960 resultados para Thermodynamic Nonideality
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Tuberculosis remains as one of the main cause of mortality worldwide due to a single infectious agent, Mycobacterium tuberculosis. The aroK-encoded M. tuberculosis Shikimate Kinase (MtSK), shown to be essential for survival of bacilli, catalyzes the phosphoryl transfer from ATP to the carbon-3 hydroxyl group of shikimate (SKH), yielding shikimate-3-phosphate and ADP. Here we present purification to homogeneity, and oligomeric state determination of recombinant MtSK. Biochemical and biophysical data suggest that the chemical reaction catalyzed by monomeric MtSK follows a rapid-equilibrium random order of substrate binding, and ordered product release. Isothermal titration calorimetry (ITC) for binding of ligands to MtSK provided thermodynamic signatures of non-covalent interactions to each process. A comparison of steady-state kinetics parameters and equilibrium dissociation constant value determined by ITC showed that ATP binding does not increase the affinity of MtSK for SKH. We suggest that MtSK would more appropriately be described as an aroL-encoded type II shikimate kinase. Our manuscript also gives thermodynamic description of SKH binding to MtSK and data for the number of protons exchanged during this bimolecular interaction. The negative value for the change in constant pressure heat capacity (ΔCp) and molecular homology model building suggest a pronounced contribution of desolvation of non-polar groups upon binary complex formation. Thermodynamic parameters were deconvoluted into hydrophobic and vibrational contributions upon MtSK:SKH binary complex formation. Data for the number of protons exchanged during this bimolecular interaction are interpreted in light of a structural model to try to propose the likely amino acid side chains that are the proton donors to bulk solvent following MtSK:SKH complex formation. © 2013 Rosado et al.
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This work aims to study the thermodynamic, ecological and fluid-dynamic aspects of a circulating fluidized bed gasifier using sugar cane bagasse as biomass, in order to estimate a model of its normal operation. In the initial stage was analysed the composition of biomass selected (sugar cane bagasse) and its lower heating value (LHV) was calculated. The energy balance of the gasifier was done, being the volumetric flow of air, synthesis gas and biomass estimated. Also the power produced by this gasifier was theoretically estimated. Then the circulating fluidized bed gasifier was designed for operation with approximately 100 kg/h of processed biomass. Cross-sectional area of the reactor, feeder size, diameter of the exit zone of the gases and minimum height of the expanded bed were selected. Some bed gasifier hydrodynamic factors were also studied. The minimum fluidization velocity, fluidization terminal velocity, and average fluidizing velocity were calculated, in order to understand the fluid-dynamic behaviour of gasification of this fuel. It was obtained a theoretical model that can support a possible prototype of circulating fluidized bed gasifier biomass. Finally, there were studied the ecological aspects of the gasifier, through an overall methodology. Ecological efficiencies were estimated for two scenarios: first considering the carbon cycle and thereafter disregarding the carbon cycle. In both cases, it can be proved the ecological viability of the project. © 2013 Elsevier Ltd. All rights reserved.
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Synthesis, characterization and thermal decomposition of bivalent transition metal α-hydroxyisobutyrates, M(C4H7O 3)2·nH2O (M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II)), as well as the thermal behaviour of α-hydroxyisobutyric acid and its sodium salt were investigated employing simultaneous thermogravimetry and differential scanning calorimetry (TG-DSC), infrared spectroscopy (FTIR), TG-DSC coupled to FTIR, elemental analysis and complexometry. All the compounds were obtained as dihydrated, except the copper one which was obtained in the anhydrous state. The thermal decomposition of the anhydrous compounds occurs in a single or two steps and the final residue up to 235 C (Mn), 300 C (Fe), 305 C (Co), 490 C (Ni), 260 C (Cu) and 430 C (Zn) is Mn2O3, Fe2O3, Co3O 4, NiO, CuO and ZnO, respectively. The results also provided information concerning the ligand's denticity and identification of the gaseous products evolved during the thermal decomposition of these compounds. Copyright © 2013 Published by Elsevier B.V. All rights reserved.
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Two different cationic polymers of the same chemical type and with very similar chemical structures were reacted with a natural bentonite over a wide range of polymer/clay ratios. This study involved the synthesis of cationic aliphatic ammonium polyionenes, specifically 3,6-ionene and 3,6-dodecylionene. Ionenes are ion-containing polymers that contain quaternary nitrogen atoms in the main macromolecular chain as opposed to a pendant chain. The CHN content, basal spacing, and elemental composition of each of the polymer-clay complexes were analyzed by X-ray diffraction, X-ray fluorescence, and thermogravimetry. All the polycations reacted to form interlayer complexes with clay, which displaced more Na+ and little Ca2+. Sodium and calcium were both present as interlayer cations in the clay and its complexes. The TG/DTG curves show that both polymers underwent thermal degradation in more than one stage. Specifically, 3,6-ionene was found to undergo two stages of decomposition and 3,6-dodecylionene undergo three stages. The behavior of the TG/DTG curves and the activation energy values suggest that 3,6-dodecylionene (E = 174,85 kJ mol-1) complexes have greater thermal stability than 3,6-ionene (E = 115,52 kJ mol-1) complexes. The mechanism of degradation suggests a direct interaction with the dodecyl chain containing 12 carbons, which are present in 3,6-dodecylionene but not in 3,6-ionene. © 2012 Akadémiai Kiadó, Budapest, Hungary.
Sintering of porous alumina obtained by biotemplate fibers for low thermal conductivity applications
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In this research report, a sintering process of porous ceramic materials based on Al2O3 was employed using a method where a cation precursor solution is embedded in an organic fibrous cotton matrix. For porous green bodies, the precursor solution and cotton were annealed at temperatures in the range of 100-1600°C using scanning electron microscopy (SEM) and thermogravimetric (TG) analysis to obtain a porous body formation and disposal process containing organic fibers and precursor solution. In a structure consisting of open pores and interconnected nanometric grains, despite the low porosity of around 40% (calculated geometrically), nitrogen physisorption determined a specific surface area of 14m2/g, which shows much sintering of porous bodies. Energy dispersive X-ray (EDX) and X-ray diffraction (XRD) analytical methods revealed a predominant amount of α-Al2O3 in the sintered samples. Thermal properties of the sintered Al2O3 fibers were obtained by using the Laser Flash which resulted in the lower thermal conductivity obtained by α-Al2O3 and therefore improved its potential use as an insulating material. © 2012 Elsevier Ltd.
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Chemical compatibility between geomembranes and site-specific waste liquids should be assessed since the waste liquids are highly complex mixtures. This paper presents some considerations about the chemical compatibility of geomembranes and some results of mechanical tests in HDPE and PVC geomembranes that were exposed to leachate and chemical residue (niobium). PVC and HDPE geomembranes of two thicknesses were tested: 1.0, 2.0 mm (PVC) and 0.8, 2.5 mm (HDPE). The results obtained show that after exposure the PVC geomembranes (1.0, 2.0 mm) were more rigid and stiffer than fresh samples. The HDPE geomembranes, on the other hand, when exposed to leachate and niobium residue presented increases in deformation. Melt flow index (MFI) tests were also carried out to verify the oxidation. © 2013 ejge.
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This work describes the synthesis and characterization of a new octakis[3-(2,2'-dipyridylamine)propyl]octasilsesquioxane (T8-Pr-DPA), and a study of the metal ion preconcentration in fuel ethanol. Batch and column experiments were conducted to investigate for the removal of heavy metal ions from fuel ethanol. The results showed that the Langmuir allowed to describe the sorption equilibrium data of the metal ions on T8-Pr-DPA in a satisfactory way. The following maximum adsorption capacities (in mmolg-1) were determined: 3.62 for Fe (III), 3.32 for Cr (III), 2.15 for Cu (II), 1.80 for Co (II), 1.62 for Pb (II), 1.32 for Ni (II) and 0.88 for Zn (II). The thermodynamic parameters for the adsorption process such as free energy of adsorption (δG), enthalpy of adsorption (δH) and entropy of adsorption (δS) were calculated. Thermodynamic parameters showed that the system has favorable enthalpic, Gibbs free energy, and entropic values. The sorption-desorption of the metal ions has made possible the development of a preconcentration and determination method of metal ions at trace level in fuel ethanol. The method of quantitative analysis for Fe, Cu, Ni and Zn in fuel ethanol by Flame AAS was validated. Several parameters have been taken into account and evaluated for the validation of method, namely: linearity, limit of detection, limit of quantification, and the relative standard deviation and accuracy. The accuracy of the method was assessed by testing analyte recovery in the fuel ethanol samples. © 2013 Elsevier B.V.
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In this work we study two different spin-boson models. Such models are generalizations of the Dicke model, it means they describe systems of N identical two-level atoms coupled to a single-mode quantized bosonic field, assuming the rotating wave approximation. In the first model, we consider the wavelength of the bosonic field to be of the order of the linear dimension of the material composed of the atoms, therefore we consider the spatial sinusoidal form of the bosonic field. The second model is the Thompson model, where we consider the presence of phonons in the material composed of the atoms. We study finite temperature properties of the models using the path integral approach and functional methods. In the thermodynamic limit, N→∞, the systems exhibit phase transitions from normal to superradiant phase at some critical values of temperature and coupling constant. We find the asymptotic behavior of the partition functions and the collective spectrums of the systems in the normal and the superradiant phases. We observe that the collective spectrums have zero energy values in the superradiant phases, corresponding to the Goldstone mode associated to the continuous symmetry breaking of the models. Our analysis and results are valid in the limit of zero temperature β→∞, where the models exhibit quantum phase transitions. © 2013 Elsevier B.V. All rights reserved.
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The vortex matter in a superconducting disk with a linear configuration of metallic and superconducting defects is studied. Effects associated to the pinning (anti-pinning) force of the metallic (superconducting) defect on the vortex configuration and on the thermodynamic critical fields are analyzed in the framework of the Ginzburg Landau theory. We calculate the loop of the magnetization, vorticity and free energy curves as a function of the magnetic field for a thin disk. Due to vortex-defect attraction for a metallic defect (repulsion for a superconducting defect), the vortices always (never) are found to be sitting on the defect position. © 2013.
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The biosorption of Cd(II) and Pb(II) ions on biomass and exopolysaccharide (EPS) produced by Colletotrichum sp. fungus has been investigated as a function of contact time, initial pH, initial metal ion concentration, and initial adsorbent concentration in a batch system. Adsorption equilibrium was described by Freundlich and Langmuir isotherms. Adsorption was characterized through granulometry, SEM and EDX analysis. Then, studies were performed to regenerate the adsorbent. Biosorption of metals by biomass and EPS were best described by the Langmuir and Freundlich isotherm, respectively. Results of thermodynamic investigations showed that adsorption reactions were spontaneous (ΔG° < 0), exothermal, and mainly physical. The EPS was able to remove 79 and 98% of cadmium and lead, respectively, and the biomass removed 85 and 84% of cadmium and lead, respectively, in a solution with initial concentration 100 mg L-1, and the four adsorption-desorption cycles of all adsorbents showed up with great regenerative capacity and relative stability after these four cycles, the high potential of these biological materials in sorption has been shown. © 2013 Copyright Balaban Desalination Publications.
Thermophysical properties of cotton, canola, sunflower and soybean oils as a function of temperature
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Vegetable oils are used in the industry of processed food, including deep-fat frying. This work determined data on the thermophysical properties of cotton, canola, sunflower, corn, and soybean oils. Thermal conductivity, heat capacity, density, and viscosity were measured within the temperature range of 299.15-433.15 K. The data showed that the temperature influenced the thermophysical properties of the oils studied. The developed correlations could be used to predict these properties within the range of temperatures studied. © 2013 Copyright Taylor and Francis Group, LLC.
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Natural rubber/gold nanoparticles membranes (NR/Au) were studied by ultrasensitive detection and chemical analysis through surface-enhanced Raman scattering and surface-enhanced resonance Raman scattering in our previous work (Cabrera et al., J. Raman Spectrosc. 2012, 43, 474). This article describes the studies of thermal stability and mechanical properties of SERS-active substrate sensors. The composites were prepared using NR membranes obtained by casting the latex solution as an active support (reducing/establishing agents) for the incorporation of colloidal gold nanoparticles (AuNPs). The nanoparticles were synthesized by in situ reduction at different times. The characterization of these sensors was carried out by thermogravimetry, differential scanning calorimetry, scanning electron microscopy (SEM) microscopy, and tensile tests. It is suggested an influence of nanoparticles reduction time on the thermal degradation of NR. There is an increase in thermal stability without changing the chemical properties of the polymer. For the mechanical properties, the tensile rupture was enhanced with the increase in the amount of nanoparticles incorporated in the material. © 2013 Wiley Periodicals, Inc.
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Glossoscolex paulistus (HbGp) hemoglobin is an oligomeric protein, presenting a quaternary structure constituted by 144 globin and 36 non-globin chains (named linkers) with a total molecular mass of 3.6MDa. SDS effects on the oxy-HbGp thermal stability were studied, by DLS and SAXS, at pH 5.0, 7.0 and 9.0. DLS and SAXS data show that the SDS-oxy-HbGp interactions induce a significant decrease of the protein thermal stability, with the formation of larger aggregates, at pH 5.0. At pH 7.0, oxy-HbGp undergoes complete oligomeric dissociation, with increase of temperature, in the presence of SDS. Besides, oxy-HbGp 3.0mg/mL, pH 7.0, in the presence of SDS, has the oligomeric dissociation process reduced as compared to 0.5mg/mL of protein. At pH 9.0, oxy-HbGp starts to dissociate at 20°C, and the protein is totally dissociated at 50°C. The thermal dissociation kinetic data show that oxy-HbGp oligomeric dissociation at pH 7.0, in the presence of SDS, is strongly dependent on the protein concentration. At 0.5mg/mL of protein, the oligomeric dissociation is complete and fast at 40 and 42°C, with kinetic constants of (2.1±0.2)×10-4 and (5.5±0.4)×10-4s-1, respectively, at 0.6mmol/L SDS. However, at 3.0mg/mL, the oligomeric dissociation process starts at 46°C, and only partial dissociation, accompanied by aggregates formation is observed. Moreover, our data show, for the first time, that, for 3.0mg/mL of protein, the oligomeric dissociation, denaturation and aggregation phenomena occur simultaneously, in the presence of SDS. Our present results on the surfactant-HbGp interactions and the protein thermal unfolding process correspond to a step forward in the understanding of SDS effects. © 2013 Elsevier B.V.
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)