Molecular Ordering in Layer-by-Layer Polyelectrolyte Films Studied by Sum-Frequency Vibrational Spectroscopy: The Effects of Drying Procedures

Sum-Frequency Vibrational Spectroscopy (SFVS) has been used to investigate the effect of nitrogen-flow drying on the molecular ordering of Layer-by-Layer (LbL) films of poly(allylamine hydrochloride) (PAH) alternated with poly(styrene sulfonate) (PSS). We find that films dried by spontaneous water evaporation are more ordered and homogeneous than films dried by nitrogen flow. The latter are quite inhomogeneous and may have regions with highly disordered polymer conformation. We propose that drying by spontaneous water evaporation reduces the effect of drag by the drying front, while during nitrogen-flow drying the fast evaporation of water ""freezes"" the disordered conformation of adsorbed polyelectrolyte molecules. These findings are important for many applications of LbL films, since device performance usually depends on film morphology and its molecular structure.

A Simple and Fast Method for the Production and Characterization of Methylic and Ethylic Biodiesels from Tucum Oil via an Alkaline Route

A simple, fast, and complete route for the production of methylic and ethylic biodiesel from tucum oil is described. Aliquots of the oil obtained directly from pressed tucum (pulp and almonds) were treated with potassium methoxide or ethoxide at 40 degrees C for 40 min. The biodiesel form was removed from the reactor and washed with 0.1 M HCl aqueous solution. A simple distillation at 100 degrees C was carried out in order to remove water and alcohol species from the biodiesel. The oxidative stability index was obtained for the tucum oil as well as the methylic and ethylic biodiesel at 6.13, 2.90, and 2.80 h, for storage times higher than 8 days. Quality control of the original oil and of the methylic and ethylic biodiesels, such as the amount of glycerin produced during the transesterification process, was accomplished by the TLC, GC-MS, and FT-IR techniques. The results obtained in this study indicate a potential biofuel production by simple treatment of tucum, an important Amazonian fruit.

Fast ray-tracing algorithm for circumstellar structures (FRACS) II. Disc parameters of the B[e] supergiant CPD-57 degrees 2874 from VLTI/MIDI data

Context. B[e] supergiants are luminous, massive post-main sequence stars exhibiting non-spherical winds, forbidden lines, and hot dust in a disc-like structure. The physical properties of their rich and complex circumstellar environment (CSE) are not well understood, partly because these CSE cannot be easily resolved at the large distances found for B[e] supergiants (typically greater than or similar to 1 kpc). Aims. From mid-IR spectro-interferometric observations obtained with VLTI/MIDI we seek to resolve and study the CSE of the Galactic B[e] supergiant CPD-57 degrees 2874. Methods. For a physical interpretation of the observables (visibilities and spectrum) we use our ray-tracing radiative transfer code (FRACS), which is optimised for thermal spectro-interferometric observations. Results. Thanks to the short computing time required by FRACS (<10 s per monochromatic model), best-fit parameters and uncertainties for several physical quantities of CPD-57 degrees 2874 were obtained, such as inner dust radius, relative flux contribution of the central source and of the dusty CSE, dust temperature profile, and disc inclination. Conclusions. The analysis of VLTI/MIDI data with FRACS allowed one of the first direct determinations of physical parameters of the dusty CSE of a B[e] supergiant based on interferometric data and using a full model-fitting approach. In a larger context, the study of B[e] supergiants is important for a deeper understanding of the complex structure and evolution of hot, massive stars.

BONA FIDE, STRONG-VARIABLE GALACTIC LUMINOUS BLUE VARIABLE STARS ARE FAST ROTATORS: DETECTION OF A HIGH ROTATIONAL VELOCITY IN HR CARINAE

We report optical observations of the luminous blue variable (LBV) HR Carinae which show that the star has reached a visual minimum phase in 2009. More importantly, we detected absorptions due to Si lambda lambda 4088-4116. To match their observed line profiles from 2009 May, a high rotational velocity of nu(rot) similar or equal to 150 +/- 20 km s(-1) is needed (assuming an inclination angle of 30 degrees), implying that HR Car rotates at similar or equal to 0.88 +/- 0.2 of its critical velocity for breakup (nu(crit)). Our results suggest that fast rotation is typical in all strong-variable, bona fide galactic LBVs, which present S-Dor-type variability. Strong-variable LBVs are located in a well-defined region of the HR diagram during visual minimum (the ""LBV minimum instability strip""). We suggest this region corresponds to where nu(crit) is reached. To the left of this strip, a forbidden zone with nu(rot)/nu(crit) > 1 is present, explaining why no LBVs are detected in this zone. Since dormant/ex LBVs like P Cygni and HD 168625 have low nu(rot), we propose that LBVs can be separated into two groups: fast-rotating, strong-variable stars showing S-Dor cycles (such as AG Car and HR Car) and slow-rotating stars with much less variability (such as P Cygni and HD 168625). We speculate that supernova (SN) progenitors which had S-Dor cycles before exploding (such as in SN 2001ig, SN 2003bg, and SN 2005gj) could have been fast rotators. We suggest that the potential difficulty of fast-rotating Galactic LBVs to lose angular momentum is additional evidence that such stars could explode during the LBV phase.

Development and validation of a fast RP-HPLC method to determine the analogue of the thyroid hormone, 3,5,3 '-triiodothyroacetic acid (TRIAC), in polymeric nanoparticles

The objective of this work was to develop and validate a rapid Reversed-Phase High-Performance Liquid Chromatography method for the quantification of 3,5,3 '-triiodothyroacetic acid (TRIAC) in nanoparticles delivery system prepared in different polymeric matrices. Special attention was given to developing a reliable reproductive technique for the pretreatment of the samples. Chromatographic runs were performed on an Agilent 1200 Series HPLC with a RP Phenomenex (R) Gemini C18 (150 x 4, 6 mm i.d., 5 mu m) column using acetonitrile and triethylamine buffer 0.1% (TEA) (40 : 60 v/v) as a mobile phase in an isocratic elution, pH 5.6 at a flow rate of 1 ml min(-1). TRIAC was detected at a wavelength of 220 nm. The injection volume was 20 mu l and the column temperature was maintained at 35 degrees C. The validation characteristics included accuracy, precision, specificity, linearity, recovery, and robustness. The standard curve was found to have a linear relationship (r(2) - 0.9996) over the analytical range of 5-100 mu g ml(-1) . The detection and quantitation limits were 1.3 and 3.8 mu g ml(-1), respectively. The recovery and loaded TRIAC in colloidal system delivery was nearly 100% and 98%, respectively. The method was successfully applied in polycaprolactone, polyhydroxybutyrate, and polymethylmethacrylate nanoparticles.

Intermolecular vibrations and fast relaxations in supercooled ionic liquids

Short-time dynamics of ionic liquids has been investigated by low-frequency Raman spectroscopy (4 < omega < 100 cm(-1)) within the supercooled liquid range. Raman spectra are reported for ionic liquids with the same anion, bis(trifluoromethylsulfonyl)imide, and different cations: 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-butyl-1-methylpiperidinium, trimethylbutylammonium, and tributylmethylammonium. It is shown that low-frequency Raman spectroscopy provides similar results as optical Kerr effect (OKE) spectroscopy, which has been used to study intermolecular vibrations in ionic liquids. The comparison of ionic liquids containing aromatic and non-aromatic cations identifies the characteristic feature in Raman spectra usually assigned to librational motion of the imidazolium ring. The strength of the fast relaxations (quasi-elastic scattering, QES) and the intermolecular vibrational contribution (boson peak) of ionic liquids with non-aromatic cations are significantly lower than imidazolium ionic liquids. A correlation length assigned to the boson peak vibrations was estimated from the frequency of the maximum of the boson peak and experimental data of sound velocity. The correlation length related to the boson peak (similar to 19 angstrom) does not change with the length of the alkyl chain in imidazolium cations, in contrast to the position of the first-sharp diffraction peak observed in neutron and X-ray scattering measurements of ionic liquids. The rate of change of the QES intensity in the supercooled liquid range is compared with data of excess entropy, free volume, and mean-squared displacement recently reported for ionic liquids. The temperature dependence of the QES intensity in ionic liquids illustrates relationships between short-time dynamics and long-time structural relaxation that have been proposed for glass-forming liquids. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3604533]

Exploiting Mn(III)/EDTA complex in a flow system with solenoid micro-pumps coupled to long pathlength spectrophotometry for fast manganese determination

The formation of the Mn(III)/EDTA complex in a flow system with solenoid micro-pumps was exploited for fast manganese determination in freshwater. Manganese(II) was oxidized in a solid-phase reactor containing lead dioxide immobilized on polyester. Long pathlength spectrophotometry was exploited to increase sensitivity, aiming to reach the threshold limit established by environmental legislation. A linear response was observed from 25 to 1500 mu g L(-1), with a detection limit of 6 mu g L(-1) (99.7% confidence level). Sample throughput and coefficient of variation were 36 samples/h and 2.6% (n = 10), respectively. EDTA consumption and waste generation were estimated as 500 mu g and 3 mL per determination, respectively. The amount of Pb in the residue corresponds to 250 mu g per determination and a solid-phase reactor could be used for up to 1600 determinations. Adsorption in active charcoal avoided interferences caused by organic matter and the developed procedure was successfully applied for determination of manganese in freshwater samples. Results were in agreement with those attained by GFAAS at the 95% confidence level. (C) 2010 Elsevier B.V. All rights reserved.

High accuracy and fast acquisition time of polarisation nulling-based OSNR monitor

A technique for improving the performance of an OSNR monitor based on a polarisation nulling method with the downhill simplex algorithm is demonstrated. Establishing a compromise between accuracy and acquisition time, the monitor has been calibrated to 0.72 dB/390 ms and 0.98 dB/320 ms, over a range of nearly 21 dB. As far as is known, these are the best values achieved with such an OSNR monitoring method.

Influence of the Solvent Evaporation Rate on the Crystalline Phases of Solution-Cast Poly(Vinylidene Fluoride) Films

The influence of the solvent-evaporation rate on the formation of of. and P crystalline phases in solution-cast poly(vinylidene fluoride) (PVDF) films was systematically investigated. Films were crystallized from PVDF/N,N-dimethylformamide solutions with concentrations of 2.5, 5.0, 10, and 20 wt % at different temperatures. During crystallization, the solvent evaporation rate was monitored in situ by means of a semianalytic balance. With this system, it was possible to determine the evaporation rate for different concentrations and temperatures of the solution under specific ambient conditions (pressure, temperature, and humidity). Fourier-Transform InfraRed spectroscopy with Attenuated Total Reflectance revealed the P-phase content in the PVDF films and its dependence on previous evaporation rates. Based on the relation between the evaporation rate and the PVDF phase composition, a consistent explanation for the different amounts of P phase observed at the upper and lower sample surfaces is achieved. Furthermore, the role of the sample thickness has also been studied. The experimental results show that not only the temperature but also the evaporation rate have to be controlled to obtain the desired crystalline phases in solution-cast PVDF films. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 116: 785-791, 2010

New prediction methods for CO2 evaporation inside tubes: Part I - A two-phase flow pattern map and a flow pattern based phenomenological model for two-phase flow frictional pressure drops

An updated flow pattern map was developed for CO2 on the basis of the previous Cheng-Ribatski-Wojtan-Thome CO2 flow pattern map [1,2] to extend the flow pattern map to a wider range of conditions. A new annular flow to dryout transition (A-D) and a new dryout to mist flow transition (D-M) were proposed here. In addition, a bubbly flow region which generally occurs at high mass velocities and low vapor qualities was added to the updated flow pattern map. The updated flow pattern map is applicable to a much wider range of conditions: tube diameters from 0.6 to 10 mm, mass velocities from 50 to 1500 kg/m(2) s, heat fluxes from 1.8 to 46 kW/m(2) and saturation temperatures from -28 to +25 degrees C (reduced pressures from 0.21 to 0.87). The updated flow pattern map was compared to independent experimental data of flow patterns for CO2 in the literature and it predicts the flow patterns well. Then, a database of CO2 two-phase flow pressure drop results from the literature was set up and the database was compared to the leading empirical pressure drop models: the correlations by Chisholm [3], Friedel [4], Gronnerud [5] and Muller-Steinhagen and Heck [6], a modified Chisholm correlation by Yoon et al. [7] and the flow pattern based model of Moreno Quiben and Thome [8-10]. None of these models was able to predict the CO2 pressure drop data well. Therefore, a new flow pattern based phenomenological model of two-phase flow frictional pressure drop for CO2 was developed by modifying the model of Moreno Quiben and Thome using the updated flow pattern map in this study and it predicts the CO2 pressure drop database quite well overall. (C) 2007 Elsevier Ltd. All rights reserved.

New prediction methods for CO2 evaporation inside tubes: Part II - An updated general flow boiling heat transfer model based on flow patterns

Corresponding to the updated flow pattern map presented in Part I of this study, an updated general flow pattern based flow boiling heat transfer model was developed for CO2 using the Cheng-Ribatski-Wojtan-Thome [L. Cheng, G. Ribatski, L. Wojtan, J.R. Thome, New flow boiling heat transfer model and flow pattern map for carbon dioxide evaporating inside horizontal tubes, Int. J. Heat Mass Transfer 49 (2006) 4082-4094; L. Cheng, G. Ribatski, L. Wojtan, J.R. Thome, Erratum to: ""New flow boiling heat transfer model and flow pattern map for carbon dioxide evaporating inside tubes"" [Heat Mass Transfer 49 (21-22) (2006) 4082-4094], Int. J. Heat Mass Transfer 50 (2007) 391] flow boiling heat transfer model as the starting basis. The flow boiling heat transfer correlation in the dryout region was updated. In addition, a new mist flow heat transfer correlation for CO2 was developed based on the CO2 data and a heat transfer method for bubbly flow was proposed for completeness sake. The updated general flow boiling heat transfer model for CO2 covers all flow regimes and is applicable to a wider range of conditions for horizontal tubes: tube diameters from 0.6 to 10 mm, mass velocities from 50 to 1500 kg/m(2) s, heat fluxes from 1.8 to 46 kW/m(2) and saturation temperatures from -28 to 25 degrees C (reduced pressures from 0.21 to 0.87). The updated general flow boiling heat transfer model was compared to a new experimental database which contains 1124 data points (790 more than that in the previous model [Cheng et al., 2006, 2007]) in this study. Good agreement between the predicted and experimental data was found in general with 71.4% of the entire database and 83.2% of the database without the dryout and mist flow data predicted within +/-30%. However, the predictions for the dryout and mist flow regions were less satisfactory due to the limited number of data points, the higher inaccuracy in such data, scatter in some data sets ranging up to 40%, significant discrepancies from one experimental study to another and the difficulties associated with predicting the inception and completion of dryout around the perimeter of the horizontal tubes. (C) 2007 Elsevier Ltd. All rights reserved.

Fast experimental identification of suspension models for control design

This paper presents both the theoretical and the experimental approaches of the development of a mathematical model to be used in multi-variable control system designs of an active suspension for a sport utility vehicle (SUV), in this case a light pickup truck. A complete seven-degree-of-freedom model is successfully quickly identified, with very satisfactory results in simulations and in real experiments conducted with the pickup truth. The novelty of the proposed methodology is the use of commercial software in the early stages of the identification to speed up the process and to minimize the need for a large number of costly experiments. The paper also presents major contributions to the identification of uncertainties in vehicle suspension models and in the development of identification methods using the sequential quadratic programming, where an innovation regarding the calculation of the objective function is proposed and implemented. Results from simulations of and practical experiments with the real SUV are presented, analysed, and compared, showing the potential of the method.

Fast Transforms for Acoustic Imaging-Part I: Theory

The classical approach for acoustic imaging consists of beamforming, and produces the source distribution of interest convolved with the array point spread function. This convolution smears the image of interest, significantly reducing its effective resolution. Deconvolution methods have been proposed to enhance acoustic images and have produced significant improvements. Other proposals involve covariance fitting techniques, which avoid deconvolution altogether. However, in their traditional presentation, these enhanced reconstruction methods have very high computational costs, mostly because they have no means of efficiently transforming back and forth between a hypothetical image and the measured data. In this paper, we propose the Kronecker Array Transform ( KAT), a fast separable transform for array imaging applications. Under the assumption of a separable array, it enables the acceleration of imaging techniques by several orders of magnitude with respect to the fastest previously available methods, and enables the use of state-of-the-art regularized least-squares solvers. Using the KAT, one can reconstruct images with higher resolutions than was previously possible and use more accurate reconstruction techniques, opening new and exciting possibilities for acoustic imaging.

Fast Transforms for Acoustic Imaging-Part II: Applications

In Part I [""Fast Transforms for Acoustic Imaging-Part I: Theory,"" IEEE TRANSACTIONS ON IMAGE PROCESSING], we introduced the Kronecker array transform (KAT), a fast transform for imaging with separable arrays. Given a source distribution, the KAT produces the spectral matrix which would be measured by a separable sensor array. In Part II, we establish connections between the KAT, beamforming and 2-D convolutions, and show how these results can be used to accelerate classical and state of the art array imaging algorithms. We also propose using the KAT to accelerate general purpose regularized least-squares solvers. Using this approach, we avoid ill-conditioned deconvolution steps and obtain more accurate reconstructions than previously possible, while maintaining low computational costs. We also show how the KAT performs when imaging near-field source distributions, and illustrate the trade-off between accuracy and computational complexity. Finally, we show that separable designs can deliver accuracy competitive with multi-arm logarithmic spiral geometries, while having the computational advantages of the KAT.

Thin titanium oxide films deposited by e-beam evaporation with additional rapid thermal oxidation and annealing for ISFET applications

Titanium oxide (TiO(2)) has been extensively applied in the medical area due to its proved biocompatibility with human cells [1]. This work presents the characterization of titanium oxide thin films as a potential dielectric to be applied in ion sensitive field-effect transistors. The films were obtained by rapid thermal oxidation and annealing (at 300, 600, 960 and 1200 degrees C) of thin titanium films of different thicknesses (5 nm, 10 nm and 20 nm) deposited by e-beam evaporation on silicon wafers. These films were analyzed as-deposited and after annealing in forming gas for 25 min by Ellipsometry, Fourier Transform Infrared Spectroscopy (FTIR), Raman Spectroscopy (RAMAN), Atomic Force Microscopy (AFM), Rutherford Backscattering Spectroscopy (RBS) and Ti-K edge X-ray Absorption Near Edge Structure (XANES). Thin film thickness, roughness, surface grain sizes, refractive indexes and oxygen concentration depend on the oxidation and annealing temperature. Structural characterization showed mainly presence of the crystalline rutile phase, however, other oxides such Ti(2)O(3), an interfacial SiO(2) layer between the dielectric and the substrate and the anatase crystalline phase of TiO(2) films were also identified. Electrical characteristics were obtained by means of I-V and C-V measured curves of Al/Si/TiO(x)/Al capacitors. These curves showed that the films had high dielectric constants between 12 and 33, interface charge density of about 10(10)/cm(2) and leakage current density between 1 and 10(-4) A/cm(2). Field-effect transistors were fabricated in order to analyze I(D) x V(DS) and log I(D) x Bias curves. Early voltage value of -1629 V, R(OUT) value of 215 M Omega and slope of 100 mV/dec were determined for the 20 nm TiO(x) film thermally treated at 960 degrees C. (C) 2009 Elsevier B.V. All rights reserved.