Design and experimental validation of a nonlinear controller for underactuated surface vessels

Nonlinear Dynamics - This paper addresses the problem of trajectory tracking control of an underactuated surface vessel moving in a two-dimensional space in the presence of unknown disturbances. In...     

Synthesis of Enantiomeric Pure E-Nor-15-azayohimbines

A stereodivergent synthesis of enantiomerically pure E-nor-15-azayohimbines via condensation of tryptamine with derivatives of pyroglutamate 4 is reported. When the Pictet-Spengler reaction was induced in refluxing aqueous AcOH a nearly equimolar ratio of lactams 7 and 8 was obtained, whereas under kinetic control (TFA, room temperature) the trans-derivative 8 was the major product. In contrast, cyclization of amido acetal 12 with TsOH gave the cis-derivative 7 as preponderant component.     

Structural Elucidation of an Atropisomeric Entcassiflavan-(4β→8)-Epicatechin Isolated from Dalbergia monetaria L.f. Based on NMR and ECD Calculations in Comparison to Experimental Data

A rare dihydoxyflavan-epicatechin proanthocyanidin, entcassiflavan-(4β→8)-epicatechin, was isolated from Dalbergia monetaria, a plant widely used by traditional people from the Amazon to treat urinary tract infections. The constitution and relative configuration of the compound were elucidated by HR-MS and detailed 1D- and 2D-NMR measurements. By comparing the experimental electronic circular dichroism (ECD) spectrum with the calculated ECD spectra of all 16 possible isomers, the absolute configuration, the interflavan linkage, and the atropisomers could be determined.     

Direct determination of glyphosate using hydrophilic interaction chromatography with coulometric detection at copper microelectrode

A simple, rapid, and low-cost coulometric method for direct detection of glyphosate using hydrophilic interaction chromatography is presented. The principle of detection is based on the enhancement of the anodic current of copper microelectrode in the presence of complexing agents, such as glyphosate, with the formation of a soluble Cu(II) complex. Under optimized conditions, the limit of detection (S/R = 3) for glyphosate was 0.1 mg L⁻¹ (0.59 μM) without any preconcentration method. The calibration curve has been found linear in all concentration range tested (from limit of detection to 34 mg L⁻¹) with an excellent correlation coefficient (0.9999). The present method was successfully applied for the determination of glyphosate in fruit juices without any kind of extraction, clean-up, or preconcentration step, with recoveries of 92 and 90% for apple and grape juice, respectively.     

Supramolecular Luminescent Lanthanide Dimers for Fluoride Sequestering and Sensing

Lanthanide complexes (Ln=Eu, Tb, and Yb) that are based on a C₂‐symmetric cyclen scaffold were prepared and characterized. The addition of fluoride anions to aqueous solutions of the complexes resulted in the formation of dinuclear supramolecular compounds in which the anion is confined into the cavity that is formed by the two complexes. The supramolecular assembly process was monitored by UV/Vis absorption, luminescence, and NMR spectroscopy and high‐resolution mass spectrometry. The X‐ray crystal structure of the europium dimer revealed that the architecture of the scaffold is stabilized by synergistic effects of the Eu? F? Eu bridging motive, π stacking interactions, and a four‐component hydrogen‐bonding network, which control the assembly of the two [EuL] entities around the fluoride ion. The strong association in water allowed for the luminescence sensing of fluoride down to a detection limit of 24 nM .     

Prediction of the pH‐rate profile for dimethyl sulfide oxidation by hydrogen peroxide: The role of elusive H3O2+ Ion

Experimental kinetics of sulfide oxidation by hydrogen peroxide presents a pH‐dependent profile. In this article, it was carried out a detailed study of the mechanism and kinetics of dimethyl sulfide (DMS) oxidation by H₂O₂ in neutral, acid, and basic aqueous medium using ab initio calculations. The results point out that DMS oxidation in neutral aqueous medium occurs through its direct reaction with H₂O₂. In acid medium, cluster‐continuum model calculations shows that cluster is the best representation of the very reactive species. In basic medium, there is formation of the species. However, the pathway involving this species has high free energy barrier, making this pathway unfeasible. The theoretical pH‐rate profile is in good agreement with the experimental observations. © 2013 Wiley Periodicals, Inc.     

Production and Characterization of β-Glucanase Secreted by the Yeast Kluyveromyces marxianus

An extracellular β-glucanase secreted by Kluyveromyces marxianus was identified for the first time. The optimal conditions for the production of this enzyme were evaluated by response surface methodology. The optimal conditions to produce β-glucanase were a glucose concentration of 4 % (w/v), a pH of 5.5, and an incubation temperature of 35 °C. Response surface methodology was also used to determine the pH and temperature required for the optimal enzymatic activity. The highest enzyme activity was obtained at a pH of 5.5 and a temperature of 55 °C. Furthermore, the enzyme was partially purified and sequenced, and its specificity for different substrates was evaluated. The results suggest that the enzyme is an endo-β-1,3(4)-glucanase. After optimizing the conditions for β-glucanase production, the culture supernatant was found to be effective in digesting the cell wall of the yeast Saccharomyces cerevisiae, showing the great potential of β-glucanase in the biotechnological production of soluble β-glucan.     

Influence of fused deposition modeling parameters on the mechanical properties of ABS parts

This work aims to determine the influence of fused deposition modeling (FDM) printing parameters on the mechanical properties of parts fabricated on an Ultimaker2 printer with acrylonitrile butadiene styrene (ABS). The effect of several parameters such as interlayer cooling time (ILCT), nozzle diameter, infill density, raster angle and layer thickness on the ultimate tensile strength, yield strength, and elastic modulus of produced parts was evaluated. Two independent studies were conducted: a first study dedicated to the ILCT and a second study where the influence of other parameters was evaluated through a design of experiments (DoE) approach. Both studies were carried out through the execution of standard tensile tests. The statistical analysis of tensile tests results was processed with the ANOVA methodology. The obtained results indicate that a reduced ILCT improves the tensile strength of parts. It is shown that nozzle diameter and infill density are the parameters that most influence the mechanical properties of ABS, with the upper range selected values improving the studied mechanical properties. The raster angle configuration of (?45^o/45^o) benefits UTS and yield strength of ABS samples. Interactions of nozzle diameter on layer thickness were detected. It was observed that smaller layer thickness promotes a higher elastic modulus and UTS; however, for thinner layers (0.06‐0.10 mm), no significant differences were found on strength of samples due to potential high distortion levels.