On the behavior of the Pt(1 0 0) and vicinal surfaces in alkaline media

We address in this paper a voltammetric study of the charge transfer processes characteristic of Pt(1 0 0) and vicinal surfaces in alkaline media. The electrochemical behavior of a series of stepped surfaces of the type Pt(S)[n(1 0 0) × (1 1 1)] has been characterized using cyclic voltammetry at different pHs, charge displacement measurements and FTIR experiments for adsorbed CO. The results from these techniques allow assigning the different peaks appearing in the voltammogram to hydrogen and/or OH adsorption on the different sites of these surfaces, namely, terrace and step sites. Additionally, the potential of zero total charge (pztc) of the electrodes was determined. The resulting pztc values shift to more negative values when the step density increases on the surface up to n = 5. FTIR spectroscopy experiments have been used to monitor the adsorption of CO on the different surfaces as well as the consequent CO oxidation, accompanying a positive potential sweep. The oxidation of adsorbed CO on (1 0 0) terraces is catalyzed by the presence of the (1 1 1) steps. The FTIR spectra revealed that CO is mostly bonded in bridge configuration at low potentials interconverting to on-top when the electrode potential is increased.

Geometrical study of the three-dimensional temperature–composition diagrams. An important aid to understand the behavior of the liquid–vapour equilibrium in ternary systems

In this work the usefulness of qualitatively studying and drawing three-dimensional temperature–composition diagrams for ternary systems is pointed out to understand and interpret the particular behavior of the liquid–vapour equilibrium of non-ideal ternary systems. Several examples have been used in order to highlight the interest and the possibilities of this tool, which should be an interesting support not only for lecturers, but also for researchers interested in experimental equilibrium data determination.

Behavior of different soot combustion catalysts under NOx/O2. Importance of the catalyst–soot contact

Four different catalysts (Pt/Al2O3, Ce0.8Zr0.2O2, PrO2−x and SrTiCuO3) have been investigated on a laboratory scale to evaluate their potential as diesel soot combustion catalysts under different experimental conditions, which simulate the situation found in a continuous regeneration technology trap (dual-bed configuration of catalyst and soot) or a catalyst-coated filter system (single-bed configuration, both catalyst and soot particles mixed under loose-contact mode). Under dual-bed configuration, the behavior of the catalysts towards soot combustion are very similar, despite the differences observed in the NO2 production profiles. However, under single-bed configuration, there are important differences in the soot combustion activities and in the NO2 slip profiles. The configurations chosen have an enormous impact on CO/(CO + CO2) ratios of combustion products as well. The most active catalyst under NOx + O2 is PrO2−x combining a high contribution of active oxygen-assisted soot combustion as well as high NO2 production activity along the catalytic bed.

Competition for procurement shares

We propose a new procurement procedure that allocates shares of the total amount to be procured depending on the bids of suppliers. Among the properties of the mechanism are the following: (i) Bidders have an incentive to participate in the procurement procedure, as equilibrium payoffs are strictly positive. (ii) The mechanism allows variations in the extent to which affirmative action objectives, like promoting local industries, are pursued. (iii) Surprisingly, even while accomplishing affirmative action goals, procurement expenditures might be lower than under a standard auction format.

Inclusion of immersive virtual learning environments and visual control systems to support the learning of students with Asperger syndrome

This paper presents the use of immersive virtual reality systems in the educational intervention with Asperger students. The starting points of this study are features of these students' cognitive style that requires an explicit teaching style supported by visual aids and highly structured environments. The proposed immersive virtual reality system, not only to assess the student's behavior and progress, but also is able to adapt itself to the student's specific needs. Additionally, the immersive reality system is equipped with sensors that can determine certain behaviors of the students. This paper determines the possible inclusion of immersive virtual reality as a support tool and learning strategy in these particular students' intervention. With this objective two task protocols have been defined with which the behavior and interaction situations performed by participant students are recorded. The conclusions from this study talks in favor of the inclusion of these virtual immersive environments as a support tool in the educational intervention of Asperger syndrome students as their social competences and executive functions have improved.

A systematic study on the influence of carbon on the behavior of hard-to-ionize elements in inductively coupled plasma–mass spectrometry

A systematic study on the influence of carbon on the signal of a large number of hard-to-ionize elements (i.e. B, Be, P, S, Zn, As, Se, Pd, Cd, Sb, I, Te, Os, Ir, Pt, Au, and Hg) in inductively coupled plasma–mass spectrometry has been carried out. To this end, carbon matrix effects have been evaluated considering different plasma parameters (i.e. nebulizer gas flow rate, r.f. power and sample uptake rate), sample introduction systems, concentration and type of carbon matrix (i.e. glycerol, citric acid, potassium citrate and ammonium carbonate) and type of mass spectrometer (i.e. quadrupole filter vs. double-focusing sector field mass spectrometer). Experimental results show that P, As, Se, Sb, Te, I, Au and Hg sensitivities are always higher for carbon-containing solutions than those obtained without carbon. The other hard-to-ionize elements (Be, B, S, Zn, Pd, Cd, Os, Ir and Pt) show no matrix effect, signal enhancement or signal suppression depending on the experimental conditions selected. The matrix effects caused by the presence of carbon are explained by changes in the plasma characteristics and the corresponding changes in ion distribution in the plasma (as reflected in the signal behavior plot, i.e. the signal intensity as a function of the nebulizer gas flow rate). However, the matrix effects for P, As, Se, Sb, Te, I, Au and Hg are also related to an increase in analyte ion population caused as a result of charge transfer reactions involving carbon-containing charged species in the plasma. The predominant specie is C+, but other species such as CO+, CO2+, C2+ and ArC+ could also play a role. Theoretical data suggest that B, Be, S, Pd, Cd, Os, Ir and Pt could also be involved in carbon based charge transfer reactions, but no experimental evidence substantiating this view has been found.

Seismic behavior of a masonry chimney with severe cracking condition: preliminary study

This paper presents a structural analysis of a masonry chimney built in the 1940s, which is currently being cataloged as local interest heritage. This structure has not served any industrial purpose for the last thirty years. The chimney is located in the town of Agost (Alicante - Spain) and directly exposed to the prevailing winds from the sea, as it is approximately 12 km away from the waterfront and there are not any significant barriers, which could protect the structure against the wind. There are longitudinal cracks and fissures all along the shaft because of the chimney’s geometrical characteristics, the effect of the masonry creep and especially the lack of maintenance. Moreover, there is also a permanent bending deformation in the upper 1/3 of the height due to the wind pressure. A numerical analysis for the static behavior against gravity and wind loads was performed using the structure’s current conditions after a detailed report of its geometry, its construction system and the cracking pattern. Afterwards, the dynamic behavior was studied, i.e. a seismic analysis using both response spectra and accelerograms in order to examine the structural stability. This work shows the pre-monitoring analysis before any experimental testing. Using the current results the future test conditions will be determined (e.g. number of sensors and monitoring point location, excitation systems, etc) prior to a possible structural reinforcement by applying composite material (fiber reinforced polymers).

Modifying enzyme activity and selectivity by immobilization

Immobilization of enzymes may produce alterations in their observed activity, specificity or selectivity. Although in many cases an impoverishment of the enzyme properties is observed upon immobilization (caused by the distortion of the enzyme due to the interaction with the support) in some instances such properties may be enhanced by this immobilization. These alterations in enzyme properties are sometimes associated with changes in the enzyme structure. Occasionally, these variations will be positive. For example, they may be related to the stabilization of a hyperactivated form of the enzyme, like in the case of lipases immobilized on hydrophobic supports via interfacial activation. In some other instances, these improvements will be just a consequence of random modifications in the enzyme properties that in some reactions will be positive while in others may be negative. For this reason, the preparation of a library of biocatalysts as broad as possible may be a key turning point to find an immobilized biocatalyst with improved properties when compared to the free enzyme. Immobilized enzymes will be dispersed on the support surface and aggregation will no longer be possible, while the free enzyme may suffer aggregation, which greatly decreases enzyme activity. Moreover, enzyme rigidification may lead to preservation of the enzyme properties under drastic conditions in which the enzyme tends to become distorted thus decreasing its activity. Furthermore, immobilization of enzymes on a support, mainly on a porous support, may in many cases also have a positive impact on the observed enzyme behavior, not really related to structural changes. For example, the promotion of diffusional problems (e.g., pH gradients, substrate or product gradients), partition (towards or away from the enzyme environment, for substrate or products), or the blocking of some areas (e.g., reducing inhibitions) may greatly improve enzyme performance. Thus, in this tutorial review, we will try to list and explain some of the main reasons that may produce an improvement in enzyme activity, specificity or selectivity, either real or apparent, due to immobilization.

Role of potassium orbitals in the metallic behavior of K3picene

Detailed electronic structure calculations of picene clusters doped by potassium modeling the crystalline K3picene structure show that while two electrons are completely transferred from potassium atoms to the lowest-energy unoccupied molecular orbital of pristine picene, the third one remains closely attached to both material components. Multiconfigurational analysis is necessary to show that many structures of almost degenerate total energies compete to define the cluster ground state. Our results prove that the 4s orbital of potassium should be included in any interaction model describing the material. We propose a quarter-filled two-orbital model as the most simple model capable of describing the electronic structure of K-intercalated picene. Precise solutions obtained by a development of the Lanczos method show low-energy electronic excitations involving orbitals located at different positions. Consequently, metallic transport is possible in spite of the clear dominance of interaction over hopping.

Industry-specific effect of CSR initiatives: hotels and airlines

Purpose – This study aims to examine the relationships between a firm's corporate social responsibility (CSR) activities and its performance and risk. The authors hypothesize that industry-level effects are highly determinant of the sign and magnitude of these relationships to establish a ranking of industries to identify the position of the most prominent tourism-related industries: hotels and airlines. Based on the cybernetic model of decision making and the heuristics thereof, shareholders base their investment decisions derived from CSR announcements on the idea that the industries behave differently; their fixed costs being a relevant factor. Design/methodology/approach – The authors estimate the industry-specific effects of CSR initiatives on firms' performance and risk using a sample of 583 announcements from the Spanish Stock Market. Findings – The results show that while CSR announcements have a positive effect on performance when the authors do not account for industry-specific factors, once the authors incorporate these factors into the analysis, the authors find that firm performance and risk vary quite substantially as a function of the industry to which the firm belongs. Interestingly, while the hotel industry presents an average behavior (standing at 9th position in returns, 15th in terms of risk, and 8th according to the ratio returns/volatility), the airline industry presents the worst situation of all industries: last in performance and last in risk. Practical implications – The results help managers assess their decisions and allocate CSR resources optimally. Originality/value – This article is the first attempt to empirically test and comprehensively detect the different relationships between CSR and firm performance across industries.

How can an invasive grass affect fire behavior in a tropical savanna? A community and individual plant level approach

Some invasive grasses have been reported to change fire behavior in invaded plant communities. Urochloa brizantha is an aggressive invasive grass in the Brazilian Cerrado, an ecosystem where fire is a common disturbance. We investigated the effects of U. brizantha on fire behavior in an open Cerrado physiognomy in Central Brazil. Using experimental burnings we compared fire behavior at both the community and the individual plant level in invaded (UJ) and non-invaded (NJ) areas burned in July. We also assessed the effect of fire season in invaded areas by comparing July (UJ) and October (UO) burnings. We evaluated the following variables: fuel load, fuel moisture, combustion efficiency, maximum fire temperature, flame height, and fire intensity. Additionally, we evaluated the temperatures reached under invasive and native grass tussocks in both seasons. Fuel load, combustion efficiency, and fire intensity were higher in NJ than in UJ, whilst flame height showed the opposite trend. Fuel amount and fire intensity were higher in October than in July. At the individual plant level, U. brizantha moisture was higher than that of native species, however, temperatures reaching ≥600 °C at ground level were more frequent under U. brizantha tussocks than under native grasses. At the community level, the invasive grass modified fire behavior towards lower intensity, lower burning efficiency, and higher flame height. These results provide essential information for the planning of prescribed burnings in invaded Cerrado areas.

Prosocial behavior and self-concept of Spanish students of Compulsory Secondary Education

This study analyzed the relationship between prosocial behavior and self-concept dimensions in a sample of 2022 Spanish students (51.1% males) of Compulsory Secondary Education. The prosocial behavior was measured with the Prosocial Behavior scale of the Teenage Inventory of Social Skills (TISS) and the self-concept was measured with the Self-Description Questionnaire-II (SDQ-II). Logistic regression analyses revealed that prosocial behavior is a positive and significant statistically predictor of high scores on the following self-concept dimensions: physical ability, parent relations, same-sex relations, opposite-sex relations, verbal, school, trustworthiness, and self-esteem. Those results were found in males, females and every Compulsory Secondary education year. However, prosocial behavior is not a significant statistically predictor of high scores on physical appearance, math, and emotional stability.

Influence of the metal precursor on the catalytic behavior of Pt/Ceria catalysts in the preferential oxidation of CO in the presence of H2 (PROX)

The effect of the metal precursor (presence or absence of chlorine) on the preferential oxidation of CO in the presence of H2 over Pt/CeO2 catalysts has been studied. The catalysts are prepared using (Pt(NH3)4)(NO3)2 and H2PtCl6, as precursors, in order to ascertain the effect of the chlorine species on the chemical properties of the support and on the catalytic behavior of these systems in the PROX reaction. The results show that chloride species exert an important effect on the redox properties of the oxide support due to surface chlorination. Consequently, the chlorinated catalyst exhibits a poorer catalytic activity at low temperatures compared with the chlorine-free catalyst, and this is accompanied by a higher selectivity to CO2 even at high reaction temperatures. It is proposed that the CO oxidation mechanism follows different pathways on each catalyst.

Physico-chemical characterization of metal-doped bone chars and their adsorption behavior for water defluoridation

New bone chars for fluoride adsorption from drinking water have been synthetized via metallic doping using aluminum and iron salts. A detailed statistical analysis of the metal doping process using the signal-to-noise ratios from Taguchi's experimental designs and its impact on the fluoride adsorption properties of modified bone chars have been performed. The best conditions, including the proper metallic salt, for metal doping were identified to improve the fluoride uptakes of modified bone chars. Results showed that the fluoride adsorption properties of bone chars can be enhanced up to 600% using aluminum sulfate for the surface modification. This aluminum-based adsorbent showed an adsorption capacity of 31 mg/g, which outperformed the fluoride uptakes reported for several adsorbents. Surface interactions involved in the defluoridation process were established using FTIR, DRX and XPS analysis. Defluoridation using the metal-doped bone chars occurred via an ion exchange process between fluoride ions and the hydroxyl groups on the adsorbent surface, whereas the Al(OH)xFy, FexFy, and CaF2 interactions could play also an important role in the removal process. These metal-doped adsorbents anticipate a promising behavior in water treatment, especially in developing countries where the efficiency – cost tradeoff is crucial for implementing new defluoridation technologies.