TAP reactor investigation of methane coupling over samarium oxide catalysts

The adsorption and reaction characteristics of a Ba/Sr/Sm2O3 catalyst for methane coupling has been investigated using the TAP (Temporal Analysis of Products) reactor system. Pulsed adsorption experiments using methane, oxygen and krypton at temperatures ranging from 17°C to 800°C show that the transient response of methane is similar to that of Kr and is either not adsorbed, or weakly adsorbed on the catalyst. By contrast, oxygen is strongly adsorbed at temperatures above 500°C which suggests incorporation into the lattice with possible formation of surface anions. Pump-probe experiments in which methane and oxygen are introduced over the catalyst were also performed to investigate the effect of lifetimes of suspected surface intermediates on the relative yields of ethane and ethene. It is shown that the relative yields of both species increase with increasing values of the pulse valve time delay between introduction of the oxygen and methane. An explanation of these results using current knowledge and reasonable speculation of the mechanism is provided

Ti/Zr/O Mixed Oxides for the Catalytic Transfer Hydrogenation of Furfural to GVL in a Liquid-Phase Continuous-Flow Reactor

This work aims to develop an efficient catalyst for the cascade reaction from furfural to y-valerolactone in a liquid-phase continuous reactor. This process requires both Lewis and Brønsted acidity; hence, a bifunctional catalyst is necessary to complete the one-pot reaction. Ti/Zr/O mixed oxide-based catalysts were chosen to this end as balancing metal oxide composition allows the acidity characteristics of the overall material to be modulated. Oxides with different compositions were then synthesized using the co-precipitation method. After characterization via porosimetry and NH3-TPD, the catalyst with equimolar quantities of the two components was demonstrated to be the best one in terms of superficial area (279 m2/g) and acid site density (0.67 mmol/g). The synthesized materials were then tested using a plug flow reactor at 180 C, with a 10 min contact time. Ti/Zr/O (1:1) was demonstrated to be the most promising catalyst during the recycling tests as it allowed obtaining the highest selectivities in the desired products (about 45% in furfuryl isopropyl ether and 20% in y-valerolactone) contemporaneously with 100% furfural conversion

A graph-theoretic approach for classification and structure prediction of transmembrane β-barrel proteins

BACKGROUND: Non-synonymous coding SNPs (nsSNPs) that are associated to disease can also be related with alterations in protein stability. Computational methods are available to predict the effect of single amino acid substitutions (SASs) on protein stability based on a single folded structure. However, the native state of a protein is not unique and it is better represented by the ensemble of its conformers in dynamic equilibrium. The maintenance of the ensemble is essential for protein function. In this work we investigated how protein conformational diversity can affect the discrimination of neutral and disease related SASs based on protein stability estimations. For this purpose, we used 119 proteins with 803 associated SASs, 60% of which are disease related. Each protein was associated with its corresponding set of available conformers as found in the Protein Conformational Database (PCDB). Our dataset contains proteins with different extensions of conformational diversity summing up a total number of 1023 conformers. RESULTS: The existence of different conformers for a given protein introduces great variability in the estimation of the protein stability (\u394\u394G) after a single amino acid substitution (SAS) as computed with FoldX. Indeed, in 35% of our protein set at least one SAS can be described as stabilizing, destabilizing or neutral when a cutoff value of \ub12 kcal/mol is adopted for discriminating neutral from perturbing SASs. However, when the \u394\u394G variability among conformers is taken into account, the correlation among the perturbation of protein stability and the corresponding disease or neutral phenotype increases as compared with the same analysis on single protein structures. At the conformer level, we also found that the different conformers correlate in a different way to the corresponding phenotype. CONCLUSIONS: Our results suggest that the consideration of conformational diversity can improve the discrimination of neutral and disease related protein SASs based on the evaluation of the corresponding Gibbs free energy change

Vapor phase Beckmann rearrangement using high silica zeolite catalyst

Vapor phase Beckmann rearrangement of cyclohexanone oxime to e-caprolactam has been studied using high silica zeolite catalysts. Catalysts with different crystal sizes and gel-ageing times have been activated by ionic exchange in different conditions by means of a highly basic solution and a nearly neutral solution both containing ammonium salts. Samples have been calcined at different temperatures in order modify the number of defective sites. We observed that samples exchanged by means of a highly basic solution (pH > 10)1,2 and calcined at a relatively lower temperature (450 C) show the most interesting catalytic results. X-ray powder diffraction patterns of these samples show2 retention of the unit cell symmetry (orthorhombic cell) if compared to the dried sample. NH3-TPD confirms the low acidity of high silica zeolites, however a higher amount of desorbed ammonia is observed for the samples exchanged at higher pH and calcined at 450 C. Due to silanol nests the IR spectra of the same samples show the formation of Si\u2013NH2 bonds which are absent in the same material exchanged by other methods. Such sites seem to promote the high stability of the high silica zeolite catalysts also to the regeneration which is needed to remove the heavy carbonaceous compounds from the catalyst surface

AUTODETERMINAZIONE E AIUTO AL SUICIDIO

IL VOLUME RACCOGLIE GLI ATTI DEL CONVENGO INTERNAZIONALE SVOLTOSI PRESSO L'UNIVERSITA' DI VERONA NEI GIORNI 5 E 6 APRILE 2019 CHE ALLA LUCE DEL CASO CAPPATO - DJ FABO HA ESAMINATO LE PROBLMATICHE AFFRONTATE DALLA CORTE COSTITUZIONALE NELLA PROSPETTIVA STORICA E COMPARATA DELLA DISCIPLINA PENALE IN MATERIA DI ISTIGAZIONE E AIUTO AL SUICIDIO. PERTANTO VI E' STATO UN CONTRIBUTO DI DIVERSE DISCIPLINE, NON SOLO PENALI MA ANCHE MEDICO-LEGALI, COSTITUZIONALI, CIVILI, ECC., CHE HANNO PORTATO A IMPORTANTI CONVERGENZE SULLA NECESSITA' DI INTERVENTI RIFORMATORI NELL'ORDINAMENTO ITALIANO

Seismic background noise levels in the Italian strong-motion network

The Italian strong-motion network monitors the seismic activity in the region, with more than 585 stations with continuous data acquisition. In this study, we determine the background seismic noise characteristics of the network by using the data collected in 2022. We analyse the spatial and temporal characteristics of the background noise. It is found that most of the stations suffer from anthropogenic noises, since the strong-motion network is designed to capture the peak ground motions in populated areas. Hence, human activities enrich the low periods of noise. Therefore, land usage of the area where the stations are located affects the background noise levels. Stations can be noisier during the day, up to 12 dB, and during the weekday, up to 5 dB, in short periods. In long periods (≥ 5 s), accelerometric stations converge to similar noise levels and there are no significant daily or weekly changes. It is found that more than half of the stations exceed the background noise model designed for strong-motion stations in Switzerland by Cauzzi and Clinton (2013) in at least one of the calculated periods. We also develop an accelerometric seismic background noise model for periods between 0.0124 and 100 s for Italy by using the power spectral densities of the network. The model is in agreement with the background noise model developed by D’Alessandro et al. (2021) using broadband data for Italy in short periods, but in long periods there is no correlation among studies.</p

Aquivion® PFSA-based spray-freeze dried composite materials with SiO2 and TiO2 as hybrid catalysts for the gas phase dehydration of ethanol to ethylene in mild conditions

Aquivion PFSA resin, a perfluorinated ion-exchange polymer, has been used as a heterogeneous strong acid catalyst for a range of reactions; however, the activity of this material is limited due to the extremely low surface area of the polymer. In this paper we described the one-step synthesis of Aquivion® PFSA-based hybrid materials using heterocoagulation and spray-freeze-drying of sols containing the precursor of the active phases. The intimated encapsulation of different nano-oxides, such as TiO2 and SiO2 in the superacid resin matrix was easily obtained using this technique and compared with similar catalysts prepared by the impregnation conventional route. The approach led to the preparation of porous micro-granules characterised by a high homogeneity in the phase distribution and high surface area. The prepared materials were active and selective for the gas phase dehydration of ethanol to ethylene in mild conditions. The increase of the porosity improved the activity of the composites, compared to the pure Aquivion® PFSA, and allowed to reduce the amount of the superacid resin. Moreover, the type of encapsulated oxide, TiO2 or SiO2, modified the improved performance of the catalysts, having TiO2 the higher efficiency for ethanol conversion and selectivity in ethylene at very low temperature