Interaction of isobutene and methacrolein with silica-supported uranium and molybdenum oxide catalysts

The adsorption of isobutene (in the temperature range 309–341K) and methacrolein (in the temperature range 296–336 K) on a Mo/(Mo+U)=0.89 catalyst were studied. The equilibrium data were analysed according to Freundlich's model. The high coverages observed at lower temperatures suggest some participation of physical adsorption in the reversible adsorption. Entropy calculations showed that these adsorbed species are best described by a mobile model which assumes bidimensional translation and two rotational degrees of freedom. Isobutene is weakly chemisorbed, producing reversible species which were identified as a π-complex formed by interaction with surface OH groups through π-electrons (infrared bands at 1655, 1615, 1470 and 1375 cm^?1), and only a small fraction of isobutene interacts strongly via lattice oxygen forming intermediate species in the oxidation reaction. However, in the presence of oxygen at 523 K a majority of the surface species are strongly held by the surface (infrared bands at 1775, 1723, 1610, 1460 and 1350 cm^?1 associated to a methacrylic complex and bands at 1590 and 1538 cm^?1 of carbonate-carboxylate species).     

A CAVE-like environment as a tool for full-size train design

Simulations of models, in all different areas, is an expanding, attractive line of work. More and more applications are taking advantage of the improvements in technology and knowledge in this field, thus achieving results that would have been impossible to achieve with a real model, or foreseeing facts that otherwise would have been encountered too late in the production process. The rail industry is one possible beneficiary of this approach. Usually, before commencing the fabrication process of a new train, the construction of a full-size model is mandatory. Instead of building this full-size real model, which leaves little room for later, last-minute modifications, a virtual model can be built in the digital realm, thus offering a new platform for easier interaction with it. In this article, a simulation of a train is presented in order to tackle visual, aesthetic and ergonomic issues. The simulation runs on a PC-based CAVE-like architecture, offering a certain degree of interaction to the user, and combines static and dynamic computer-generated imagery, both with and without stereoscopy for 3D visualisation, as well as augmented virtuality techniques for the integration of the train with its environment.     

Background synaptic activity as a switch between dynamical states in a network

A bright red light may trigger a sudden motor action in a driver crossing an intersection: stepping at once on the brakes. The same red light, however, may be entirely inconsequential if it appears, say, inside a movie theater. Clearly, context determines whether a particular stimulus will trigger a motor response, but what is the neural correlate of this? How does the nervous system enable or disable whole networks so that they are responsive or not to a given sensory signal? Using theoretical models and computer simulations, I show that networks of neurons have a built-in capacity to switch between two types of dynamic state: one in which activity is low and approximately equal for all units, and another in which different activity distributions are possible and may even change dynamically. This property allows whole circuits to be turned on or off by weak, unstructured inputs. These results are illustrated using networks of integrate-and-fire neurons with diverse architectures. In agreement with the analytic calculations, a uniform background input may determine whether a random network has one or two stable firing levels; it may give rise to randomly alternating firing episodes in a circuit with reciprocal inhibition; and it may regulate the capacity of a center-surround circuit to produce either self-sustained activity or traveling waves. Thus, the functional properties of a network may be drastically modified by a simple, weak signal. This mechanism works as long as the network is able to exhibit stable firing states, or attractors.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in the air of Seveso,Italy, 26 years after the explosion

This study reports the current levels of polychlorinated dibenzo-p-dioxins (PCDDs) and furans (PCDFs) in air at Seveso, where an explosion in a 2,4,5,-trichlorophenol production reactor occurred 26 years ago. The aims were to assess if residues of the 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) released during the accident and still present in soil could contaminate the above air and to investigate other potential sources in the area. Long-term air collection was carried out in zones A and B in Seveso and in a reference location in Milan, and samples were analyzed for PCDD and PCDF concentrations by gas chromatography-mass spectrometry (GC-MS). Experimental results showed that no important contribution to the air concentrations is due to the soil contamination and that contemporary sources essentially control the atmospheric burden of PCDDs and PCDFs in the Seveso area. The theoretical release of 2,3,7,8-TCDD from the soils of zones A and B of Seveso was calculated using the SoilFug model. In the worst case, the model simulated an enrichment in atmospheric 2,3,7,8-TCDD concentrations of 4 and 22% for zones A and B, respectively. The investigation of the potential emission sources in the area indicated that combustion of wood residues from furniture factories may be an additional local source of PCDDs and PCDFs.     

Specific interactions study in complexes of poly(mono-n-alkyl itaconates) with tertiary polyamides

This paper reports an FT-IR study of blends of poly(mono-n-alkyl itaconates) with poly(N,N-dimethylacrylamide) (PDMA) and poly(ethyloxazoline) (PEOX). Strong hydrogen bonding has been found, and both polybases have shown similar acceptor strengths. Derivative techniques show asymmetric profiles for the free carbonyl band of the polybases, resulting in shifted band locations. The extent of the interassociation has been estimated by spectral curve fitting of the polybase carbonyl band. The results show that the interaction degree in blends with PEOX does not depend on the length of the poly(monoalkyl itaconate) side group, while an inter-associating ability loss is observed in blends with PDMA as the side-group size of the polyacid increases. This different behavior is attributed to the greater interspacing between vicinal carbonyl groups in PEOX. This band shows conformational sensitivity and reflects the conformational changes that occur as the steric hindrances present in the medium (due to the bulky side groups of the polyacids) increase.     

Dosage individualization of erythropoietin using a profile-dependent support vector regression

The external administration of recombinant human erythropoietin is the chosen treatment for those patients with secondary anemia due to chronic renal failure in periodic hemodialysis. The objective of this paper is to carry out an individualized prediction of the EPO dosage to be administered to those patients. The high cost of this medication, its side-effects and the phenomenon of potential resistance which some individuals suffer all justify the need for a model which is capable of optimizing dosage individualization. A group of 110 patients and several patient factors were used to develop the models. The support vector regressor (SVR) is benchmarked with the classical multilayer perceptron (MLP) and the Autoregressive Conditional Heteroskedasticity (ARCH) model. We introduce a priori knowledge by relaxing or tightening the epsilon-insensitive region and the penalization parameter depending on the time period of the patients' follow-up. The so-called profile-dependent SVR (PD-SVR) improves results of the standard SVR method and the MLP. We perform sensitivity analysis on the MLP and inspect the distribution of the support vectors in the input and feature spaces in order to gain knowledge about the problem.     

Sensitivity Analysis Methods to Design Optimal Ship Hulls

Automatic procedures for the design of ship hull geometries yielding minimal wave resistance and wave breaking are an attractive opportunity from both the economical and practical standpoints. Estimating the cost function gradient according to the Sensitivity Equation and Adjoint Methods (SEM, AM) instead of using the standard finite difference approximations has the potential of reducing the computational cost of the overall optimization procedure. Aim of this paper is to assess the actual extent of the cost reduction. Speed-up factors of up to 3.3 have been obtained in the evaluation of the cost function gradient and of about 1.6 in the overall optimization procedure applied to an optimal shape design problem of an existing tanker ship. The SEM and AM methods perform better than finite differences mainly because of (i) the smaller number of flow solutions needed to compute the cost function gradient and (ii) the opportunity of using the same LU factored matrix for both the flow solver and the SEM or AM equations, a circumstance arising as a consequence of having chosen a linearized potential flow model of the 3D free-surface problem.     

Geobag Performance as Scour Countermeasure for Bridge Abutments

This paper presents observations and data from a sequence of laboratory experiments conducted to evaluate geobags as a countermeasure to protect bridge-abutment foundations from failure attributable to scour of the alluvial-river channel in which they are placed. Geobags comprise geotextile cloth bags filled with local sediment or concrete. The experiments focused on the performance of geobags placed as an apron around pile-supported wing-wall abutments retaining erodible embankments, and subject to live-bed and clear-water flow conditions. Though an apron of geobags is shown to substantially reduce or eliminate scour immediately at the abutment, the apron must be formed flexibly of linked geobags. Moreover, a performance concern is that the apron may shift scour to a location flanking or downstream of the apron, and in so doing imperil a nearby pier or riverbank. The experiments indicate the importance of protecting the embankment region beneath and immediately behind the abutment’s pile cap. Live-bed conditions proved to be the more critical for abutment protection, owing to the capacity of dunes to destabilize geobags around the edges of the apron. Design guidelines are given and include using current riprap configurations for sizing and placing geobags.