-chlorotrifluoroethylene) membranes with tailored morphology, piezoelectric phase content and mechanical properties

Poly(vinylidene fluoride-co-chlorotrifluoroethylene) – P(VDF-CTFE) membranes are increasingly interesting for a wide range of applications, including battery separators, filtration membranes and biomedical applications. This work reports on the morphology, hydrophobicity, thermal and mechanical properties variation of P(VDF-CTFE) membranes processed by nonsolvent induced phase separation technique (NIPS) as a function of the main processing parameters. All membranes show a porous structure composed of large spherulites, (interconnected) micropores and/or microvoids depending on the processing conditions used that in turn affect their hydrophobicity and mechanical properties. The degree of crystallinity of the membranes remains approximately constant with a value of about 15 %, except for the membranes immediately immersed in ethanol, which is of about 23 %. In turn, the crystalline phases present in the copolymer is mainly affected by the temperature and nonsolvent characteristics of the coagulation bath, the β-phase content ranging from 33 to 100 %, depending on those processing parameters. It was show that the temperature of water-based coagulation bath plays an important role in order to produce structurally uniform and homogeneous porous membranes, which is particularly important from the point of view of technological applications.

Variation of the physicochemical and morphological characteristics of solvent casted poly(vinylidene fluoride) along its binary phase diagram with dimethylformamide

Poly(vinylidene fluoride), PVDF, films and membranes were prepared by solvent casting from dimethylformamide, DMF, by systematically varying polymer/solvent ratio and solvent evaporation temperature. The effect of the processing conditions on the morphology, degree of porosity, mechanical and thermal properties and crystalline phase of the polymer were evaluated. The obtained microstructure is explained by the Flory-Huggins theory. For the binary system, the porous membrane formation is attributed to a spinodal decomposition of the liquid-liquid phase separation. The morphological features were simulated through the correlation between the Gibbs total free energy and the Flory-Huggins theory. This correlation allowed the calculation of the PVDF/DMF phase diagram and the evolution of the microstructure in different regions of the phase diagram. Varying preparation conditions allow tailoring polymer 2 microstructure while maintaining a high degree of crystallinity and a large β crystalline phase content. Further, the membranes show adequate mechanical properties for applications in filtration or battery separator membranes.

Influence of oxygen plasma treatment parameters on poly(vinylidene fluoride) electrospun fiber mats wettability

Electrospun poly(vinylidene fluoride) (PVDF) fiber mats find applications in an increasing number of areas, such as battery separators, filtration and detection membranes, due to their excellent properties. However, there are limitations due to the hydrophobic nature and low surface energy of PVDF. In this work, oxygen plasma treatment has been applied in order to modify the surface wettability of PVDF fiber mats and superhydrophilic PVDF electrospun membranes have been obtained. Further, plasma treatment does not significantly influences fiber average size (~400 ± 200 nm), morphology, electroactive -phase content (~80-85%) or the degree of crystallinity (Xc of 42 ± 2%), allowing to maintain the excellent physical-chemical characteristics of PVDF. Plasma treatment mainly induces surface chemistry modifications, such as the introduction of oxygen and release of fluorine atoms that significantly changes polymer membrane wettability by a reduction of the contact angle of the polymer fibers and an overall decrease of the surface tension of the membranes.

Erratum: Influence of oxygen plasma treatment parameters on poly(vinylidene fluoride) electrospun fiber mats wettability

Electrospun poly(vinylidene fluoride) (PVDF) fiber mats find applications in an increasing number of areas, such as battery separators, filtration and detection membranes, due to their excellent properties. However, there are limitations due to the hydrophobic nature and low surface energy of PVDF. In this work, oxygen plasma treatment has been applied in order to modify the surface wettability of PVDF fiber mats and superhydrophilic PVDF electrospun membranes have been obtained. Further, plasma treatment does not significantly influences fiber average size (~400 ± 200 nm), morphology, electroactive -phase content (~80-85%) or the degree of crystallinity (Xc of 42 ± 2%), allowing to maintain the excellent physical-chemical characteristics of PVDF. Plasma treatment mainly induces surface chemistry modifications, such as the introduction of oxygen and release of fluorine atoms that significantly changes polymer membrane wettability by a reduction of the contact angle of the polymer fibers and an overall decrease of the surface tension of the membranes.

An assessment of chronic kidney diseases

Kidney renal failure means that one’s kidney have unexpectedlystoppedfunctioning,i.e.,oncechronicdiseaseis exposed, the presence or degree of kidney dysfunction and its progression must be assessed, and the underlying syndrome has to be diagnosed. Although the patient’s history and physical examination may denote good practice, some key information has to be obtained from valuation of the glomerular filtration rate, and the analysis of serum biomarkers. Indeed, chronic kidney sickness depicts anomalous kidney function and/or its makeup, i.e., there is evidence that treatment may avoid or delay its progression, either by reducing and prevent the development of some associated complications, namely hypertension, obesity, diabetes mellitus, and cardiovascular complications. Acute kidney injury appears abruptly, with a rapiddeteriorationoftherenalfunction,butisoftenreversible if it is recognized early and treated promptly. In both situations, i.e., acute kidney injury and chronic kidney disease, an early intervention can significantly improve the prognosis. The assessment of these pathologies is therefore mandatory, although it is hard to do it with traditional methodologies and existing tools for problem solving. Hence, in this work, we will focus on the development of a hybrid decision support system, in terms of its knowledge representation and reasoning procedures based on Logic Programming, that will allow onetoconsiderincomplete,unknown,and evencontradictory information, complemented with an approach to computing centered on Artificial Neural Networks, in order to weigh the Degree-of-Confidence that one has on such a happening. The present study involved 558 patients with an age average of 51.7 years and the chronic kidney disease was observed in 175 cases. The dataset comprise twenty four variables, grouped into five main categories. The proposed model showed a good performance in the diagnosis of chronic kidney disease, since the sensitivity and the specificity exhibited values range between 93.1 and 94.9 and 91.9–94.2 %, respectively.

An evaluation of parchments' degradation a hybrid approach

Parchment stands for a multifaceted material made from animal skin, which has been used for centuries as a writing support or as bookbinding. Due to the historic value of objects made of parchment, understanding their degradation and their condition is of utmost importance to archives, libraries and museums, i.e., the assessment of parchment degradation is mandatory, although it is hard to do with traditional methodologies and tools for problem solving. Hence, in this work we will focus on the development of a hybrid decision support system, in terms of its knowledge representation and reasoning procedures, under a formal framework based on Logic Programming, complemented with an approach to computing centered on Artificial Neural Networks, to evaluate Parchment Degradation and the respective Degree-of-Confidence that one has on such a happening.

Assessment and management of the geomorphological heritage of Monte Pindo (NW Spain): a landscape as a symbol of identity

This study focuses on the granite mountain known as Monte Pindo (627 m above sea level) in the Autonomous Community of Galicia (NW Spain). This territory is included in the area classified as “Costa da Morte” in the “Politica de Ordenación Litoral” (POL) (Coastal Planning Policy) for the region of Galicia. This coastal unit, located between “Rías Baixas” and “Cape Fisterra” has great potential for demonstrating geological processes and its geomorphological heritage is characterized by a high degree of geodiversity of granite landforms. The main objective of our work is to assess the geomorphological heritage of the site, thus revealing its wide geodiversity. We shall analyze and highlight: its scientific value, developing an inventory of granite landforms; its educational valuel and its geotouristic potential. It must be ensured that the Administration understands that natural diversity is composed of both geodiversity and biodiversity. Only then will the sustainable management of Monte Pindo become possible by integrating natural and cultural heritage values. The goal is to ensure that Monte Pindo and its immediate surroundings become a geopark with the aim of promoting local development projects based on the conservation and valorization of its geological heritage.

Efficacy of a gas permeable contact lens to induce peripheral myopic defocus

Purpose. The purpose of this work was to evaluate the potential of a novel custom-designed rigid gas permeable (RGP) contact lens to modify the relative peripheral refractive error in a sample of myopic patients. Methods. Fifty-two right eyes of 52 myopic patients (mean [TSD] age, 21 [T2] years) with spherical refractive errors ranging from j0.75 to j8.00 diopters (D) and refractive astigmatism of 1.00 D or less were fitted with a novel experimental RGP (ExpRGP) lens designed to create myopic defocus in the peripheral retina. A standard RGP (StdRGP) lens was used as a control in the same eye. The relative peripheral refractive error was measured without the lens and with each of two lenses (StdRGP and ExpRGP) using an open-field autorefractometer from 30 degrees nasal to 30 degrees temporal, in 5-degree steps. The effectiveness of the lens design was evaluated as the amount of relative peripheral refractive error difference induced by the ExpRGP compared with no lens and with StdRGP conditions at 30 degrees in the nasal and temporal (averaged) peripheral visual fields. Results. Experimental RGP lens induced a significant change in relative peripheral refractive error compared with the nolens condition (baseline), beyond the 10 degrees of eccentricity to the nasal and temporal side of the visual field (p G 0.05). The maximum effect was achieved at 30 degrees. Wearing the ExpRGP lens, 60% of the eyes had peripheral myopia exceeding j1.00 D, whereas none of the eyes presented with this feature at baseline. There was no significant correlation (r = 0.04; p = 0.756) between the degree of myopia induced at 30 degrees of eccentricity of the visual field with the ExpRGP lens and the baseline refractive error. Conclusions. Custom-designed RGP contact lenses can generate a significant degree of relative peripheral myopia in myopic patients regardless of their baselin spherical equivalent refractive error.