Optimization of organo‐layered double hydroxide dispersion in LDPE‐based nanocomposites

Low‐density polyethylene/layered double hydroxide (LDPE/LDH) nanocomposites were prepared via melt extrusion using organo‐LDH particles and maleic anhydride functionalized polyethylene as compatibilizer. Processing parameters, preparation method, and feed composition were properly modulated until obtaining nanocomposites with intercalated/exfoliated morphologies, and an uniform distribution of nanolayers, as evidenced by X‐ray diffraction and transmission electron microscopy analysis. These materials showed a significant improvement of the thermal‐oxidative stability, which increased of about 50°C during the first step of the degradation process. Moreover, a remarkable reduction of the oxygen permeability, proportional to the aspect ratio of LDH stacks dispersed in the polyolefin matrix was evidenced, indicating the possible application of nanocomposite films as food packaging materials. As highlighted by dynamic mechanical thermal analysis, interactions at the interface between LDH layers and polymer chains caused a shift of the LDPE β‐relaxation toward higher temperatures and a reduction of the peak intensity with respect to the matrix. It was also found that the storage modulus of the nanocomposites was lower in all the temperature range with respect to the reference samples. Finally, on‐line capillary rheometer measurements evidenced that the shear thinning behavior of the nanocomposites was dominated by the matrix so that the melt processability was not compromised by the presence of the filler. Copyright © 2010 John Wiley & Sons, Ltd.     

Electroactive multilayer assemblies of bilirubin oxidase and human cytochrome C mutants: insight in formation and kinetic behavior

Here, we report on cytochrome c/bilirubin oxidase multilayer electrodes with different cytochrome c (cyt c) forms including mutant forms of human cyt c, which exhibit different reaction rates with bilirubin oxidase (BOD) in solution. The multilayer formation via the layer-by-layer technique and the kinetic behavior of the mono (only cyt c) and biprotein (cyt c and BOD) multilayer systems are studied by SPR and cyclic voltammetry. For the layer construction, sulfonated polyaniline is used. The only cyt c containing multilayer electrodes show that the quantity of deposited protein and the kinetic behavior depend on the cyt c form incorporated. In the case of the biprotein multilayer with BOD, it is demonstrated that the catalytic signal chain from the electrode via cyt c to BOD and oxygen can be established with all chosen cyt c forms. However, the magnitude of the catalytic current as well as the kinetic behavior differ significantly. We conclude that the different cytochrome c forms affect three parameters, identified here, to be important for the functionality of the multilayer system: the amount of molecules per layer, which can be immobilized on the electrodes, the cyt c self-exchange rate, and the rate constant for the reaction with BOD.     

Chiral optical films based on achiral chromophore guests

Films constituted by an achiral host polymer and an achiral guest chromophore, which exhibit intense chiral optical responses for both host and guest peaks in the infrared as well as in the UV-visible regions, have been obtained. Such films can have any thickness from the nanoscale up to the macroscopic scale. This unexpected chiral optical behavior is easily achieved by crystallization of a robust commercial stereoregular host polymer (syndiotactic polystyrene, s-PS) from the amorphous phase as induced by a nonracemic guest, followed by exchange of the nonracemic guest with the achiral guest, leading to the formation of polymer-host/chromophore-guest cocrystalline phases. This finding opens the possibility to achieve s-PS-based films with chiral optical response at selected wavelengths. It has been also found that the chiral optical cocrystalline phase of s-PS with azulene exhibits a monoclinic δ-clathrate form with equal proportions of left- and right-handed helices. This confirms that the observed chiral optical behavior arises by the nonracemic native morphology of the crystalline regions, which has been induced by the temporary nonracemic guest.     

SARs for the Antiparasitic Plant Metabolite Pulchrol. 3. Combinations of New Substituents in A/B-Rings and A/C-Rings

The natural products pulchrol and pulchral, isolated from the roots of the Mexican plant Bourreria pulchra, have previously been shown to possess antiparasitic activity towards Trypanosoma cruzi, Leishmania braziliensis and L. amazonensis, which are protozoa responsible for Chagas disease and leishmaniasis. These infections have been classified as neglected diseases, and still require the development of safer and more efficient alternatives to their current treatments. Recent SARs studies, based on the pulchrol scaffold, showed which effects exchanges of its substituents have on the antileishmanial and antitrypanosomal activity. Many of the analogues prepared were shown to be more potent than pulchrol and the current drugs used to treat leishmaniasis and Chagas disease (miltefosine and benznidazole, respectively), in vitro. Moreover, indications of some of the possible interactions that may take place in the binding sites were also identified. In this study, 12 analogues with modifications at two or three different positions in two of the three rings were prepared by synthetic and semi-synthetic procedures. The molecules were assayed in vitro towards T. cruzi epimastigotes, L. braziliensis promastigotes, and L. amazonensis promastigotes. Some compounds had higher antiparasitic activity than the parental compound pulchrol, and in some cases even benznidazole and miltefosine. The best combinations in this subset are with carbonyl functionalities in the A-ring and isopropyl groups in the C-ring, as well as with alkyl substituents in both the A- and C-rings combined with a hydroxyl group in position 1 (C-ring). The latter corresponds to cannabinol, which indeed was shown to be potent towards all the parasites.     

Numerical integration based on trivariate C 2 quartic spline quasi-interpolants

In this paper we consider the space generated by the scaled translates of the trivariate C ² quartic box spline B defined by a set X of seven directions, that forms a regular partition of the space into tetrahedra. Then, we construct new cubature rules for 3D integrals, based on spline quasi-interpolants expressed as linear combinations of scaled translates of B and local linear functionals. We give weights and nodes of the above rules and we analyse their properties. Finally, some numerical tests and comparisons with other known integration formulas are presented.     

On entropy weak solutions of Hughes’ model for pedestrian motion

We consider a generalized version of Hughes’ macroscopic model for crowd motion in the one-dimensional case. It consists in a scalar conservation law accounting for the conservation of the number of pedestrians, coupled with an eikonal equation giving the direction of the flux depending on pedestrian density. As a result of this non-trivial coupling, we have to deal with a conservation law with space–time discontinuous flux, whose discontinuity depends non-locally on the density itself. We propose a definition of entropy weak solution, which allows us to recover a maximum principle. Moreover, we study the structure of the solutions to Riemann-type problems, and we construct them explicitly for small times, depending on the choice of the running cost in the eikonal equation. In particular, aiming at the optimization of the evacuation time, we propose a strategy that is optimal in the case of high densities. All results are illustrated by numerical simulations.     

Differences in brain regions of three mice strains identified by label-free micro-Raman

The analysis of different central nervous system regions is interesting and necessary as each one is involved in specific physiological processes and pathologies. On that matter, differences in the chemical composition between the same brain regions in different mice strains have been reported. In this sense, the development of a simple method for the identification of these regions depending on their chemical composition becomes relevant. Raman microspectroscopy, a non-destructive analytical chemical approach for biological samples, is a widely used method for qualitative, quantitative, and structural analysis in biochemical research. Ten brain structures in three different mice strains (Triple transgenic for Alzheimer Disease, 3xTgAD; Cluster 57 black 6, C57BL/6; and the Swiss strain, CD1) were analyzed, and variations among samples from several brain regions were found. Particularly, the pattern of signals from the hippocampus, the prefrontal and temporal cortices, the basal forebrain, the striatum, the cerebellum, and the hypothalamus was discernable. Interestingly, notable signals regarding non-peptide small neurotransmitters were observed, including those related to acetylcholine. These bands were present in the Raman spectra of the basal forebrain and prefrontal cortex in the three mice strains, consistent with the relative abundance of this neurotransmitter in those regions. However, signals with lower intensities appeared in the basal forebrain of C57BL/6 in comparison with the same tissue of the other two strains. In addition, the Raman intensity of bands assigned to catecholamines in the striatum was lower in the 3xTgAD than those from both CD1 and C57BL/6 mice strains. This approach, as well as the reported differences, has potential application for designing analysis on specific murine models of brain diseases.     

An efficient numerical tool for dose deposition prediction applied to synchrotron medical imaging and radiation therapy

Medical imaging and radiation therapy are widely used synchrotron‐based techniques which have one thing in common: a significant dose delivery to typically biological samples. Among the ways to provide the experimenters with image guidance techniques indicating optimization strategies, Monte Carlo simulation has become the gold standard for accurately predicting radiation dose levels under specific irradiation conditions. A highly important hampering factor of this method is, however, its slow statistical convergence. A track length estimator (TLE) module has been coded and implemented for the first time in the open‐source Monte Carlo code GATE/Geant4. Results obtained with the module and the procedures used to validate them are presented. A database of energy‐absorption coefficients was also generated, which is used by the TLE calculations and is now also included in GATE/Geant4. The validation was carried out by comparing the TLE‐simulated doses with experimental data in a synchrotron radiation computed tomography experiment. The TLE technique shows good agreement versus both experimental measurements and the results of a classical Monte Carlo simulation. Compared with the latter, it is possible to reach a pre‐defined statistical uncertainty in about two to three orders of magnitude less time for complex geometries without loss of accuracy.     

A Nyström interpolant for some weakly singular nonlinear Volterra integral equations

We consider a second kind weakly singular nonlinear Volterra–Hammerstein integral equation defined by a compact operator and derive a Nyström type interpolant of the solution based on Gauss–Radau nodes. We prove the convergence of the interpolant and derive convergence estimates. For equations with nonlinearity of algebraic kind, we improve the rate of convergence by using a smoothing transformation. Some numerical examples are given.