Redox-active cytotoxic diorganotin(IV) cycloalkylhydroxamate complexes with different ring sizes: Reduction behaviour and theoretical interpretation

Two series of new diorganotin(IV) cycloalkylhydroxamate complexes with different ring sizes (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl), formulated as the mononuclear [R2Sn(HL)(2)] (1:2) (a, R=Bu-n and Ph) and the polymeric [R2SnL](n) (1:1) (b, R=Bu-n) compounds, were prepared and fully characterized. Single crystal X-ray diffraction for [(Bu2Sn)-Bu-n{C5H9C(O)NHO}(2)] (3a) discloses the cis geometry and strong intermolecular NH center dot center dot center dot O interactions. The in vitro cytotoxic activities of the complexes were evaluated against HL-60, Bel-7402, BGC-823 and KB human tumour cell lines, the greater activity concerning [(Bu2Sn)-Bu-n(HL)(2)] [HL=C3H5C(O)NHO (1a), C6H11C(O)NHO (4a)] towards BGC-823. The complexes undergo, by cyclic voltammetry and controlled-potential electrolysis, one irreversible overall two-electron cathodic process at a reduction potential that does not appear to correlate with the antitumour activity. The electrochemical behaviour of [R2Sn(C5H9C(O)NHO)(2)] [R=Bu-n (3a), Ph (7a)] was also investigated using density functional theory (DFT) methods, showing that the ultimate complex structure and the mechanism of its formation are R dependent: for the aromatic (R = Ph) complex, the initial reduction step is centred on the phenyl ligands and at the metal, being followed by a second reduction with Sn-O and Sn-C ruptures, whereas for the alkyl (R=Bu-n) complex the first reduction step is centred on one of the hydroxamate ligands and is followed by a second reduction with Sn-O bond cleavages and preservation of the alkyl ligands. In both cases, the final complexes are highly coordinative unsaturated Sn-II species with the cis geometry, features that can be of biological significance.

Os modelos na compreensão dos números racionais fracionários

Relatório de Estágio apresentado à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Ensino do 1.º e do 2.º Ciclo do Ensino Básico

Complex dynamics in the trajectory control of redundant manipulators

Redundant manipulators allow the trajectory optimization, the obstacle avoidance, and the resolution of singularities. For this type of manipulators, the kinematic control algorithms adopt generalized inverse matrices that may lead to unpredictable responses. Motivated by these problems this paper studies the complexity revealed by the trajectory planning scheme when controlling redundant manipulators. The results reveal fundamental properties of the chaotic phenomena and give a deeper insight towards the development of superior trajectory control algorithms.

Which differintegration?

Despite the great advances in the theory and applications of fractional calculus, some topics remain unclear, making a systematic use difficult. In this paper, the fractional differintegration definition problem is studied from a systems point of view. Both local (Grunwald-Letnikov) and global (convolutional) definitions are considered. It is shown that the Cauchy formulation should be adopted since it is coherent with usual practice in signal processing and control applications.

From cheating to teaching: a path for conversion of illegal gambling machines

Video poker machines, a former symbol of fraud and gambling in Brazil, are now being converted into computer-based educational tools for Brazilian public primary schools and also for governmental and non-governmental institutions dealing with communities of poverty and social exclusion, in an attempt to reduce poverty risks (decrease money spent on gambling) and promote social inclusion (increase access and motivation to education). Thousands of illegal gambling machines are seized by federal authorities, in Brazil, every year, and usually destroyed at the end of the criminal apprehension process. This paper describes a project developed by the University of Southern Santa Catarina, Brazil, responsible for the conversion process of gambling machines, and the social inclusion opportunities derived from it. All project members worked on a volunteer basis, seeking to promote social inclusion of Brazilian young boys and girls, namely through digital inclusion. So far, the project has been able to convert over 200 gambling machines and install them in over 40 public primary schools, thus directly benefiting more than 12,000 schoolchildren. The initial motivation behind this project was technology based, however the different options arising from the conversion process of the gambling machines have also motivated a rather innovative and unique experience in allowing schoolchildren and young people with special (educational) needs to access to computer-based pedagogical applications. The availability of these converted machines also helps to place Information and Communication Technologies (ICT) in the very daily educational environment of these children and youngsters, thus serving social and cultural inclusion aspects, by establishing a dialogue with the community and their technological expectations, and also directly contributing to their digital literacy.

The European Project Semester at ISEP: Learning to Learn Engineering

The European Project Semester at ISEP (EPS@ISEP) is a one semester project-based learning programme addressed to engineering students from diverse scientific backgrounds and nationalities. The students, organized in multicultural teams, are challenged to solve real world multidisciplinary problems, accounting for 30 ECTU. The EPS package, although focused on project development (20 ECTU), includes a series of complementary seminars aimed at fostering soft, project-related and engineering transversal skills (10 ECTU). This paper presents the study plan, resources, operation and results of the EPS@ISEP that was created in 2011 to apply the best engineering education practices and promote the internationalization of ISEP. The results show that the EPS@ISEP students acquire during one semester the scientific, technical and soft competences necessary to propose, design and implement a solution for a multidisciplinary problem.

Multi-Agent Based Smart Grid Management and Simulation: Situation Awareness and Learning in a Test Bed with Simulated and Real Installations and Players

The rising usage of distributed energy resources has been creating several problems in power systems operation. Virtual Power Players arise as a solution for the management of such resources. Additionally, approaching the main network as a series of subsystems gives birth to the concepts of smart grid and micro grid. Simulation, particularly based on multi-agent technology is suitable to model all these new and evolving concepts. MASGriP (Multi-Agent Smart Grid simulation Platform) is a system that was developed to allow deep studies of the mentioned concepts. This paper focuses on a laboratorial test bed which represents a house managed by a MASGriP player. This player is able to control a real installation, responding to requests sent by the system operators and reacting to observed events depending on the context.

MASCEM Restructuring: Ontologies For Scenarios Generation in Power Systems Simulators

The electricity market restructuring, along with the increasing necessity for an adequate integration of renewable energy sources, is resulting in an rising complexity in power systems operation. Various power system simulators have been introduced in recent years with the purpose of helping operators, regulators, and involved players to understand and deal with this complex environment. This paper focuses on the development of an upper ontology which integrates the essential concepts necessary to interpret all the available information. The restructuring of MASCEM (Multi-Agent System for Competitive Electricity Markets), and this system’s integration with MASGriP (Multi-Agent Smart Grid Platform), and ALBidS (Adaptive Learning Strategic Bidding System) provide the means for the exemplification of the usefulness of this ontology. A practical example is presented, showing how common simulation scenarios for different simulators, directed to very distinct environments, can be created departing from the proposed ontology.

Towards a unified European electricity market: The contribution of data-mining to support realistic simulation studies

Worldwide electricity markets have been evolving into regional and even continental scales. The aim at an efficient use of renewable based generation in places where it exceeds the local needs is one of the main reasons. A reference case of this evolution is the European Electricity Market, where countries are connected, and several regional markets were created, each one grouping several countries, and supporting transactions of huge amounts of electrical energy. The continuous transformations electricity markets have been experiencing over the years create the need to use simulation platforms to support operators, regulators, and involved players for understanding and dealing with this complex environment. This paper focuses on demonstrating the advantage that real electricity markets data has for the creation of realistic simulation scenarios, which allow the study of the impacts and implications that electricity markets transformations will bring to the participant countries. A case study using MASCEM (Multi-Agent System for Competitive Electricity Markets) is presented, with a scenario based on real data, simulating the European Electricity Market environment, and comparing its performance when using several different market mechanisms.

Chronic hepatitis C virus infections in Brazilian patients: association with genotypes, clinical parameters and response to long term alpha interferon therapy

The present study assessed the clinical significance of hepatitis C virus (HCV) genotypes and their influence on response to long term recombinant-interferon-alpha (r-IFN-a) therapy in Brazilian patients. One hundred and thirty samples from patients previously genotyped for the HCV and with histologically confirmed chronic hepatitis C (CH-C) were evaluated for clinical and epidemiological parameters (sex, age, time of HCV infection and transmission routes). No difference in disease activity, sex, age or mode and time of transmission were seen among patients infected with HCV types 1, 2 or 3. One hundred and thirteen of them were treated with 3 million units of r-IFN-a, 3 times a week for 12 months. Initial response (IR) was significantly better in patients with genotype 2 (100%) and 3 (46%) infections than in patients with genotype 1 (29%) (p < 0.005). Among subtypes, difference in IR was observed between 1b and 2 (p < 0.005), and between 1b and 3a (p < 0.05). Sustained response (SR) was observed in 12% for (sub)type 1a, 13% for 1b, 19% for 3a, and 40% for type 2; significant differences were found between 1b and 2 (p < 0.001), and between 1b and 3a (p < 0.05). Moreover, presence of cirrhosis was significantly associated with non response and response with relapse (p < 0.05). In conclusion, non-1 HCV genotype and lack of histological diagnosis of cirrhosis were the only baseline features associated with sustained response to treatment. These data indicate that HCV genotyping may have prognostic relevance in the responsiveness to r-IFN-a therapy in Brazilian patients with chronic HCV infection, as seen in other reports worldwide.

SIR performance evaluation of MB-OFDM UWB system with residual timing offset

Signal-to-interference ratio (SIR) performance of a multiband orthogonal frequency division multiplexing ultra-wideband system with residual timing offset is investigated. To do so, an exact mathematical derivation of the SIR of this system is derived. It becomes obvious that, unlike a cyclic prefixing based system, a zero padding based system is sensitive to residual timing offset.

Distribution of hepatitis C virus genotypes among blood donors from mid-west region of Brazil

In order to investigate the hepatitis C virus (HCV) genotypes in mid-west region of Brazil, 250 anti-HCV positive blood donors were studied. Among them, the anti-HCV serological status was confirmed in 205 (82%). HCV RNA was detected in 165 samples, which were genotyped. HCV types 1, 2 and 3 were found in 67.9%, 3% and 29.1% of the donors, respectively. In Goiás state, subtype 1a (50%) was the most prevalent, followed by subtypes 3a (30.9%) and 1b (16.7%). In Mato Grosso state, subtype 1a was also predominant (41%), followed by subtypes 1b (29.5%) and 3a (25%). In Mato Grosso do Sul state, subtypes 1a and 1b were detected equally (36.8%), followed by 3a (21.1%). Subtype 2b was rare (2.4%, 4.5% and 5.3%, respectively). In Distrito Federal, subtype 3a (39%) was more frequent than 1a (31.7%) and the remaining (29.3%) belonged to subtype 1b.

Hepatitis C virus genotypes in hemodialysis patients in the Federal District, Brazil

Hepatitis C virus (HCV) genotypes and subtypes were determined in hemodialysis patients in the Federal District, Brazil, by sequencing of the 5' noncoding (NC) and nonstructural 5B (NS5B) regions. From 761 patients, 66 anti-HCV-positive samples were tested for HCV RNA. All 51 HCV RNA-positive samples by PCR of the 5' NC region were genotyped as genotypes 1 (90.2%) and 3 (9.8%). Subtype 1a (82.3%) was the most prevalent, followed by subtypes 3a (9.8%), 1b (5.9%) and 1a/1b (2.0%). Forty-two samples could be amplified and genotyped in the NS5B region: 38 (90.5%) as genotype 1, subtypes 1a, and 8 (9.5%) as genotype 3, subtype 3a. For the 42 samples sequenced in both regions, the genotypes and subtypes determined were concordant in 100% and 95.2% of cases, respectively. Two samples presented discrepant results, with the 5' NC region not distinguishing correctly the subtypes 1a and 1b. These findings indicate that the HCV genotype 1, subtype 1a, is the most prevalent among hemodialysis patients in the Federal District, Brazil.

HEPATOCELLULAR CARCINOMA IN A NON-CIRRHOTIC PATIENT WITH SUSTAINED VIROLOGICAL RESPONSE AFTER HEPATITIS C TREATMENT

Chronic infection by hepatitis C virus (HCV) is one of the main risk factors for the development of liver cirrhosis and hepatocellular carcinoma. However, the emergence of hepatocellular carcinoma (HCC) in non-cirrhotic HCV patients, especially after sustained virological response (SVR) is an unusual event. Recently, it has been suggested that HCV genotype 3 may have a particular oncogenic mechanism, but the factors involved in these cases as well as the profile of these patients are still not fully understood. Thus, we present the case of a non-cirrhotic fifty-year-old male with HCV infection, genotype 3a, who developed HCC two years after treatment with pegylated-interferon and ribavirin, with SVR, in Brazil.

Estudo do gene FOXE1 e identificação de novos genes de susceptibilidade para o cancro da tiróide familiar

Dissertação para obtenção do Grau de Mestre em Genética Molecular e Biomedicina