16 resultados para frequency-domain spectroscopy, photon migration, absorption, reduced scattering, Intralipid, temperature measurement

em Biblioteca Digital da Produção Intelectual da Universidade de São Paulo


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Two-photon cooperative absorption is common in solid-state physics. In a sample of trapped cold atoms, this effect may open up new possibilities for the study of nonlinear effects. The experiment described herein starts with two colliding Na atoms in the S hyperfine ground state. The pair absorb two photons, resulting in both a P-1/2 and a P-3/2 atom. This excitation is observed by ionization using an external light source. A simple model that considers only dipole-dipole interactions between the atoms allows us to understand the basic features observed in the experimental results. Both the pair of generated atoms and the photons originating from their decay are correlated and may have interesting applications that remain to be explored.

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In the optimization or parametric analyses of risers, several configurations must be analyzed. It is laborious to perform time domain solutions for the dynamic analysis, since they are time-consuming tasks. So, frequency domain solutions appear to be a possible alternative, mainly in the early stages of a riser design. However, frequency domain analysis is linear and requires that nonlinear effects are treated. The aim of this paper is to present a possible way to treat some of these nonlinearities, using an iterative process together with an analytical correction, and compare the results of a frequency domain analysis with the those of a full nonlinear analysis. [DOI: 10.1115/1.4006149]

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Intense phytoplankton blooms were observed along the Patagonian shelf-break with satellite ocean color data, but few in situ optical observations were made in that region. We examine the variability of phytoplankton absorption and particulate scattering coefficients during such blooms on the basis of field data. The chlorophyll-a concentration, [Chla], ranged from 0.1 to 22.3 mg m−3 in surface waters. The size fractionation of [Chla] showed that 80% of samples were dominated by nanophytoplankton (N-group) and 20% by microphytoplankton (M-group). Chlorophyll-specific phytoplankton absorption coefficients at 440 and 676 nm, a*ph(440) and a*ph(676), and particulate scattering coefficient at 660 nm, b*p(660), ranged from 0.018 to 0.173, 0.009 to 0.046, and 0.031 to 2.37 m2 (mg Chla)−1, respectively. Both a*ph(440) and a*ph(676) were statistically higher for the N-group than M-group and also considerably higher than expected from global trends as a function of [Chla]. This result suggests that size of phytoplankton cells in Patagonian waters tends to be smaller than in other regions at similar [Chla]. The phytoplankton cell size parameter, Sf, derived from phytoplankton absorption spectra, proved to be useful for interpreting the variability in the data around the general inverse dependence of a*ph(440), a*ph(676), and b*p(660) on [Chla]. Sf also showed a pattern along the increasing trend of a*ph(440) and a*ph(676) as a function of the ratios of some accessory pigments to [Chla]. Our results suggest that the variability in phytoplankton absorption and scattering coefficients in Patagonian waters is caused primarily by changes in the dominant phytoplankton cell size accompanied by covariation in the concentrations of accessory pigments.

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Understanding how magnetic materials respond to rapidly varying magnetic fields, as in dynamic hysteresis loops, constitutes a complex and physically interesting problem. But in order to accomplish a thorough investigation, one must necessarily consider the effects of thermal fluctuations. Albeit being present in all real systems, these are seldom included in numerical studies. The notable exceptions are the Ising systems, which have been extensively studied in the past, but describe only one of the many mechanisms of magnetization reversal known to occur. In this paper we employ the Stochastic Landau-Lifshitz formalism to study high-frequency hysteresis loops of single-domain particles with uniaxial anisotropy at an arbitrary temperature. We show that in certain conditions the magnetic response may become predominantly out-of-phase and the loops may undergo a dynamic symmetry loss. This is found to be a direct consequence of the competing responses due to the thermal fluctuations and the gyroscopic motion of the magnetization. We have also found the magnetic behavior to be exceedingly sensitive to temperature variations, not only within the superparamagnetic-ferromagnetic transition range usually considered, but specially at even lower temperatures, where the bulk of interesting phenomena is seen to take place. (C) 2011 Elsevier B.V. All rights reserved.

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The equilibrium of meso-tetrakis(4-N-methylpyridiniumyl)porphyrin (TMPyP) in aqueous solution in the presence of surfactants was studied by optical spectroscopic techniques and SAXS (small angle X-ray scattering). Anionic SDS (sodium dodecyl sulfate), zwitterionic HPS (N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate) and nonionic TRITON X-100 (t-octyl-phenoxypolyethoxyethanol), surfactants were used. TMPyP is characterized by a protonation equilibrium with a pK(a) around 1.0, associated with the diacid-free base transition, and a second pK(a) around 12.0 related with the transition between the free base and the monoanion form. Three independent species were observed for TMPyP at pH 6.0 as a function of SDS concentration: free TMPyP, TMPyP-SDS aggregates and porphyrin monomer bound to micelles. For HPS and TRITON X-100, the equilibrium of TMPyP as a function of pH is quite similar to that obtained in pure aqueous solution: no aggregation was observed, suggesting that electrostatic contribution is the major factor in the interaction between TMPyP and surfactants. SAXS data analysis demonstrated a prolate ellipsoidal shape for SDS micelles; no significant changes in shape and size were observed for SDS-TMPyP co-micelles. Moreover, the ionization coefficient, alpha, decreases with the increase of the porphyrin concentration, suggesting the ""screening"" of the anionic charge of SDS by the cationic porphyrin. These results are consistent with optical absorption, fluorescence and RLS (resonance light scattering) spectroscopies data, allowing to conclude that neutral surfactants present a smaller interaction with the cationic porphyrin as compared with an ionic surfactant. Therefore, the interaction of TMPyP with the ionic and nonionic surfactants is predominantly due to the electrostatic contribution. Copyright (c) 2008 Society of Porphyrins & Phthalocyanines.

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The interaction of the cationic meso-tetrakis 4-N-methylpyridyl porphyrin (TMPyP) with large unilamellar vesicles (LUVs) was investigated in the present study. LUVs were formed by mixtures of the zwitterionic 1,2-dipalmitoyl-sn-glycero-phosphatidylcholine (DPPC) and anionic 1,2-dipalmitoyl-sn-glycero-3-phosphoglycerol (DPPG) phospholipids, at different DPPG molar percentages. All investigations were carried out above (50 degrees C) and below (25 degrees C) the main phase transition temperature of the LUVs (similar to 41 degrees C). The binding constant values, K-b, estimated from the time-resolved fluorescence study, showed a significant increase of the porphyrin affinity at higher mol% DPPG. This affinity is markedly increased when the LUVs are in the liquid crystalline state. For both situations, the increase of the K-b value was also followed by a higher porphyrin fraction bound to the LUVs. The displacement of the vesicle-bound porphyrins toward the aqueous medium, upon titration with the salt potassium chloride (KCl), was also studied. Altogether, our steady-state and frequency-domain fluorescence quenching data results indicate that the TMPyP is preferentially located at the LUVs Stern layer. This is supported by the zeta potential studies, where a partial neutralization of the LUVs surface charge, upon porphyrin titration, was observed. Dynamic light scattering (DLS) results showed that, for some phospholipid systems, this partial neutralization leads to the LUVs flocculation. (C) 2012 Elsevier Inc. All rights reserved.

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This work presents a study on the effects of the particle size, material concentration and radiation energy on the X-ray absorption. CuO nanoparticles and microparticles were incorporated separately into a polymeric resin in concentrations of 5%, 10% and 30% relative to the resin mass. X-ray absorption by these materials was analyzed with a CdTe detector. The X-ray absorption is higher for the nanostructured material compared to the microstructured one for low energy X-ray beams for all CuO concentrations. (c) 2011 Elsevier Ltd. All rights reserved.

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Titan's optical and near-IR spectra result primarily from the scattering of sunlight by haze and its absorption by methane. With a column abundance of 92 km amagat (11 times that of Earth), Titan's atmosphere is optically thick and only similar to 10% of the incident solar radiation reaches the surface, compared to 57% on Earth. Such a formidable atmosphere obstructs investigations of the moon's lower troposphere and surface, which are highly sensitive to the radiative transfer treatment of methane absorption and haze scattering. The absorption and scattering characteristics of Titan's atmosphere have been constrained by the Huygens Probe Descent Imager/Spectral Radiometer (DISR) experiment for conditions at the probe landing site (Tomasko, M.G., Bezard, B., Doose, L., Engel, S., Karkoschka, E. 120084 Planet. Space Sci. 56, 624-247: Tomasko, M.G. et al. [2008b] Planet. Space Sci. 56, 669-707). Cassini's Visual and Infrared Mapping Spectrometer (VIMS) data indicate that the rest of the atmosphere (except for the polar regions) can be understood with small perturbations in the high haze structure determined at the landing site (Penteado, P.F., Griffith, CA., Tomasko, M.G., Engel, S., See, C., Doose, L, Baines, K.H., Brown, R.H., Buratti, B.J., Clark, R., Nicholson, P., Sotin, C. [2010]. Icarus 206, 352-365). However the in situ measurements were analyzed with a doubling and adding radiative transfer calculation that differs considerably from the discrete ordinates codes used to interpret remote data from Cassini and ground-based measurements. In addition, the calibration of the VIMS data with respect to the DISR data has not yet been tested. Here, VIMS data of the probe landing site are analyzed with the DISR radiative transfer method and the faster discrete ordinates radiative transfer calculation; both models are consistent (to within 0.3%) and reproduce the scattering and absorption characteristics derived from in situ measurements. Constraints on the atmospheric opacity at wavelengths outside those measured by DISR, that is from 1.6 to 5.0 mu m, are derived using clouds as diffuse reflectors in order to derive Titan's surface albedo to within a few percent error and cloud altitudes to within 5 km error. VIMS spectra of Titan at 2.6-3.2 mu m indicate not only spectral features due to CH4 and CH3D (Rannou, P., Cours, T., Le Mouelic, S., Rodriguez, S., Sotin, C., Drossart, P., Brown, R. [2010]. Icarus 208, 850-867), but also a fairly uniform absorption of unknown source, equivalent to the effects of a darkening of the haze to a single scattering albedo of 0.63 +/- 0.05. Titan's 4.8 mu m spectrum point to a haze optical depth of 0.2 at that wavelength. Cloud spectra at 2 mu m indicate that the far wings of the Voigt profile extend 460 cm(-1) from methane line centers. This paper releases the doubling and adding radiative transfer code developed by the DISR team, so that future studies of Titan's atmosphere and surface are consistent with the findings by the Huygens Probe. We derive the surface albedo at eight spectral regions of the 8 x 12 km(2) area surrounding the Huygens landing site. Within the 0.4-1.6 mu m spectral region our surface albedos match DISR measurements, indicating that DISR and VIMS measurements are consistently calibrated. These values together with albedos at longer 1.9-5.0 mu m wavelengths, not sampled by DISR, resemble a dark version of the spectrum of Ganymede's icy leading hemisphere. The eight surface albedos of the landing site are consistent with, but not deterministic of, exposed water ice with dark impurities. (C) 2011 Elsevier Inc. All rights reserved.

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The ionic liquid butyltrimethylammonium bis(trifluoromethylsulfonyl)imide, [C4C1C1C1N][Tf2N], is a glass-forming liquid that exhibits partial crystallization depending on the cooling rate. Differential scanning calorimetry (DSC) indicates crystallization at T-c = 227 K, melting at T-m = 258 K, glass transition at T-g similar to 191 K, and also cold crystallization at T-cc similar to 219 K. Raman spectroscopy shows that the crystalline structure obtained by slow cooling is formed with [Tf2N](-) in cisoid conformation, whereas [Tf2N](-) in transoid conformation results from fast cooling. No preferred conformation of the butyl chain of the [C4C1C1C1N](+) cation is favored by slow or fast cooling of [C4C1C1C1N][Tf2N]. Low-frequency Raman spectroscopy shows that crystalline domains developing in the supercooled liquid result in a glacial state made of a mixture of crystallites and amorphous phase. However, these crystalline structures obtained by slow cooling or cold crystallization are not the same because anion-cation interactions promote local structures with distinct conformations of the [Tf2N](-) anion.

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O objetivo deste estudo foi analisar a reprodutibilidade de parâmetros no domínio da frequência do sinal eletromiográfico (EMG) utilizados na caracterização da fadiga muscular localizada. Quinze sujeitos do sexo masculino foram submetidos a um teste de fadiga baseado na extensão isométrica de joelho, sendo realizados em três momentos distintos com intervalos de sete dias. Para avaliar a reprodutibilidade dos dados entres os testes calculou-se o coeficiente de correlação intraclasse (CCI) para a frequência mediana (Fmed) no tempo total de exercício (FmedT), para a Fmed obtida a cada 10% do tempo de exercício (Fmed10%) e para as potências das bandas de frequência, obtidas da divisão do espectro de potência a cada 20 Hz. Os resultados demonstraram: (1) boa reprodutibilidade para a FmedT; (2) boa reprodutibilidade para a Fmed10%; e (3) maior variação no sinal EMG nas bandas de 20 a 120 Hz, no qual se destacam as bandas de 20-40 Hz e de 40-60 Hz, demonstrando maior sensibilidade ao processo de fadiga muscular. Conclui-se que a Fmed é uma variável que apresenta boa reprodutibilidade e que a análise fragmentada do espectro de potência, por meio das bandas de frequência, demonstrou-se sensível as variações que ocorrem no sinal EMG durante a instalação do processo de fadiga, tendo potencial para se tornar um novo método para a caracterização da fadiga muscular localizada.

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We report herein for the first time a facile synthesis method to obtain SrTi1-xFexO3 nanocubes by means by a microwave-assisted hydrothermal (MAH) method at 140 degrees C. The effect of iron addition on the structural and morphological properties of SrTiO3 was investigated. X-ray diffraction measurements show that all STFO samples present a cubic perovskite structure. X-ray absorption spectroscopy at Fe absorption K-edge measurements revealed that iron ions are in a mixed Fe2+/Fe3+ oxidation state and preferentially occupy the Ti4+-site. UV-visible spectra reveal a reduction in the optical gap (E-gap) of STFO samples as the amount of iron is increased. An analysis of the data obtained by field emission scanning electron microscopy points out that the nanoparticles present a cubic morphology independently of iron content. According to high-resolution transmission electron microscopy results, these nanocubes are formed by a self-assembly process of small primary nanocrystals.

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Self-assembly of poly(4-vynil-N-alkyl)pyridinium bromide with alkyl side chains of 2, 5, 7, 10, or 16 carbons from ethanolic solutions onto flat silica surfaces was studied by means of ellipsometry, atomic force microscopy (AFM), contact angle measurements, and sum-frequency generation (SFG) vibrational spectroscopy in the CH3 and CH2 stretch region. Ab initio quantum-chemical calculations on the N-alkylpyridinium side-group with restricted Hartree-Fock (RHF) method and 6-311G (d,p) basis set were C one to estimate the charge distribution along the pyridinium ring and the alkyl side-chain. SFG results showed that longer side chains promote the disorientation of the alkyl groups at the surface, corroborating with the contact angle values. AFM images revealed film homogeneity, regardless the alkyl side group. However, after 24 h contact with water, ringlike structures appeared on the film surfaces, when the polycation alkyl side chain had 7 or less carbons, and as the alkyl chain increased to 10 or 16 carbons, the films dewetted because the hydrophobic interactions prevailed over the electrostatic interactions between the pyridinium charged groups and the negatively charged SiO2 surface. Under acid conditions (HCl 0.1 mol.L-1), the film mean thickness values decreased up to 50% of original values when the alkyl side chains were ethyl or pentyl groups due to ion-pair disruption, but for longer groups they remained unchanged. Quantum-chemical optimization and Mulliken electron population showed that (i) from C2 to C15 the positive charge at the headgroup (HG) decreased 0.025, while the charge at combined HG + alpha-CH2 increased 0.037; and (ii) for C6 or longer, the alkyl side group presents a tilt in the geometry, moving away from the plane. Such effects summed up over the whole polymer chain give support to suggest that when the side chains are longer than 7 carbons, the hydrophobic interaction decreases film stability and increases acid resistance.

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This Letter reports an investigation on the optical properties of copper nanocubes as a function of size as modeled by the discrete dipole approximation. In the far-field, our results showed that the extinction resonances shifted from 595 to 670 nm as the size increased from 20 to 100 nm. Also, the highest optical efficiencies for absorption and scattering were obtained for nanocubes that were 60 and 100 nm in size, respectively. In the near-field, the electric-field amplitudes were investigated considering 514, 633 and 785 nm as the excitation wavelengths. The E-fields increased with size, being the highest at 633 nm. (c) 2012 Elsevier B.V. All rights reserved.

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The Large Scale Biosphere Atmosphere Experiment in Amazonia (LBA) is a long term (20 years) research effort aimed at the understanding of the functioning of the Amazonian ecosystem. In particular, the strong biosphere-atmosphere interaction is a key component looking at the exchange processes between vegetation and the atmosphere, focusing on aerosol particles. Two aerosol components are the most visible: The natural biogenic emissions of aerosols and VOCs, and the biomass burning emissions. A large effort was done to characterize natural biogenic aerosols that showed detailed organic characterization and optical properties. The biomass burning component in Amazonia is important in term of aerosol and trace gases emissions, with deforestation rates decreasing, from 27,000 Km2 in 2004 to about 5,000 Km2 in 2011. Biomass burning emissions in Amazonia increases concentrations of aerosol particles, CO, ozone and other species, and also change the surface radiation balance in a significant way. Long term monitoring of aerosols and trace gases were performed in two sites: a background site in Central Amazonia, 55 Km North of Manaus (called ZF2 ecological reservation) and a monitoring station in Porto Velho, Rondonia state, a site heavily impacted by biomass burning smoke. Several instruments were operated to measured aerosol size distribution, optical properties (absorption and scattering at several wavelengths), composition of organic (OC/EC) and inorganic components among other measurements. AERONET and MODIS measurements from 5 long term sites show a large year-to year variability due to climatic and socio-economic issues. Aerosol optical depths of more than 4 at 550nm was observed frequently over biomass burning areas. In the pristine Amazonian atmosphere, aerosol scattering coefficients ranged between 1 and 200 Mm-1 at 450 nm, while absorption ranged between 1 and 20 Mm-1 at 637 nm. A strong seasonal behavior was observed, with greater aerosol loadings during the dry season (Jul-Nov) as compared to the wet season (Dec-Jun). During the wet season in Manaus, aerosol scattering (450 nm) and absorption (637 nm) coefficients averaged, respectively, 14 and 0.9 Mm-1. Angstrom exponents for scattering were lower during the wet season (1.6) in comparison to the dry season (1.9), which is consistent with the shift from biomass burning aerosols, predominant in the fine mode, to biogenic aerosols, predominant in the coarse mode. Single scattering albedo, calculated at 637 nm, did not show a significant seasonal variation, averaging 0.86. In Porto Velho, even in the wet season it was possible to observe an impact from anthropogenic aerosol. Black Carbon was measured at a high 20 ug/m³ in the dry season, showing strong aerosol absorption. This work presents a general description of the aerosol optical properties in Amazonia, both during the Amazonian wet and dry seasons.

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A low-energy new method based in a one-step synthesis at room temperature produces very small maghemite nanopar ticles. The fast neutralization reaction (co-precipitation) of a ferric solution (FeCl3 aqueous) in a basic medium (NH4OH concentrated) produces an intermediate phase, presumably two-line ferrihydrite, that in oxidizing conditions is transformed to maghemite nanopar ticles. That “primordial soup” is characterized by small atom arrangements that are the base for maghemite tiny crystals. The final product of the reaction was characterized by X-ray diffraction, high-resolution transmission electron microscopy, X-ray absorption fine structure, Mössbauer spectroscopy, and magnetometry.