Synthesis, structure and electrochemical behaviour of Na, Mg-II, Mn-II, Cd-II and Ni-II complexes of 3-(2-carboxyphenylhydrazone)pentane-2,4-dione

Mononuclear manganese(II) [Mn(kappa O-HL)(2)(CH3OH)(4)] (4), nickel(II) [Ni(kappa O-2, kappa N-L)(H2O)(3)] (5), cadmium(II) [Cd(kappa O-2-HL)(2)(CH3OH)(3)] (7), tetranuclear zinc(II) [Zn-4(mu-OH)(2)(1 kappa O:2 kappa O-HL)(4)(kappa O-HL)(2)(H2O)(4)] (6) and polynuclear aqua sodium(I) [Na(H2O)(2)(mu-H2O)(2)](n)(HL)(n) (2) and magnesium(II) [Mg(OH)(H2O)(mu-H2O)(2)](n)(-HL)(n) (3) complexes were synthesized using 3-(2-carboxyphenyl-hydrazone)pentane-2,4-dione (H2L, 1) as a ligand precursor. The complexes were characterized by single crystal X-ray diffraction, elemental analysis, IR, H-1 and C-13 NMR (for 2, 3, 6 and 7) spectroscopies. Mono- or dianionic deprotonated derivatives of H2L display different coordination modes and lead to topologies and nuclearities of the complexes depending on metal ions and conditions used for the syntheses. Extensive intermolecular H-bonds form supramolecular arrangements in 1D chains (4 and 6), 1D chains of the organic anion and 2D networks of the metal-aqua aggregates (2 and 3), 2D networks (7) or even 3D frameworks (5). Electrochemical studies, by cyclic voltammetry and controlled potential electrolysis, show ligand centred redox processes as corroborated by theoretical DFT calculations in terms of LUMO and HOMO compositions. (C) 2012 Elsevier Ltd. All rights reserved.

Efeito da combina����o de antibi��ticos e sinvastatina sobre microrganismos de interesse endod��ntico e na express��o de marcadores odontobl��sticos

Funda����o de Amparo �� Pesquisa do Estado de S��o Paulo (FAPESP)

By-catch de espadarte (Xiphias gladius) e tintureira (Prionace glauca) juvenil no palangre de superf��cie

Disserta����o de Mestrado, Estudos Integrados dos Oceanos, 11 de Outubro 2013, Universidade dos A��ores.

Terpinen-4-ol: estudo do efeito sin��rgico/aditivo, ades��o em co-cultura e altera����o dos fatores de virul��ncia sobre Candida spp

Funda����o de Amparo �� Pesquisa do Estado de S��o Paulo (FAPESP)

Water quality issues in rivers, lakes and reservoirs in Asian countries: an approach to the problems and the methodologies

Water covers over 70% of the Earth's surface, and is vital for all known forms of life. But only 3% of the Earth's water is fresh water, and less than 0.3% of all freshwater is in rivers, lakes, reservoirs and the atmosphere. However, rivers and lakes are an important part of fresh surface water, amounting to about 89%. In this Master Thesis dissertation, the focus is on three types of water bodies ��� rivers, lakes and reservoirs, and their water quality issues in Asian countries. The surface water quality in a region is largely determined both by the natural processes such as climate or geographic conditions, and the anthropogenic influences such as industrial and agricultural activities or land use conversion. The quality of the water can be affected by pollutants discharge from a specific point through a sewer pipe and also by extensive drainage from agriculture/urban areas and within basin. Hence, water pollutant sources can be divided into two categories: Point source pollution and Non-point source (NPS) pollution. Seasonal variations in precipitation and surface run-off have a strong effect on river discharge and the concentration of pollutants in water bodies. For example, in the rainy season, heavy and persistent rain wash off the ground, the runoff flow increases and may contain various kinds of pollutants and, eventually, enters the water bodies. In some cases, especially in confined water bodies, the quality may be positive related with rainfall in the wet season, because this confined type of fresh water systems allows high dilution of pollutants, decreasing their possible impacts. During the dry season, the quality of water is largely related to industrialization and urbanization pollution. The aim of this study is to identify the most common water quality problems in Asian countries and to enumerate and analyze the methodologies used for assessment of water quality conditions of both rivers and confined water bodies (lakes and reservoirs). Based on the evaluation of a sample of 57 papers, dated between 2000 and 2012, it was found that over the past decade, the water quality of rivers, lakes, and reservoirs in developing countries is being degraded. Water pollution and destruction of aquatic ecosystems have caused massive damage to the functions and integrity of water resources. The most widespread NPS in Asian countries and those which have the greatest spatial impacts are urban runoff and agriculture. Locally, mine waste runoff and rice paddy are serious NPS problems. The most relevant point pollution sources are the effluents from factories, sewage treatment plant, and public or household facilities. It was found that the most used methodology was unquestionably the monitoring activity, used in 49 of analyzed studies, accounting for 86%. Sometimes, data from historical databases were used as well. It can be seen that taking samples from the water body and then carry on laboratory work (chemical analyses) is important because it can give an understanding of the water quality. 6 papers (11%) used a method that combined monitoring data and modeling. 6 papers (11%) just applied a model to estimate the quality of water. Modeling is a useful resource when there is limited budget since some models are of free download and use. In particular, several of used models come from the U.S.A, but they have their own purposes and features, meaning that a careful application of the models to other countries and a critical discussion of the results are crucial. 5 papers (9%) focus on a method combining monitoring data and statistical analysis. When there is a huge data matrix, the researchers need an efficient way of interpretation of the information which is provided by statistics. 3 papers (5%) used a method combining monitoring data, statistical analysis and modeling. These different methods are all valuable to evaluate the water quality. It was also found that the evaluation of water quality was made as well by using other types of sampling different than water itself, and they also provide useful information to understand the condition of the water body. These additional monitoring activities are: Air sampling, sediment sampling, phytoplankton sampling and aquatic animal tissues sampling. Despite considerable progress in developing and applying control regulations to point and NPS pollution, the pollution status of rivers, lakes, and reservoirs in Asian countries is not improving. In fact, this reflects the slow pace of investment in new infrastructure for pollution control and growing population pressures. Water laws or regulations and public involvement in enforcement can play a constructive and indispensable role in environmental protection. In the near future, in order to protect water from further contamination, rapid action is highly needed to control the various kinds of effluents in one region. Environmental remediation and treatment of industrial effluent and municipal wastewaters is essential. It is also important to prevent the direct input of agricultural and mine site runoff. Finally, stricter environmental regulation for water quality is required to support protection and management strategies. It would have been possible to get further information based in the 57 sample of papers. For instance, it would have been interesting to compare the level of concentrations of some pollutants in the diferente Asian countries. However the limit of three months duration for this study prevented further work to take place. In spite of this, the study objectives were achieved: the work provided an overview of the most relevant water quality problems in rivers, lakes and reservoirs in Asian countries, and also listed and analyzed the most common methodologies.

Materiais de mudan��a de fase em revestimentos

Disserta����o para obten����o do grau de Mestre em Engenharia Civil na ��rea de especializa����o em Edifica����es

Efic��cia do Constraint-Induced Movement Therapy, em utentes com sequelas de Acidente Vascular Encef��lico, at�� 9 meses

O Acidente Vascular Encef��lico �� uma das principais causas de morte, tornando-se cada vez mais iminente processos de reabilita����o que minimizem as sequelas, nomeadamente as limita����es do membro superior que dificultam o envolvimento em atividades da vida di��ria. O Constraint-Induced Movement Therapy, surge como uma abordagem que incrementa o uso do membro superior mais afetado. A presente investiga����o trata-se de um estudo de casos m��ltiplos. Pretende-se verificar se existem melhorias na funcionalidade do membro superior mais afetado, analisar em que atividades da vida di��ria s��o vis��veis melhorias funcionais e compreender se o maior envolvimento nas atividades di��rias est�� diretamente relacionado com a melhoria na capacidade funcional. Pretende-se ainda que os valores obtidos no Wolf Motor Function Test sejam um contributo para a sua valida����o para a popula����o portuguesa. Utilizou-se um question��rio para recolha de dados pessoais e cl��nicos (amplitudes de movimento, dor e espasticidade); o Wolf Motor Function Test e o Action Research Arm Test para verificar a funcionalidade do membro superior mais afetado; e a Motor Activity Log que avalia o envolvimento em atividades da vida di��ria. O grupo �� constitu��do por 3 utentes que sofreram um primeiro Acidente Vascular Encef��lico at�� 9 meses de evolu����o, internados na Santa Casa da Miseric��rdia de Mon����o e que cumpriam os crit��rios de inclus��o. O programa foi implementado tr��s horas/dia, durante 10 dias, mantendo a restri����o no membro superior menos afetado durante 90% do dia acordado. Como se trata de um estudo de casos m��ltiplos, analisou-se cada participante individualmente e verificou-se a diferen��a entre os resultados finais e iniciais para cada uma das vari��veis. Os resultados obtidos revelam ganhos na amplitude de movimento, velocidade de execu����o e capacidade funcional do membro superior mais afetado, nomeadamente nas fun����es de preens��o e pin��a da m��o, bem como se testemunhou minimiza����o do fen��meno learned nonuse. Verificaram-se ganhos funcionais em todos os participantes nas atividades da vida di��ria apesar de serem diferentes de participante para participante. Dois participantes afirmaram que voltariam a participar no programa.Conclui-se, assim que a t��cnica resulta em ganhos funcionais nestes utentes, indicando um caminho alternativo a outras abordagens de reabilita����o.

Viver no singular

Disserta����o de Mestrado, Ci��ncias Sociais, 12 de Mar��o de 2015, Universidade dos A��ores.

Processos de purifica����o/ valoriza����o do glicerol proveniente da produ����o de biodiesel

Mestrado em Engenharia Qu��mica - Ramo optimiza����o energ��tica na ind��stria qu��mica

Copper and lead removal by peanut hulls: equilibrium and kinetic studies

This research work aims to study the use of peanut hulls, an agricultural and food industry waste, for copper and lead removal through equilibrium and kinetic parameters evaluation. Equilibrium batch studies were performed in a batch adsorber. The influence of initial pH was evaluated (3���5) and it was selected between 4.0 and 4.5. The maximum sorption capacities obtained for the Langmuir model were 0.21 �� 0.03 and 0.18 �� 0.02 mmol/g, respectively for copper and lead. In bi-component systems, competitive sorption of copper and lead was verified, the total amount adsorbed being around 0.21 mmol of metal per gram of material in both mono and bi-component systems. In the kinetic studies equilibrium was reached after 200 min contact time using a 400 rpm stirring rate, achieving 78% and 58% removal, in mono-component system, for copper and lead respectively. Their removal follows a pseudo-second-order kinetics. These studies show that most of the metals removal occurred in the first 20 min of contact, which shows a good uptake rate in all systems.

Economic, environmental and mixed objective functions in non-linear process optimization using simulated annealing and tabu search

Screening of topologies developed by hierarchical heuristic procedures can be carried out by comparing their optimal performance. In this work we will be exploiting mono-objective process optimization using two algorithms, simulated annealing and tabu search, and four different objective functions: two of the net present value type, one of them including environmental costs and two of the global potential impact type. The hydrodealkylation of toluene to produce benzene was used as case study, considering five topologies with different complexities mainly obtained by including or not liquid recycling and heat integration. The performance of the algorithms together with the objective functions was observed, analyzed and discussed from various perspectives: average deviation of results for each algorithm, capacity for producing high purity product, screening of topologies, objective functions robustness in screening of topologies, trade-offs between economic and environmental type objective functions and variability of optimum solutions.

Self-mated tribological systems based on multilayer micro/nanocrystalline CVD diamond coatings

The tribological response of multilayer micro/nanocrystalline diamond coatings grown by the hot filament CVD technique is investigated. These multigrade systems were tailored to comprise a starting microcrystalline diamond (MCD) layer with high adhesion to a silicon nitride (Si3N4) ceramic substrate, and a top nanocrystalline diamond (NCD) layer with reduced surface roughness. Tribological tests were carried out with a reciprocating sliding configuration without lubrication. Such composite coatings exhibit a superior critical load before delamination (130���200 N), when compared to the mono- (60���100 N) and bilayer coatings (110 N), considering ���10 ��m thick films. Regarding the friction behaviour, a short-lived initial high friction coefficient was followed by low friction regimes (friction coefficients between 0.02 and 0.09) as a result of the polished surfaces tailored by the tribological solicitation. Very mild to mild wear regimes (wear coefficient values between 4.1��10���8 and 7.7��10���7 mm3 N���1 m���1) governed the wear performance of the self-mated multilayer coatings when subjected to high-load short-term tests (60���200 N; 2 h; 86 m) and medium-load endurance tests (60 N; 16 h; 691 m).

Caracteriza����o qu��mica e ecotoxicol��gica de esc��rias e cinzas resultantes da co-combust��o de lamas e carv��o

Em 1999 a Funda����o para a Ci��ncia e a Tecnologia aprovou o financiamento do projecto ���Behaviour of Heavy Metals on the Thermal Treatment of Residues��� cujo acr��nimo era Bimetal. Este projecto, cujos parceiros eram o Departamento de Engenharia Energ��tica e Controlo Ambiental do Instituto Nacional de Engenharia e Tecnologia Industrial (INETI) e o Grupo de Disciplinas de Ecologia da Hidrosfera (GDEH) da Faculdade de Ci��ncias e Tecnologia da Universidade Nova de Lisboa, tinha como objectivo a avalia����o do comportamento de metais pesados durante a combust��o de res��duos. Neste sentido, a equipa do INETI efectuou quatro ensaios de incinera����o: dois de mono-combust��o de uma lama residual urbana, um de co-combust��o de lama residual urbana e carv��o e, finalmente, um de mono-combust��o de carv��o. Cada ensaio de incinera����o produziu uma cinza de fundo e duas cinzas volantes, provenientes de dois ciclones. A equipa do GDEH foi respons��vel pela caracteriza����o f��sico-qu��mica e ecotoxicol��gica das cinzas provenientes dos ensaios realizados pela equipa do INETI. A avalia����o incidiu em dois aspectos: 1) a determina����o da composi����o das cinzas, relativamente a um dado conjunto de par��metros f��sico-qu��micos considerados; e 2) produ����o de lixiviados a partir do contacto das cinzas com um agente lixiviante. Estes lixiviados foram submetidos �� caracteriza����o f��sico-qu��mica, relativamente a um dado conjunto de par��metros f��sico-qu��micos e, ainda, �� caracteriza����o ecotoxicol��gica, recorrendo a dois indicadores biol��gicos. A determina����o da composi����o das cinzas permitiu efectuar um balan��o de massas dos ensaios de incinera����o realizados e, com isto, determinar as taxas de emiss��o, dos par��metros analisados, para a atmosfera. Os ensaios de lixivia����o permitiram classificar, de acordo com a metodologia de classifica����o de res��duos a que se recorreu, as doze cinzas produzidas pela equipa do INETI e os materiais que lhes deram origem, a areia do leito, o carv��o e a lama residual urbana. De um modo geral, as duas cinzas volantes apresentaram uma concentra����o superior, dos par��metros considerados, relativamente �� cinza de fundo. Entre as duas cinzas volantes, a cinza do 2�� ciclone apresentou um maior teor, relativamente aos par��metros analisados, do que as cinzas do 1�� ciclone.

Non-adherence to telemedicine interventions for drug users: systematic review

OBJECTIVE To estimate rates of non-adherence to telemedicine strategies aimed at treating drug addiction. METHODS A systematic review was conducted of randomized controlled trials investigating different telemedicine treatment methods for drug addiction. The following databases were consulted between May 18, 2012 and June 21, 2012: PubMed, PsycINFO, SciELO, Wiley (The Cochrane Library), Embase, Clinical trials and Google Scholar. The Grading of Recommendations Assessment, Development and Evaluation was used to evaluate the quality of the studies. The criteria evaluated were: appropriate sequence of data generation, allocation concealment, blinding, description of losses and exclusions and analysis by intention to treat. There were 274 studies selected, of which 20 were analyzed. RESULTS Non-adherence rates varied between 15.0% and 70.0%. The interventions evaluated were of at least three months duration and, although they all used telemedicine as support, treatment methods differed. Regarding the quality of the studies, the values also varied from very poor to high quality. High quality studies showed better adherence rates, as did those using more than one technique of intervention and a limited treatment time. Mono-user studies showed better adherence rates than poly-user studies. CONCLUSIONS Rates of non-adherence to treatment involving telemedicine on the part of users of psycho-active substances differed considerably, depending on the country, the intervention method, follow-up time and substances used. Using more than one technique of intervention, short duration of treatment and the type of substance used by patients appear to facilitate adherence.

Synthesis and structural characterization of new Piano-stool Ruthenium(II) complexes bearing 1-Butylimidazole heteroaromatic ligand

New cationic ruthenium(II) complexes with the formula [Ru(eta(5)-C5H5)(LL)(1-BuIm)] [Z], with (LL) = 2PPh(3) or DPPE, and Z = CF3SO3-, PF6-, BPh4-, have been synthesized and fully characterized. Spectroscopic and electrochemical studies revealed that the electronic properties of the coordinated 1-butylimidazole were clearly influenced by the nature of the phosphane coligands (LL) and also by the different counter ions. The solid state structures of the six complexes determined by X-ray crystallographic studies, confirmed the expected distorted three-legged piano stool structure. However the geometry of the 1-butylimidazole ligand was found considerably different in all six compounds, being governed by the stereochemistry of the mono and bidentate coligands (PPh3 or DPPE).