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.

Magnetic Tuning of All-Organic Binary Alloys between Two Stable Radicals

Mixtures of 2-(4,5,6,7-tetrafluorobenzimidazol-2-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (F4BImNN) and 2-(benzi-midazol-2-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (BImNN.) crystallize as solid solutions (alloys) across a wide range of binary compositions. (F4BImNN)(x)(BImNN)((1-x)) with x < 0.8 gives orthorhombic unit cells, while x >= 0.9 gives monoclinic unit cells. In all crystalline samples, the dominant intermolecular packing is controlled by one-dimensional (1D) hydrogen-bonded chains that lead to quasi-1D ferromagnetic behavior. Magnetic analysis over 0.4-300 K indicates ordering with strong 1D ferromagnetic exchange along the chains (J/k = 12-22 K). Interchain exchange is estimated to be 33- to 150-fold weaker, based on antiferromagnetic ordered phase formation below Neel temperatures in the 0.4-1.2 K range for the various compositions. The ordering temperatures of the orthorhombic samples increase linearly as (1 - x) increases from 0.25 to 1.00. The variation is attributed to increased interchain distance corresponding to decreased interchain exchange, when more F4BImNN is added into the orthorhombic lattice. The monoclinic samples are not part of the same trend, due to the different interchain arrangement associated with the phase change.

A cyclic bipolar wind in the interacting binary V 393 Scorpii

V393 Scorpii is a double periodic variable characterized by a relatively stable non-orbital photometric cycle of 253 d. Mennickent et al. argue for the presence of a massive optically thick disc around the more massive B-type component and describe the evolutionary stage of the system. In this paper, we analyse the behaviour of the main spectroscopic optical lines during the long non-orbital photometric cycle. We study the radial velocity of the donor determining its orbital elements and find a small but significant orbital eccentricity (e = 0.04). The donor spectral features are modelled and removed from the spectrum at every observing epoch using the light-curve model given by Mennickent et al. We find that the line emission is larger during eclipses and mostly comes from a bipolar wind. We also find that the long cycle is explained in terms of a modulation of the wind strength; the wind has a larger line and continuum emissivity at the high state. We report the discovery of highly variable chromospheric emission in the donor, as revealed by the Doppler maps of the emission lines Mg II 4481 and C I 6588. We discuss notable and some novel spectroscopic features like discrete absorption components, especially visible at blue depressed O I 7773 absorption wings during the second half-cycle, Balmer double emission with V/R curves showing 'Z-type' and 'S-type' excursions around secondary and main eclipses, respectively, and H beta emission wings extending up to +/- 2000 km s(-1). We also discuss possible causes for these phenomena and for their modulations with the long cycle.

MHD numerical simulations of colliding winds in massive binary systems - I. Thermal versus non-thermal radio emission

In the past few decades detailed observations of radio and X-ray emission from massive binary systems revealed a whole new physics present in such systems. Both thermal and non-thermal components of this emission indicate that most of the radiation at these bands originates in shocks. O and B-type stars and WolfRayet (WR) stars present supersonic and massive winds that, when colliding, emit largely due to the freefree radiation. The non-thermal radio and X-ray emissions are due to synchrotron and inverse Compton processes, respectively. In this case, magnetic fields are expected to play an important role in the emission distribution. In the past few years the modelling of the freefree and synchrotron emissions from massive binary systems have been based on purely hydrodynamical simulations, and ad hoc assumptions regarding the distribution of magnetic energy and the field geometry. In this work we provide the first full magnetohydrodynamic numerical simulations of windwind collision in massive binary systems. We study the freefree emission characterizing its dependence on the stellar and orbital parameters. We also study self-consistently the evolution of the magnetic field at the shock region, obtaining also the synchrotron energy distribution integrated along different lines of sight. We show that the magnetic field in the shocks is larger than that obtained when the proportionality between B and the plasma density is assumed. Also, we show that the role of the synchrotron emission relative to the total radio emission has been underestimated.

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.

Polarimetry of the binary PDS 144

Aims. Our goal is to study the circumstellar environment associated with each component of the wide intermediate-mass pre-main sequence binary system PDS 144 using broadband polarimetry. Methods. We present near-infrared (NIR) linear polarimetric observations of PDS 144 gathered with the IAGPOL imaging polarimeter along with the CamIV infrared camera at the Observatorio do Pico dos Dias (OPD). In addition, we re-analyzed OPD archive optical polarization to separate the binary and estimate the interstellar polarization using foreground stars. Results. After discounting the interstellar component, we found that both stars of the binary system are intrinsically polarized. The polarization vectors at optical and NIR bands of both components are aligned with the local magnetic field and the jet axis. These findings indicate an interplay between the interstellar magnetic field and the formation of the binary system. We also found that the PDS 144N is less polarized than its southern companion in the optical. However, in the NIR PDS 144N is more polarized. Our polarization data can only be explained by high inclinations (i greater than or similar to 80 degrees) for the disks of both members. In particular, comparisons of our NIR data with young stellar objects disk models suggest predominantly small grains in the circumstellar environment of PDS 144N. In spite of the different grain types in each component, the infrared spectral indexes indicate a coeval system. We also found evidence of coplanarity between the disks.

Latent residual analysis in binary regression with skewed link

Model diagnostics is an integral part of model determination and an important part of the model diagnostics is residual analysis. We adapt and implement residuals considered in the literature for the probit, logistic and skew-probit links under binary regression. New latent residuals for the skew-probit link are proposed here. We have detected the presence of outliers using the residuals proposed here for different models in a simulated dataset and a real medical dataset.

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.

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.

Biaxial nematic phase in the Maier-Saupe model for a mixture of discs and cylinders

We analyze the global phase diagram of a Maier-Saupe lattice model with the inclusion of shape-disordered degrees of freedom to mimic a mixture of oblate and prolate molecules (discs and cylinders). In the neighborhood of a Landau multicritical point, solutions of the statistical problem can be written as a Landau-de Gennes expansion for the free energy. If the shape-disordered degrees of freedom are quenched, we confirm the existence of a biaxial nematic structure. If orientational and disorder degrees of freedom are allowed to thermalize, this biaxial solution becomes thermodynamically unstable. Also, we use a two-temperature formalism to mimic the presence of two distinct relaxation times, and show that a slight departure from complete thermalization is enough to stabilize a biaxial nematic phase.

Binary and ternary inclusion complexes of dapsone in cyclodextrins and polymers: preparation, characterization and evaluation

Dapsone (DAP) is a synthetic sulfone drug with bacteriostatic activity, mainly against Mycobacterium leprae. In this study we have investigated the interactions of DAP with cyclodextrins, 2-hydroxypropyl-beta-cyclodextrin (HP beta CD) and beta-cyclodextrin (beta CD), in the presence and absence of water-soluble polymers, in order to improve its solubility and bioavailability. Solid systems DAP/HP beta CD and DAP/beta CD, in the presence or absence of polyvinylpyrrolidone (PVP K30) or hydroxypropyl methylcellulose (HPMC), were prepared. The binary and ternary systems were evaluated and characterized by SEM, DSC, XRD and NMR analysis as well as phase solubility assays, in order to investigate the interactions between DAP and the excipients in aqueous solution. This study revealed that inclusion complexes of DAP and cyclodextrins (HP beta CD and beta CD) can be produced in order to improve DAP solubility and bioavailability in the presence or absence of polymers (PVP K30 and HPMC). The more stable inclusion complex was obtained with HP beta CD, and consequently HP beta CD was more efficient in improving DAP solubility than beta CD, and the addition of polymers had no influence on DAP solubility or on the stability of the DAP/CDs complexes.

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.

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.

Incorporating label dependency into the binary relevance framework for multi-label classification

In multi-label classification, examples can be associated with multiple labels simultaneously. The task of learning from multi-label data can be addressed by methods that transform the multi-label classification problem into several single-label classification problems. The binary relevance approach is one of these methods, where the multi-label learning task is decomposed into several independent binary classification problems, one for each label in the set of labels, and the final labels for each example are determined by aggregating the predictions from all binary classifiers. However, this approach fails to consider any dependency among the labels. Aiming to accurately predict label combinations, in this paper we propose a simple approach that enables the binary classifiers to discover existing label dependency by themselves. An experimental study using decision trees, a kernel method as well as Naive Bayes as base-learning techniques shows the potential of the proposed approach to improve the multi-label classification performance.

Automatic lumen segmentation in IVOCT images using binary morphological reconstruction

Abstract Background Atherosclerosis causes millions of deaths, annually yielding billions in expenses round the world. Intravascular Optical Coherence Tomography (IVOCT) is a medical imaging modality, which displays high resolution images of coronary cross-section. Nonetheless, quantitative information can only be obtained with segmentation; consequently, more adequate diagnostics, therapies and interventions can be provided. Since it is a relatively new modality, many different segmentation methods, available in the literature for other modalities, could be successfully applied to IVOCT images, improving accuracies and uses. Method An automatic lumen segmentation approach, based on Wavelet Transform and Mathematical Morphology, is presented. The methodology is divided into three main parts. First, the preprocessing stage attenuates and enhances undesirable and important information, respectively. Second, in the feature extraction block, wavelet is associated with an adapted version of Otsu threshold; hence, tissue information is discriminated and binarized. Finally, binary morphological reconstruction improves the binary information and constructs the binary lumen object. Results The evaluation was carried out by segmenting 290 challenging images from human and pig coronaries, and rabbit iliac arteries; the outcomes were compared with the gold standards made by experts. The resultant accuracy was obtained: True Positive (%) = 99.29 ± 2.96, False Positive (%) = 3.69 ± 2.88, False Negative (%) = 0.71 ± 2.96, Max False Positive Distance (mm) = 0.1 ± 0.07, Max False Negative Distance (mm) = 0.06 ± 0.1. Conclusions In conclusion, by segmenting a number of IVOCT images with various features, the proposed technique showed to be robust and more accurate than published studies; in addition, the method is completely automatic, providing a new tool for IVOCT segmentation.