Effects of oxidante acid treatments on carbon-templated hierarchical SAPO-11 materials: synthesis, characterization and catalytic evaluation in n-decane hydroiosomerization

Hierarchical SAPO-11 was synthesized using a commercial Merck carbon as template. Oxidant acid treatments were performed on the carbon matrix in order to investigate its influence on the properties of SAPO-11. Structural, textural and acidic properties of the different materials were evaluated by XRD, SEM, N-2 adsorption, pyridine adsorption followed by IR spectroscopy and thermal analyses. The catalytic behavior of the materials (with 0.5 wt.% Pt, introduced by mechanic mixture with Pt/Al2O3), were studied in the hydroisomerization of n-decane. The hierarchical samples showed higher yields in monobranched isomers than typical microporous SAPO-11, as a direct consequence of the modification on both porosity and acidity, the later one being the most predominant. (C) 2014 Elsevier B.V. All rights reserved.

From cellulosic based liquid crystalline sheared solutions to 1D and 2D soft materials

Liquid crystalline cellulosic-based solutions described by distinctive properties are at the origin of different kinds of multifunctional materials with unique characteristics. These solutions can form chiral nematic phases at rest, with tuneable photonic behavior, and exhibit a complex behavior associated with the onset of a network of director field defects under shear. Techniques, such as Nuclear Magnetic Resonance (NMR), Rheology coupled with NMR (Rheo-NMR), rheology, optical methods, Magnetic Resonance Imaging (MRI), Wide Angle X-rays Scattering (WAXS), were extensively used to enlighten the liquid crystalline characteristics of these cellulosic solutions. Cellulosic films produced by shear casting and fibers by electrospinning, from these liquid crystalline solutions, have regained wider attention due to recognition of their innovative properties associated to their biocompatibility. Electrospun membranes composed by helical and spiral shape fibers allow the achievement of large surface areas, leading to the improvement of the performance of this kind of systems. The moisture response, light modulated, wettability and the capability of orienting protein and cellulose crystals, opened a wide range of new applications to the shear casted films. Characterization by NMR, X-rays, tensile tests, AFM, and optical methods allowed detailed characterization of those soft cellulosic materials. In this work, special attention will be given to recent developments, including, among others, a moisture driven cellulosic motor and electro-optical devices.

Positive radial solutions of the Dirichlet problem for the Minkowski-Curvature equation in a ball

We study the existence and multiplicity of positive radial solutions of the Dirichlet problem for the Minkowski-curvature equation { -div(del upsilon/root 1-vertical bar del upsilon vertical bar(2)) in B-R, upsilon=0 on partial derivative B-R,B- where B-R is a ball in R-N (N >= 2). According to the behaviour off = f (r, s) near s = 0, we prove the existence of either one, two or three positive solutions. All results are obtained by reduction to an equivalent non-singular one-dimensional problem, to which variational methods can be applied in a standard way.

Investigation of structural effects and behaviour of pseudomonas aeruginosa amidase encapsulated in reserved micelles

The acetohydroxamic acid synthesis reaction was studied using whole cells, cell-free extract and purified amidase from the strains of Pseudomonas aeruginosa L10 and A13 entrapped in a reverse micelles system composed of cationic surfactant tetradecyltrimethyl ammonium bromide. The specific activity of amidase, yield of synthesis and storage stability were determined for the reversed micellar system as well as for free amidase in conventional buffer medium. The results have revealed that amidase solutions in the reverse micelles system exhibited a substantial increase in specific activity, yield of synthesis and storage stability. In fact, whole cells from P. aeruginosa L10 and AI3 in reverse micellar medium revealed an increase in specific activity of 9.3- and 13.9-fold, respectively, relatively to the buffer medium. Yields of approximately 92% and 66% of acetohydroxamic acid synthesis were obtained for encapsulated cell free extract from P. aeruginosa L10 and A13, respectively. On the other hand, the half-life values obtained for the amidase solutions encapsulated in reverse micelles were overall higher than that obtained for the free amidase solution in buffer medium. Half-life values obtained for encapsulated purified amidase from P. aeruginosa strain L10 and encapsulated cell-free extract from P. aeruginosa strain AI3 were of 17.0 and 26.0 days, respectively. As far as the different sources biocatalyst are concerned, the data presented in this work has revealed that the best results, in both storage stability and biocatalytic efficiency, were obtained when encapsulated cell-free extract from P. aeruginosa strain AI3 at 14/0 of 10 were used. Conformational changes occurring upon encapsulation of both strains enzymes in reverse micelles of TAB in heptane/octanol were additionally identified by FTIR spectroscopy which clarified the biocatalysts performances.

Hydrogenating activity of Pt/zeolite catalysts focusing acid support and metal dispersion influence

Toluene hydrogenation was studied over catalysts based on Pt supported on large pore zeolites (HUSY and HBEA) with different metal/acid ratios. Acidity of zeolites was assessed by pyridine adsorption followed by FTIR showing only small changes before and after Pt introduction. Metal dispersion was determined by H2–O2 titration and verified by a linear correlation with the intensity of Pt0–CO band obtained by in situ FTIR. It was also observed that the electronic properties of Pt0 clusters were similar for the different catalysts. Catalytic tests showed rapid catalyst deactivation with an activity loss of 80–95% after 60 min of reaction. The turnover frequency of fresh catalysts depended both on metal dispersion and the support. For the same support, it changed by a 1.7-fold (HBEA) and 4.0-fold (HUSY) showing that toluene hydrogenation is structure-sensitive, i.e. hydrogenating activity is not a unique function of accessible metal. This was proposed to be due to the contribution to the overall activity of the hydrogenation of adsorbed toluene on acid sites via hydrogen spillover. Taking into account the role of zeolite acidity, the catalysts series were compared by the activity per total adsorbing sites which was observed to increase steadily with nPt/(nPt + nA). An increase of the accessible Pt atoms leads to an increase on the amount of spilled over hydrogen available in acid sites therefore increasing the overall activity. Pt/HBEA catalysts were found to be more active per total adsorbing site than Pt/HUSY which is proposed to be due to an augmentation in the efficiency of spilled over hydrogen diffusion related to the proximity between Pt clusters and acid sites. The intervention of Lewis acid sites in a greater extent than that measured by pyridine adsorption may also contribute to this higher activity of Pt/HBEA catalysts. These results reinforce the importance of model reactions as a closer perspective to the relevant catalyst properties in reaction conditions.

On the analytical solutions of the Hindmarsh-Rose neuronal model

In this article we analytically solve the Hindmarsh-Rose model (Proc R Soc Lond B221:87-102, 1984) by means of a technique developed for strongly nonlinear problems-the step homotopy analysis method. This analytical algorithm, based on a modification of the standard homotopy analysis method, allows us to obtain a one-parameter family of explicit series solutions for the studied neuronal model. The Hindmarsh-Rose system represents a paradigmatic example of models developed to qualitatively reproduce the electrical activity of cell membranes. By using the homotopy solutions, we investigate the dynamical effect of two chosen biologically meaningful bifurcation parameters: the injected current I and the parameter r, representing the ratio of time scales between spiking (fast dynamics) and resting (slow dynamics). The auxiliary parameter involved in the analytical method provides us with an elegant way to ensure convergent series solutions of the neuronal model. Our analytical results are found to be in excellent agreement with the numerical simulations.

Soliton-type and other travelling wave solutions for an improved class of nonlinear sixth-order Boussinesq equations

An improved class of nonlinear bidirectional Boussinesq equations of sixth order using a wave surface elevation formulation is derived. Exact travelling wave solutions for the proposed class of nonlinear evolution equations are deduced. A new exact travelling wave solution is found which is the uniform limit of a geometric series. The ratio of this series is proportional to a classical soliton-type solution of the form of the square of a hyperbolic secant function. This happens for some values of the wave propagation velocity. However, there are other values of this velocity which display this new type of soliton, but the classical soliton structure vanishes in some regions of the domain. Exact solutions of the form of the square of the classical soliton are also deduced. In some cases, we find that the ratio between the amplitude of this wave and the amplitude of the classical soliton is equal to 35/36. It is shown that different families of travelling wave solutions are associated with different values of the parameters introduced in the improved equations.

Arylhydrazones of barbituric acid: synthesis, coordination ability and catalytic activity of their CoII, CoII/IIIand CuIIcomplexes toward peroxidative oxidation of alkanes

New ortho-substituted arylhydrazones of barbituric acid, 5-(2-(2-hydroxyphenyl)hydrazono) pyrimidine-2,4,6(1H,3H,5H)-trione (H4L1) and the sodium salt of 2-(2-(2,4,6-trioxotetra-hydropyrimidin-5(2H)-ylidene)hydrazinyl) benzenesulfonic acid (H4L2), [Na(H3L2)(mu-H2O)(H2O)(2)](2) (1), were used in the synthesis of Cu-II, Co-II and Co-II/III complexes, [Cu(H2L1)(H2O)(im)]center dot 3H(2)O (im = imidazole) (2), [Co(H2O)(6)] [Co(H2L1)(2)](2)center dot 8H(2)O (3), [Co(H2L2)(im)(3)] (4), [Cu(H2L2)(im)(2)]center dot H2O (5) and [Co(H2O)(6)][H3L2](2)center dot 8H(2)O (6). The complexes are water soluble and the mono-or di-deprotonated ligands display different coordination modes, depending on the synthetic conditions. The electrochemical behaviour of all the compounds was investigated by cyclic voltammetry and controlled potential electrolysis, revealing that the ligands are also redox active. All the compounds were evaluated as catalysts for the peroxidative (with H2O2) oxidation of cyclohexane at room temperature. The compounds 2 and 3 are the most active ones (yields up to 21% and TON up to 213 are achieved, in the presence of 3).

Comparing clustering solutions: the use of adjusted paired indices

In the present paper we compare clustering solutions using indices of paired agreement. We propose a new method - IADJUST - to correct indices of paired agreement, excluding agreement by chance. This new method overcomes previous limitations known in the literature as it permits the correction of any index. We illustrate its use in external clustering validation, to measure the accordance between clusters and an a priori known structure. The adjusted indices are intended to provide a realistic measure of clustering performance that excludes agreement by chance with ground truth. We use simulated data sets, under a range of scenarios - considering diverse numbers of clusters, clusters overlaps and balances - to discuss the pertinence and the precision of our proposal. Precision is established based on comparisons with the analytical approach for correction specific indices that can be corrected in this way are used for this purpose. The pertinence of the proposed correction is discussed when making a detailed comparison between the performance of two classical clustering approaches, namely Expectation-Maximization (EM) and K-Means (KM) algorithms. Eight indices of paired agreement are studied and new corrected indices are obtained.