Strukturanalytische Untersuchungen an Folgeprodukten aus Sulfonamiden. V. Infrarotspektroskopische und thermoanalytische Untersuchungen an polymorphen Modifikationen von N-substituierten S-Methyl-N′-tosyl-isothioharnstoffen

Structure-Analytical Investigations of Consecutive Products of Sulphonamides. V. Infrared Spectroscopic and Thermoanalytical Studies of Polymorphic Modifications of N-Substituted S-Methyl-N′-tosyl-isothioureas Four compounds ( 1d, 1e, 1h, 1p ) out of twelve N-substituted S-methyl-N′-tosylisothioureas were shown to form polymorphic modifications. Attempts were made to isolate each single specimen and to characterize it by means of differential scanning calorimetry and infrared spectroscopy. The results clearly revealed that both different hydrogen bonding and conformational effects are responsible for the formation of the polymorphic species. With the help of ¹⁵N labeled compounds the presence of the sulphonylimino structure in any modification was proved. The v(NH) and δ_s(SO₂) band positions are used to divide the polymorphs into two groups A and B.     

Characterization of the Fouled Ballast Layer in the Substructure of a 19th Century Railway Track Under Renewal

The purpose of these field and lab studies undertaken during rehabilitation work being done on an ancient railway line was to characterize a layer of ballast fouled with soil found in the track substructure. The field studies included the characterization of the thickness, grain size distribution and void ratio of the fouled ballast layer, as well as a large number of plate load tests, both on the fouled ballast layer and on the subgrade. The resilient behaviour of the fouled ballast was evaluated in the lab by cyclic triaxial tests on large size reconstituted specimens with distinct fouling indexes (different grain size distribution) and distinct humidity states (dry or wet). The results obtained were used as support for the decision to maintain the fouled ballast layer under the new sub-ballast in a number of stretches of the renewed line.     

Design of PI and PID controllers with transient performance specification

Proportional-integral-derivative (PID) controllers are widely used in industrial control systems because of the reduced number of parameters to be tuned. The most popular design technique is the Ziegler-Nichols method, which relies solely on parameters obtained from the plant step response. However, besides being suitable only for systems with monotonic step response, the compensated systems whose controllers are tuned in accordance with the Ziegler-Nichols method have generally a step response with a high-percent overshoot. In this paper, tuning methods for proportional-integral (PI) and PID controllers are proposed that, like the Ziegler-Nichols method, need only parameters obtained from the plant step response. The methodology also encompasses the design of PID controllers for plants with underdamped step response and provides the means for a systematic adjustment of the controller gain in order to meet transient performance specifications. In addition, since all the development of the methodology relies solely on concepts introduced in a frequency-domain-based control course, the paper has also a didactic contribution.     

Volatile organic compounds in rural atmospheres of central Portugal

Atmospheric concentrations of volatile organic compounds were measured at two rural sites in central Portugal. The sites were chosen to be in line with the summer northwesterly sea breezes in order to study the evolution of the chemical composition of air masses during transport to inland areas. The most abundant non-oxygenated hydrocarbon in the ambient air was isoprene and the monoterpenes alpha-pinene, beta-pinene and 1,8 cineol. The maximum isoprene levels (6-7 ppb) were recorded at the most inland site, suggesting an enrichment of coastal air masses with biogenic emissions during transport over eucalyptus forests. Formaldehyde was the most prominent carbonyl compound in the atmosphere but acetaldehyde and acrolein were also abundant. Concentrations of carbonyl compounds had a tendency to be higher inland, particularly for glyoxal, methyl glyoxal, methyl vinyl ketone, metacrolein and pentanal. The observed increases indicate that carbonyls were produced by photochemical oxidation of biogenic hydrocarbons in aged air masses with coastal origin. Isoprene, monoterpenes and various carbonyls exhibited pronounced diurnal variations, which are explained on the basis of emissions from vegetation, oxidation pathways of biogenic hydrocarbons and meteorological conditions.     

Cleavage Stress Required to Produce Fracture Path Deflection in Cold-Drawn Prestressing Steel Wires

Cold-drawn prestressing steel wires exhibit strength anisotropy in the form of fracture path deflection towards a direction approaching the wire axis, or cold drawing line, as a consequence of the pearlitic microstructure orientation induced by the manufacturing procedure. Such a crack path deflection is initiated at certain nuclei (fracture origins) at which axial cracking appears in the cold drawing direction (or wire axis) in the form of micro-cleavage units that produce in the load-displacement curve a macroscopic phenomenon of pop-in. This paper shows that such fracture initiators appear at a certain distance from the fatigue pre-crack tip at which a local maximum of the cleavage stress is located.     

Jaboticaba berry peel intake prevents insulin‐resistance‐induced tau phosphorylation in mice

The hyperphosphorylation of microtubule‐associated protein tau (tau) in the hippocampus can be caused by central and peripheral insulin resistance and these alterations are related to the development of tauopathies, such as Alzheimer's disease. In this study, we used a high‐fat diet to induce obesity and insulin resistance in adult Swiss mice and checked whether supplementation with Myrciaria jaboticaba berry peel for 10 weeks could improve insulin sensitivity, learning/memory performance, and prevent tau phosphorylation in the hippocampus. Furthermore, adipocytokines, inflammatory markers, and oxidative stress were assessed. Myrciaria jaboticaba peel has phenolic compounds (e.g., cyanidin, ellagic acid), dietary fiber and carotenoids, which contribute to great antioxidant capacity. Supplementation of the high‐fat diet with 4% M. jaboticaba peel prevented fat weight gain and reduced peripheral insulin resistance. The treated group also showed lower tau phosphorylation in the hippocampus corroborating better learning/memory performance in the Morris water maze test. Maintenance of neuronal viability, lower levels of hippocampal inflammatory markers, and improved brain antioxidant defenses were also related to the consumption of M. jaboticaba peel. These findings contribute to a better understanding of how a high‐fat diet supplemented with jaboticaba berry peel counteracts the impairment of cognitive functions caused by high‐fat diet intake and diet‐induced insulin resistance.     

NbO/Nb2O5 core–shells by thermal oxidation

Niobium oxides have been reported as an alternative to tantalum, and its oxide, for the production of capacitors, but these materials still require a further and exhaustive study. Understanding the dynamics of the oxidation process from NbO to Nb₂O₅ is essential to explain and control the properties of a niobium oxide based capacitors. In situ XRD analysis of NbO powders was performed from 100 to 1100 °C, which showed a temperature range where only amorphous phase is present. The capacitor anodes, formed from the same type of NbO powders, were then heat-treated in air from room-temperature (RT) to 550 °C and recorded with a video camera to see the colour shift. The presence of core–shell structures and the increase of the shell thickness/amount with temperature are visible in SEM. Finally, in situ spectroscopy studies were performed, in order to observe the interference spectra which are responsible for the observed colours.     

Phenol degradation by Aureobasidium pullulans FE13 isolated from industrial effluents

The degradation of phenol (2-30 mM) by free cells and by alginate-immobilized cells of Aureobasidium pullulans FE13 isolated from stainless steel effluents was studied in batch cultures with saline solution not supplemented with nutrients or yeast extract. The rate at which the immobilized cells degrade phenol was similar to the rate at which the suspended cells could degrade phenol, for a concentration of up to 16 mM of phenol. The maximum phenol volumetric degradation rate for 16 mM phenol was found to be 18.35 mg l(-1)h(-1) in the assays with free cells and 20.45 mg l(-1)h(-1) in the assays with alginate-immobilized cells, 18 mM phenol and cellular concentration of 0.176 g/l. At concentrations higher than this, an inhibitory effect was observed, resulting in the lowering of the phenol degradation rates. The immobilization was detrimental to the catechol 1,2-dioxygenase activity. However, the immobilized cells remained viable for a longer period, increasing the efficiency of phenol degradation. The yeast showed catechol 1,2-dioxygenase activity only after growth in the phenol, which was induced at phenol concentrations as low as 0.05 mM and up to 25 mM at 45 h of incubation at 30 degrees C. Phenol concentrations higher than 6mM were inhibitory to the enzyme. Addition of glucose, lactate, succinate, and benzoate reduced the rate at which phenol is consumed by cells. Our results suggest that inoculants based on immobilized cells of A. pullulans FE13 has potential application in the biodegradation of phenol and possibly in the degradation of other related aromatic compounds.