Properties of patchy colloidal particles close to a surface: a Monte Carlo and density functional study

We investigate the behavior of a patchy particle model close to a hard-wall via Monte Carlo simulation and density functional theory (DFT). Two DFT approaches, based on the homogeneous and inhomogeneous versions of Wertheim's first order perturbation theory for the association free energy are used. We evaluate, by simulation and theory, the equilibrium bulk phase diagram of the fluid and analyze the surface properties for two isochores, one of which is close to the liquid side of the gas-liquid coexistence curve. We find that the density profile near the wall crosses over from a typical high-temperature adsorption profile to a low-temperature desorption one, for the isochore close to coexistence. We relate this behavior to the properties of the bulk network liquid and find that the theoretical descriptions are reasonably accurate in this regime. At very low temperatures, however, an almost fully bonded network is formed, and the simulations reveal a second adsorption regime which is not captured by DFT. We trace this failure to the neglect of orientational correlations of the particles, which are found to exhibit surface induced orientational order in this regime.

n-Hexane hydroisomerisation over bifunctional Pt/MCM-22 catalysts. Influence of the mode of Pt introduction

Three different methods were used to introduce 1.0 wt.% of Pt in bifunctional Pt/MCM-22 zeolite catalysts: ion exchange with Pt(NH3)(4)(2+), incipient wetness impregnation with PtCl6H2 and mechanical mixture with Pt/Al2O3. The Pt dispersion was estimated by transmission electron microscopy and the hydrogenating activity with toluene hydrogenation at 110 degrees C. From these experiments, it can be concluded that with the ion exchanged sample, platinum was located within the inner micropores and on the outer surface, whereas with the impregnated one, platinum was essentially on the outer surface under the form of large particles. With all the samples there is a fast initial decrease in the activity for n-hexane hydroisomerisation at 250 degrees C. With exchanged and impregnated samples, this decrease is followed by a plateau, the activity value being then higher with impregnated sample. For the sample prepared by mechanical mixture a continuous decrease in activity can be observed. All these differences can be related with the distinct locations of Pt.

Hydroisomerization of n-decane over SAPO-11 catalysts synthesized with methylamine as co-template

The present work deals with preliminary studies concerning a new synthesis approach to prepare SAPO materials with AEL structure and evaluate their catalytic behavior in the hydroisomerization of long paraffins. The new SAPO-11 catalysts were synthesized with the help of a small amine (methylamine, MA) added during the preparation of the initial gel. As MA incorporates into the structure of the final materials, it contributes, together with DPA (dipropylamine), to an increase in Si incorporation as isolated species, which results in Bronsted acid sites. Thus, this new and original synthesis strategy allows to obtain materials with enhanced Bronsted acidity when compared with free MA materials. The catalysts were tested in n-decane hydroisomerization (n-decane was used as a model molecule) and confirmed the effect of MA on the acidic properties of the catalysts. The samples synthesized with MA present a higher number of acid sites that increase the catalytic conversion but have a negative effect in the isomerization selectivity, i.e. a more significant amount of cracking products is formed.

Lightning Data Observed With Lightning Location System in Portugal

This paper presents an investigation into cloud-to-ground lightning activity over the continental territory of Portugal with data collected by the national Lightning Location System. The Lightning Location System in Portugal is first presented. Analyses about geographical, seasonal, and polarity distribution of cloud-to-ground lightning activity and cumulative probability of peak current are carried out. An overall ground flash density map is constructed from the database, which contains the information of more than five years and almost four million records. This map is compared with the thunderstorm days map, produced by the Portuguese Institute of Meteorology, and with the orographic map of Portugal. Finally, conclusions are duly drawn.

From unthinned continent to ocean: The deep structure of the West Iberia passive continental margin at 38 degrees N

The crustal and lithospheric mantle structure at the south segment of the west Iberian margin was investigated along a 370 km long seismic transect. The transect goes from unthinned continental crust onshore to oceanic crust, crossing the ocean-continent transition (OCT) zone. The wide-angle data set includes recordings from 6 OBSs and 2 inland seismic stations. Kinematic and dynamic modeling provided a 2D velocity model that proved to be consistent with the modeled free-air anomaly data. The interpretation of coincident multi-channel near-vertical and wide-angle reflection data sets allowed the identification of four main crustal domains: (i) continental (east of 9.4 degrees W); (ii) continental thinning (9.4 degrees W-9.7 degrees W): (iii) transitional (9.7 degrees W-similar to 10.5 degrees W); and (iv) oceanic (west of similar to 10.5 degrees W). In the continental domain the complete crustal section of slightly thinned continental crust is present. The upper (UCC, 5.1-6.0 km/s) and the lower continental crust (LCC, 6.9-7.2 km/s) are seismically reflective and have intermediate to low P-wave velocity gradients. The middle continental crust (MCC, 6.35-6.45 km/s) is generally unreflective with low velocity gradient. The main thinning of the continental crust occurs in the thinning domain by attenuation of the UCC and the LCC. Major thinning of the MCC starts to the west of the LCC pinchout point, where it rests directly upon the mantle. In the thinning domain the Moho slope is at least 13 degrees and the continental crust thickness decreases seaward from 22 to 11 km over a similar to 35 km distance, stretched by a factor of 1.5 to 3. In the oceanic domain a two-layer high-gradient igneous crust (5.3-6.0 km/s; 6.5-7.4 km/s) was modeled. The intra-crustal interface correlates with prominent mid-basement, 10-15 km long reflections in the multi-channel seismic profile. Strong secondary reflected PmP phases require a first order discontinuity at the Moho. The sedimentary cover can be as thick as 5 km and the igneous crustal thickness varies from 4 to 11 km in the west, where the profile reaches the Madeira-Tore Rise. In the transitional domain the crust has a complex structure that varies both horizontally and vertically. Beneath the continental slope it includes exhumed continental crust (6.15-6.45 km/s). Strong diffractions were modeled to originate at the lower interface of this layer. The western segment of this transitional domain is highly reflective at all levels, probably due to dykes and sills, according to the high apparent susceptibility and density modeled at this location. Sub-Moho mantle velocity is found to be 8.0 km/s, but velocities smaller than 8.0 km/s confined to short segments are not excluded by the data. Strong P-wave wide-angle reflections are modeled to originate at depth of 20 km within the lithospheric mantle, under the eastern segment of the oceanic domain, or even deeper at the transitional domain, suggesting a layered structure for the lithospheric mantle. Both interface depths and velocities of the continental section are in good agreement to the conjugate Newfoundland margin. A similar to 40 km wide OCT having a geophysical signature distinct from the OCT to the north favors a two pulse continental breakup.

Multi-stage evolution of a sub-aerial volcanic ridge over the last 1.3 Myr: S. Jorge Island, Azores Triple Junction

New K/Ar dating and geochemical analyses have been carried out on the WNW-ESE elongated oceanic island of S. Jorge to reconstruct the volcanic evolution of a linear ridge developed close to the Azores triple junction. We show that S. Jorge sub-aerial construction encompasses the last 1.3 Myr, a time interval far much longer than previously reported. The early development of the ridge involved a sub-aerial building phase exposed in the southeast end of the island and now constrained between 1.32 +/- 0.02 and 1.21 +/- 0.02 Ma. Basic lavas from this older stage are alkaline and enriched in incompatible elements, reflecting partial melting of an enriched mantle source. At least three differentiation cycles from alkaline basalts to mugearites are documented within this stage. The successive episodes of magma rising, storage and evolution suggest an intermittent reopening of the magma feeding system, possibly due to recurrent tensional or trans-tensional tectonic events. Present data show a gap in sub-aerial volcanism before a second main ongoing building phase starting at about 750 ka. Sub-aerial construction of the S. Jorge ridge migrated progressively towards the west, but involved several overlapping volcanic episodes constrained along the main WNW-ESE structural axis of the island. Malic magmas erupted during the second phase have been also generated by partial melting of an enriched mantle source. Trace element data suggest, however, variable and lower degrees of partial melting of a shallower mantle domain, which is interpreted as an increasing control of lithospheric deformation on the genesis and extraction of primitive melts during the last 750 kyr. The multi-stage development of the S. Jorge volcanic ridge over the last 1.3 Myr has most likely been greatly influenced by regional tectonics, controlled by deformation along the diffuse boundary between the Nubian and the Eurasian plates, and the increasing effect of sea-floor spreading at the Mid-Atlantic Ridge.

New physics contributions to A(FB)(t(t)over-bar) at the Tevatron

The Tevatron has measured a discrepancy relative to the standard model prediction in the forward-backward asymmetry in top quark pair production. This asymmetry grows with the rapidity difference of the two top quarks. It also increases with the invariant mass of the t (t) over bar pair, reaching, for high invariant masses, 3.4 standard deviations above the next-to-leading order prediction for the charge asymmetry of QCD. However, perfect agreement between experiment and the standard model was found in both total and differential cross section of top quark pair production. As this result could be a sign of new physics we have parametrized this new physics in terms of a complete set of dimension six operators involving the top quark. We have then used a Markov chain Monte Carlo approach in order to find the best set of parameters that fits the data, using all available data regarding top quark pair production at the Tevatron. We have found that just a very small number of operators are able to fit the data better than the standard model.

Solubility of red 153 and blue 1 in supercritical carbon dioxide

Solubilities of red 153, (3-[[4-[[5,6(or 6,7)-dichloro-2-benzothiazolyl]azo]phenyl]ethylamino]propanenitrile), an azo compound, and disperse blue1 (1,4,5,8-tetraaminoantraquinone) in supercritical carbon dioxide (SC CO(2)) were measured at T = (333.2 to 393.2) K over the pressure range (12.0 to 40.0) MPa by a flow type apparatus. The solubility of red 153 (0.985. 10(-6) to 37.2. 10(-6)) in the overall region of measurements is found to be significantly higher than that of disperse blue 1 (1.12.10(-7) to 4.89.10(-7)). The solubility behavior of disperse red 153 follows the general solubility trend displayed by disperse dyes with a crossover pressure at about 20 MPa. On the other hand, blue 1, which is a disperse anthraquinone dye, exhibits unexpected behavior not recorded previously there is no crossover pressure at the temperature and pressure ranges studied, and the dye's solubility at T = 333.2 K practically does not increase with pressure. To the best of our knowledge, there are no previous measurements of blue 1 solubility in SC CO(2) reported in the literature. The experimental data were correlated by using the Soave Redlich Kwong equation of state (EoS) with the one-fluid van der Waals mixing rule, and an acceptable correlation of the solubility data for both dyes was obtained.

Ensino de léxico e texto descritivo

Dissertação apresentada à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Didáctica da Língua Portuguesa no 1.º e 2.º Ciclos do Ensino Básico

Nonmonotonic Magnetic Susceptibility of Dipolar Hard-Spheres at Low Temperature and Density

We investigate, via numerical simulations, mean field, and density functional theories, the magnetic response of a dipolar hard sphere fluid at low temperatures and densities, in the region of strong association. The proposed parameter-free theory is able to capture both the density and temperature dependence of the ring-chain equilibrium and the contribution to the susceptibility of a chain of generic length. The theory predicts a nonmonotonic temperature dependence of the initial (zero field) magnetic susceptibility, arising from the competition between magnetically inert particle rings and magnetically active chains. Monte Carlo simulation results closely agree with the theoretical findings. DOI: 10.1103/PhysRevLett.110.148306

Biodiesel production from waste frying oils over lime catalysts

Biodiesel production from semi-refined oils (SRO) and waste frying oils (WFO) was studied using commercial CaO as heterogeneous catalyst. The methanolysis tests were carried out in mild reaction conditions (62 A degrees C, atmospheric pressure). With such conditions, SRO (soybean and rapeseed) allowed to produce a biodiesel containing 97-98 % of methyl esters (FAME), whereas WFO only provided 86-87 % of FAME. The lower FAME yield for WFO oil is ascribable to the partial neutralization of the catalyst by free fatty acids. Also, soaps formation from the WFO oil reduced the weight yield of the oil phase (containing FAME) obtained and increased the MONG content of the glycerin phase. The catalysts stability tests showed high stability even when WFO oil was processed. Catalytic tests performed with blends of WFO/semi-refined oils showed blending as a good strategy to process low value raw oils with minor decay of the catalyst performance. Both WFO and semi-refined oils showed S-shape kinetics curves thus discarding significant differences of the reaction mechanisms.

Design and performance of a novel low-density parity-check code for distributed video coding

Low-density parity-check (LDPC) codes are nowadays one of the hottest topics in coding theory, notably due to their advantages in terms of bit error rate performance and low complexity. In order to exploit the potential of the Wyner-Ziv coding paradigm, practical distributed video coding (DVC) schemes should use powerful error correcting codes with near-capacity performance. In this paper, new ways to design LDPC codes for the DVC paradigm are proposed and studied. The new LDPC solutions rely on merging parity-check nodes, which corresponds to reduce the number of rows in the parity-check matrix. This allows to change gracefully the compression ratio of the source (DCT coefficient bitplane) according to the correlation between the original and the side information. The proposed LDPC codes reach a good performance for a wide range of source correlations and achieve a better RD performance when compared to the popular turbo codes.

Integration of biomonitoring and instrumental techniques to assess the air quality in an industrial area located in the coastal of Central Asturias, Spain

Throughout the world, epidemiological studies were established to examine the relationship between air pollution and mortality rates and adverse respiratory health effects. However, despite the years of discussion the correlation between adverse health effects and atmospheric pollution remains controversial, partly because these studies are frequently restricted to small and well-monitored areas. Monitoring air pollution is complex due to the large spatial and temporal variations of pollution phenomena, the high costs of recording instruments, and the low sampling density of a purely instrumental approach. Therefore, together with the traditional instrumental monitoring, bioindication techniques allow for the mapping of pollution effects over wide areas with a high sampling density. In this study, instrumental and biomonitoring techniques were integrated to support an epidemiological study that will be developed in an industrial area located in Gijon in the coastal of central Asturias, Spain. Three main objectives were proposed to (i) analyze temporal patterns of PM10 concentrations in order to apportion emissions sources, (ii) investigate spatial patterns of lichen conductivity to identify the impact of the studied industrial area in air quality, and (iii) establish relationships amongst lichen conductivity with some site-specific characteristics. Samples of the epiphytic lichen Parmelia sulcata were transplanted in a grid of 18 by 20 km with an industrial area in the center. Lichens were exposed for a 5-mo period starting in April 2010. After exposure, lichen samples were soaked in 18-MΩ water aimed at determination of water electrical conductivity and, consequently, lichen vitality and cell damage. A marked decreasing gradient of lichens conductivity relative to distance from the emitting sources was observed. Transplants from a sampling site proximal to the industrial area reached values 10-fold higher than levels far from it. This finding showed that lichens reacted physiologically in the polluted industrial area as evidenced by increased conductivity correlated to contamination level. The integration of temporal PM10 measurements and analysis of wind direction corroborated the importance of this industrialized region for air quality measurements and identified the relevance of traffic for the urban area.

Risk factors for metabolic bone disease in Crohn's disease patients

Background: The aim was to evaluate the presence of metabolic bone disease (MBD) in patients with Crohn’s disease (CD) and to identify potential etiologic factors. Methods: The case–control study included 99 patients with CD and 56 controls with a similar age and gender distribution. Both groups had dual-energy x-ray absorptionmetry and a nutritional evaluation. Single nucleotide polymorphisms at the IL1, TNF-a, LTa, and IL-6 genes were analyzed in patients only. Statistical analysis was performed using SPSS software. Results: The prevalence of MBD was significantly higher in patients (P ¼ 0.006). CD patients with osteoporosis were older (P < 0.005), small bowel involvement and surgical resections were more frequent (P < 0.005), they more often exhibited a penetrating or stricturing phenotype (P < 0.05), duration of disease over 15 years (P < 0.005), and body mass index (BMI) under 18.5 kg/m2 (P < 0.01) were more often found. No association was found with steroid use. Patients with a Z-score < 2.0 more frequently had chronic active disease (P < 0.05). With regard to diet, low vitamin K intake was more frequent (P ¼ 0.03) and intake of total, monounsaturated, and polyunsaturated fat was higher in patients with Z-score < 2.0 (P < 0.05). With respect to genetics, carriage of the polymorphic allele for LTa252 A/G was associated with a higher risk of osteoporosis (P ¼ 0.02). Regression analysis showed that age over 40 years, chronic active disease, and previous colonic resections were independently associated with the risk of developing MBD. Conclusions: The prevalence of MBD was significantly higher in CD patients. Besides the usual risk factors, we observed that factors related to chronic active and long-lasting disease increased the risk of MBD.

A New Method to Determine the Density and Water Absorption of Fine Recycled Aggregates

The construction industry keeps on demanding huge quantities of natural resources, mainly minerals for mortars and concrete production. The depletion of many quarries and environmental concerns about reducing the dumping of construction and demolition waste in quarries have led to an increase in the procuring and use of recycled aggregates from this type of waste. If they are to be incorporated in concrete and mortars it is essential to know their properties to guarantee the adequate performance of the end products, in both mechanical and durability-related terms. Existing regulated tests were developed for natural aggregates, however, and several problems arise when they are applied to recycled aggregates, especially fine recycled aggregates (FRA). This paper describes the main problems encountered with these tests and proposes an alternative method to determine the density and water absorption of FRA that removes them. The use of sodium hexametaphosphate solutions in the water absorption test has proven to improve its efficiency, minimizing cohesion between particles and helping to release entrained air.