Structure and anomalous solubility for hard spheres in an associating lattice gas model

In this paper we investigate the solubility of a hard-sphere gas in a solvent modeled as an associating lattice gas. The solution phase diagram for solute at 5% is compared with the phase diagram of the original solute free model. Model properties are investigated both through Monte Carlo simulations and a cluster approximation. The model solubility is computed via simulations and is shown to exhibit a minimum as a function of temperature. The line of minimum solubility (TmS) coincides with the line of maximum density (TMD) for different solvent chemical potentials, in accordance with the literature on continuous realistic models and on the "cavity" picture. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4743635]

Estimation and diagnostics for heteroscedastic nonlinear regression models based on scale mixtures of skew-normal distributions

An extension of some standard likelihood based procedures to heteroscedastic nonlinear regression models under scale mixtures of skew-normal (SMSN) distributions is developed. This novel class of models provides a useful generalization of the heteroscedastic symmetrical nonlinear regression models (Cysneiros et al., 2010), since the random term distributions cover both symmetric as well as asymmetric and heavy-tailed distributions such as skew-t, skew-slash, skew-contaminated normal, among others. A simple EM-type algorithm for iteratively computing maximum likelihood estimates of the parameters is presented and the observed information matrix is derived analytically. In order to examine the performance of the proposed methods, some simulation studies are presented to show the robust aspect of this flexible class against outlying and influential observations and that the maximum likelihood estimates based on the EM-type algorithm do provide good asymptotic properties. Furthermore, local influence measures and the one-step approximations of the estimates in the case-deletion model are obtained. Finally, an illustration of the methodology is given considering a data set previously analyzed under the homoscedastic skew-t nonlinear regression model. (C) 2012 Elsevier B.V. All rights reserved.

Using the Hard, Randy, and Rittler Test to Evaluate Color Vision in Capuchins (Cebus libidinosus)

The identification of color vision types in primates is fundamental to understanding the evolution and biological function of color perception. The Hard, Randy, and Rittler (HRR) pseudoisochromatic test categorizes human color vision types successfully. Here we provide an experimental setup to employ HRR in a nonhuman primate, the capuchin (Cebus libidinosus), a platyrrhine with polymorphic color vision. The HRR test consists of plates with a matrix composed of gray circles that vary in size and brightness. Differently colored circles form a geometric shape (X, O, or Delta) that is discriminated visually from the gray background pattern. The ability to identify these shapes determines the type of dyschromatopsy (deficiency in color vision). We tested six capuchins in their own cages under natural sunlight. The subjects chose between two HRR plates in each trial: one with the gray pattern only and the other with a colored shape, presented on the left or right side at random. We presented the test 40 times and calculated the 95 % confidence limits for chance performance based on the binomial test. We also genotyped all subjects for exons 3 and 5 of the X-linked opsin genes. The HRR test diagnosed two subjects as protan dichromats (missing or defective L-cone), three as deutan dichromats (missing or defective M-cone), and one female as trichromat. Genetic analysis supported the behavioral data for all subjects. These findings show that the HRR test can be applied to diagnose color vision in nonhuman primates.

Application of Electrochemical Degradation of Wastewater Composed of Mixtures of Phenol-Formaldehyde

The industrial wastewater from resin production plants contains as major components phenol and formaldehyde, which are traditionally treated by biological methods. As a possible alternative method, electrochemical treatment was tested using solutions containing a mixture of phenol and formaldehyde simulating an industrial effluent. The anode used was a dimensionally stable anode (DSAA (R)) of nominal composition Ti/Ru0.3Ti0.7O2, and the solution composition during the degradation process was analyzed by liquid chromatography and the removal of total organic carbon. From cyclic voltammetry, it is observed that for formaldehyde, a small offset of the beginning of the oxygen evolution reaction occurs, but for phenol, the reaction is inhibited and the current density decreases. From the electrochemical degradations, it was determined that 40 mA cm(-2) is the most efficient current density and the comparison of different supporting electrolytes (Na2SO4, NaNO3, and NaCl) indicated a higher removal of total organic carbon in NaCl medium.

Solvation in aqueous binary mixtures: consequences of the hydrophobic character of the ionic liquids and the solvatochromic probes

Information on the solvation in mixtures of water, W, and the ionic liquids, ILs, 1-allyl-3-R-imidazolium chlorides; R = methyl, 1-butyl, and 1-hexyl, has been obtained from the responses of the following solvatochromic probes: 2,6-dibromo-4-[(E)-2-(1-R-pyridinium-4-yl)ethenyl] phenolate, R = methyl, MePMBr2; 1-octyl, OcPMBr(2), and the corresponding quinolinium derivative, MeQMBr(2). A model developed for solvation in binary mixtures of W and molecular solvents has been extended to the present mixtures. Our objective is to assess the relevance to solvation of hydrogen-bonding and the hydrophobic character of the IL and the solvatochromic probe. Plots of the medium empirical polarity, E-T(probe) versus its composition revealed non-ideal behavior, attributed to preferential solvation by the IL and, more efficiently, by the IL-W hydrogen-bonded complex. The deviation from linearity increases as a function of increasing number of carbon atoms in the alkyl group of the IL, and is larger than that observed for solvation by W plus molecular solvents (1-propanol and 2-(1-butoxy)ethanol) that are more hydrophobic than the ILs investigated. This enhanced deviation is attributed to the more organized structure of the ILs proper, which persists in their aqueous solutions. MeQMBr(2) is more susceptible to solvent lipophilicity than OcPMBr(2), although the former probe is less lipophilic. This enhanced susceptibility agrees with the important effect of annelation on the contributions of the quinonoid and zwitterionic limiting structures to the ground and excited states of the probe, hence on its response to both medium composition and lipophilicity of the IL.

Kinetics and product distribution of p-nitrophenyl phosphate dianion solvolysis in ternary DMSO/alcohol/water mixtures are compatible with metaphosphate formation

The rate of solvolysis of p-nitrophenyl phosphate (PNPP) dianion in DMSO/water strongly decreases by increasing water concentration. Addition of linear alcohols (methanol, propanol, butanol, pentanol, and hexanol) at constant DMSO/water molar ratio produced an even sharper rate decrease. Alkyl phosphate formation, resulting from PNPP solvolysis in ternary DMSO/water/alcohol mixtures, increased with alcohol concentration and was essentially temperature independent. Methanol and hexanol were the poorest nucleophiles under all conditions. Activation energies and enthalpies for solvolysis in ternary mixtures were similar and entropies varied with alcohol concentration. Taken together these results can be best interpreted in terms of a dissociative mechanism with the intervention of metaphosphate. Copyright (C) 2011 John Wiley & Sons, Ltd.

Morphology and topography analysis of mesoporous titania templated by micrometric latex sphere arrays

In this work, mesoporous titania is prepared by templating latex sphere arrays with four different sphere diameters at the micrometric scale (phi > 1 mu m). The mesoporous titania homogeneously covers the latex spheres and substrate, forming a thin coating characterized by N-2 adsorption isotherm, small angle X-rays scattering, atomic force, field emission and transmission electronic microscopies. Mesoporous titania has been templated into different shapes such as hollow particles and monoliths according to the amount of sol used to fill the voids of the close packed latex spheres. Titania topography strongly depends on the adsorption of polymeric segments over latex spheres surface, which could be decreased by changing the dimensions of latex spheres (phi = 9.5 mu m) generating a lamellar architecture. Thus, micrometric latex sphere arrays can be used to achieve new surface patterns for mesoporous materials via a fast and inexpensive chemical route for construction of functional devices in different technological fields such as energy conversion, inclusion chemistry and biomaterials. (C) 2011 Elsevier Inc. All rights reserved.

Comparison of the n-Alkanes and Polycyclic Aromatic Hydrocarbons Concentrations in the Atmosphere during the Preparation of Warm and Hot Mixtures Asphalt for Pavements

Asphalt binder is used in the production of hot mixes asphalt (HMA) for paving and, due to the high temperatures used, generates fumes thatcontainn-alkanes and polycyclic aromatic hydrocarbons (PAH). Asphalt mixes prepared at lower temperatures, such as warm mixes asphalt (WMA), may contribute to reduce the emissions of those compounds and save energy. This paper investigatesn-alkanes and PAH in the total suspended particles during the preparation of WMA, in comparison with HMA, in laboratory. The results showed that the n-alkanes of the WMA and HMA presented C-max at n-C-26 and n-C-28, respectively; also, the total content of n-alkanes was higher for the HMA than forthe WMA. Besides, benzo[b]fluoranthene and benzo[a]anthracene were the major PAH in the WMA, while the higher temperatures of the HMA were observed to volatilize all larger PAH, demonstrating higher potential of inhalation exposure.

Hard Thermal Loops in the n-Dimensional phi(3) Theory

We derive a closed-form result for the leading thermal contributions which appear in the n-dimensional I center dot (3) theory at high temperature. These contributions become local only in the long wavelength and in the static limits, being given by different expressions in these two limits.

Photo-activated phase separation in giant vesicles made from different lipid mixtures

Using giant unilamellar vesicles (GUVs) made from POPC. DPPC, cholesterol and a small amount of a porphyrin-based photosensitizer that we name PE-porph, we investigated the response of the lipid bilayer under visible light, focusing in the formation of domains during the lipid oxidation induced by singlet oxygen. This reactive species is generated by light excitation of PE-porf in the vicinity of the membrane, and thus promotes formation of hydroperoxides when unsaturated lipids and cholesterol are present. Using optical microscopy we determined the lipid compositions under which GUVs initially in the homogeneous phase displayed Lo-Ld phase separation following irradiation. Such an effect is attributed to the in situ formation of both hydroperoxized POPC and cholesterol. The boundary line separating homogeneous Lo phase and phase coexistence regions in the phase diagram is displaced vertically towards the higher cholesterol content in respect to ternary diagram of POPC:DPPC:cholesterol mixtures in the absence of oxidized species. Phase separated domains emerge from sub-micrometer initial sizes to evolve over hours into large Lo-Ld domains completely separated in the lipid membrane. This study provides not only a new tool to explore the kinetics of domain formation in mixtures of lipid membranes, but may also have implications in biological signaling of redox misbalance. (C) 2011 Elsevier B.V. All rights reserved.

Influence of adenotonsillectomy on hard palate dimensions

Objective: To evaluate hard palate width and height in mouth-breathing children pre- and post-adenotonsillectomy. Methods: We evaluated 44 children in the 3-6 year age bracket, using dental study casts in order to determine palatal height, intercanine width, and intermolar width. The children were divided into two groups: nasal breathing (n = 15) and mouth breathing (n = 29). The children in the latter group underwent adenotonsillectomy. The study casts were obtained prior to adenotonsillectomy, designated time point 1(11), at 13 months after adenotonsillectomy (T2), and at 28 months after adenotonsillectomy (13). Similar periods of observation were obtained for nasal breathing children. Results: At T1, there was a significantly lower intercanine width in mouth breathing children; intermolar width and palate height were similar between groups. After surgery, there was a significant increase in all the analyzed parameters in both groups, probably due to facial growth. Instead, the increase in intercanine width was substantially more prominent in mouth breathing children than in nasal breathing children, and the former difference failed in significance after the procedure. Conclusions: There were no significant differences between the nasal-breathing and mouth-breathing children in terms of intermolar width and palatal height prior to or after tonsillectomy. Although intercanine width was initially narrower in the mouth-breathing children, it showed normalization after the surgical procedure. These results confirm that the restoration of nasal breathing is central to proper occlusal development. (C) 2012 Elsevier Ireland Ltd. All rights reserved.

Comparison of the n-alkanes and polycyclic aromatic hydrocarbons concentrations in the atmosphere during the preparation of warm and hot mixtures asphalt for pavements

O asfalto é utilizado na produção de misturas asfálticas a quente (HMA) para a pavimentação e, devido às altas temperaturas empregadas, gera fumos que contêm n-alcanos e hidrocarbonetos policíclicos aromáticos (HPAs). As misturas asfálticas preparadas em temperaturas mais baixas, como as misturas asfálticas mornas (WMA), podem contribuir na redução das emissões daqueles compostos e economizar energia. Este trabalho investiga os n-alcanos e os HPAs nas partículas totais em suspensão durante a preparação de uma WMA, em comparação com uma HMA, em laboratório. Os resultados mostraram que os n-alcanos da WMA e da HMA apresentaram Cmáx no n-C26 e n-C28, respectivamente, e o teor de n-alcanos total foi maior na HMA do que na WMA. Ademais, verificou-se que o benzo[b]fluoranteno e benzo[a]antraceno constituíam os maiores HPAs na WMA, enquanto as temperaturas mais altas da HMA volatilizaram todos seus grandes HPAs, demonstrando maior potencial de exposição por inalação.

Weighted Fourier–Laplace transforms in reproducing kernel Hilbert spaces on the sphere

We study the action of a weighted Fourier–Laplace transform on the functions in the reproducing kernel Hilbert space (RKHS) associated with a positive definite kernel on the sphere. After defining a notion of smoothness implied by the transform, we show that smoothness of the kernel implies the same smoothness for the generating elements (spherical harmonics) in the Mercer expansion of the kernel. We prove a reproducing property for the weighted Fourier–Laplace transform of the functions in the RKHS and embed the RKHS into spaces of smooth functions. Some relevant properties of the embedding are considered, including compactness and boundedness. The approach taken in the paper includes two important notions of differentiability characterized by weighted Fourier–Laplace transforms: fractional derivatives and Laplace–Beltrami derivatives.

Sharp estimates for eigenvalues of integral operators generated by dot product kernels on the sphere

We obtain explicit formulas for the eigenvalues of integral operators generated by continuous dot product kernels defined on the sphere via the usual gamma function. Using them, we present both, a procedure to describe sharp bounds for the eigenvalues and their asymptotic behavior near 0. We illustrate our results with examples, among them the integral operator generated by a Gaussian kernel. Finally, we sketch complex versions of our results to cover the cases when the sphere sits in a Hermitian space.