Y Trinuclear Cu-II structural isomers coordination, magnetism, electrochemistry and catalytic activity towards the oxidation of alkanes

The reaction of the Schiff base (3,5-di-tert-butyl-2-hydroxybenzylidene)-2-hydroxybenzohydrazide (H3L) with copper(II) nitrate, acetate or metaborate has led to the isomeric complexes [Cu-3(L)(2)(MeOH)(4)] (1), [Cu-3(L)(2)(MeOH)(2)]2MeOH (2) and [Cu-3(L)(2)(MeOH)(4)] (3), respectively, in which the ligand L exhibits dianionic (HL2-, in 1) or trianionic (L3-, in 2 and 3) pentadentate 1O,O,N:2N,O chelation modes. Complexes 1-3 were characterized by elemental analysis, IR spectroscopy, single-crystal X-ray crystallography, electrochemical methods and variable-temperature magnetic susceptibility measurements, which indicated that the intratrimer antiferromagnetic coupling is strong in the three complexes and that there exists very weak ferromagnetic intermolecular interactions in 1 but weak antiferromagnetic intermolecular interactions in both 2 and 3. Electrochemical experiments showed that in complexes 1-3 the Cu-II ions can be reduced, in distinct steps, to Cu-I and Cu-0. All the complexes act as efficient catalyst precursors under mild conditions for the peroxidative oxidation of cyclohexane to cyclohexyl hydroperoxide, cyclohexanol and cyclohexanone, leading to overall yields (based on the alkane) of up to 31% (TON = 1.55x10(3)) after 6 h in the presence of pyrazinecarboxylic acid.

Classification Performance of Multilayer Perceptrons with Different Risk Functionals

In the present paper we assess the performance of information-theoretic inspired risks functionals in multilayer perceptrons with reference to the two most popular ones, Mean Square Error and Cross-Entropy. The information-theoretic inspired risks, recently proposed, are: HS and HR2 are, respectively, the Shannon and quadratic Rényi entropies of the error; ZED is a risk reflecting the error density at zero errors; EXP is a generalized exponential risk, able to mimic a wide variety of risk functionals, including the information-thoeretic ones. The experiments were carried out with multilayer perceptrons on 35 public real-world datasets. All experiments were performed according to the same protocol. The statistical tests applied to the experimental results showed that the ubiquitous mean square error was the less interesting risk functional to be used by multilayer perceptrons. Namely, mean square error never achieved a significantly better classification performance than competing risks. Cross-entropy and EXP were the risks found by several tests to be significantly better than their competitors. Counts of significantly better and worse risks have also shown the usefulness of HS and HR2 for some datasets.

Kinematic parameters of throwing performance in patients with schizophrenia using a markerless motion capture system

Motor dysfunction is consistently reported but understudied in schizophrenia. It has been hypothesized that this abnormality may reflect a neuro-developmental disorder underlying this illness. The main goal of this study was to analyze movement patterns used by participants with schizophrenia and healthy controls during overarm throwing performance, using a markerless motion capture system. Thirteen schizophrenia patients and 16 healthy control patients performed the overarm throwing task in a markerless motion capture system. Participants were also examined for the presence of motor neurological soft signs (mNSS) using the Brief Motor Scale. Schizophrenia patients demonstrated a less developed movement pattern with low individualization of components compared to healthy controls. The schizophrenia group also displayed a higher incidence of mNSS. The presence of a less mature movement pattern can be an indicator of neuro-immaturity and a marker for atypical neurological development in schizophrenia. Our findings support the understanding of motor dysfunction as an intrinsic part of the disorder of schizophrenia.

Performance evaluation of a cooperative reputation system for vehicular delay-tolerant networks

In the last decade, both scientific community and automotive industry enabled communications among vehicles in different kinds of scenarios proposing different vehicular architectures. Vehicular delay-tolerant networks (VDTNs) were proposed as a solution to overcome some of the issues found in other vehicular architectures, namely, in dispersed regions and emergency scenarios. Most of these issues arise from the unique characteristics of vehicular networks. Contrary to delay-tolerant networks (DTNs), VDTNs place the bundle layer under the network layer in order to simplify the layered architecture and enable communications in sparse regions characterized by long propagation delays, high error rates, and short contact durations. However, such characteristics turn contacts very important in order to exchange as much information as possible between nodes at every contact opportunity. One way to accomplish this goal is to enforce cooperation between network nodes. To promote cooperation among nodes, it is important that nodes share their own resources to deliver messages from others. This can be a very difficult task, if selfish nodes affect the performance of cooperative nodes. This paper studies the performance of a cooperative reputation system that detects, identify, and avoid communications with selfish nodes. Two scenarios were considered across all the experiments enforcing three different routing protocols (First Contact, Spray and Wait, and GeoSpray). For both scenarios, it was shown that reputation mechanisms that punish aggressively selfish nodes contribute to increase the overall network performance.

Durability performance of self-compacting concrete (SCC) with binary and ternary mixes of fly ash and limestone filler

The basic objective of this work is to evaluate the durability of self-compacting concrete (SCC) produced in binary and ternary mixes using fly ash (FA) and limestone filler (LF) as partial replacement of cement. The main characteristics that set SCC apart from conventional concrete (fundamentally its fresh state behaviour) essentially depend on the greater or lesser content of various constituents, namely: greater mortar volume (more ultrafine material in the form of cement and mineral additions); proper control of the maximum size of the coarse aggregate; use of admixtures such as superplasticizers. Significant amounts of mineral additions are thus incorporated to partially replace cement, in order to improve the workability of the concrete. These mineral additions necessarily affect the concrete’s microstructure and its durability. Therefore, notwithstanding the many well-documented and acknowledged advantages of SCC, a better understanding its behaviour is still required, in particular when its composition includes significant amounts of mineral additions. An ambitious working plan was devised: first, the SCC’s microstructure was studied and characterized and afterwards the main transport and degradation mechanisms of the SCC produced were studied and characterized by means of SEM image analysis, chloride migration, electrical resistivity, and carbonation tests. It was then possible to draw conclusions about the SCC’s durability. The properties studied are strongly affected by the type and content of the additions. Also, the use of ternary mixes proved to be extremely favourable, confirming the expected beneficial effect of the synergy between LF and FA. © 2015 RILEM.

A gestão do risco em instituições bancárias: uma análise com recurso a medidas de avaliação da performance ajustadas ao risco

Dissertação de Mestrado apresentado ao Instituto de Contabilidade e Administração do Porto para a obtenção do grau de Mestre em Auditoria sob orientação do Mestre Carlos Mota

O processo de Internacionalização na ótica da gestão estratégica. Análise de performance Grupo EDP

Dissertação de Mestrado apresentado ao Instituto de Contabilidade e Administração do Porto para a obtenção do grau de Mestre em Contabilidade e Finanças, sob orientação de Doutora Cláudia Pereira

Design and performance evaluation of turbo FDE receivers

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do Grau de Mestre em Engenharia Electrotécnica e de Computadores

Performance assessment in the portuguese public administration

Apresentação realizada na Conferência "Changing Public Sevice in a Changing World" realizada em Budapeste a 24 de Abril de 2009

Malaria serology: performance of six Plasmodium falciparum antigen extracts and of three ways of determining serum titers in IgG and IgM-ELISA

The study evaluated six Plasmodium falciparum antigen extracts to be used in the IgG and IgM enzyme-linked immunosorbent assays (ELISA), for malaria diagnosis and epidemiological studies. Results obtained with eighteen positive and nine negative control sera indicated that there were statistically significant differences among these antigen extracts (Multifactor ANOVA, p< 0.0001). Urea, sodium deoxycholate and Zwittergent antigen extracts performed better than did the three others, their features being very similar for the detection of IgG antibodies. Urea, alkaline and sodium deoxycholate antigen extracts proved to be better than the others for the detection of IgM antibodies. A straight line relationship was found between the optical densities (or their respective log 10) and the log 10 of antibody dilutions, with a very constant slope. Thus serum titers could be determined by direct titration and by two different equations, needing only one serum dilution. For IgM antibody detections, log 10 expression gave results that better correlated with direct titration (95% Bonferroni). For IgG antibody detections, the titer differences were not significant. The reproducibility of antibody titers and antigen batches was also evaluated, giving satisfactory results.

Destruction of the tar present in syngas by combustion in porous media

The cleaning of syngas is one of the most important challenges in the development of technologies based on gasification of biomass. Tar is an undesired byproduct because, once condensed, it can cause fouling and plugging and damage the downstream equipment. Thermochemical methods for tar destruction, which include catalytic cracking and thermal cracking, are intrinsically attractive because they are energetically efficient and no movable parts are required nor byproducts are produced. The main difficulty with these methods is the tendency for tar to polymerize at high temperatures. An alternative to tar removal is the complete combustion of the syngas in a porous burner directly as it leaves the particle capture system. In this context, the main aim of this study is to evaluate the destruction of the tar present in the syngas from biomass gasification by combustion in porous media. A gas mixture was used to emulate the syngas, which included toluene as a tar surrogate. Initially, CHEMKIN was used to assess the potential of the proposed solution. The calculations revealed the complete destruction of the tar surrogate for a wide range of operating conditions and indicated that the most important reactions in the toluene conversion are C6H5CH3 + OH <-> C6H5CH2 + H2O, C6H5CH3 + OH <-> C6H4CH3 + H2O, and C6H5CH3 + O <-> OC6H4CH3 + H and that the formation of toluene can occur through C6H5CH2 + H <-> C6H5CH3. Subsequently, experimental tests were performed in a porous burner fired with pure methane and syngas for two equivalence ratios and three flow velocities. In these tests, the toluene concentration in the syngas varied from 50 to 200 g/Nm(3). In line with the CHEMKIN calculations, the results revealed that toluene was almost completely destroyed for all tested conditions and that the process did not affect the performance of the porous burner regarding the emissions of CO, hydrocarbons, and NOx.

Risk factors associated with the professional performance of civil servants with impairment

Apresentação realizada na "8th Conference of European Academy of Occupational Health Psychology", que decorreu em Valência, Espanha, de 12 a 14 novembro de 2008

Proposal for shared services performance management model applied to portugueses public administration

Comunicação apresentada no 8º Congresso Nacional de Administração Pública - Desafios e Soluções, em Carcavelos de 21 a 22 de Novembro de 2011.

Pozzolanic activity of oil-refining catalyst: evaluation by electron and atomic microscopy

The reuse of waste fluid catalytic cracking (FCC) catalyst as partial surrogate for cement can reduce the environmental impact of both the oil-refinery and cement production industries [1,2]. FCC catalysts can be considered as pozzolanic materials since in the presence of water they tend to chemically react with calcium hydroxide to produce compounds possessing cementitious properties [3,4]. In addition, partial replacement of cement with FCC catalysts can enhance the performance of pastes and mortars, namely by improving their compressive strength [5,6]. In the present work the reaction of waste FCC catalyst with Ca(OH)2 has been investigated after a curing time of 28 days by scanning electron microscopy (SEM) with electron backscattered signal (BSE) combined with X-ray energy dispersive spectroscopy (EDS) carried out with a JEOL JSM 7001F instrument operated at 15 kV coupled to an INCA pentaFetx3 Oxford spectrometer. The polished cross-sections of FCC particles embedded in resin have also been evaluated by atomic force microscopy (AFM) in contact mode (CM) using a NanoSurf EasyScan 2 instrument. The SEM/EDS results revealed that an inward migration of Ca occurred during the reaction. A weaker outward migration of Si and Al was also apparent (Fig. 1). The migration of Ca was not homogeneous and tended to follow high-diffusivity paths within the porous waste FCC catalyst particles. The present study suggests that the porosity of waste FCC catalysts is key for the migration/reaction of Ca from the surrounding matrix, playing an important role in the pozzolanic activity of the system. The topography images and surface roughness parameters obtained by atomic force microscopy can be used to infer the local porosity in waste FCC catalyst particles (Fig. 2).

Road drivers performance appraisal using a MCDA method: a case study in the road transport company

Performance evaluation increasingly assumes a more important role in any organizational environment. In the transport area, the drivers are the company’s image and for this reason it is important to develop and increase their performance and commitment to the company goals. This evaluation can be used to motivate driver to improve their performance and to discover training needs. This work aims to create a performance appraisal evaluation model of the drivers based on the multi-criteria decision aid methodology. The MMASSI (Multicriteria Methodology to Support Selection of Information Systems) methodology was adapted by using a template supporting the evaluation according to the freight transportation company in study. The evaluation process involved all drivers (collaborators being evaluated), their supervisors and the company management. The final output is a ranking of the drivers, based on their performance, for each one of the scenarios used.