Monte Carlo thermodynamic and structural properties of the TIP4P water model: dependence on the computational conditions

Classical Monte Carlo simulations were carried out on the NPT ensemble at 25°C and 1 atm, aiming to investigate the ability of the TIP4P water model [Jorgensen, Chandrasekhar, Madura, Impey and Klein; J. Chem. Phys., 79 (1983) 926] to reproduce the newest structural picture of liquid water. The results were compared with recent neutron diffraction data [Soper; Bruni and Ricci; J. Chem. Phys., 106 (1997) 247]. The influence of the computational conditions on the thermodynamic and structural results obtained with this model was also analyzed. The findings were compared with the original ones from Jorgensen et al [above-cited reference plus Mol. Phys., 56 (1985) 1381]. It is notice that the thermodynamic results are dependent on the boundary conditions used, whereas the usual radial distribution functions g(O/O(r)) and g(O/H(r)) do not depend on them.

Avaliação clínica de sinais e sintomas da disfunção temporomandibular em crianças

OBJETIVO: avaliar a freqüência dos sinais e sintomas, dos hábitos parafuncionais e das características oclusais de 80 crianças, pacientes da clínica de Ortodontia Preventiva da Faculdade de Odontologia de Araçatuba - UNESP. METODOLOGIA: o exame clínico constituiu-se de avaliação das características oclusais do paciente e observação da presença de hábitos parafuncionais. As crianças foram submetidas a uma entrevista, supervisionadas pelos pais, cujas perguntas relacionavam-se com os sinais e sintomas da disfunção. RESULTADOS E CONCLUSÕES: concluiu-se que os sinais e sintomas mais freqüentes foram o hábito de ranger os dentes, dores de cabeça e ruídos na ATM. A onicofagia e o bruxismo foram os hábitos parafuncionais mais prevalentes. A freqüência de sinais e sintomas da disfunção temporomandibular pode ser verificada em crianças por meio da entrevista e exame clínico minucioso.

Confiabilidade de um formulário para diagnóstico da severidade da disfunção temporomandibular

CONTEXTUALIZAÇÃO: Disfunção temporomandibular (DTM) é um termo coletivo que engloba vários problemas clínicos envolvendo a musculatura da mastigação, as articulações temporomandibulares (ATM) e suas estruturas associadas, com alta prevalência nas populações. OBJETIVOS: Sabendo-se que estudos brasileiros vêm utilizando o instrumento proposto por da Fonseca et al. (1994) para diagnóstico da severidade desta disfunção, realizou-se este estudo com o objetivo de verificar e estimar a consistência interna e a reprodutibilidade do mesmo. MÉTODOS: O delineamento amostral adotado foi o probabilístico, e participaram 1230 indivíduos moradores da cidade de Ribeirão Preto (SP), maiores de 18 anos de idade. As entrevistas foram realizadas por um único entrevistador por meio de ligações telefônicas. Para estudo da consistência interna, calculou-se o Coeficiente de Kuder-Richardson (kr-20) e para estimar a reprodutibilidade, utilizou-se a estatística Kappa (κ). RESULTADOS: A consistência interna do formulário foi de 0,5594, apontando para uma validação abaixo do desejado. Observou-se maior contribuição das questões 1, 2, 3, 6 e 7 para o coeficiente kr-20 total e maior consistência do instrumento quando composto apenas pelas mesmas (0,7044). Observou-se reprodutibilidade Boa e Ótima para as questões. CONCLUSÕES: Frente ao exposto, sugere-se que o formulário proposto por da Fonseca et al. (1994) seja adaptado, ficando composto apenas pelas questões 1, 2, 3, 6 e 7 da versão inicial, colaborando, assim, para aumento da confiabilidade do instrumento. Deve-se ressaltar ainda a necessidade da realização de estudos de validade para assegurar adequadas características psicométricas à nova versão do instrumento.

Hydrodechlorination of 1,2-dichloroethane by rhodium catalysts under water gas shift reaction conditions

Homogeneous catalysts prepared from rhodium trichloride in aqueous aromatic amines have been shown to reduce C-CI bonds under mild water gas shift conditions (T=100 degrees C, P-CO = 1.0 atm). In a 4-picoline/water solvent mixture, 1,2-dichloroethane is reduced to ethylene and ethane in yields compatible with the consumption of the reducing agent CO and with the formation of CO2. Variation of the catalyst solutions by using different substituted pyridines shows a pattern of catalytic activity parallel to that reported previously for H-2 production from the shift reaction, There is a moderate dependence of activity on the basicity of the aromatic amine, but a methyl group at the alpha-position exercises a strong negative steric effect. Long term studies show decrease of the activity with the time perhaps due to the build up of chloride in the medium. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Noether and topological currents equivalence and soliton/particle correspondence in affine sl(2)((1)) Toda theory coupled to matter

A submodel of the so-called conformal affine Toda model coupled to the matter field (CATM) is defined such that its real Lagrangian has a positive-definite kinetic term for the Toda field and a usual kinetic term for the (Dirac) spinor field. After spontaneously broken the conformal symmetry by means of BRST analysis, we end up with an effective theory, the off-critical affine Toda model coupled to the matter (ATM). It is shown that the ATM model inherits the remarkable properties of the general CATM model such as the soliton solutions, the particle/soliton correspondence and the equivalence between the Noether and topological currents. The classical solitonic spectrum of the ATM model is also discussed. (C) 2001 Elsevier B.V. B.V. All rights reserved.

The sl(2) affine Toda model coupled to the matter: solitons and confinement

The so-called conformal affine Toda theory coupled to the matter fields (CATM), associated to the (s) over capl(2) affine Lie algebra, is studied. The conformal symmetry is fixed by setting a connection to zero, then one defines an off-critical model, the affine Toda model coupled to the matter (ATM). Using the dressing transformation method we construct the explicit forms of the two-soliton classical solutions, and show that a physical bound soliton-antisoliton pair (breather) does not exist. Moreover, we verify that these solutions share some features of the sine-Gordon (massive Thirring) solitons, and satisfy the classical equivalence of topological and Noether currents in the ATM model. We show, using bosonization techniques that the ATM theory decouples into a sine-Gordon model and a free scalar. Imposing the Noether and topological currents equivalence as a constraint, one can show that the ATM model leads to a bag model like mechanism for the confinement of the color charge inside the sine-Gordon solitons (baryons).

Modelling short-term temporal changes of bare soil CO2 emissions in a tropical agrosystem by using meteorological data

Determining the variability of carbon dioxide emission from soils is an important task as soils are among the largest sources of carbon in biosphere. In this work the temporal variability of bare soil CO2 emissions was measured over a 3-week period. Temporal changes in soil CO2 emission were modelled in terms of the changes that occurred in solar radiation (SR), air temperature (T-air), air humidity (AR), evaporation (EVAP) and atmospheric pressure (ATM) registered during the time period that the experiment was conducted. The multiple regression analysis (backward elimination procedure) includes almost all the meteorological variables and their interactions into the final model (R-2 = 0.98), but solar radiation showed to be the one of the most relevant variables. The present study indicates that meteorological data could be taken into account as the main forces driving the temporal variability of carbon dioxide emission from bare soils, where microbial activity is the sole source of carbon dioxide emitted. (C) 2003 Elsevier B.V. All rights reserved.

C-H center dot center dot center dot O and N-H center dot center dot center dot O hydrogen bonds in liquid amides investigated by Monte Carlo simulation

Monte Carlo simulations of liquid formamide, N-methylformamide (MF), and N,N-dimethylformamide (DMF) have been performed in the isothermal and isobaric ensemble at 298 K and 1 atm, aiming to investigate the C-H ... O and N-H ... O hydrogen bonds. The interaction energy was calculated using the classical 6-12 Lennard-Jones pairwise potential plus a Coulomb term on a rigid six-site molecular model with the potential parameters being optimized in this work. Theoretical values obtained for heat of vaporization and liquid densities are in good agreement with the experimental data. The radial distribution function [RDF, g(r)] obtained compare well with R-X diffraction data available. The RDF and molecular mechanics (MM2) minimization show that the C-H ... O interaction has a significant role in the structure of the three liquids. These results are supported by ab initio calculations. This Interaction is particularly important in the structure of MF. The intensity of the N-H ... O hydrogen bond is greater in the MF than formamide. This could explain some anomalous properties verified in MF. (C) 1997 John Wiley & Sons, Inc.

Titanium and zirconium complexes containing sterically hindered hydrotris(pyrazolyl)borate ligands: synthesis, structural characterization, and ethylene polymerization studies

The synthesis, characterization and ethylene polymerization behavior of a set of Tp'MCl3 complexes (4, M = Ti, Tp' HB(3-neopentyl-pyrazolyl)(3)(-) (Tp(NP)); 5, M = Ti, Tp'= HB(3-tert-butyl-pyrazolyl)(3)(-) (Tp(tBu)); 6, M = Ti, Tp' = HB(3-phenyl-pyrazolyl)(3)(-) (Tp(Ph)); 7, M = Zr, Tp' = HB(3-phenyl-pyrazolyl)(3)(-) (Tp(ph)); 8, M = Zr, Tp' = HB(3-tert-butyl-pyrazolyl)(3)(-) (Tp(tBu))) is described. Treatment of these tris(pyrazolyl)borate Group IV compounds with methylalumoxane (MAO) generates active catalysts for ethylene polymerization. For the polymerization reactions performed in toluene at 60 degreesC and 3 atm of ethylene pressure, the activities varied between 1.3 and 5.1 X 10(3) g of PE/mol[M](.)h. The highest activity is reached using more sterically open catalyst precursor 4. The viscosity-average molecular weights ((M-v) over bar) of the PE's produced with these catalyst precursors varying from 3.57 to 20.23 x 10(5) gmol(-1) with melting temperatures in the range of 127-134 degreesC. Further polymerization studies employing 7 varying Al/Zr molar ratio and temperature of polymerization showed that the activity as well as the polymer properties are dependent on these parameters. In that case, higher activity was attained at 60 degreesC. The viscosity-average molecular weights of the polyethylene's decreases with increasing AI/Zr molar ratio. (C) 2003 Elsevier B.V. All rights reserved.

Design, manufacturing, and testing of a Nb3Sn coil employing Ti alloy as structural material

We describe the design, manufacturing, and testing results of a Nb3Sn superconducting coil in which TiAIV alloys were used instead of stainless steel to reduce the magnetization contribution caused by the heat treatment for the A-15 Nb-3 Sn phase formation that affects the magnetic field homogeneity. Prior to the coil manufacturing several structural materials were studied and evaluated in terms of their mechanical and magnetic properties in as-worked, welded, and heat-treated conditions. The manufacturing process employed the wind-and-react technique followed by vacuum-pressure impregnation(VPI) at 1 MPa atm. The critical steps of the manufacturing process, besides the heat treatment and impregnation, are the wire splicing and joint manufacturing in which copper posts supported by Si3N4 ceramic were used. The coil was tested with and without a background NbTi coil and the results have shown performance exceeding the design quench current confirming the successful coil construction.

Skin water uptake and renal function in the toad

1. 1. Water balance in the toad Bufo marinus ictericus was studied by evaluating cutaneous water uptake and renal excretion. 2. 2. The permeability of the skin to water was 78 ± 6 nl min -1 cm -2 atm -1 in 60 toads anaesthetized by chloralose and preincubated in water for 3 hr. Injection of Ringer's solution did not reduce the water uptake by the skin, while hemorrhage, or injection of vasopressin, or oxytocin approximately doubled the rates of water transport. In vivo values of skin water permeability were similar to those observed in vitro. 3. 3. The renal parameters of the water balance were significantly reduced by hemorrhage and by injection of vasopressin. Injection of Ringer's solution promoted a significant increase of the urinary flow and osmolar clearance. 4. 4. It is suggested that the fight against water deprivation could proceed initially by the triggering of the urinary mechanisms of water retention, while the increase of the skin water permeability would occur in a later stage. © 1981.

C - H ⋯ 0 and N - H ⋯ 0 hydrogen bonds in liquid amides investigated by monte carlo simulation

Monte Carlo simulations of liquid formamide, N-methylformamide (MF), and N, N-dimethytformamide (DMF) have been performed in the isothermal and isobaric ensemble at 298 K and 1 atm, aiming to investigate the C-H ⋯ O and N-H ⋯ O hydrogen bonds. The interaction energy was calculated using the classical 6-12 Lennard-Jones pairwise potential plus a Coulomb term on a rigid six-site molecular model with the potential parameters being optimized in this work. Theoretical values obtained for heat of vaporization and liquid densities are in good agreement with the experimental data. The radial distribution function [RDF, g(r)] obtained compare well with R-X diffraction data available. The RDF and molecular mechanics (MM2) minimization show that the C-H ⋯ O interaction has a significant role in the structure of the three liquids. These results are supported by ab initio calculations. This interaction is particularly important in the structure of MF. The intensity of the N - H ⋯ O hydrogen bond is greater in the MF than formamide. This could explain some anomalous properties verified in MF. © 1997 John Wiley & Sons, Inc.

Study of water and dimethylformamide interaction by computer simulation

Monte Carlo simulations of water-dimethylformamide (DMF) mixtures were performed in the isothermal and isobaric ensemble at 298.15 K and 1 atm. The intermolecular interaction energy was calculated using the classical 6-12 Lennard-Jones pairwise potential plus a Coulomb term. The TIP4P model was used for simulating water molecules, and a six-site model previously optimised by us was used to represent DMF. The potential energy for the water-DMF interaction was obtained via standard geometric combining rules using the original potential parameters for the pure liquids. The radial distribution functions calculated for water-DMF mixtures show well characterised hydrogen bonds between the oxygen site of DMF and hydrogen of water. A structureless correlation curve was observed for the interaction between the hydrogen site of the carbonyl group and the oxygen site of water. Hydration effects on the stabilisation of the DMF molecule in aqueous solution have been investigated using statistical perturbation theory. The results show that energetic changes involved in the hydration process are not strong enough to stabilise another configuration of DMF than the planar one.

Optimization of neutral hydrolysis reaction of post-consumer PET for chemical recycling

The neutral hydrolysis reaction of post-consumer poly(ethylene terephthalate) in solid state was studied through the reaction of the polymer with water at the molar ratio 1:91 with autogenous pressure. Two sizes of post-consumer PET flakes and temperatures of 135 °C, 170°C and 205°C with pressures of 4.0 atm, 7.5 atm and 13.5 atm, respectively, were considered. With reaction time equal to 6h, the method reached 99% depolymerization at 205°C, 8.2% at 170 °C and 1.7% at 135°C. The reaction extension was measured by separating the terephthalic acid formed in the process and calculating by gravimetry how much material could still be reacted. Through the viscosimetry of diluted, solutions and the counting of carboxylic end groups in the remaining material from the gravimetric assay, it was possible to suggest that the reaction occurs randomly and in the whole volume of the polymeric particle and not solely on the surface. The terephthalic acid obtained and then purified was characterized by elemental analysis, magnetic nuclear resonance, size and panicle size distribution and spectrophotometry in the visible spectrum, and it was similar to the petrochemical equivalent, with purity recorded in carbon base equal to 99.9%.

Thermodynamic analysis of direct steam reforming of ethanol in molten carbonate fuel cell

Fuel cell as MCFC (molten carbonate fuel cell) operate at high temperatures, and due to this issue, cogeneration processes may be performed, sending heat for own process or other purposes as steam generation in an industry. The use of ethanol for this purpose is one of the best options because this is a renewable and less environmentally offensive fuel, and cheaper than oil-derived hydrocarbons (in the case of Brazil). In the same country, because of technical, environmental and economic advantages, the use of ethanol by steam reforming process have been the most investigated process. The objective of this study is to show a thermodynamic analysis of steam reforming of ethanol, to determine the best thermodynamic conditions where are produced the highest volumes of products, making possible a higher production of energy, that is, a most-efficient use of resources. To attain this objective, mass and energy balances are performed. Equilibrium constants and advance degrees are calculated to get the best thermodynamic conditions to attain higher reforming efficiency and, hence, higher electric efficiency, using the Nernst equation. The advance degree of reforming increases when the operation temperature also increases and when the operation pressure decreases. But at atmospheric pressure (1 atm), the advance degree tends to the stability in temperatures above 700°C, that is, the volume of supplemental production of reforming products is very small for the high use of energy resources necessary. Reactants and products of the steam-reforming of ethanol that weren't used may be used for the reforming. The use of non-used ethanol is also suggested for heating of reactants before reforming. The results show the behavior of MCFC. The current density, at same tension, is higher at 700°C than other studied temperatures as 600 and 650°C. This fact occurs due to smaller use of hydrogen at lower temperatures that varies between 46.8 and 58.9% in temperatures between 600 and 700°C. The higher calculated current density is 280 mA/cm 2. The power density increases when the volume of ethanol to be used also increases due to higher production of hydrogen. The highest produced power at 190 mW/cm 2 is 99.8, 109.8 and 113.7 mW/cm2 for 873, 923 and 973K, respectively. The thermodynamic efficiency has the objective to show the connection among operational conditions and energetic factors, which are some parameters that describes a process of internal steam reforming of ethanol.