Hydroxycinnamic acid antioxidants: an electrochemical overview

Hydroxycinnamic acids (such as ferulic, caffeic, sinapic, and p-coumaric acids) are a group of compounds highly abundant in food that may account for about one-third of the phenolic compounds in our diet. Hydroxycinnamic acids have gained an increasing interest in health because they are known to be potent antioxidants. These compounds have been described as chain-breaking antioxidants acting through radical scavenging activity, that is related to their hydrogen or electron donating capacity and to the ability to delocalize/stabilize the resulting phenoxyl radical within their structure.The free radical scavenger ability of antioxidants can be predicted from standard one-electron potentials. Thus, voltammetric methods have often been applied to characterize a diversity of natural and synthetic antioxidants essentially to get an insight into their mechanism and also as an important tool for the rational design of new and potent antioxidants.The structure-property-activity relationships (SPARs) correlations already established for this type of compounds suggest that redox potentials could be considered a good measure of antioxidant activity and an accurate guideline on the drug discovery and development process. Due to its magnitude in the antioxidant field, the electrochemistry of hydroxycinnamic acid-based antioxidants is reviewed highlighting the structure-property-activity relationships (SPARs) obtained so far.

Evaluating P-NET message's response time with fixed priority queuing at application process level

P-NET is a multi-master fieldbus standard based on a virtual token passing scheme. In P-NET each master is allowed to transmit only one message per token visit. In the worst-case, the communication response time can be derived considering that, in each token cycle, all stations use the token to transmit a message. In this paper, we define a more sophisticated P-NET model, which considers the actual token utilisation. We then analyse the possibility of implementing a local priority-based scheduling policy to improve the real-time behaviour of P-NET.

Supporting real-time distributed computer-controlled systems with multi-hop P-NET networks

Fieldbus communication networks aim to interconnect sensors, actuators and controllers within process control applications. Therefore, they constitute the foundation upon which real-time distributed computer-controlled systems can be implemented. P-NET is a fieldbus communication standard, which uses a virtual token-passing medium-access-control mechanism. In this paper pre-run-time schedulability conditions for supporting real-time traffic with P-NET networks are established. Essentially, formulae to evaluate the upper bound of the end-to-end communication delay in P-NET messages are provided. Using this upper bound, a feasibility test is then provided to check the timing requirements for accessing remote process variables. This paper also shows how P-NET network segmentation can significantly reduce the end-to-end communication delays for messages with stringent timing requirements.

Communication response time in P-NET networks: worst-case analysis considering the actual token utilisation

Fieldbus networks aim at the interconnection of field devices such as sensors, actuators and small controllers. Therefore, they are an effective technology upon which Distributed Computer Controlled Systems (DCCS) can be built. DCCS impose strict timeliness requirements to the communication network. In essence, by timeliness requirements we mean that traffic must be sent and received within a bounded interval, otherwise a timing fault is said to occur. P-NET is a multi-master fieldbus standard based on a virtual token passing scheme. In P-NET each master is allowed to transmit only one message per token visit, which means that in the worst-case the communication response time could be derived considering that the token is fully utilised by all stations. However, such analysis can be proved to be quite pessimistic. In this paper we propose a more sophisticated P-NET timing analysis model, which considers the actual token utilisation by different masters. The major contribution of this model is to provide a less pessimistic, and thus more accurate, analysis for the evaluation of the worst-case communication response time in P-NET fieldbus networks.

Princípios orientadores da formação, ao nível do 1º ciclo: a cooperação Portugal/P.A.L.O.P.'s

Os Países Africanos de Língua Oficial Portuguesa (P.A.L.O.P.'s), tal como a grande maioria de todo o continente africano, apresentam graves deficiências quanto a alfabetização das suas populações, tomando-se, assim, o ensino primário uma prioridade absoluta. De entre todas as limitações que existem ao nível dos respectivos sistemas educativos, talvez, a mais grave seja a fraca preparação científica e pedagógica que a maioria dos professores apresenta, para além, evidentemente, do seu reduzido número. Assim, a formação de professores tornou-se numa das apostas mais fortes dos P.A.L.O.P.'s, no campo da educação. Portugal, na área da cooperação com estes países, participa num Projecto de Consolidação dos Sistemas Educativos, no âmbito do qual desenvolve um programa de Acções de Formação de Formadores.

Adding local priority-based dispatching mechanisms to P-NET networks: a fixed priority approach

In this paper we address the real-time capabilities of P-NET, which is a multi-master fieldbus standard based on a virtual token passing scheme. We show how P-NET’s medium access control (MAC) protocol is able to guarantee a bounded access time to message requests. We then propose a model for implementing fixed prioritybased dispatching mechanisms at each master’s application level. In this way, we diminish the impact of the first-come-first-served (FCFS) policy that P-NET uses at the data link layer. The proposed model rises several issues well known within the real-time systems community: message release jitter; pre-run-time schedulability analysis in non pre-emptive contexts; non-independence of tasks at the application level. We identify these issues in the proposed model and show how results available for priority-based task dispatching can be adapted to encompass priority-based message dispatching in P-NET networks.

Scheduling real-time communications with P-NET

In this paper we address the P-NET Medium Access Control (MAC) ability to schedule traffic according to its real-time requirements, in order to support real-time distributed applications. We provide a schedulability analysis based on the P-NET standard, and propose mechanisms to overcome priority inversion problems resulting from the use of FIFO outgoing buffers

Pre-run-time schedulability analysis of P-NET fieldbus networks

P-NET is a fieldbus industrial communication standard, which uses a Virtual Token Passing MAC mechanism. In this paper we establish pre-run-time schedulability conditions for supporting real-time traffic with P-NET. Essentially we provide formulae to evaluate the minimum message deadline, ensuring the transmission of real-time messages within a maximum time bound

Aedes aegypti entomological indices in an endemic area for dengue in Sao Paulo State, Brazil

OBJECTIVE: To evaluate the most productive types of properties and containers for Aedes aegypti and the spatial distribution of entomological indices.METHODS: Between December 2006 and February 2007, the vector's immature forms were collected to obtain entomological indices in 9,875 properties in the Jaguare neighborhood of Sao Jose do Rio Preto, SP, Southeastern Brazil. In March and April 2007, a questionnaire about the conditions and characteristics of properties was administered. Logistic regression was used to identify variables associated with the presence of pupae at the properties. Indices calculated per block were combined with a geo-referenced map, and thematic maps of these indices were obtained using statistical interpolation.RESULTS: The properties inspected had the following Ae. aegypti indices: Breteau Index = 18.9, 3.7 larvae and 0.42 pupae per property, 5.2 containers harboring Ae. aegypti per hectare, 100.0 larvae and 11.6 pupae per hectare, and 1.3 larvae and 0.15 pupae per inhabitant. The presence of yards, gardens and animals was associated with the presence of pupae.CONCLUSIONS: Specific types of properties and containers that simultaneously had low frequencies among those positive for the vector and high participation in the productivity of larvae and pupae were not identified. The use of indices including larval and pupal counts does not provide further information beyond that obtained from the traditional Stegomyia indices in locations with characteristics similar to those of São José do Rio Preto. The indices calculated per area were found to be more accurate for the spatial assessment of infestation. The Ae. aegypti infestation levels exhibited extensive spatial variation, indicating that the assessment of infestation in micro areas is needed.

Task assignment algorithms for two-type heterogeneous multiprocessors

Consider the problem of assigning real-time tasks on a heterogeneous multiprocessor platform comprising two different types of processors — such a platform is referred to as two-type platform. We present two linearithmic timecomplexity algorithms, SA and SA-P, each providing the follow- ing guarantee. For a given two-type platform and a given task set, if there exists a feasible task-to-processor-type assignment such that tasks can be scheduled to meet deadlines by allowing them to migrate only between processors of the same type, then (i) using SA, it is guaranteed to find such a feasible task-to- processor-type assignment where the same restriction on task migration applies but given a platform in which processors are 1+α/2 times faster and (ii) SA-P succeeds in finding 2 a feasible task-to-processor assignment where tasks are not allowed to migrate between processors but given a platform in which processors are 1+α/times faster, where 0<α≤1. The parameter α is a property of the task set — it is the maximum utilization of any task which is less than or equal to 1.

Estudo da influência das concentrações de N e P sobre o desenvolvimento de cianobactérias em cultura mista

Ao longo de 40 anos, muitos trabalhos têm vindo a ser desenvolvidos no âmbito do tema da eutrofização e desenvolvimento de biomassa fitoplanctónica. Em todos eles, eram sugeridos factores responsáveis, desde a latitude, luz, temperatura, mistura da coluna de água e os inputs de nutrientes. Toda a controvérsia gerada em torno da eutrofização, levou a que a inércia adoptada em situações de risco induzisse a degradação de muitos sistemas aquáticos. É quando, além da degradação estética, os problemas começam a surgir, que se compreende a necessidade de que surjam medidas de gestão e requalificação das lagoas e bacias hidrográficas. A tendência para a ocorrência de florescências de organismos como cianobactérias, implica a necessidade de maiores cuidados nos usos das massas de água, principalmente ao nível da produção de água para consumo humano e do uso recreativo. Uma boa gestão, implica um conhecimento aprofundado do comportamento destes organismos. Este trabalho, apresenta as respostas de organismos recolhidos em florescências naturais, na Lagoa das Furnas – ilha de S. Miguel (Açores) em meios com diferentes teores de azoto. As diferenças entre os resultados, permitem retirar algumas conclusões sobre as condições preferenciais ao seu desenvolvimento. De um modo geral, as culturas comportaram-se da forma esperada, desenvolvendo-se mais com doses de azoto mais elevadas. Este desenvolvimento foi verificado tanto pelo aumento das partículas ao longo de todo o ensaio, mas também pelos valores de pigmentos registados no fim deste. Por outro lado, o facto do azoto ter sido adicionado sob a forma amoniacal ou de nitratos, permite concluir que os organismos presentes nas florescências preferem assimilar as formas azotadas que impliquem um menor consumo energético. Daí que se tenham verificado desenvolvimentos mais significativos em meios em que foi adicionado azoto amoniacal. O facto de ser tratar de um trabalho baseado nas condições de desenvolvimento de organismos vivos, era de esperar alguma imprevisibilidade dos comportamentos. Sendo assim, será recomendável aprofundar o conhecimento das reacções dos organismos em cultura mista para doses diferentes de azoto, assim como a realização de ensaios em que para uma dose de N fixa, se façam variar as concentrações de P.

Synthesis, characterization and reactivity of new cobalt, palladium and nickel complexes bearing α-diimines and P, O ligands

This work describes the synthesis and characterization of a series of new α-diimine and P,O, β-keto and acetamide phosphines ligands, and their complexation to Ni(II), Co(II),Co(III) and Pd(II) to obtain a series of new compounds aiming to study their structural characteristics and to test their catalytic activity. All the compounds synthesized were characterized by the usual spectroscopic and spectrometric techniques: Elemental Analysis, MALDI-TOF-MS spectrometry, IR, UV-vis, 1H, 13C and 31P NMR spectroscopies. Some of the paramagnetic compounds were also characterized by EPR. For the majority of the compounds it was possible to solve their solid state structure by single crystal X-ray diffraction. Tests for olefin polymerization were performed in order to determine the catalytic activity of the Co(II) complexes. Chapter I presents a brief introduction to homogenous catalysis, highlighting the reactions catalyzed by the type of compounds described in this thesis, namely olefin polymerization and oligomerization and reactions catalyzed by the complexes bearing α-diimines and P,O type ligands. Chapter II is dedicated to the description of the synthesis of new α-diimines cobalt (II) complexes, of general formula [CoX2(α-diimine)], where X = Cl or I and the α-diimines are bis(aryl)acenaphthenequinonediimine) (Ar-BIAN) and 1,4-diaryl-2,3-dimethyl-1,4-diaza-1,3-butadiene (Ar-DAB). Structures solved by single crystal X-ray diffraction were obtained for all the described complexes. For some of the compounds, X-band EPR measurements were performed on polycrystalline samples, showing a high-spin Co(II) (S = 3/2) ion, in a distorted axial environment. EPR single crystal experiments on two of the compounds allowed us to determine the g tensor orientation in the molecular structure. In Chapter III we continue with the synthesis and characterization of more cobalt (II)complexes bearing α-diimines of general formula [CoX2(α-diimine)], with X = Cl or I and α-diimines are bis(aryl)acenaphthenequinonediimine) (Ar-BIAN) and 1,4-diaryl-2,3-dimethyl- 1,4-diaza-1,3-butadiene (Ar-DAB). The structures of three of the new compounds synthesized were determined by single crystal X-ray diffraction. A NMR paramagnetic characterization of all the compounds described is presented. Ethylene polymerization tests were done to determine the catalytic activity of several of the Co(II) complexes described in Chapter II and III and their results are shown. In Chapter IV a new rigid bidentate ligand, bis(1-naphthylimino)acenaphthene, and its complexes with Zn(II) and Pd(II), were synthesized. Both the ligand and its complexes show syn and anti isomers. Structures of the ligand and the anti isomer of the Pd(II) complex were solved by single crystal X-ray diffraction. All the compounds were characterized by elemental analysis, MALDI-TOF-MS spectrometry, and by IR, UV-vis, 1H, 13C, 1H-1H COSY, 1H-13C HSQC, 1H-13C HSQC-TOCSY and 1H-1H NOESY NMR when necessary. DFT studies showed that both conformers of [PdCl2(BIAN)] are isoenergetics and can be obtain experimentally. However, we can predict that the isomerization process is not available in square-planar complex, but is possible for the free ligand. The molecular geometry is very similar in both isomers, and only different orientations for naphthyl groups can be expected. Chapter V describes the synthesis of new P, O type ligands, β-keto phosphine, R2PCH2C(O)Ph, and acetamide phosphine R2PNHC(O)Me, as well as a series of new cobalt(III) complexes namely [(η5-C5H5)CoI2{Ph2PCH2C(O)Ph}], and [(η5- C5H5)CoI2{Ph2PNHC(O)Me}]. Treating these Co(III) compounds with an excess of Et3N, resulted in complexes η2-phosphinoenolate [(η5-C5H5)CoI{Ph2PCH…C(…O)Ph}] and η2- acetamide phosphine [(η5-C5H5)CoI{Ph2PN…C(…O)Me}]. Nickel (II) complexes were also obtained: cis-[Ni(Ph2PN…C(…O)Me)2] and cis-[Ni((i-Pr)2PN…C(…O)Me)2]. Their geometry and isomerism were discussed. Seven structures of the compounds described in this chapter were determined by single crystal X-ray diffraction. The general conclusions of this work can be found in Chapter VI.

Chiroptical and emissive properties of a calix[4]arene-containing chiral poly (P-phenylene ethynylene) with enantioselective recognition ability

Supramolecular chirality was achieved in solutions and thin films of a calixarene-containing chiral aryleneethynylene copolymer. The observed chiroptical activity, which is primarily allied with the formation of aggregates of high molecular weight polymer chains, is the result of a combination of intrachain and interchain effects. The former arises by the adoption of an induced helix-sense by the polymer main-chain while the latter comes from the exciton coupling of aromatic backbone transitions. The co-existence of bulky bis-calixKlarene units and chiral side-chains on the polymer skeleton prevents efficient pi-stacking of neighbouring chains, keeping the chiral assembly highly emissive. In contrast, for a model polymer lacking calixarene moieties, the chiroptical activity is dominated by strong interchain exciton couplings as a result of more favourable packing of polymer chains, leading to a marked decrease of photoluminescence in the aggregate state. The enantiomeric recognition abilities of both polymers towards (R)- and (S)-alpha-methylbenzylamine were examined. It was found that a significant enantiodiscrimination is exhibited by the calixarene-based polymer in the aggregate state.

Cultura da (in) segurança nos contextos de trabalho em enfermagem: o caso do Hospital do Espírito Santo de Évora - E.P.E.

Mestrado em Intervenção Sócio-Organizacional na Saúde - Área de especialização: Políticas de Administração e Gestão de Serviços de Saúde