Electrophilic aromatic nitration: understanding its mechanism and substituent effects

Theoretical calculations and gas-phase mass spectrometric studies were performed for the reaction of the naked (NO2+) and monosolvated (CH3NO2.NO2+) nitronium ion with several monosubstituted aromatic compounds. From these studies, we propose a general model for regioselectivity based on the single-electron transfer (SET) mechanism and an alternative mechanistic scheme for electrophilic aromatic nitration. This scheme considers the SET and the polar (Ingold-Hughes) mechanisms as extremes in a continuum pathway, the occurrence and extents of both mechanisms being governed mainly by the ability, or lack of ability, of the aromatic compound to transfer an electron to NO2+.     

Lipase production by solid-state fermentation

The production of lipase by Penicillium simplicissimum in solid-state fermentation was studied using babassu cake as the basal medium. Tray-type and packed-bed bioreactors were employed. In the former, the influence of temperature; content of the medium, and medium supplementation with olive oil, sugarcane molasses, corn steep liquor, and yeast hydrolysate was studied. For all combinations of supplements, a temperature of 30°C, a moisture content of 70%, and a concentration of carbon source of 6.25% (m/m, dry basis) provided optimum conditions for lipase production. When used as single supplements olive oil and molasses also were able to provide high lipase activities (20 U/g). Using packed-bed bioreactors and molasses-supplemented medium, optimum conditions for enzyme production were air superficial velocities above 55 cm/min and temperatures below 28°C. The lower temperature optimum found for these reactors is probably related to radial heat gradient formation inside the packed bed. Maximum lipase activities obtained in these bioreactors (26.4 U/g) were 30% higher than in tray-type reactors.     

ESR investigation of graphite-like amorphous carbon films revealing itinerant states as the ones responsible for the signal

The origin of paramagnetic centers in graphite-like amorphous carbon is investigated. The films were deposited by the ion beam assisted deposition (IBAD) and have a concentration of sp² sites of about 90% and zero energy band gap. The density of the film and the electrical resistivity are close to these of crystalline graphite. However, the hardness and stress of the films are similar to those of diamond-like carbon. Electron spin resonance (ESR) performed at the X-band (9.4 GHz) revealed an unexpected low density of paramagnetic centers, ascribed to conduction electrons with a g-value of about 2.003.     

Thermography Applied to the Study of Fatigue Crack Propagation in Polycarbonate

Thermography was used to study the propagation of fatigue cracks during cyclic loading of pre-cracked SAE keyhole polycarbonate specimens. A micro-bolometer infrared camera (FLIR A655sc) and a commercially available software program (DeltaTherm2) were employed. The stress intensity factors were determined using a hybrid thermoelastic stress analysis (TSA) technique. The crack growth rate was determined via thermography using two different approaches. The first approach used the output of the crack-tip position from the developed TSA algorithm and the number of cycles between data sets. The second approach used temperature measurement as a new way to determine da/dN (crack growth rate) directly. As a result, da/dN vs ΔK (stress intensity factor range) graphs were plotted and fitted using Paris’ law. A comparison between the resultant da/dN vs ΔK curves and results found in the literature, as well as curves from the finite element method (FEM) simulations showed good agreement. The conclusion was that thermography is a very powerful tool that can detect, measure and monitor fatigue cracks in polycarbonate.