Computational analysis of quinoxalines N,N-Dioxide and ITS Derivates

A quinoxalina e seus derivativos são uma importante classe de compostos heterocíclicos, onde os elementos N, S e O substituem átomos de carbono no anel. A fórmula molecular da quinoxalina é C8H6N2, formada por dois anéis aromáticos, benzeno e pirazina. É rara em estado natural, mas a sua síntese é de fácil execução. Modificações na estrutura da quinoxalina proporcionam uma grande variedade de compostos e actividades, tais como actividades antimicrobiana, antiparasitária, antidiabética, antiproliferativa, anti-inflamatória, anticancerígena, antiglaucoma, antidepressiva apresentando antagonismo do receptor AMPA. Estes compostos também são importantes no campo industrial devido, por exemplo, ao seu poder na inibição da corrosão do metal. A química computacional, ramo natural da química teórica é um método bem desenvolvido, utilizado para representar estruturas moleculares, simulando o seu comportamento com as equações da física quântica e clássica. Existe no mercado uma grande variedade de ferramentas informaticas utilizadas na química computacional, que permitem o cálculo de energias, geometrias, frequências vibracionais, estados de transição, vias de reação, estados excitados e uma variedade de propriedades baseadas em várias funções de onda não correlacionadas e correlacionadas. Nesta medida, a sua aplicação ao estudo das quinoxalinas é importante para a determinação das suas características químicas, permitindo uma análise mais completa, em menos tempo, e com menos custos.

Estudo de viabilidade de utilização de VLC em infra-estruturas ITS baseadas em semáforos rodoviários a LEDs

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia de Electrónica e Telecomunicações

Should the U.S. adapt to the world? The first debate on american exceptionalism and its impact on the founding of the United States

This paper aims at putting into perspective the recent, post 9/11 debate on the United States‘ alleged exceptionalism and its impact on the definition of American foreign policy. It reminds the readers that the United States was born as a result of a similar debate, at a time when a crucial choice for its future was to be made. Indeed, the Founding Fathers discarded the revolutionary idea that America was altogether different from other (European) nations and, as such, could succeed in saving republicanism and concentrate on domestic affairs. As Gordon Wood and Harvey Mansfield have shown, the 1787 version of republicanism stood as a departure from its earlier version, and such a change was necessary to the creation of a full-fledged federation, therefore paving the way to the current powerful Federal Republic. The early failure of the exceptionalist creed did not cause its disappearance, as the contemporary form of exceptionalism demonstrates, but created conditions that made an enduring and powerful influence very difficult.

Electroanalytical determination of oxadiazon and characterization of its base-catalyzed ring-opening products

The electrochemical behavior of the hydrolysis products of oxadiazon was studied by cyclic and square-wave voltammetry using a glassy carbon electrode. Maximum currents were obtained at pH 12.8 in an aqueous electrolyte solution containing 30% ethanol and the current did not decrease with time showing that there was little adsorption of the reaction products on the electrode surface. The hydrolysis products of oxadiazon were identi®ed, after isolation and puri®cation, as 1-trimethylacetyl-2-(2,4-dichloro-5-isopropoxyphenyl)-2-ethoxycarbonylhydrazine (Oxa1) and 1-trimethylacetyl-2-(2,4-dichloro-5-isopropoxyphenyl) hydrazine (Oxa2) with redox potentials 0.6Vand 70.1V (vs. Ag=AgCl), respectively. Based on the electrochemical behavior of 1-trimethylacetyl-2-(2,4-dichloro-5-isopropoxyphenyl) hydrazine (Oxa2) a simple electroanalytical procedure was developed for the determination of oxadiazon in commercial products used in the treatment of rice crops in Portugal that contain oxadiazon as the active ingredient. The detection limit was 161074 M, the mean content and relative standard deviation obtained for seven samples of two different commercial products by the electrochemical method were 28.4 0.8% (Ronstar) and 1.9 0.2% (Ronstar GR), and the recoveries were 100.3 5.4% and 101.1 5.3 %, respectively.

Static and hydrodynamic monitoring of citalopram based on its electro-oxidation behavior at a glassy-carbon surface

The electrooxidative behavior of citalopram (CTL) in aqueous media was studied by cyclic voltammetry (CV) and square-wave voltammetry (SWV) at a glassy-carbon electrode. The electrochemical behaviour of CTL involves two electrons and two protons in the irreversible and diffusion controlled oxidation of the tertiary amine group. The maximum analytical signal was obtained in a phosphate buffer (pH ¼ 8.2). For analytical purposes, an SWV method and a flow-injection analysis (FIA) system with amperometric detection were developed. The optimised SWV method showed a linear range between 1.10 10 5–1.20 10 4 molL 1, with a limit of detection (LOD) of 9.5 10 6 molL 1. Using the FIA method, a linear range between 2.00 10 6–9.00 10 5 molL 1 and an LODof 1.9 10 6 molL 1 were obtained. The validation of both methods revealed good performance characteristics confirming applicability for the quantification of CTL in several pharmaceutical products.

Oxidative behaviour of apomorphine and its metabolites

The metabolism of apomorphine is quite complex due to interactions with proteins and other tissue components that affect its pharmacokinetic profile. The electrochemical oxidation mechanism of apomorphine and of some synthesised apomorphine derivatives was studied. It was found to be related to the reaction of o-diphenol and tertiary amine groups and strongly dependent on pH.

Determination of free formaldehyde in foundry resins as its 2,4-dinitrophenylhydrazone by liquid chromatography

Formaldehyde is a toxic component that is present in foundry resins. Its quantification is important to the characterisation of the resin (kind and degradation) as well as for the evaluation of free contaminants present in wastes generated by the foundry industry. The complexity of the matrices considered suggests the need for separative techniques. The method developed for the identification and quantification of formaldehyde in foundry resins is based on the determination of free carbonyl compounds by derivatization with 2,4-dinitrophenylhydrazine (DNPH), being adapted to the considered matrices using liquid chromatography (LC) with UV detection. Formaldehyde determinations in several foundry resins gave precise results. Mean recovery and R.S.D. were, respectively, >95 and 5%. Analyses by the hydroxylamine reference method gave comparable results. Results showed that hydroxylamine reference method is applicable just for a specific kind of resin, while the developed method has good performance for all studied resins.

Study of the voltammetric behaviour of metam and its application to an amperometric flow system

The electrochemical behaviour of the pesticide metam (MT) at a glassy carbon working electrode (GCE) and at a hanging mercury drop electrode (HMDE) was investigated. Different voltammetric techniques, including cyclic voltammetry (CV) and square wave voltammetry (SWV), were used. An anodic peak (independent of pH) at +1.46 V vs AgCl/Ag was observed in MTaqueous solution using the GCE. SWV calibration curves were plotted under optimized conditions (pH 2.5 and frequency 50 Hz), which showed a linear response for 17–29 mg L−1. Electrochemical reduction was also explored, using the HMDE. A well defined cathodic peak was recorded at −0.72 V vs AgCl/ Ag, dependent on pH. After optimizing the operating conditions (pH 10.1, frequency 150 Hz, potential deposition −0.20 V for 10 s), calibration curves was measured in the concentration range 2.5×10−1 to 1.0 mg L−1 using SWV. The electrochemical behaviour of this compound facilitated the development of a flow injection analysis (FIA) system with amperometric detection for the quantification of MT in commercial formulations and spiked water samples. An assessment of the optimal FIA conditions indicated that the best analytical results were obtained at a potential of +1.30 V, an injection volume of 207 μL and an overall flow rate of 2.4 ml min−1. Real samples were analysed via calibration curves over the concentration range 1.3×10−2 to 1.3 mg L−1. Recoveries from the real samples (spiked waters and commercial formulations) were between 97.4 and 105.5%. The precision of the proposed method was evaluated by assessing the relative standard deviation (RSD %) of ten consecutive determinations of one sample (1.0 mg L−1), and the value obtained was 1.5%.

Does diaphragmatic breathing technique really improve its range of motion? An objective assessment

Purpose - To verify the results of a diaphragmatic breathing technique (DBT) on diaphragmatic range of motion in healthy subjects. Methods - A total of 51 healthy subjects (10 male; 41 female), mean age 20 years old and a body mass index (BMI) ranging from 15.6 to 34.9 kg/m2, were enrolled in this study. Diaphragmatic range of motion was assessed by M-mode ultrasound imaging. Measurements were made before and after the DBT implementation in a standard protocol, based on 3 seconds of inspiration starting from a maximum expiration. Differences between assessments were analyzed by descriptive statistics and t-test (p < 0.05). Results - Mean value range of motion before DBT was 55.3 ± 13.4 mm and after DBT was 63.8 ± 13.2 mm showing a significant improvement of 8.5 ± 14.7 mm (p < 0.001). A strong correlation between the slope and the range of motion was found (r = 0.71, p < 0.001). Conclusions - Based on ultrasound measurements, it has been proved that DBT really contributes to a higher diaphragmatic range of motion. Future studies are needed in order to understand the influence of protocol parameters (e.g. inspiration time). Clinical implications - In the contest of evidence-based practice in physiotherapy, it has been showed by objective measurements that DBT improves the diaphragm range of motion, translating into a more efficient ventilatory function and thus can be used in clinical setting. To our knowledge this is the first study to assess the effects of DBT on range of motion of diaphragm muscle with ultrasound imaging.

Determination of methiocarb and Its degradation products, methiocarb sulfoxide and methiocarb sulfone, in bananas using QuEChERS extraction

The present work describes the development of an analytical method for the determination of methiocarb and its degradation products (methiocarb sulfoxide and methiocarb sulfone) in banana samples, using the QuEChERS (quick, easy, cheap, effective, rugged, and safe) procedure followed by liquid chromatography coupled to photodiode array detector (LCPAD). Calibration curves were linear in the range of 0.5−10 mg L−1 for all compounds studied. The average recoveries, measured at 0.1 mg kg−1 wet weight, were 92.0 (RSD = 1.8%, n = 3), 84.0 (RSD = 3.9%, n = 3), and 95.2% (RSD = 1.9%, n = 3) for methiocarb sulfoxide, methiocarb sulfone, and methiocarb, respectively. Banana samples treated with methiocarb were collected from an experimental field. The developed method was applied to the analysis of 24 samples (peel and pulp) and to 5 banana pulp samples. Generally, the highest levels were found for methiocarb sulfoxide and methiocarb. Methiocarb sulfone levels were below the limit of quantification, except in one sample (not detected).

Modern epidemiology and its discontents

The goal of this article is to present a snapshot of an ongoing debate within epidemiology, pitching opposing sides in the struggle to define the path it should follow in the years to come. The debate among epidemiologists in the mid-90s pitted those who defended the idea that epidemiology should necessarily deal with a wide context against those who believed that science and public health are better served by focusing on the individual level. Ian Hacking’s concept of styles of reasoning was used as a theoretical tool. The literature was reviewed using a core set of articles as an entry point, seeking articles that cited them, and then back-tracking the citations of the resulting set in the Scopus database. The main arguments are presented according to levels (ontological, epistemological, axiological and pragmatic), in order to show an even deeper disagreement, in the very conception of science and its relation to social issues and public policy.

Attention performance among Brazilian truck drivers and its association with amphetamine use: pilot study

The aim of this article was to describe the attention functioning of twenty-two truck drivers and its relationship with amphetamine use. Those drivers who reported using amphetamines in the twelve months previous to the interview had the best performance in a test evaluating sustained attention functioning. Although amphetamine use may initially seem advantageous to the drivers, it may actually impair safe driving. The findings suggest the importance of monitoring the laws regarding amphetamine use in this country.

Slotted wiDom: schedulability analysis and its experimental validation

WiDom is a wireless prioritized medium access control protocol which offers a very large number of priority levels. Hence, it brings the potential to employ non-preemptive static-priority scheduling and schedulability analysis for a wireless channel assuming that the overhead of WiDom is modeled properly. One schedulability analysis for WiDom has already been proposed but recent research has created a new version of WiDom (we call it: Slotted WiDom) with lower overhead and for this version of WiDom no schedulability analysis exists. In this paper we propose a new schedulability analysis for slotted WiDom and extend it to work also for message streams with release jitter. We have performed experiments with an implementation of slotted WiDom on a real-world platform (MicaZ). We find that for each message stream, the maximum observed response time never exceeds the calculated response time and hence this corroborates our belief that our new scheduling theory is applicable in practice.

Practical aspects of slot-based task- splitting dispatching in its schedulability analysis

Consider the problem of scheduling a set of sporadic tasks on a multiprocessor system to meet deadlines using a tasksplitting scheduling algorithm. Task-splitting (also called semipartitioning) scheduling algorithms assign most tasks to just one processor but a few tasks are assigned to two or more processors, and they are dispatched in a way that ensures that a task never executes on two or more processors simultaneously. A certain type of task-splitting algorithms, called slot-based task-splitting, is of particular interest because of its ability to schedule tasks at high processor utilizations. We present a new schedulability analysis for slot-based task-splitting scheduling algorithms that takes the overhead into account and also a new task assignment algorithm.

The globalisation in the clothing sector and its implications for work organisation: a view from the Portuguese case

The clothing sector in Portugal is still seen, in many aspects as a traditional sector with some average characteristics, such as: low level of qualifications, less flexible labour legislation and stronger unionisation, very low salaries and low capability of investment in innovation and new technology. Is, nevertheless, a very important sector in terms of labour market, with increased weight in the exporting structure. Globalisation and delocalisation are having a strong impact in the organisation of work and in occupational careers in the sector. With the pressure of global competitiveness in what concerns time and prices, very few companies are able to keep a position in the market without changes in organisation of work and workers. And those that can perform good responses to such challenges are achieving a better economical stability. The companies have found different ways to face this reality according to size, capital and position. We could find two main paths: one where companies outsource a part or the entire production to another territory (for example, several manufacturing tasks), close and/or dismissal the workers. Other path, where companies up skilled their capacities investing, for example, in design, workers training, conception and introduction of new or original products. This paper will present some results from the European project WORKS – Work organisation and restructuring in the knowledge society (6th Framework Programme), focusing the Portuguese case studies in several clothing companies in what concern implications of global context for the companies in general and for the workers in particular, in a comparative analysis with some other European countries.