Mechanistic Implications of Zinc(II) Ions on the Degradation of Phenol by the Fenton Reaction

A study of the interference of Zn2+ ions on phenol degradation by Fenton reaction (Fe2+/Fe3(+) + H2O2) is reported. One of the first intermediates formed in the reaction, catechol, can reduce Fe3+ to Fe2+ and, in the presence of H2O2 initiates an efficient catalytic redox cycle. In the initial stages of the reaction, this catechol-mediated cycle becomes the principal route of thermal degradation of phenol and its oxidation products. The Zn2+ ion addition enhances the persistence time of catechol, probably by stabilization of the corresponding semiquinone radical via complexation.

Phenol biodegradation by a microbial consortium: application of artificial neural network (ANN) modelling

In this study, an effective microbial consortium for the biodegradation of phenol was grown under different operational conditions, and the effects of phosphate concentration (1.4 g L-1, 2.8 g L-1, 4.2 g L-1), temperature (25 degrees C, 30 degrees C, 35 degrees C), agitation (150 rpm, 200 rpm, 250 rpm) and pH (6, 7, 8) on phenol degradation were investigated, whereupon an artificial neural network (ANN) model was developed in order to predict degradation. The learning, recall and generalization characteristics of neural networks were studied using data from the phenol degradation system. The efficiency of the model generated by the ANN was then tested and compared with the experimental results obtained. In both cases, the results corroborate the idea that aeration and temperature are crucial to increasing the efficiency of biodegradation.

ESTIMATING REACTION CONSTANTS BY AB INITIO MOLECULAR MODELING: A STUDY ON THE OXIDATION OF PHENOL TO CATECHOL AND HYDROQUINONE IN ADVANCED OXIDATION PROCESSES

Molecular modeling is growing as a research tool in Chemical Engineering studies, as can be seen by a simple research on the latest publications in the field. Molecular investigations retrieve information on properties often accessible only by expensive and time-consuming experimental techniques, such as those involved in the study of radical-based chain reactions. In this work, different quantum chemical techniques were used to study phenol oxidation by hydroxyl radicals in Advanced Oxidation Processes used for wastewater treatment. The results obtained by applying a DFT-based model showed good agreement with experimental values available, as well as qualitative insights into the mechanism of the overall reaction chain. Solvation models were also tried, but were found to be limited for this reaction system within the considered theoretical level without further parameterization.

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.

Form III-like conformation and Form I-like packing in a chloroform channel solvate of the diuretic drug chlortalidone

Chlortalidone (CTD) is an antihypertensive drug for which only two solid state phases have been structurally elucidated thus far. Here, we have prepared a chloroform solvate thereof, namely, CTD Form IV, and its structure was compared to those of Form I and Form III. Its two conformers exhibit a dual structural feature in relation to the antecedent polymorphs. Both CTD molecules of Form IV adopt a Form III-like conformation, which is featured, if the conformation of CTD Form I is used as a reference, by a rotation of about 90 degrees on the axis of the C-C bond bridging the substituted benzene and isoindolinyl rings. However, CTD Form IV assembles as in the Form I crystal packing despite the different stacking fashion of their centrosymmetric dimers. In contrast to Form I, there is no offset stacking in Form IV, which forces a bend of ca. 24 degrees between the planes passing through the isoindolinyl moieties of two [100]-stacked dimers. Chloroform molecules at a maximum stoichiometry of 0.25 mol per mol of the drug play a stabilizing role in the assembly of Form IV by filling the channels formed on the crystals.

Integral form of Yang-Mills equations and its gauge invariant conserved charges

Despite the fact that the integral form of the equations of classical electrodynamics is well known, the same is not true for non-Abelian gauge theories. The aim of the present paper is threefold. First, we present the integral form of the classical Yang-Mills equations in the presence of sources and then use it to solve the long-standing problem of constructing conserved charges, for any field configuration, which are invariant under general gauge transformations and not only under transformations that go to a constant at spatial infinity. The construction is based on concepts in loop spaces and on a generalization of the non-Abelian Stokes theorem for two-form connections. The third goal of the paper is to present the integral form of the self-dual Yang-Mills equations and calculate the conserved charges associated with them. The charges are explicitly evaluated for the cases of monopoles, dyons, instantons and merons, and we show that in many cases those charges must be quantized. Our results are important in the understanding of global properties of non-Abelian gauge theories.

String Quartet n degrees 02 by Villa-Lobos: a dialogue with the cyclic form of Franck, Debussy and Ravel

This article investigates Villa-Lobos's String Quartet n degrees 02, an early work by this composer, written according cyclic sonata principles, as developed by Cesar Franck and systematized by Vincent d'Indy. Another important source are the string quartets composed by Franck (1889), Debussy (1893) and Ravel (1903), which possibly served as compositional models to Villa-Lobos. In this light, the themes of the Exposition in the first movement were analyzed and this procedure reveals some harmonic and rhythmic aspects throughout all the other movements.

Evolution of form and function: morphophysiological relationships and locomotor performance in tropidurine lizards

Locomotor capacity is often considered an excellent measure of whole animal performance because it requires the integrated functioning of many morphological, physiological (and biochemical) traits. However, because studies tend to focus on either structural or functional suits of traits, we know little on whether and how morphological and physiological traits coevolve to produce adequate locomotor capacities. Hence, we investigate the evolutionary relationships between morphological and physiological parameters related to exercise physiology, using tropidurine lizards as a model. We employ a phylogenetic principal component analysis (PCA) to identify variable clusters (factors) related to morphology, energetic metabolism and muscle metabolism, and then analyze the relationships between these clusters and measures of locomotor performance, using two models (star and hierarchical phylogenies). Our data indicate that sprint performance is enhanced by simultaneous evolutionary tendencies affecting relative limb and tail size and physiological traits. Specifically, the high absolute sprint speeds exhibited by tropidurines from the sand dunes are explained by longer limbs, feet and tails and an increased proportion of glycolytic fibers in the leg muscle, contrasting with their lower capacity for overall oxidative metabolism [principal component (PC1)]. However, when sprint speeds are corrected for body size, performance correlates with a cluster (PC3) composed by moderate loads for activity metabolic rate and body size. The simultaneous measurement of morphological and physiological parameters is a powerful tool for exploring patterns of coadaptation and proposing morphophysiological associations that are not directly predictable from theory. This approach may trigger novel directions for investigating the evolution of form and function, particularly in the context of organismal performance.

Fatal septic shock due to a disseminated chronic form of paracoccidioidomycosis in an aged woman

Once rare, septic shock (SS) due to disseminated fungal infections has been increasingly reported due to a growing number of immunocompromised patients, but remains rare in non-immune-compromised individuals. In paracoccidioidomycosis, it has been described in only three patients with the severe, acute form of the disease. We describe the development of a refractory, fatal septic shock due to a severe disseminated chronic form of paracoccidioidomycosis in an older woman without any other microbial insults. A striking event in the evolution of her case was the severe depletion of lymphocytes from the peripheral blood and lymphoid organs. Lymphocyte depletion due to apoptosis is described in the late phase of sepsis and can contribute both to immunosuppression and the progression of SS. The possible mechanisms involved in the induction of SS in the chronic form of paracoccidioidomycosis are discussed.

The processing of polyelectrolyte-covered magnetite nanoparticles in the form of nanostructured thin films

Magnetic nanoparticles are promising for a variety of applications, such as biomedical devices, spin electronics, magnetic data storage media, to name a few. However, these goals may only be reached if stable and organized structures are fabricated. In this article, we report on a single-step synthetic route with the coprecipitation method, in which iron oxide magnetic nanoparticles (Fe3O4 NPs) were stabilized in aqueous media using the poly(diallyldimethylammonium chloride) (PDAC) polyelectrolyte. The Fe3O4 NPs had a diameter of ca. 5 nm, according to transmission electron microscopy (TEM) images, being arranged in an inverse spinel structure typical of magnetite. An investigation with infrared spectroscopy indicated that the mechanisms of stabilization in the polymer matrix were based on the interaction between quaternary amide groups from PDAC and the nanoparticle surface. The Fe3O4-PDAC NPs exhibited considerable magnetic susceptibility, with a monotonic increase in the magnetization with decreasing temperature. These Fe3O4-PDAC NPs were immobilized in layer-by-layer (LbL) films, being alternated with layers of poly(vinylsulfonic acid) (PVS). The LbL films were much rougher than typical films made with polyelectrolytes, and Fe3O4-PDAC NPs have been responsible for the high electrocatalytic activity toward H2O2 reduction, with an overpotential shift of 0.69 V. Overall, the stability, magnetic properties and film-forming ability indicate that the Fe3O4-PDAC NPs may be used for nanoelectronics and bioelectrochemical devices requiring reversible and magnetic redox materials.

Toward supramolecular architectures of the anti-HIV drug lamivudine: understanding the effect of the inclusion of water in a hydrochloride form

Two salts of the anti-HIV drug lamivudine, namely, lamivudine hydrochloride and lamivudine hydrochloride monohydrate, were prepared for the first time. Structural relationships and the role of water in crystal assembly and lamivudine conformation were established and allowed for a rational approach to understand how solid state properties could be changed by engineering new salts of the drug.

No-pole condition in Landau gauge: Properties of the Gribov ghost form factor and a constraint on the 2d gluon propagator

We study general properties of the Landau-gauge Gribov ghost form factor sigma(p(2)) for SU(N-c) Yang-Mills theories in the d-dimensional case. We find a qualitatively different behavior for d = 3, 4 with respect to the d = 2 case. In particular, considering any (sufficiently regular) gluon propagator D(p(2)) and the one-loop-corrected ghost propagator, we prove in the 2d case that the function sigma(p(2)) blows up in the infrared limit p -> 0 as -D(0) ln(p(2)). Thus, for d = 2, the no-pole condition sigma(p(2)) < 1 (for p(2) > 0) can be satisfied only if the gluon propagator vanishes at zero momentum, that is, D(0) = 0. On the contrary, in d = 3 and 4, sigma(p(2)) is finite also if D(0) > 0. The same results are obtained by evaluating the ghost propagator G(p(2)) explicitly at one loop, using fitting forms for D(p(2)) that describe well the numerical data of the gluon propagator in two, three and four space-time dimensions in the SU(2) case. These evaluations also show that, if one considers the coupling constant g(2) as a free parameter, the ghost propagator admits a one-parameter family of behaviors (labeled by g(2)), in agreement with previous works by Boucaud et al. In this case the condition sigma(0) <= 1 implies g(2) <= g(c)(2), where g(c)(2) is a "critical" value. Moreover, a freelike ghost propagator in the infrared limit is obtained for any value of g(2) smaller than g(c)(2), while for g(2) = g(c)(2) one finds an infrared-enhanced ghost propagator. Finally, we analyze the Dyson-Schwinger equation for sigma(p(2)) and show that, for infrared-finite ghost-gluon vertices, one can bound the ghost form factor sigma(p(2)). Using these bounds we find again that only in the d = 2 case does one need to impose D(0) = 0 in order to satisfy the no-pole condition. The d = 2 result is also supported by an analysis of the Dyson-Schwinger equation using a spectral representation for the ghost propagator. Thus, if the no-pole condition is imposed, solving the d = 2 Dyson-Schwinger equations cannot lead to a massive behavior for the gluon propagator. These results apply to any Gribov copy inside the so-called first Gribov horizon; i.e., the 2d result D(0) = 0 is not affected by Gribov noise. These findings are also in agreement with lattice data.

Questionário Atitudes de Segurança: adaptação transcultural do Safety Attitudes Questionnaire - Short Form 2006 para o Brasil

O objetivo deste estudo foi realizar a adaptação transcultural do Safety Attitudes Questionnaire - Short Form 2006 para o Brasil. O instrumento foi aplicado em seis hospitais de três Regiões do Brasil. Foi realizada a validade de conteúdo, face e de construto. A análise da confiabilidade do instrumento foi realizada por meio da análise da consistência interna dos itens por meio do alfa de Cronbach. A amostra do estudo foi composta por 1.301 profissionais das enfermarias clínicas e cirúrgicas de seis hospitais. A análise confirmatória mostrou que o ajuste do modelo final dos 41 itens foi considerado satisfatório. Aversão do instrumento em Português apresentou alfa de 0,89. As correlações item/total entre os domínios foram consideradas de moderada a forte, com exceção do domínio percepção do estresse. Conclui-se, portanto, que a versão do instrumento adaptada para o Português é considerada válida e confiável nesta amostra.

The importance of plant life form on spatial associations along a subtropical coastal dune gradient

Questions Does the spatial association between isolated adult trees and understorey plants change along a gradient of sand dunes? Does this association depend on the life form of the understorey plant? Location Coastal sand dunes, southeast Brazil. Methods We recorded the occurrence of understorey plant species in 100 paired 0.25 m2 plots under adult trees and in adjacent treeless sites along an environmental gradient from beach to inland. Occurrence probabilities were modelled as a function of the fixed variables of the presence of a neighbour, distance from the seashore and life form, and a random variable, the block (i.e. the pair of plots). Generalized linear mixed models (GLMM) were fitted in a backward step-wise procedure using Akaike's information criterion (AIC) for model selection. Results The occurrence of understorey plants was affected by the presence of an adult tree neighbour, but the effect varied with the life form of the understorey species. Positive spatial association was found between isolated adult neighbour and young trees, whereas a negative association was found for shrubs. Moreover, a neutral association was found for lianas, whereas for herbs the effect of the presence of an adult neighbour ranged from neutral to negative, depended on the subgroup considered. The strength of the negative association with forbs increased with distance from the seashore. However, for the other life forms, the associational pattern with adult trees did not change along the gradient. Conclusions For most of the understorey life forms there is no evidence that the spatial association between isolated adult trees and understorey plants changes with the distance from the seashore, as predicted by the stress gradient hypothesis, a common hypothesis in the literature about facilitation in plant communities. Furthermore, the positive spatial association between isolated adult trees and young trees identified along the entire gradient studied indicates a positive feedback that explains the transition from open vegetation to forest in subtropical coastal dune environments.

Feasibility Study of a Solar Reactor for Phenol Treatment by the Photo-Fenton process in Aqueous Solution

Solar reactors can be attractive in photodegradation processes due to lower electrical energy demand. The performance of a solar reactor for two flow configurations, i.e., plug flow and mixed flow, is compared based on experimental results with a pilot-scale solar reactor. Aqueous solutions of phenol were used as a model for industrial wastewater containing organic contaminants. Batch experiments were carried out under clear sky, resulting in removal rates in the range of 96100?%. The dissolved organic carbon removal rate was simulated by an empirical model based on neural networks, which was adjusted to the experimental data, resulting in a correlation coefficient of 0.9856. This approach enabled to estimate effects of process variables which could not be evaluated from the experiments. Simulations with different reactor configurations indicated relevant aspects for the design of solar reactors.