979 resultados para characteristic time


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Time-resolved kinetic studies of silylene, SiH2, generated by laser flash photolysis of phenylsilane, have been carried out to obtain rate constants for its bimolecular reactions with oxirane, oxetane, and tetrahydrofuran (THF). The reactions were studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas, at four or five temperatures in the range 294-605 K. All three reactions showed pressure dependences characteristic of third-body-assisted association reactions with, surprisingly, SiH2 + oxirane showing the least and SiH2 + THF showing the most pressure dependence. The second-order rate constants obtained by extrapolation to the high-pressure limits at each temperature fitted the Arrhenius equations where the error limits are single standard deviations: log(k(oxirane)(infinity)/cm(3) molecule(-1) s(-1)) = (-11.03 +/- 0.07) + (5.70 +/- 0.51) kJ mol(-1)/RT In 10 log(k(oxetane)(infinity)/cm(3) molecule(-1) s(-1)) = (-11.17 +/- 0.11) + (9.04 +/- 0.78) kJ mol(-1)/RT In 10 log(k(THF)(infinity)/cm(3) molecule(-1) s(-1)) = (-10.59 +/- 0.10) + (5.76 +/- 0.65) kJ mol(-1)/RT In 10 Binding-energy values of 77, 97, and 92 kJ mol(-1) have been obtained for the donor-acceptor complexes of SiH2 with oxirane, oxetane, and THF, respectively, by means of quantum chemical (ab initio) calculations carried Out at the G3 level. The use of these values to model the pressure dependences of these reactions, via RRKM theory, provided a good fit only in the case of SiH2 + THF. The lack of fit in the other two cases is attributed to further reaction pathways for the association complexes of SiH2 with oxirane and oxetane. The finding of ethene as a product of the SiH2 + oxirane reaction supports a pathway leading to H2Si=O + C2H4 predicted by the theoretical calculations of Apeloig and Sklenak.

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Time-resolved kinetic studies of silylene, SiH2, generated by laser flash photolysis of 1-silacyclopent-3-ene and phenylsilane, have been carried out to obtain rate constants for its bimolecular reactions with methanol, ethanol, 1-propanol, 1-butanol and 2-methyl-1-butanol. The reactions were studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas, at room temperature. In the study with methanol several buffer gases were used. All five reactions showed pressure dependences characteristic of third body assisted association reactions. The rate constant pressure dependences were modelled using RRKM theory, based on Eo values of the association complexes obtained by ab initio calculation (G3 level). Transition state models were adjusted to fit experimental fall-off curves and extrapolated to obtain k∞ values in the range 1.9 to 4.5 × 10-10 cm3 molecule-1 s-1. These numbers, corresponding to the true bimolecular rate constants, indicate efficiencies of between 16 and 67% of the collision rates for these reactions. In the reaction of SiH2 + MeOH there is a small kinetic component to the rate which is second order in MeOH (at low total pressures). This suggests an additional catalysed reaction pathway, which is supported by the ab initio calculations. These calculations have been used to define specific MeOH-for-H2O substitution effects on this catalytic pathway. Where possible our experimental and theoretical results are compared with those of previous studies.

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The [Ru(phen)2(dppz)]2+ complex (1) is non-emissive in water but is highly luminescent in organic solvents or when bound to DNA, making it a useful probe for DNA binding. To date, a complete mechanistic explanation for this “light-switch” effect is still lacking. With this in mind we have undertaken an ultrafast time resolved infrared (TRIR) study of 1 and directly observe marker bands between 1280–1450 cm-1, which characterise both the emissive “bright” and the non-emissive “dark” excited states of the complex, in CD3CN and D2O respectively. These characteristic spectral features are present in the [Ru(dppz)3]2+ solvent light-switch complex but absent in [Ru(phen)3]2+, which is luminescent in both solvents. DFT calculations show that the vibrational modes responsible for these characteristic bands are predominantly localised on the dppz ligand. Moreover, they reveal that certain vibrational modes of the “dark” excited state couple with vibrational modes of two coordinating water molecules, and through these to the bulk solvent, thus providing a new insight into the mechanism of the light-switch effect. We also demonstrate that the marker bands for the “bright” state are observed for both L- and D enantiomers of 1 when bound to DNA and that photo-excitation of the complex induces perturbation of the guanine and cytosine carbonyl bands. This perturbation is shown to be stronger for the L enantiomer, demonstrating the different binding site properties of the two enantiomers and the ability of this technique to determine the identity and nature of the binding site of such intercalators.

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Amazonian oils and fats display unique triacylglycerol (TAG) profiles and, because of their economic importance as renewable raw materials and use by the cosmetic and food industries, are often subject to adulteration and forgery. Representative samples of these oils (andiroba, Brazil nut, buriti, and passion fruit) and fats (cupuacu, murumuru, and ucuba) were characterized without pre-separation or derivatization via dry (solvent-free) matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). Characteristic profiles of TAG were obtained for each oil and tat. Dry MALDI-TOF MS provides typification and direct and detailed information, via TAG profiles, of their variable combinations of fatty acids. A database from spectra could be developed and may be used for their fast and reliable typification, application screening, and quality control.

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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We study the effects of a repulsive three-body interaction on a system of trapped ultracold atoms in a Bose-Einstein condensed state. The stationary solutions of the corresponding s-wave nonlinear Schrödinger equation suggest a scenario of first-order liquid-gas phase transition in the condensed state up to a critical strength of the effective three-body force. The time evolution of the condensate with feeding process and three-body recombination losses has a different characteristic pattern. Also, the decay time of the dense (liquid) phase is longer than expected due to strong oscillations of the mean-squared radius.

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Rheology has the purpose to study the flux and deformation of materials when submitted to some tension or outer mechanical solicitation. In practice, the effective scientific field broached by rheology is restricted only to the study of homogeneous fluids behavior, in which are included eminent liquids, particles suspensions, and emulsions. The viscosity (η) and the yield stress (τ 0) are the two basic values that define the fluids' behavior. The first one is the proportionality constant that relates the shear rate (γ) with the shear stress (τ) applied, while the second indicates the minimal tension for the flowage beginning. The fluids that obey the Newton's relation - Newtonians fluids - display the constant viscosity and the null yield stress. It's the case of diluted suspensions and grate amount of the pure liquids (water, acetone, alcohol, etc.) in which the viscosity is an intrinsic characteristic that depends on temperature and, in a less significant way, pressure. The suspension, titled Cement Paste, is defined as being a mixture of water and cement with, or without, a superplasticizer additive. The cement paste has a non-Newtonian fluid behavior (pseudoplastic), showing a viscosity that varies in accord to the applied shear stress and significant deformations are obtained from a delimited yield stress. In some cases, systems can also manifest the influence of chemical additives used to modify the interactions fluid/particles, besides the introduced modifications by the presence of incorporated air. To the cement paste the rheometric rehearsals were made using the rheometer R/S Brookfield that controls shear stress and shear rate in accord to the rheological model of Herschel-Bulkley that seems to better adapt to this kind of suspension's behavior. This paper shows the results of rheometrical rehearsals on the cement paste that were produced with cements HOLCIM MC-20 RS and CPV-ARI RS with the addition of superplasticizer additives based of napthaline and polycarboxilate, with and without a constant agitation of the mixture. The obtainment of dosages of superplasticizer additives, as well as the water/cement ratio, at the cement at the fluidify rate determination, was done in a total of 12 different mixtures. It's observed that the rheological parameters seem to vary according to the cement type, the superplasticizer type, and the methodology applied at the fluidity rate determination.

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In the last decades there was a great development in the study of control systems to attenuate the harmful effect of natural events in great structures, as buildings and bridges. Magnetorheological fluid (MR), that is an intelligent material, has been considered in many proposals of project for these controllers. This work presents the controller design using feedback of states through LMI (Linear Matrix Inequalities) approach. The experimental test were carried out in a structure with two degrees of freedom with a connected shock absorber MR. Experimental tests were realized in order to specify the features of this semi-active controller. In this case, there exist states that are not measurable, so the feedback of the states involves the project of an estimator. The coupling of the MR damper causes a variation in dynamics properties, so an identification methods, based on experimental input/output signal was used to compare with the numerical application. The identification method of Prediction Error Methods - (PEM) was used to find the physical characteristics of the system through realization in modal space of states. This proposal allows the project of a semi-active control, where the main characteristic is the possibility of the variation of the damping coefficient.

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The characterization of soil CO2 emissions (FCO2) is important for the study of the global carbon cycle. This phenomenon presents great variability in space and time, a characteristic that makes attempts at modeling and forecasting FCO2 challenging. Although spatial estimates have been performed in several studies, the association of these estimates with the uncertainties inherent in the estimation procedures is not considered. This study aimed to evaluate the local, spatial, local-temporal and spatial-temporal uncertainties of short-term FCO2 after harvest period in a sugar cane area. The FCO2 was featured in a sampling grid of 60m×60m containing 127 points with minimum separation distances from 0.5 to 10m between points. The FCO2 was evaluated 7 times within a total period of 10 days. The variability of FCO2 was described by descriptive statistics and variogram modeling. To calculate the uncertainties, 300 realizations made by sequential Gaussian simulation were considered. Local uncertainties were evaluated using the probability values exceeding certain critical thresholds, while the spatial uncertainties considering the probability of regions with high probability values together exceed the adopted limits. Using the daily uncertainties, the local-spatial and spatial-temporal uncertainty (Ftemp) was obtained. The daily and mean emissions showed a variability structure that was described by spherical and Gaussian models. The differences between the daily maps were related to variations in the magnitude of FCO2, covering mean values ranging from 1.28±0.11μmolm-2s-1 (F197) to 1.82±0.07μmolm-2s-1 (F195). The Ftemp showed low spatial uncertainty coupled with high local uncertainty estimates. The average emission showed great spatial uncertainty of the simulated values. The evaluation of uncertainties associated with the knowledge of temporal and spatial variability is an important tool for understanding many phenomena over time, such as the quantification of greenhouse gases or the identification of areas with high crop productivity. © 2013 Elsevier B.V.

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Nowadays the method based on demodulation by envelope finds wide application in industry as a technique for evaluation of bearings and other components in rotating machinery. In recent years the application of Wavelets for fault diagnosis in machinery has also obtained good development. This article demonstrates the effectiveness of the combined application of Wavelets and envelope technique (also known as HFRT High-Frequency Resonance Technique) to remove background noise from signals collected from defect bearings and identification of the characteristic frequencies of defects. A comparison of the results obtained with the isolated application of only one method against the combined technique is performed showing the increased capacity in detection of faults in rolling bearings. © (2013) Trans Tech Publications, Switzerland.

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Objectives: The stair-climbing test as measured in meters or number of steps has been proposed to predict the risk of postoperative complications. The study objective was to determine whether the stair-climbing time can predict the risk of postoperative complications. Methods: Patients aged more than 18 years with a recommendation of thoracotomy for lung resection were included in the study. Spirometry was performed according to the criteria by the American Thoracic Society. The stair-climbing test was performed on shaded stairs with a total of 12.16 m in height, and the stair-climbing time in seconds elapsed during the climb of the total height was measured. The accuracy test was applied to obtain stair-climbing time predictive values, and the receiver operating characteristic curve was calculated. Variables were tested for association with postoperative cardiopulmonary complications using the Student t test for independent populations, the Mann-Whitney test, and the chi-square or Fisher exact test. Logistic regression analysis was performed. Results: Ninety-eight patients were evaluated. Of these, 27 showed postoperative complications. Differences were found between the groups for age and attributes obtained from the stair-climbing test. The cutoff point for stair-climbing time obtained from the receiver operating characteristic curve was 37.5 seconds. No differences were found between the groups for forced expiratory volume in 1 second. In the logistic regression, stair-climbing time was the only variable associated with postoperative complications, suggesting that the risk of postoperative complications increases with increased stair-climbing time. Conclusions: The only variable showing association with complications, according to multivariate analysis, was stair-climbing time. © 2013 by The American Association for Thoracic Surgery.

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Despite its high incidence, patellofemoral pain etiology remains unclear. No prior study has compared surface electromyography frequency domain parameters and surface electromyography time domain variables, which have been used as a classic analysis of patellofemoral pain. Thirty one women with patellofemoral pain and twenty eight pain-free women were recruited. Each participant was asked to descend a seven step staircase and data from five successful trials were collected. During the task, the vastus medialis and vastus lateralis muscle activities were monitored by surface electromyography. The data were processed and analyzed in four variables of the frequency domain (median frequency, low, medium and high frequency bands) and three time domain variables (Automatic, Cross-correlation and Visual Onset between the vastus medialis and vastus lateralis muscles). Reliability, Receiver Operating Characteristic curves and regression models were performed. The medium frequency band was the most reliable variable and different between the groups for both muscles, also demonstrated the best values of sensitivity and sensibility, 72% and 69% for the vastus medialis and 68% and 62% for the vastus lateralis, respectively. The frequency variables predicted the pain of individuals with patellofemoral pain, 26% for the vastus medialis and 20% for the vastus lateralis, being better than the time variables, which achieved only 7%. The frequency domain parameters presented greater reliability, diagnostic accuracy and capacity to predict pain than the time domain variables during stair descent and might be a useful tool to diagnose individuals with patellofemoral pain.

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The leaf area index (LAI) is a key characteristic of forest ecosystems. Estimations of LAI from satellite images generally rely on spectral vegetation indices (SVIs) or radiative transfer model (RTM) inversions. We have developed a new and precise method suitable for practical application, consisting of building a species-specific SVI that is best-suited to both sensor and vegetation characteristics. Such an SVI requires calibration on a large number of representative vegetation conditions. We developed a two-step approach: (1) estimation of LAI on a subset of satellite data through RTM inversion; and (2) the calibration of a vegetation index on these estimated LAI. We applied this methodology to Eucalyptus plantations which have highly variable LAI in time and space. Previous results showed that an RTM inversion of Moderate Resolution Imaging Spectroradiometer (MODIS) near-infrared and red reflectance allowed good retrieval performance (R-2 = 0.80, RMSE = 0.41), but was computationally difficult. Here, the RTM results were used to calibrate a dedicated vegetation index (called "EucVI") which gave similar LAI retrieval results but in a simpler way. The R-2 of the regression between measured and EucVI-simulated LAI values on a validation dataset was 0.68, and the RMSE was 0.49. The additional use of stand age and day of year in the SVI equation slightly increased the performance of the index (R-2 = 0.77 and RMSE = 0.41). This simple index opens the way to an easily applicable retrieval of Eucalyptus LAI from MODIS data, which could be used in an operational way.