The isotropic nuclear magnetic shielding constants of acetone in supercritical water: A sequential Monte Carlo/quantum mechanics study including solute polarization

The nuclear isotropic shielding constants sigma((17)O) and sigma((13)C) of the carbonyl bond of acetone in water at supercritical (P=340.2 atm and T=673 K) and normal water conditions have been studied theoretically using Monte Carlo simulation and quantum mechanics calculations based on the B3LYP/6-311++G(2d,2p) method. Statistically uncorrelated configurations have been obtained from Monte Carlo simulations with unpolarized and in-solution polarized solute. The results show that solvent effects on the shielding constants have a significant contribution of the electrostatic interactions and that quantitative estimates for solvent shifts of shielding constants can be obtained modeling the water molecules by point charges (electrostatic embedding). In supercritical water, there is a decrease in the magnitude of sigma((13)C) but a sizable increase in the magnitude of sigma((17)O) when compared with the results obtained in normal water. It is found that the influence of the solute polarization is mild in the supercritical regime but it is particularly important for sigma((17)O) in normal water and its shielding effect reflects the increase in the average number of hydrogen bonds between acetone and water. Changing the solvent environment from normal to supercritical water condition, the B3LYP/6-311++G(2d,2p) calculations on the statistically uncorrelated configurations sampled from the Monte Carlo simulation give a (13)C chemical shift of 11.7 +/- 0.6 ppm for polarized acetone in good agreement with the experimentally inferred result of 9-11 ppm. (C) 2008 American Institute of Physics.

Modeling and simulation of severe slugging in air-water pipeline-riser systems

A mathematical model, numerical simulations and stability and flow regime maps corresponding to severe slugging in pipeline riser systems, are presented. In the simulations air and water were used as flowing fluids. The mathematical model considers continuity equations for liquid and gas phases, with a simplified momentum equation for the mixture, neglecting inertia. A drift-flux model, evaluated for the local conditions in the riser, is used as a closure law. The developed model predicts the location of the liquid accumulation front in the pipeline and the liquid level in the riser, so it is possible to determine which type of severe slugging occurs in the system. The numerical procedure is convergent for different nodalizations. A comparison is made with experimental results corresponding to a catenary riser, showing very good results for slugging cycle and stability and flow regime maps. (c) 2010 Elsevier Ltd. All rights reserved.

Influence of Water Content, Time, and Temperature on the Rheological Behavior of Polyethylene Terephtalate

In this work, the main factors affecting the rheological behavior of polyethylene terephtalate (PET) in the linear viscoelastic regime (water content, time delay before test, duration of experiment, and temperature) were accessed. Small amplitude oscillatory shear tests were performed after different time delays ranging from 300 to 5000 s for samples with water contents ranging from 0.02 to 0.45 wt %. Time sweep tests were carried out for different durations to explain the changes undergone by PET before and during small amplitude oscillatory shear measurements. Immediately after the time sweep tests, the PET samples were removed from the rheometer, analyzed by differential scanning calorimetry and their molar mass was obtained by viscometry analysis. It was shown that for all the samples, the delay before test and residence time within the rheometer (i.e. duration of experiment) result in structural changes of the PET samples, such as increase or decrease of molar mass, broadening of molar mass distribution, and branching phenomena. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 116: 3525-3533, 2010

ANALYSIS OF PRESSURE FLUCTUATIONS DURING WATER EVAPORATION IN SPOUTED BED

The aim of this work was to study the behaviour of conventional spouted beds during water evaporation and to analyze the pressure fluctuations at the maximum water evaporative capacity for different bed heights and air flow rates. The results showed that spout pressure drop could not indicate the proximity of maximum evaporative capacity; however this condition is denoted by a minimum in fountain height. The standard deviation and amplitude of the pressure fluctuations also showed a minimum point at the maximum water evaporation capacity. The frequency domain analysis of pressure fluctuations revealed that the dry bed has a dominant frequency varying from 6 to 8.2 Hz and that the peak of dominant frequency tends to disappear with the increase in water feed rate.

Satellite Rainfall Estimates Over South America - Possible Applicability to the Water Management of Large Watersheds1

This work analyzes high-resolution precipitation data from satellite-derived rainfall estimates over South America, especially over the Amazon Basin. The goal is to examine whether satellite-derived precipitation estimates can be used in hydrology and in the management of larger watersheds of South America. High spatial-temporal resolution precipitation estimates obtained with the CMORPH method serve this purpose while providing an additional hydrometeorological perspective on the convective regime over South America and its predictability. CMORPH rainfall estimates at 8-km spatial resolution for 2003 and 2004 were compared with available rain gauge measurements at daily, monthly, and yearly accumulation time scales. The results show the correlation between satellite-derived and gauge-measured precipitation increases with accumulation period from daily to monthly, especially during the rainy season. Time-longitude diagrams of CMORPH hourly rainfall show the genesis, strength, longevity, and phase speed of convective systems. Hourly rainfall analyses indicate that convection over the Amazon region is often more organized than previously thought, thus inferring that basin scale predictions of rainfall for hydrological and water management purposes have the potential to become more skillful. Flow estimates based on CMORPH and the rain gauge network are compared to long-term observed average flow. The results suggest this satellite-based rainfall estimation technique has considerable utility. Other statistics for monthly accumulations also suggest CMORPH can be an important source of rainfall information at smaller spatial scales where in situ observations are lacking.

Polarization and Spectral Shift of Benzophenone in Supercritical Water

Monte Carlo simulation and quantum mechanics calculations based on the INDO/CIS and TD-DFT methods were utilized to study the solvatochromic shift of benzophenone when changing the environment from normal water to supercritical (P = 340.2 atm and T = 673 K) condition. Solute polarization increases the dipole moment of benzophenone, compared to gas phase, by 88 and 35% in normal and supercritical conditions, giving the in-solvent dipole value of 5.8 and 4.2 D, respectively. The average number of solute-solvent hydrogen bonds was analyzed, and a large decrease of 2.3 in normal water to only 0.8 in the supercritical environment was found. By using these polarized models of benzophenone in the two different conditions of water, we performed MC simulations to generate statistically uncorrelated configurations of the solute surrounded by the solvent molecules and subsequent quantum mechanics calculations on these configurations. When changing from normal to supercritical water environment, INDO/CIS calculations explicitly considering all valence electrons of the 235 solvent water molecules resulted in a solvatochromic shift of 1425 cm(-1) for the most intense transition of benzophenone, that is, slightly underestimated in comparison with the experimentally inferred result of 1700 cm(-1). TD-B3LYP/6-311+G(2d,p) calculations on the same configurations but with benzophenone electrostatically embedded in the 320 water molecules resulted in a solvatochromic shift of 1715 cm(-1) for this transition, in very good agreement with the experimental result. When using the unpolarized model of the benzophenone, this calculated solvatochromic shift was only 640 cm(-1). Additional calculations were also made by using BHandHLYP/6-311+G(2d,p) to analyze the effect of the asymptotic decay of the exchange functional. This study indicates that, contrary to the general expectation, there is a sizable solute polarization even in the low-density regime of supercritical condition and that the inclusion of this polarization is important for a reliable description of the spectral shifts considered here.

Effect of cement type and water storage time on the push-out bond strength of a glass fiber post

This study investigated the effects of the cement type and the water storage time on the push-out bond strength of a glass fiber post. Glass fiber posts (Fibrekor, Jeneric Pentron) were luted to post spaces using a self-cured resin cement (C&B Cement [CB]), a glass ionomer cement (Ketac Cem [KC]) or a resin-modified glass ionomer cement (GC FujiCEM [FC]) according to the manufacturers’ instructions. For each luting agent, the specimens were exposed to one of the following water storage times (n=5): 1 day (T1), 7 days (T7), 90 days (T90) and 180 days (T180). Push-out tests were performed after the storage times. Control specimens were not exposed to water storage, but subjected to the push-out test 10 min after post cementation. Data (in MPa) were analyzed by Kruskal-Wallis and Dunn`s test (α=0.05). Cement type and water storage time had a significant effect (p<0.05) on the push-out bond strength. CB showed significantly higher values of retention (p<0.05) than KC and FC, irrespective of the water storage time. Water storage increased significantly the push-out bond strength in T7 and T90, regardless of the cement type (p<0.05). The results showed that fiber posts luted to post spaces with the self-cured resin cement exhibited the best bonding performance throughout the 180-day water storage period. All cements exhibited a tendency to increase the bond strength after 7 and 90 days of water storage, decreasing thereafter.

Variabilidade do regime de monções sobre o Brasil: o clima presente e projeções para um cenário com 2xCO2 usando o modelo MIROC

Este trabalho investiga a variabilidade do Sistema de Monções da América do Sul (SMAS) sobre o Brasil com particular interesse na região do cerrado brasileiro. O início, final e total de precipitação durante as monções de verão são examinados utilizando estimativas de precipitação por satélite (pêntadas) do Global Precipitation Climatology Project (GPCP) entre 1979-2004. Analogamente, as características do regime de monção simuladas pelo modelo climático global acoplado MIROC (Model for interdisciplinary Research on Climate) do IPCC (Intergovernmental Panel for Climate Change) são examinadas em dois cenários distintos: o clima do século XX (1981-2000) e o clima em uma condição com o dobro da concentração atual de CO2 (2xCO2) na atmosfera (2061-2080). Mostra-se que a variabilidade espacial do início da monção de verão sobre o cerrado na simulação do clima do século XX pelo MIROC corresponde bem às observações. Além disso, há indicação de uma mudança das caudas da distribuição sazonal da precipitação no Cerrado para um cenário com 2xCO2, comparativamente com o clima presente. Este resultado sugere uma mudança na probabilidade de ocorrência de eventos extremos (secos ou úmidos) em um cenário com 2xCO2 sobre o cerrado, o que de acordo com o MIROC, indica uma maior exposição da região às conseqüências de possíveis mudanças climáticas resultantes do aumento de gases de efeito estufa.

Nutritional reserves of Vochysiaceae seeds: chemical diversity and potential economic uses

Contents of proteins, carbohydrates and oil of seeds of 57 individuals of Vochysiaceae, involving one species of Callisthene, six of Qualea, one of Salvertia and eight of Vochysia were determined. The main nutritional reserves of Vochysiaceae seeds are proteins (20% in average) and oils (21. 6%). Mean of carbohydrate contents was 5. 8%. Callisthene showed the lowest protein content (16. 9%), while Q. cordata was the species with the highest content (30% in average). The contents of ethanol soluble carbohydrates were much higher than those of water soluble carbohydrates. Oil contents lay above 20% for most species (30. 4% in V. pygmaea and V. pyramidalis seeds). The predominant fatty acids are lauric (Q. grandiflora), oleic (Qualea and Salvertia) or acids with longer carbon chains (Salvertia and a group of Vochysia species). The distribution of Vochysiaceae fatty acids suggests for seeds of some species an exploitation as food sources (predominance of oleic acid), for other species an alternative to cocoa butter (high contents or predominance of stearic acid) or the production of lubricants, surfactants, detergents, cosmetics and plastic (predominance of acids with C20 or C22 chains) or biodiesel (predominance of monounsaturated acids). The possibility of exploitation of Vochysiaceae products in a cultivation regimen and in extractive reserves is discussed.

Brasil e brasileiros: notas sobre modelagem de significados políticos na crise do Antigo Regime português na América

Partindo da análise do significado político de Brasil e de brasileiro em documentos escritos por colonos em meados dos setecentos, o artigo aponta para a importância analítica do caráter desviante de variantes americanas da matriz societária portuguesa de tipo Ancien Régime. Trabalhando com os conceitos de memória e experiência, sustenta-se nele a idéia de que, por se tornarem assimétricas, as estruturas nacionais portuguesas dos dois hemisférios também se tornaram irredutíveis a um mesmo enquadramento constitucional quando da instauração da conjuntura revolucionária do final dos anos vinte do século XIX.

Analyzing the n→π* Electronic Transition of Formaldehyde in Water. A Sequential Monte Carlo/Time-Dependent Density Functional Theory

The n→π* absorption transition of formaldehyde in water is analyzed using combined and sequential classical Monte Carlo (MC) simulations and quantum mechanics (QM) calculations. MC simulations generate the liquid solute-solvent structures for subsequent QM calculations. Using time-dependent density functional theory in a localized set of gaussian basis functions (TD-DFT/6-311++G(d,p)) calculations are made on statistically relevant configurations to obtain the average solvatochromic shift. All results presented here use the electrostatic embedding of the solvent. The statistically converged average result obtained of 2300 cm-1 is compared to previous theoretical results available. Analysis is made of the effective dipole moment of the hydrogen-bonded shell and how it could be held responsible for the polarization of the solvent molecules in the outer solvation shells.

Analytical procedures for determining Pb and Sr isotopic compositions in water samples by ID-TIMS

Few articles deal with lead and strontium isotopic analysis of water samples. The aim of this study was to define the chemical procedures for Pb and Sr isotopic analyses of groundwater samples from an urban sedimentary aquifer. Thirty lead and fourteen strontium isotopic analyses were performed to test different analytical procedures. Pb and Sr isotopic ratios as well as Sr concentration did not vary using different chemical procedures. However, the Pb concentrations were very dependent on the different procedures. Therefore, the choice of the best analytical procedure was based on the Pb results, which indicated a higher reproducibility from samples that had been filtered and acidified before the evaporation, had their residues totally dissolved, and were purified by ion chromatography using the Biorad® column. Our results showed no changes in Pb ratios with the storage time.

Unusual 1,6-diphenyl-1,3,5-hexatriene (DPH) spectrophotometric behavior in water/ethanol and water/DMSO mixtures

The absorption spectra of DPH at fixed concentration do not change with water content in organic solvents. It exhibits monomer bands, such as those obtained in ethanol. The absorption did not change for solutions up to 54 and 46% of water in ethanol and DMSO, respectively, for [DPH] = 5.0 × 10-6 mol L-1 at 30 °C. However, at the same experimental conditions, a gradual sharp decay of the DPH fluorescence is observed. It is proposed that water molecules below these water concentration limits act as quenchers of the excited states of DPH. Stern-Volmer quenching constants by intensities measurements are 7.4 × 10-2 (water/ethanol) and 2.6 × 10-2 L mol-1 (water/DMSO). DPH lifetime measurements in the absence and presence of water resulted in 7.1 × 10-2 L mol-1 in water/ethanol, which pointed out that the process is a dynamic quenching by water molecules. For experiments using DPH as probe, this process can affect data, leading to misunderstanding interpretation.

Rheology of decane/water and triglyceride/water emulsions stabilized by β-casein and sodium caseinate

β-Casein and sodium caseinate stabilized emulsions were produced and had their rheological properties investigated as a function of the nature of the oil phase, ionic strength and pH. Oil phases of distinct structural characteristics, namely decane and vegetable oil of high triglyceride content, were assayed. The former was much more effectively emulsified than the latter. Effects of pH and ionic strength were minor. Emulsion rheological properties were strikingly distinct in each case, with viscoelastic, solid-like structures being formed with decane (G' >> G"), differently from what is observed for samples containing triglycerides as the oil phase, in which viscoelasticity was not even apparent. The relevance of the spatial features of the oil phase structure in the development of the emulsion viscoelastic character is discussed. Factors responding for the system distinct behaviour possibly reside at the emulsion droplet interface, unapproachable by optical microscopy, rather than on aspects related to particle size or shape.