Structural, physical, and chemical modifications induced by microwave heating on native agar-like galactans

Native agars from Gracilaria vermiculophylla produced in sustainable aquaculture systems (IMTA) were extracted under conventional (TWE) and microwave (MAE) heating. The optimal extracts from both processes were compared in terms of their properties. The agars’ structure was further investigated through Fourier transform infrared and NMR spectroscopy. Both samples showed a regular structure with an identical backbone, β-D-galactose (G) and 3,6-anhydro-α-L-galactose (LA) units; a considerable degree of methylation was found at C6 of the G units and, to a lesser extent, at C2 of the LA residues. The methylation degree in the G units was lower for MAEopt agar; the sulfate content was also reduced. MAE led to higher agar recoveries with drastic extraction time and solvent volume reductions. Two times lower values of [η] and Mv obtained for the MAEopt sample indicate substantial depolymerization of the polysaccharide backbone; this was reflected in its gelling properties; yet it was clearly appropriate for commercial application in soft-texture food products.

Ajustes posturais para o alcance funcional dos membros superiores - migração do centro de pressão na posição de sentado

Objetivos: Pretende-se verificar as modificações neuromotoras após uma intervenção baseada no conceito de Bobath ao nível dos ajustes posturais durante o alcance funcional dos membros superiores, em três crianças com paralisia cerebral. Pretende-se também, verificar o efeito desta abordagem nas atividades e participação, bem como destacar os aspetos individuais das mesmas crianças com a capacidade de mudança após a intervenção. Metodologia: A avaliação foi realizada antes e três meses após a intervenção em fisioterapia segundo o conceito de Bobath. Optou-se por um registo observacional com uma Máquina Fotográfica Digital, um sistemas de Câmaras de Vídeo, uma Plataforma de Forças e, utilizaram-se ainda instrumentos como o Gross Motor Functional Measure– versão 88 itens, o Gross Motor Function Classification System, o Teste de Alcance Funcional Modificado e a ferramenta, Classificação Internacional de Funcionalidade, Incapacidade e Saúde – crianças e jovens. Resultados: Verificou-se um progresso nos ajustes posturais e na funcionalidade em geral, o que se repercutiu na restrição da participação e na limitação da actividade. A postura na posição de sentado, o deslocamento do centro de pressão, a capacidade de deslocamento no sentido anterior, bem como as capacidades motoras grosseiras modificaram-se em todas as crianças, tendo a criança B apresentado a maior e a criança A a menor capacidade de mudança após a intervenção. Conclusão: A intervenção segundo o Conceito de Bobath promoveu modificações neuromotoras, o que levaram a uma melhoria da funcionalidade geral, da mobilidade e do controlo postural da criança, refletindo-se nos ajustes posturais durante o alcance funcional dos membros superiores na posição de sentado. Verificou-se ainda, uma melhoria na restrição da participação e na limitação da actividade diária.

Avaliação da posição ortostática em plataforma de forças de dois indivíduos com acidente vascular encefálico antes e após uma intervenção baseado no conceito Bobath

Introdução: O acidente vascular encefálico (AVE) é uma importante e frequente condição de saúde que se repercute na funcionalidade do indivíduo. No sentido de reabilitar a função perdida, é comum o recurso a intervenções de fisioterapia baseado o conceito de Bobath. Como tal, importa verificar, as modificações no âmbito do controlo postural, através da migração do centro de pressão na base de suporte, face à aplicação de uma intervenção segundo abordagem baseada no conceito de Bobath em dois indivíduos com AVE. Métodos e participantes: Foram recrutados dois indivíduos com diagnóstico de AVE num hospital da zona do grande Porto. Dados referentes ao equilíbrio estático na condição de medição “olhos abertos ou fechados” e “calçado ou descalço” foram obtidos através de plataforma de forças, antes e após uma intervenção baseado no conceito de Bobath durante 13 semanas (M0 e M1). Nestes dois momentos foram ainda avaliados a mobilidade, função cognitiva, participação, equilíbrio através do teste Timed Up & Go (TUG) e Timed Up & Go Modificado (TUGM), e das escalas Mini Mental State Examination (MMSE), Postural Assessment for Stroke Scale (PASS), Escala de Berg (EB) e Índice de Barthel Modificado (IBM). Resultados: Os participantes obtiveram em ambos os momentos pontuação máxima no MMSE. Ambos os indivíduos atingiram o valor máximo no IBM em M1 (Mo: A: 78; B: 65). Ambos os indivíduos aumentaram o score entre M0 e M1, relativamente ao PASS (A: M0:21; M1:33; B: M0: 26; M1:34) e EB (A: M0:48; M1:54; B: M0: 30; M1:50). O tempo de realização do TUG e do TUGM diminuíram entre momentos em ambos os indivíduos (respectivamente: A: 15''13'' a 13''27''; B: 24''13'' a 13''88'' e A: 19''08''' a 13''27''; B: 29''60''' a 17''64'''). A área de deslocação do centro de pressão (CP) variou entre momentos em todas as condições de avaliação, sendo menor na condição “olhos abertos e descalço” em ambos os participantes (“olhos abertos e calçado”: A: M0= 1,364, M1=2,796; B: M0=1,892, M1=2,979; “olhos abertos e descalço”: A: M0= 0,758, M1=0,727; B: M0=3,064, M1=1,952; “olhos fechados e calçado”: A: M0= 2,360, M1=2,998; B: M0=2,232, M1= 4,392; “olhos fechados e descalço”: A: M0= 1,347, M1=2,388; B: M0=1,652, M1= 1,016). O desvio padrão das deslocações anteroposteriores variou entre momentos, sendo tendencialmente maior em M1 e na condição “descalço e olhos abertos”(“olhos abertos e calçado”: A: M0= 0,201, M1=0,500; B: M0=0,252, M1=0,310; “olhos abertos e descalço”: A: M0= 0,118, M1=0,165; B: M0=0,282, M1=0,276; “olhos fechados e calçado”: A: M0= 0,308, M1=0,398; B: M0=0,274, M1= 0,471; “olhos fechados e descalço”: A: M0= 0,158 , M1=0,373; B: M0=0,230, M1= 0,172), o desvio padrão das deslocações médio-lateral seguem a mesma tendência (“olhos abertos e calçado”: A: M0= 0,370 , M1=0,473; B: M0=0,454, M1=0,517; “olhos abertos e descalço”: A: M0= 0,354, M1=0,236 ; B: M0=0,584, M1=0,381; “olhos fechados e calçado”: A: M0= 0,425, M1=0,463; B: M0=0,462, M1= 0,583; “olhos fechados e descalço”: A: M0= 0,475, M1=0,416; B: M0=0,389, M1= 0,342). A velocidade de oscilação na direcção antero – posterior variou entre momentos, sendo tendencialmente menor em M1, em ambos os participantes e em todas as condições de avaliação: “olhos abertos e calçado”: A: M0= 0,886 , M1=0,532; B: M0=2,507, M1=01,072; “olhos abertos e descalço”: A: M0= 2,562, M1=3,815 ; B: M0=4,367, M1=0,262; “olhos fechados e calçado”: A: M0= 2,689, M1=1,757; B: M0=2,821, M1= 0,769; “olhos fechados e descalço”: A: M0= 2,984, M1=2,525; B: M0=4,100, M1= 0,265), a velocidade de oscilação na direcção médio – lateral seguem a mesma tendência para as condições de “olhos abertos e calçado”: A: M0= 6,524 , M1=6,218; B: M0=0,467, M1=0,404; “olhos fechados e calçado”: A: M0= 6,387, M1=1,927; B: M0=0,351, M1= 0,505; mas a velocidade de oscilação aumenta para as condições de “olhos abertos e descalço”: A: M0= 3,108, M1=7,806 ; B: M0=1,150, M1=8,054; “olhos fechados e descalço”: A: M0= 3,444, M1=3,839; B: M0=1,434, M1= 7,891). Conclusão: Entre os dois momentos os indivíduos melhoraram a sua mobilidade, equilíbrio, participação e actividades, potencialmente devido à intervenção baseado no conceito de Bobath.

Steroselective synthesis of imidazolidin-4-ones from α-amino amides of the antimalarial primaquine and substituted benzaldehydes

Imidazolidin-4-ones are commonly employed as skeletal modifications in bioactive oligopeptides, either as proline surrogates or for protection of the N-terminal amino acid against aminopeptidase-catalysed hydrolysis . We have been working on the synthesis of imidazolidin-4-ones of the antimalarial primaquine , through acylation of primaquine with an α-amino acid and subsequent reaction of the resulting α-aminoamide with a ketone or aldehyde. Thus, when using racemic primaquine, an optically pure chiral α-amino acid and an aldehyde as starting materials, four imidazolidin-4-one diastereomers are to be expected (Scheme 1). However, we have recently observed that imidazolidin-4-one synthesis was stereoselective when 2-carboxybenzaldehyde (2CBA)* was used, as only two diastereomers were produced2. Computational studies have shown that the imine formed prior to ring closure had, for structures derived from 2CBA, a quasi-cyclic rigid structure2. This rigid conformation is stabilized by an intramolecular hydrogen bond involving the C=O oxygen atom of the 2-carboxyl substituent in 2CBA and the N-H group of the α-amino amide moiety2. These findings led us to postulate that the 2-carbonyl substituent in the benzaldehyde moiety was the key for the stereoselective synthesis of the imidazolidin-4-ones2.

Alterações no recrutamento dos músculos abdominais na dor lombopélvica

Objectivo: Verificar se existem alterações no padrão de recrutamento do transverso do abdómen/oblíquo interno, recto abdominal e oblíquo externo em indivíduos com história de dor lombopélvica aguda. Métodos: Foi realizado um estudo do tipo observacional, analítico e transversal, cuja amostra consistia num grupo de 15 indivíduos que nunca tiveram dor lombopélvica e por outro de 14 indivíduos do sexo feminino que tiveram pelo menos episódio de dor lombopélvica aguda nos últimos 6 meses. Foi recolhida e avaliada por electromiografia de superfície a actividade dos músculos acima referenciados e do deltóide, durante os movimentos rápidos de flexão, abdução e extensão do ombro. Analisou-se e foi comparado entre os dois grupos o padrão de recrutamento dos músculos abdominais. O teste de Mann-Whitney foi utilizado para comparar a média do tempo de activação muscular entre os dois grupos. O teste de Friedman foi efectuado para comparar o tempo de activação entre os músculos avaliados em cada direcção de movimento (com nível de significância de 5%). Resultados: Registou-se um atraso na activação do transverso do abdómen no movimento de flexão e abdução do ombro e ainda perda da activação independente entre os músculos superficiais e profundos estudados. Conclusão: O padrão de recrutamento dos músculos abdominais associado ao movimento do ombro encontra-se alterado em indivíduos com história de dor lombopélvica aguda.

The impact of safety politics in the current globalization context

The globalization is a process of economical, social, cultural and political integration motivated by the needs generated by a consumption-orientated society and a set of factors that have led to its development, such as reducing transport costs, the technological advancement and the development of communication networks. However, the phenomenon of globalization has been accompanied by increasing levels of insecurity as a result of various types of threats and transnational crimes that the International Community seeks to control and minimize. Throughout this work, we examined how the globalization process has been developing and how nations are able to maintain security levels consistent with their economical status and social development, without disturbing the normal course of organizations’ economical activity and the well-being of people. From the investigation developed we concluded that, besides the confirmation that economic integration and the opening of markets have influence on internal consumption, market globalization and migrations have been causing modifications in the consumption habits. We also concluded that the security measures implemented by States or by the International Community affect international trade, but do not imply disproportionate costs or significant delays in transactions. Likewise, we concluded that the control measures implemented in international trade are sufficient to ensure the safety of the people and nations, enabling us to confirm two of the three conjectures raised in this study.

Application-specific modified particle swarm optimization for energy resource scheduling considering vehicle-to-grid

This paper presents a modified Particle Swarm Optimization (PSO) methodology to solve the problem of energy resources management with high penetration of distributed generation and Electric Vehicles (EVs) with gridable capability (V2G). The objective of the day-ahead scheduling problem in this work is to minimize operation costs, namely energy costs, regarding he management of these resources in the smart grid context. The modifications applied to the PSO aimed to improve its adequacy to solve the mentioned problem. The proposed Application Specific Modified Particle Swarm Optimization (ASMPSO) includes an intelligent mechanism to adjust velocity limits during the search process, as well as self-parameterization of PSO parameters making it more user-independent. It presents better robustness and convergence characteristics compared with the tested PSO variants as well as better constraint handling. This enables its use for addressing real world large-scale problems in much shorter times than the deterministic methods, providing system operators with adequate decision support and achieving efficient resource scheduling, even when a significant number of alternative scenarios should be considered. The paper includes two realistic case studies with different penetration of gridable vehicles (1000 and 2000). The proposed methodology is about 2600 times faster than Mixed-Integer Non-Linear Programming (MINLP) reference technique, reducing the time required from 25 h to 36 s for the scenario with 2000 vehicles, with about one percent of difference in the objective function cost value.

Antioxidant properties of hydroxycinnamic acids: a review of structure- activity relationships

Hydroxycinnamic acids (HCAs) are important phytochemicals possessing significant biological properties. Several investigators have studied in vitro antioxidant activity of HCAs in detail. In this review, we have gathered the studies focused on the structure-activity relationships (SARs) of these compounds that have used medicinal chemistry to generate more potent antioxidant molecules. Most of the reports indicated that the presence of an unsaturated bond on the side chain of HCAs is vital to their activity. The structural features that were reported to be of importance to the antioxidant activity were categorized as follows: modifications of the aromatic ring, which include alterations in the number and position of hydroxy groups and insertion of electron donating or withdrawing moieties as well as modifications of the carboxylic function that include esterification and amidation process. Furthermore, reports that have addressed the influence of physicochemical properties including redox potential, lipid solubility and dissociation constant on the antioxidant activity were also summarized. Finally, the pro-oxidant effect of HCAs in some test systems was addressed. Most of the investigations concluded that the presence of ortho-dihydroxy phenyl group (catechol moiety) is of significant importance to the antioxidant activity, while, the presence of three hydroxy groups does not necessarily improve the activity. Optimization of the structure of molecular leads is an important task of modern medicinal chemistry and its accomplishment relies on the careful assessment of SARs. SAR studies on HCAs can identify the most successful antioxidants that could be useful for management of oxidative stress-related diseases.

Wine and grape polyphenols — a chemical perspective

Phenolic compounds constitute a diverse group of secondary metabolites which are present in both grapes and wine. The phenolic content and composition of grape processed products (wine) are greatly influenced by the technological practice to which grapes are exposed. During the handling and maturation of the grapes several chemical changes may occur with the appearance of new compounds and/or disappearance of others, and consequent modification of the characteristic ratios of the total phenolic content as well as of their qualitative and quantitative profile. The non-volatile phenolic qualitative composition of grapes and wines, the biosynthetic relationships between these compounds, and the most relevant chemical changes occurring during processing and storage will be highlighted in this review.

Regulation of histone H2A.Z expression is mediated by sirtuin 1 in prostate cancer

Histone variants seem to play a major role in gene expression regulation. In prostate cancer, H2A.Z and its acetylated form are implicated in oncogenes’ upregulation. SIRT1, which may act either as tumor suppressor or oncogene, reduces H2A.Z levels in cardiomyocytes, via proteasome-mediated degradation, and this mechanism might be impaired in prostate cancer cells due to sirtuin 1 downregulation. Thus, we aimed to characterize the mechanisms underlying H2A.Z and SIRT1 deregulation in prostate carcinogenesis and how they interact. We found that H2AFZ and SIRT1 were up- and downregulated, respectively, at transcript level in primary prostate cancer and high-grade prostatic intraepithelial neoplasia compared to normal prostatic tissues. Induced SIRT1 overexpression in prostate cancer cell lines resulted in almost complete absence of H2A.Z. Inhibition of mTOR had a modest effect on H2A.Z levels, but proteasome inhibition prevented the marked reduction of H2A.Z due to sirtuin 1 overexpression. Prostate cancer cells exposed to epigenetic modifying drugs trichostatin A, alone or combined with 5-aza-2’-deoxycytidine, increased H2AFZ transcript, although with a concomitant decrease in protein levels. Conversely, SIRT1 transcript and protein levels increased after exposure. ChIP revealed an increase of activation marks within the TSS region for both genes. Remarkably, inhibition of sirtuin 1 with nicotinamide, increased H2A.Z levels, whereas activation of sirtuin 1 by resveratrol led to an abrupt decrease in H2A.Z. Finally, protein-ligation assay showed that exposure to epigenetic modifying drugs fostered the interaction between sirtuin 1 and H2A.Z. We concluded that sirtuin 1 and H2A.Z deregulation in prostate cancer are reciprocally related. Epigenetic mechanisms, mostly histone post-translational modifications, are likely involved and impair sirtuin 1-mediated downregulation of H2A.Z via proteasome-mediated degradation. Epigenetic modifying drugs in conjunction with enzymatic modulators are able to restore the normal functions of sirtuin 1 and might constitute relevant tools for targeted therapy of prostate cancer patients

Ligand-Induced structural changes in TEM‑1 probed by molecular dynamics and relative binding free energy calculations

The TEM family of enzymes has had a crucial impact on the pharmaceutical industry due to their important role in antibiotic resistance. Even with the latest technologies in structural biology and genomics, no 3D structure of a TEM- 1/antibiotic complex is known previous to acylation. Therefore, the comprehension of their capability in acylate antibiotics is based on the protein macromolecular structure uncomplexed. In this work, molecular docking, molecular dynamic simulations, and relative free energy calculations were applied in order to get a comprehensive and thorough analysis of TEM-1/ampicillin and TEM-1/amoxicillin complexes. We described the complexes and analyzed the effect of ligand binding on the overall structure. We clearly demonstrate that the key residues involved in the stability of the ligand (hot-spots) vary with the nature of the ligand. Structural effects such as (i) the distances between interfacial residues (Ser70−Oγ and Lys73−Nζ, Lys73−Nζ and Ser130−Oγ, and Ser70−Oγ−Ser130−Oγ), (ii) side chain rotamer variation (Tyr105 and Glu240), and (iii) the presence of conserved waters can be also influenced by ligand binding. This study supports the hypothesis that TEM-1 suffers structural modifications upon ligand binding.

Implementing slot-based task-splitting multiprocessor scheduling

Consider the problem of scheduling a set of sporadic tasks on a multiprocessor system to meet deadlines using a task-splitting scheduling algorithm. Task-splitting (also called semi-partitioning) 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 particular type of task-splitting algorithms, called slot-based task-splitting dispatching, is of particular interest because of its ability to schedule tasks with high processor utilizations. Unfortunately, no slot-based task-splitting algorithm has been implemented in a real operating system so far. In this paper we discuss and propose some modifications to the slot-based task-splitting algorithm driven by implementation concerns, and we report the first implementation of this family of algorithms in a real operating system running Linux kernel version 2.6.34. We have also conducted an extensive range of experiments on a 4-core multicore desktop PC running task-sets with utilizations of up to 88%. The results show that the behavior of our implementation is in line with the theoretical framework behind it.

Effect of hole drilling at the overlap on the strength of single-lap joints

Bonded unions are gaining importance in many fields of manufacturing owing to a significant number of advantages to the traditional fastening, riveting, bolting and welding techniques. Between the available bonding configurations, the single-lap joint is the most commonly used and studied by the scientific community due to its simplicity, although it endures significant bending due to the non-collinear load path, which negatively affects its load bearing capabilities. The use of material or geometric changes in single-lap joints is widely documented in the literature to reduce this handicap, acting by reduction of peel and shear peak stresses at the damage initiation sites in structures or alterations of the failure mechanism emerging from local modifications. In this work, the effect of hole drilling at the overlap on the strength of single-lap joints was analyzed experimentally with two main purposes: (1) to check whether or not the anchorage effect of the adhesive within the holes is more preponderant than the stress concentrations near the holes, arising from the sharp edges, and modification of the joints straining behaviour (strength improvement or reduction, respectively) and (2) picturing a real scenario on which the components to be bonded are modified by some external factor (e.g. retrofitting of decaying/old-fashioned fastened unions). Tests were made with two adhesives (a brittle and a ductile one) varying the adherend thickness and the number, layout and diameter of the holes. Experimental testing showed that the joints strength never increases from the un-modified condition, showing a varying degree of weakening, depending on the selected adhesive and hole drilling configuration.

Control of a 6-DOF parallel manipulator through a mechatronic approach

This paper shows that a hierarchical architecture, distributing several control actions in growing levels of complexity and using resources of reconfigurable computing, enables one to take into account the ease of future modifications, updates and improvements in robotic applications. An experimental example of a Stewart—Gough platform control (a platform applied as the solution to countless practical problems) is presented using reconfigurable computing. The software and hardware developed are structured in independent blocks. This open architecture implementation allows easy expansion of the system and better adaptation of the platform to its related tasks.

Sensors on mobile devices for AAL

Com o envelhecimento da população, as preocupações com a garantia do seu bem-estar aumentam criando a necessidade de desenvolver ferramentas que permitam monitorizar em permanência este sector da população. A utilização de smartphones pelos mais velhos pode ser crucial no seu bem-estar e na sua autonomia contribuindo para a recolha de informação importante já que estes estão muitas vezes equipados com sensores que podem dar indicações preciosas ao cuidador sobre o estado atual do paciente. Os sensores podem fornecer dados sobre a atividade física do paciente, bem como detetar quedas ou calcular a sua posição, com a ajuda do acelerómetro, do giroscópio e do sensor de campo magnético. No entanto, funcionalidades como essas requerem, obrigatoriamente, uma frequência de amostragem mínima por parte dos sensores que permita a implementação de algoritmos, que determinarão esses parâmetros da forma mais exata possível. Dado que nem sempre os pacientes se fazem acompanhar do seu smartphone quando estão na sua residência, a criação de ambientes de AAL (Ambient Assisted Living) com recurso a dispositivos externos que podem ser “vestidos” pelos pacientes pode também ser uma solução adequada. Estes contêm normalmente os mesmos sensores que os smartphones e comunicam com estes através de tecnologias sem fios, como é o caso do Bluetooth Low Energy. Neste trabalho, avaliou-se a possibilidade de alteração da frequência dos sensores em diferentes sistemas operativos, tendo sido efectuadas modificações nas instalações por defeito de alguns sistemas operativos abertos. Com o objectivo de permitir a criação de uma solução de AAL com recurso a um dispositivo externo implementaram-se serviços e perfis num dispositivo externo, o SensorTag.