Kinetics and Mechanism of Hydrolysis of Benzimidazolylcarbamates

Synthesis of new 2-aminobenzimidazole-1-carbamates was accomplished by carbamoylation of 2-aminobenzimidazole using different substituted phenyl chloroformates. The aqueous hydrolysis of the new compounds was examined in the pH range 1-13 at 25 oC. The evaluated kinetic parameters led to the conclusion that up to pH 4 reaction proceeds by a bimolecular attack of water to the N-protonated substrate. This is the first time this behavior is described for carbamates, and can be ascribed to the higher basicity of the benzimidazolyl moiety when compared with the carbonyl oxygen. For higher values of pH, the results are consistent with a BAc2 mechanism with nucleophilic catalysis, but while between pH 4 and pH 7 water acts as the nucleophile, for pH> 7 the hydroxide ion is the acting species

Cephalometric studies of the mandible, its masticatory muscles and vasculature of growing Göttingen Minipigs — A comparative anatomical study to refine experimental mandibular surgery

Over many decades, the Göttingen Minipig has been used as a large animal model in experimental surgical research of the mandible. Recently several authors have raised concerns over the use of the Göttingen Minipig in this research area, observing problems with post-operative wound healing and loosening implants. To reduce these complications during and after surgery and to improve animal welfare in mandibular surgery research, the present study elucidated how comparable the mandible of minipigs is to that of humans and whether these complications could be caused by specific anatomical characteristics of the minipigs’ mandible, its masticatory muscles and associated vasculature. Twenty-two mandibular cephalometric parameters were measured on CT scans of Göttingen Minipigs aged between 12 and 21 months. Ultimately, we compared this data with human data reported in the scientific literature. In addition, image segmentation was used to determine the masticatory muscle morphology and the configuration of the mandibular blood vessels. Compared to data of humans, significant differences in the mandibular anatomy of minipigs were found. Of the 22 parameters measured only four were found to be highly comparable, whilst the others were not. The 3D examinations of the minipigs vasculature showed a very prominent deep facial vein directly medial to the mandibular ramus and potentially interfering with the sectional plane of mandibular distraction osteogenesis. Damage to this vessel could result in inaccessible bleeding. The findings of this study suggest that Göttingen Minipigs are not ideal animal models for experimental mandibular surgery research. Nevertheless if these minipigs are used the authors recommend that radiographic techniques, such as computed tomography, be used in the specific planning procedures for the mandibular surgical experiments. In addition, it is advisable to choose suitable age groups and customize implants based on the mandibular dimensions reported in this study

Modern estates and the production of Lisbon’s suburbs: From the planned to the lived neighbourhood

Alto da Barra and Portela are two modern estates designed by the same architect and located on two sides of the periphery of Lisbon: the west side, Costa do Sol, where the river meets the Atlantic and the east, with no label, which is upstream. The estates were planned and built in the same period (1960s to 1970s), the height of Lisbon’s urban development. This article presents a comparative analysis of these estates: their plans, implementation, social appropriation and resilience, by exploring the sociological profile and place-attachment perceptions of their inhabitants. The analysis also contextualises the development of the estates within the consolidation of these two quite different Lisbon peripheries: the west side traditionally highly valued in relation to the east. An intensive methodology was developed—case studies of the two estates—combining quantitative (survey, inter-census analysis) and qualitative (interviews and documentary analysis) methods. In addition to the differences between the two estates, which were largely due to their specificities in terms of geographic location and status, both reveal significant feelings of place-attachment and a rejection of the suburbia label.info:eu-repo/semantics/publishedVersio

Photometry of the Oort Cloud comet C/2009 P1(Garradd): pre-perihelion observations at 5.7 and 2.5 AU

The aim of this paper is to contribute to the characterization of the general properties of the Long Period Comets (LPCs) family, and in particular to report on the dust environment of comet C/2009 P1 (Garradd). The comet was observed at two epochs pre-perihelion, at ~6 AU and at ~2.5 AU: broad-band images have been used to investigate its coma morphology and properties and to model the dust production rate. Comet C/2009 P1 (Garradd) is one of the most active and “dust producing” LPCs ever observed, even at the large heliocentric distance rh~6 AU. Its coma presents a complex morphology, with subtle structures underlying the classical fan-shaped tail, and, at rh~2.5 AU, also jet-like structures and spiralling outflows. In the reference aperture of radius ρ=5°×104 km, the R-Afρ is 3693±156 cm and 6368±412 cm, in August 2010 (rh~6 AU) and July 2011 (rh~2.5 AU), respectively. The application of a first order photometric model, under realistic assumptions on grain geometric albedo, power-law dust size distribution, phase darkening function and grain dust outflow velocity, yielded a measure of the dust production rate for the two epochs of observation of Qd=7.27×102 kg/s and Qd=1.37×103 kg/s, respectively, for a reference outflow dust velocity of vsmall=25 m/s for small (0.1–10 µm) grains and vlarge=1 m/s for large (10 µm–1 cm) grains. These results suggest that comet Garradd is one of the most active minor bodies observed in recent years, highly contributing to the continuous replenishment of the Interplanetary Dust Complex also in the outer Solar System, and pose important constraints on the mechanism(s) driving the cometary activity at large heliocentric distances

Innovative airplane ground handling system for green operations

The aim of this work is to develop a new concept of taxiing, in order to reduce the pollution in terms of noise and gas emission and to introduce a higher level of safety during ground operations. In the area close to the airport gates, the airplane ground handlings are currently performed through the airplane engines, which have the task of providing the trust necessary to move the airplane to the runway. Pollutant emissions and the noise level near the gates, however, could be drastically reduced by introducing an innovative autonomous tractor called CHAT (Clean Hydrogen Autonomous Tractor), developed from the standard pushback tractor. The ground operations could be basically modified by extending the time in which the airplane engines are idle and the airplane is towed by the tractors powered by renewable energy

The dust environment of comet 67P/Churyumov–Gerasimenko: results from Monte Carlo dust tail modelling applied to a large ground-based observation data set

We present an extensive data set of ground-based observations and models of the dust environment of comet 67P/Churyumov–Gerasimenko covering a large portion of the orbital arc from about 4.5 au pre-perihelion through 3.0 au post-perihelion, acquired during the current orbit. In addition, we have also applied the model to a dust trail image acquired during this orbit, as well as to dust trail observations obtained during previous orbits, in both the visible and the infrared. The results of the Monte Carlo modelling of the dust tail and trail data are generally consistent with the in situ results reported so far by the Rosetta instruments Optical, Spectroscopic, and Infrared Remote Imaging System (OSIRIS) and Grain Impact Analyser and Dust Accumulator (GIADA). We found the comet nucleus already active at 4.5 au pre-perihelion, with a dust production rate increasing up to ∼3000 kg s−1 some 20 d after perihelion passage. The dust size distribution at sizes smaller than r = 1 mm is linked to the nucleus seasons, being described by a power law of index −3.0 during the comet nucleus southern hemisphere winter but becoming considerably steeper, with values between −3.6 and −4.3, during the nucleus southern hemisphere summer, which includes perihelion passage (from about 1.7 au inbound to 2.4 au outbound). This agrees with the increase of the steepness of the dust size distribution found from GIADA measurements at perihelion showing a power index of −3.7. The size distribution at sizes larger than 1 mm for the current orbit is set to a power law of index −3.6, which is near the average value of in situ measurements by OSIRIS on large particles. However, in order to fit the trail data acquired during past orbits previous to the 2009 perihelion passage, a steeper power-law index of −4.1 has been set at those dates, in agreement with previous trail modelling. The particle sizes are set at a minimum of r = 10 μm, and a maximum size, which increases with decreasing heliocentric distance, in the 1–40 cm radius domain. The particle terminal velocities are found to be consistent with the in situ measurements as derived from the instrument GIADA on board Rosetta

Exchange Rates and Sovereign Risk

We empirically investigate the relation between currency excess returns and sovereign risk, as measured by credit default swap (CDS) spreads. An increase in a country’s CDS spread is accompanied by a contemporaneous depreciation of its exchange rate as well as an increase of its currency volatility and crash risk. The link between currency excess returns and sovereign risk is mainly driven by exposure to global sovereign risk shocks and also emerges in a predictive setting for currency risk premia. Sovereign risk forecasts excess returns to trading exchange rates, volatility and skewness, and is strongly priced in the cross-section of currencies. Moreover, we find that sovereign risk accounts for a large share of carry trade returns, and that carry and momentum strategies generate high (low) returns across countries with high (low) sovereign risk

Atherosclerosis and Its Related Laboratory Biomarkers

Atherosclerosis constitutes a persistent inflammatory ailment, serving as the predominant underlying condition for coronary artery disease (CAD), peripheral artery disease (PAD), and cerebrovascular disease. The progressive buildup of plaques within the walls of medium- and large-caliber arteries characterizes the atherosclerotic process. This accumulation results in significant narrowing that impedes blood flow, leading to critical tissue oxygen deficiency. Spontaneous blockage of thrombotic vessels can precipitate stroke and myocardial infarction, which are complications representing the primary global causes of mortality. Present-day models for predicting cardiovascular risk incorporate conventional risk factors to gauge the likelihood of cardiovascular events over a ten-year span. In recent times, researchers have identified serum biomarkers associated with an elevated risk of atherosclerotic events. Many of these biomarkers, whether used individually or in combination, have been integrated into risk prediction models to assess whether their inclusion enhances predictive accuracy. In this review, we have conducted a comprehensive analysis of the most recently published literature concerning serum biomarkers associated with atherosclerosis. We have explored the potential utility of incorporating these markers in guiding clinical decisions

CFD NUMERICAL ANALYSIS OF A PROPOSED CHANGE IN THE CHANNEL GEOMETRY DOWNSTREAM OF A REVERSED TAINTER GATE

Reversed Tainter gates are often used to control flow in the filling and emptying locks navigation systems of high fall. High speeds and pressure fluctuations may occur in the flow downstream of these gates, the flow cavitation may occur, damaging the structure. One way proposed to mitigate this problem is through geometric changes in the channel downstream of the gate. In this study was analyzed using CFD the effect of an expansion in the roof and the base of the conduit, followed by a straight section and a subsequent contraction until returning to the original geometry. It was observed that the pressure at the base of the conduit increases with the modification, however peaks of positive and negative pressures occur due to the shape change of the geometry of the corners not be smooth. The size of recirculation downstream of the gate increases with the geometrical alteration, increasing the distance required for pressure recovery