Synthesis and Coordination Chemistry of a New N-4-Polydentate Class of Pyridyl-Functionalized Scorpionate Ligands: Complexes of Fe-II, Zn-II, V-IV, Pd-II and Use for Heterobimetallic Systems

The new potentially N-4-multidentate pyridyl-functionalized scorpionates 4-((tris-2,2,2-(pyrazol-1-ypethoxy)methyl)pyridine (TpmPy, (1)) and 4-((tris-2,2,2-(3-phenylpyrazol-1-yl)ethoxy)methyl)pyridine (TpmPy(Ph), (2)) have been synthesized and their coordination behavior toward Fe-II, Ni-II, Zn-II, Cu-II, Pd-II, and V-III centers has been studied. Reaction of (1) with Fe(BF4)(2)center dot 6H(2)O yields [Fe(TpmPy)(2)](BF4)(2) (3), that, in the solid state, shows the sandwich structure with trihapto ligand coordination via the pyrazolyl arms, and is completely low spin (LS) until 400 K. Reactions of 2 equiv of (1) or (2) with Zn-II or Ni-II chlorides give the corresponding metal complexes with general formula [MCl2(TpmPy*)(2)] (M = Zn, Ni; TpmPy* = TpmPy, TpmPy(Ph)) (4-7) where the ligand is able to coordinate through either the pyrazolyl rings (in case of [Ni(TpmPy)(2)Cl-2 (5)) or the pyridyl-side (for [ZnCl2(TpmPy)(2)] (4), [ZnCl2(TpmPy(Ph))(2)] (6) and [NiCl2(TpmPy(Ph))(2)] (7)). The reaction of (1) with VCl3 gives [VOCl2(TpmPy)] (8) that shows the N-3-pyrazolyl coordination-mode. Moreover, (1) and react with cis-[PdCl2(CH3CN)(2)] to give the disubstituted complexes [PdCl2(TprnPy)(2)] (9) and [PdCl2(TpmPy(Ph))(2)] (10), respectively, bearing the scorpionate coordinated via the pyridyl group. Compounds (9) and (10) react with Fe(BF4)(2) to give the heterobimetallic Pd/Fe systems [PdCl2(mu-TpmPy)(2)-Fe](BF4)(2) (11) and [PdCl2(mu-TpmPy(Ph))(2)Fe-2(H2O)(6)]BF4)(4) (13), respectively. Compound (11) can also be formed from reaction of (3) with cis-[PdCl2(CH3CN)(2)], while reaction of (3) with Cu(NO3)(2).2.5H(2)O generates [Fe(mu-TpmPy)(2)-Cu(NO3)(2)](BF4)(2) (12), confirming the multidentate ability of the new chelating ligands. The X-ray diffraction analyses of compounds (1), (3), (4), (5), and (9) are also reported.

Evaluation of the influence of the ADH3 ILE349VAL polymorphism in the frequency of genotoxicity biomarkers in workers exposed to formaldehyde and tobacco smoking

Formaldehyde (FA) is a colourless gas widely used in the industry and hospitals as an aqueous solution, formalin. It is extremely reactive and induces various genotoxic effects in proliferating cultured mammalian cells. Tobacco smoke has been epidemiologically associated to a higher risk of development of cancer, especially in the oral cavity, larynx and lungs, as these are places of direct contact with many carcinogenic tobacco’s compounds. Genetic polymorphisms in enzymes involved in the metabolism are very important and can make changes in the individual susceptibility to disease. Alcohol dehydrogenase class 3 (ADH3), also known as formaldehyde dehydrogenase dependent of glutathione, is the major enzyme involved in the formaldehyde oxidation, especially in the buccal mucosa. The polymorphism in study is a substitution of an isoleucine for a valine in codon 349. The cytokinesis-blocked micronucleus assay (CBMN) in human lymphocytes is one of the most commonly used methods for measuring DNA damage, namely the detection of micronucleus, nucleoplasmic bridges, and nuclear buds, classified as genotoxicity biomarkers.

Global and local detection of liver steatosis from ultrasound

Liver steatosis is a common disease usually associated with social and genetic factors. Early detection and quantification is important since it can evolve to cirrhosis. Steatosis is usually a diffuse liver disease, since it is globally affected. However, steatosis can also be focal affecting only some foci difficult to discriminate. In both cases, steatosis is detected by laboratorial analysis and visual inspection of ultrasound images of the hepatic parenchyma. Liver biopsy is the most accurate diagnostic method but its invasive nature suggest the use of other non-invasive methods, while visual inspection of the ultrasound images is subjective and prone to error. In this paper a new Computer Aided Diagnosis (CAD) system for steatosis classification and analysis is presented, where the Bayes Factor, obatined from objective intensity and textural features extracted from US images of the liver, is computed in a local or global basis. The main goal is to provide the physician with an application to make it faster and accurate the diagnosis and quantification of steatosis, namely in a screening approach. The results showed an overall accuracy of 93.54% with a sensibility of 95.83% and 85.71% for normal and steatosis class, respectively. The proposed CAD system seemed suitable as a graphical display for steatosis classification and comparison with some of the most recent works in the literature is also presented.

The usefulness of ultrasound in the classification of chronic liver disease

Chronic Liver Disease is a progressive, most of the time asymptomatic, and potentially fatal disease. In this paper, a semi-automatic procedure to stage this disease is proposed based on ultrasound liver images, clinical and laboratorial data. In the core of the algorithm two classifiers are used: a k nearest neighbor and a Support Vector Machine, with different kernels. The classifiers were trained with the proposed multi-modal feature set and the results obtained were compared with the laboratorial and clinical feature set. The results showed that using ultrasound based features, in association with laboratorial and clinical features, improve the classification accuracy. The support vector machine, polynomial kernel, outperformed the others classifiers in every class studied. For the Normal class we achieved 100% accuracy, for the chronic hepatitis with cirrhosis 73.08%, for compensated cirrhosis 59.26% and for decompensated cirrhosis 91.67%.

The 27th British liquid crystal society annual meeting 2013, Cambridge

Attending the British Liquid Crystal Society’s (BLCS) Annual Meeting was a formative experience in my days as a PhD student, starting way back in the 1990s. At that time, this involved travelling to (to me) exotic parts of the United Kingdom, such as Reading, Oxford or Manchester, away from Southampton where I was based. Some postdoctoral years in a different country followed, and three BLCS Meetings were missed, until in 1997 and 1998, I was able to attend again, in Southampton and Leeds, respectively. Not much had changed from my student days, the size and the format were still about the same, many of the leading characters were still around, and the closing talk would still be given by John Lydon. Well, at some point, I got myself a proper academic job on the Continent and stopped attending BLCS Annual Meetings altogether. The fond memories of my youth started to fade. Were the Meetings still on? It seemed so, as old friends and acquaintances would occasionally recount attending them, and even winning prizes at them. But, it all seemed rather remote now. Until, that is, it came to pass that the 27th BLCS Meeting would be held in Selwyn College, Cambridge, just down (or up, depending on how you look at it) the road from the Isaac Newton Institute, where I was spending part of my sabbatical leave. The opportunity to resume attendance could not be missed. A brief e-mail exchange with the organisers, and a cheque to cover the fee, duly secured this. And thus, it was with trepidation that I approached my first BLCS Annual Meeting in more than a decade.

A class of singular first order differential equations with applications in reaction-diffusion

Agências Financiadoras: FCT e MIUR

Aprender a cooperar na escola - um desafio para alunos do 1.º CEB

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

Automatic synthesis of VHDL Hardware Components from IOPT Petri Net models

Conferência: 39th Annual Conference of the IEEE Industrial-Electronics-Society (IECON), Vienna, Austria, Nov 10-14, 2013

Prática de ensino supervisionado no 1.º e 2.º ciclo do ensino básico: a influência da planificação no desenvolvimento da escrita de textos

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

A educação tecnológica como disciplina de opção de escola e os novos desafios do professor no ano de transição

Relatório de estágio apresentado à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Ensino da Educação Visual e Tecnológica no Ensino Básico

Desocultando questões de género pelo/no teatro

Relatório de Estágio apresentado à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Ensino no 1º e no 2º Ciclos do Ensino Básico

A criança invisual é tão apta à aprendizagem como as restantes

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

Spanish society's perceptions about socially responsible investing

The debate surrounding the financial needs of investors and the impact on society of investment is considered to be an important research topic due to the growth of socially responsible financial markets. The objective of this research is to study the perception of the Spanish public about socially responsible investing (SRI) criteria and real-life investment needs. To examine the Spanish perception of SRI, we conducted a field survey. The results show that SRI is in an early stage and Spanish investors need more exact information regarding social, environmental, and governance criteria in order to invest in socially responsible companies and products.

Medication regimen complexity in institutionalized elderly people in an aging society

Background: Complex medication regimens may adversely affect compliance and treatment outcomes. Complexity can be assessed with the medication regimen complexity index (MRCI), which has proved to be a valid, reliable tool, with potential uses in both practice and research. Objective: To use the MRCI to assess medication regimen complexity in institutionalized elderly people. Setting: Five nursing homes in mainland Portugal. Methods: A descriptive, cross-sectional study of institutionalized elderly people (n = 415) was performed from March to June 2009, including all inpatients aged 65 and over taking at least one medication per day. Main outcome measure: Medication regimen complexity index. Results: The mean age of the sample was 83.9 years (±6.6 years), and 60.2 % were women. The elderly patients were taking a large number of drugs, with 76.6 % taking more than five medications per day. The average medication regimen complexity was 18.2 (±SD = 9.6), and was higher in the females (p < 0.001). The most decisive factors contributing to the complexity were the number of drugs and dosage frequency. In regimens with the same number of medications, schedule was the most relevant factor in the final score (r = 0.922), followed by pharmaceutical forms (r = 0.768) and additional instructions (r = 0.742). Conclusion: Medication regimen complexity proved to be high. There is certainly potential for the pharmacist's intervention to reduce it as part as the medication review routine in all the patients.

Soliton-type and other travelling wave solutions for an improved class of nonlinear sixth-order Boussinesq equations

An improved class of nonlinear bidirectional Boussinesq equations of sixth order using a wave surface elevation formulation is derived. Exact travelling wave solutions for the proposed class of nonlinear evolution equations are deduced. A new exact travelling wave solution is found which is the uniform limit of a geometric series. The ratio of this series is proportional to a classical soliton-type solution of the form of the square of a hyperbolic secant function. This happens for some values of the wave propagation velocity. However, there are other values of this velocity which display this new type of soliton, but the classical soliton structure vanishes in some regions of the domain. Exact solutions of the form of the square of the classical soliton are also deduced. In some cases, we find that the ratio between the amplitude of this wave and the amplitude of the classical soliton is equal to 35/36. It is shown that different families of travelling wave solutions are associated with different values of the parameters introduced in the improved equations.