Synthesis, characterization, electrochemical behavior and in vitro protein tyrosine kinase inhibitory activity of the cymene-halogenobenzohydroxamato [Ru(eta(6)-cymene)(bha)Cl] complexes

The ruthenium(II)-cymene complexes [Ru(eta(6)-cymene)(bha)Cl] with substituted halogenobenzohydroxamato (bha) ligands (substituents = 4-F, 4-Cl, 4-Br, 2,4-F-2, 3,4-F-2, 2,5-F-2, 2,6-F-2) have been synthesized and characterized by elemental analysis, IR, H-1 NMR, C-13 NMR, cyclic voltammetry and controlled-potential electrolysis, and density functional theory (DFT) studies. The compositions of their frontier molecular orbitals (MOs) were established by DFT calculations, and the oxidation and reduction potentials are shown to follow the orders of the estimated vertical ionization potential and electron affinity, respectively. The electrochemical E-L Lever parameter is estimated for the first time for the various bha ligands, which can thus be ordered according to their electron-donor character. All complexes exhibit very strong protein tyrosine kinase (PTK) inhibitory activity, even much higher than that of genistein, the clinically used PTK inhibitory drug. The complex containing the 2,4-difluorobenzohydroxamato ligand is the most active one, and the dependences of the PTK activity of the complexes and of their redox potentials on the ring substituents are discussed. (C) 2012 Elsevier B.V. All rights reserved.

Implications of the Intervention Program for Physical Activity (IPPA) in the perception of illness and wellbeing in people with Multiple Sclerosis (MS)

The aim of this study is to examine the implications of the IPPA in the perception of illness and wellbeing in MS patients. Methods - This is a quasi experimental study non-randomized study with 24 MS patients diagnosed at least 1 year before, and with an EDSS score of under 7. We used the IPPA in 3 groups of eight people in 3 Portuguese hospitals (Lisbon, Coimbra, and Porto). The sessions were held once a week for 90 minutes, over a period of 7 weeks. The instruments used were: We asked the subjects the question “Please classify the severity of your disease?” and used the Personal Wellbeing Scale (PWS) at the beginning (time A) and end (time B) of the IPPA. We used the SPSS version 20. A non-parametric statistical hypothesis test (Wilcoxon test) was used for the variable analysis. The intervention followed the recommendations of the Helsinki Declaration. Results – The results suggest that there are differences between time A and B, the perception of illness decreased (p<0.08), while wellbeing increased (p<0.01). Conclusions: The IPPA can play an important role in modifying the perception of disease severity and personal wellbeing.

Fat intake interacts with polymorphisms of Caspase9, FasLigand and PPARgamma apoptotic genes in modulating Crohn's disease activity

Background & aims: Crohn’s disease (CD) is a multifactorial disease where resistance to apoptosis is one major defect. Also, dietary fat intake has been shown to modulate disease activity. We aimed to explore the interaction between four single nucleotide polymorphisms (SNPs) in apoptotic genes and dietary fat intake in modulating disease activity in CD patients. Methods: Polymerase Chain Reaction (PCR) and Restriction Fragment Length Polymorphism (RFLP) techniques were used to analyze Caspase9þ93C/T, FasLigand-843C/T, Peroxisome Proliferator-Activated Receptor gammaþ161C/T and Peroxisome Proliferator-Activated Receptor gamma Pro12Ala SNPs in 99 patients with CD and 116 healthy controls. Interactions between SNPs and fat intake in modulating disease activity were analyzed using regression analysis. Results: None of the polymorphisms analyzed influenced disease susceptibility and/or activity, but a high intake of total, saturated and monounsaturated fats and a higher ratio of n-6/n-3 polyunsaturated fatty acids (PUFA), was associated with a more active phenotype (p < 0.05). We observed that the detrimental effect of a high intake of total and trans fat was more marked in wild type carriers of the Caspase9þ93C/T polymorphism [O.R (95%CI) 4.64 (1.27e16.89) and O.R (95%CI) 4.84 (1.34e17.50)]. In the Peroxisome Proliferator-Activated Receptor gamma Pro12Ala SNP, we also observed that a high intake of saturated and monounsaturated fat was associated to a more active disease in wild type carriers [OR (95%CI) 4.21 (1.33e13.26) and 4.37 (1.52e12.51)]. Finally, a high intake of n-6 PUFA was associated with a more active disease in wild type carriers for the FasLigand-843C/T polymorphism [O.R (95%CI) 5.15 (1.07e24.74)]. Conclusions: To our knowledge, this is the first study to disclose a synergism between fat intake and SNPs in apoptotic genes in modulating disease activity in CD patients.

Teatro no currículo: avaliar o quê e para quê?

Nalgumas áreas curriculares disciplinares, como o Teatro, as aprendizagens e as competências não se adquirem nem desenvolvem, em geral, de acordo com a díade de estratégias que os professores parecem privilegiar, isto é: transmissão do conhecimento e, pouco depois, confirmação – na maioria das vezes através da modalidade de escrita – da aprendizagem desse conhecimento pelos alunos. Note-se, porém, que, mesmo naquelas áreas que os responsáveis políticos distinguem com um “exame nacional”, como o Português, nem todas as aprendizagens promovidas e realizadas são testáveis numa prova escrita e no imediato (como, a título de exemplo, as que se inscrevem nos domínios da comunicação oral e da leitura em voz alta, também amplamente abordadas em Teatro). Às áreas da educação artística, e do Teatro em particular, os professores associam essencialmente – ou exclusivamente – a criatividade, a imaginação e a expressividade. Sendo, embora, competências potencialmente desenvolvidas e avaliadas também nas áreas da educação artística, não são um exclusivo destas áreas. Cada área curricular disciplinar do âmbito da educação artística – e o Teatro não é exceção – assenta numa específica linguagem artística, que integra conteúdos, estratégias, atividades, recursos, técnicas, conceitos e terminologias próprios, que as crianças, com vista ao seu desenvolvimento completo e harmonioso, têm o direito de aprender e desenvolver. Daqui decorrem algumas questões: O que – e como – avaliar nas áreas da educação artística, em particular no Teatro? Que princípios poderão estar inerentes a um dispositivo de avaliação em Teatro, em contexto curricular? Terão as modalidades de avaliação não escrita estatuto de fiabilidade? O binómio teatro/currículo encerra um paradoxo a que pretendemos dar atenção: embora nem sempre abordado com regularidade e seguindo uma lógica dedesenvolvimento curricular, o Teatro constitui, apesar disso, uma das estratégias privilegiadas pelos professores de participação em projetos e iniciativas formais, na maior parte das vezes de cariz pontual (como momentos festivos ou de apresentação à comunidade), em que os alunos são sujeitos ao juízo avaliativo dos públicos. Partindo dos princípios de que (i) em contexto curricular cada atividade tem uma intencionalidade e que (ii) a “educação” artística não visa a identificação ou a valorização de “talentos”, pretendemos defender a seguinte ideia: Só depois de estabelecermos inequivocamente os objetivos da nossa ação educativa-pedagógica e, por conseguinte, uma estratégia de avaliação, é que podemos definir um percurso com sentido. Esta comunicação de natureza teórica, cuja base reflexiva decorre de mais de vinte anos de intervenção em contextos escolares, tanto do ensino básico como de formação de professores, tentará formular questões e problematizar algumas linhas de pensamento, mais do que encontrar respostas, no sentido de suscitar, principalmente da parte dos professores, a necessidade de uma mudança de atitude e de práticas face ao teatro na escola.

Synthesis, structural characterization and leishmanicidal activity evaluation of ferrocenyl N-heterocyclic compounds

Agência Financiadora: FCT - PTDC/QUI/72656/2006 ; SFRH/BPD/27454/2006; SFRH/BPD/44082/2008; SFRH/BPD/41138/2007

Do fatigue, physical activity, handgrip strength and quality of life change between pre and post liver transplant?

Analisar: níveis de fadiga, força de preensão, HRQoL, níveis de actividade física. Será que se alteram em doentes PAF após o transplante de fígado? Dado que os níveis de actividade física se encontram abaixo dos valores mínimos recomendados deveria ser encontrada uma estratégia de aumento do tempo dispendido na actividade física leve a moderada idealmente no PRÉ TRANSPLANTE.

Psychological well-being and perception of disease severity in people with multiple sclerosis, who underwent a program of self-regulation to promote physical activity

Rehabilitation is very important for in the results of treatment in individuals with multiple sclerosis. Rehabilitation processes occur through gradual changes. These changes integrate intrinsic and extrinsic mechanisms of the individual, promoting adaptations to the needs and activities of daily living according to individual goals. Recommendations for exercise in multiple sclerosis: these recommendations apply only to patients with EDSS less than 7; moderate intensity aerobic exercise for a total of 20 to 30 minutes, twice or three times for week; the resistance training with low or moderate intensity is well tolerated by patients with MS; associated with these exercises were recommended flexibility exercises of moderate intensity, as well as strengthening exercises. The aim of this study is to examine the implications of the program of self-regulation in the perception of illness and mental health (psychological well-being domain) in multiple sclerosis patients.

Importance of program physical activity in quality of life in multiple sclerosis patients, six months after the intervention

Background: Multiple Sclerosis (MS) is a chronic disease of the central nervous system that affects more often young adults in the prime of his career and personal development, with no cure and unknown causes. The most common signs and symptoms are fatigue, muscle weakness, changes in sensation, ataxia, changes in balance, gait difficulties, memory difficulties, cognitive impairment and difficulties in problem solving MS is a relatively common neurological disorder in which various impairments and disabilities impact strongly on function and daily life activities. Purpose: The aim of this study is to examine the implications of an Intervention Program of Physical Activity (IPPA) in quality of life in MS patients, six months after the intervention.

Dynamic peripheral visual performance relates to alpha activity in soccer players

Many studies have demonstrated the relationship between the alpha activity and the central visual ability, in which the visual ability is usually assessed through static stimuli. Besides static circumstance, however in the real environment there are often dynamic changes and the peripheral visual ability in a dynamic environment (i.e., dynamic peripheral visual ability) is important for all people. So far, no work has reported whether there is a relationship between the dynamic peripheral visual ability and the alpha activity. Thus, the objective of this study was to investigate their relationship. Sixty-two soccer players performed a newly designed peripheral vision task in which the visual stimuli were dynamic, while their EEG signals were recorded from Cz, O1, and O2 locations. The relationship between the dynamic peripheral visual performance and the alpha activity was examined by the percentage-bend correlation test. The results indicated no significant correlation between the dynamic peripheral visual performance and the alpha amplitudes in the eyes-open and eyes-closed resting condition. However, it was not the case for the alpha activity during the peripheral vision task: the dynamic peripheral visual performance showed significant positive inter-individual correlations with the amplitudes in the alpha band (8-12 Hz) and the individual alpha band (IAB) during the peripheral vision task. A potential application of this finding is to improve the dynamic peripheral visual performance by up-regulating alpha activity using neuromodulation techniques.

Biodiesel production over lithium modified lime catalysts: activity and deactivation

Biodiesel production by methanolysis of semi-refined rapeseed oil was studied over lime based catalysts. In order to improve the catalysts basicity a commercial CaO material was impregnated with aqueous solution of lithium nitrate (Li/Ca = 03 atomic ratio). The catalysts were calcined at 575 degrees C and 800 degrees C, for 5 h, to remove nitrate ions before reaction. The XRD patterns of the fresh catalysts, including the bare CaO, showed lines ascribable to CaO and Ca(OH)(2). The absence of XRD lines belonging to Li phases confirms the efficient dispersion of Li over CaO. In the tested condition (W-cat/W-oil = 5%; CH3OH/oil = 12 molar ratio) all the fresh catalysts provided similar biodiesel yields (FAME >93% after 4 h) but the bare CaO catalyst was more stable. The activity decay of the Li modified samples can be related to the enhanced, by the higher basicity, calcium diglyceroxide formation during methanolysis which promotes calcium leaching. The calcination temperature for Li modified catalysts plays an important role since encourages the crystals sinterization which appears to improve the catalyst stability. (C) 2013 Elsevier B.V. All rights reserved.

Chemical composition and antioxidante activity of Tunisian Origanum glandulosum Desf. essential oil and volatile oil obtain by supercritical CO2 extraction

Dried flowers and leaves of Origanum glandulosum Desf. were submitted to hydrodistillation (HD) and supercritical fluid extraction with CO2 (SFE). The essential oils isolated by HD and volatile oils obtained by SFE were analysed by GC and GC/MS. Total phenolics content and antioxidant effectiveness were performed. The main components of the essential oils from Bargou and Nefza were: p-cymene (40.4% and 39%), thymol (38.7% and 34.4%) and γ- terpinene (12.3% and 19.2%), respectively. The major components obtain by SFE in the volatile oil, from Bargou and Nefza, were: p-cymene (32.3% and 36.2%), thymol (41% and 40%) and γ-terpinene (20.3% and 13.3%). Total phenolic content, expressed in gallic acid equivalent (GAE) g kg-1 dry weight, varied from 12 to 27 g kg-1 dw, and the ability to scavenge the DPPH radicals, expressed by IC50 ranged from 44 to143 mg L-1.

Design, synthesis and biologival evaluation of novel isoniazid derivatives with potente antitubercular activity

The disturbing emergence of multidrug-resistant strains of Mycobacterium tuberculosis (Mtb) has been driving the scientific community to urgently search for new and efficient antitubercular drugs. Despite the various drugs currently under evaluation, isoniazid is still the key and most effective component in all multi-therapeutic regimens recommended by the WHO. This paper describes the QSAR-oriented design, synthesis and in vitro antitubercular activity of several potent isoniazid derivatives (isonicotinoyl hydrazones and isonicotinoyl hydrazides) against H37Rv and two resistant Mtb strains. QSAR studies entailed RFs and ASNNs classification models, as well as MLR models. Strict validation procedures were used to guarantee the models' robustness and predictive ability. Lipophilicity was shown not to be relevant to explain the activity of these derivatives, whereas shorter N-N distances and lengthy substituents lead to more active compounds. Compounds I, 2, 4, 5 and 6, showed measured activities against H37Rv higher than INH (i.e., MIC <= 0.28 mu M), while compound 9 exhibited a six fold decrease in MIC against the katG (S315T) mutated strain, by comparison with INH (Le., 6.9 vs. 43.8 mu M). All compounds were ineffective against H37Rv(INH) (Delta katG), a strain with a full deletion of the katG gene, thus corroborating the importance of KatG in the activation of INH-based compounds. The most potent compounds were also shown not to be cytotoxic up to a concentration 500 times higher than MIC. (C) 2014 Elsevier Masson SAS. All rights reserved.

Halogen-bonded tris (2,4-Bis(trichloromethyl)-1,3,5,triazapentadienato)-M(III) [M = Mn, Fe, Co] complexes and their catalytic activity in the peroxidative oxidation of 1-phenylethanol to acetophenone

One-pot template condensation of CCl3C=N with ammonia on a metal source [MnCl2 center dot 4H(2)O, FeCl3 center dot 6H(2)O or Co(CH3COO)(2)center dot 4H(2)O] in DMSO led to the formation of tris(2,4-bis(trichloromethyl)-1,3,5-triazapentadienato)-M(III) complexes, [M(NH=C(CCl3)NC(CCl3)=-NH}(3)]center dot n(CH3)(2)SO [M = Mn, n = 1 (1); M = Fe, n = 2 (2); M = Co, n = 2 (3)1, which were characterized using elemental analysis, and IR, ESI-MS and single-crystal X-ray analysis. The role of inter- and intramolecular non-covalent halogen and hydrogen bonds in the synthesis of 1-3 is discussed. It is shown that the crystal ionic radii of the metal ions [68.5 (Co) < 69 (Fe) < 72 (Mn), pm] are related to the corresponding Cl center dot center dot center dot Cl distances [3.178 (3) > 3.155 (2) > 3.133 (1) Al. Compounds 1-3 and the related di(triazapentadienato)-Cu(v) complex [Cu(NH=C(CCl3)NC(CCl3)=NH}2]center dot 2(CH3)(2)SO (4) act as catalyst precursors for the additive-free microwave (MW) assisted homogeneous oxidation of 1-phenylethanol with tert-butylhydroperoxide (TBHP), leading to the formation of acetophenone with yields up to 99% and TONs up to 5.0 x 10(3) after 1 h of low power (10 W) MW irradiation.

New iron(II) cyclopentadienyl derivative complexes: synthesis and antitumor activity against human leucemia cancer cells

A new family of "Fe-II(eta(5)-C5H5)" half sandwich compounds bearing a N-heteroaromatic ligand coordinated to the iron center by a nitrile functional group has been synthesized and fully characterized by NMR and UV-Vis spectroscopy. X-ray analysis of single crystal was achieved for complexes 1 and 3, which crystallized in the monoclinic P2(1)/c and monoclinic P2(1)/n space groups, respectively. Studies of interaction of these five new complexes with plasmid pBR322 DNA by atomic force microscopy showed very strong and different types of interaction. Antiproliferative tests were examined on human leukemia cancer cells (HL-60) using the MTT assay, and the IC50 values revealed excellent antiproliferative activity compared to cisplatin. (C) 2014 Elsevier B.V. All rights reserved.

New water-soluble Ruthenium(II) cytotoxic complex: biological activity and celular distribution

A novel water soluble organometallic compound, [RuCp(mTPPMSNa)(2,2'-bipy)][CF3SO3] (TM85, where Cp=eta(5)-cyclopentadienyl, mTPPMS = diphenylphosphane-benzene-3-sulfonate and 2,2'-bipy = 2,2'-bipyridine) is presented herein. Studies of interactions with relevant proteins were performed to understand the behavior and mode of action of this complex in the biological environment. Electrochemical and fluorescence studies showed that TM85 strongly binds to albumin. Studies carried out to study the formation of TM85 which adducts with ubiquitin and cytochrome c were performed by electrospray ionization mass spectrometry (ESI-MS). Antitumor activity was evaluated against a variety of human cancer cell lines, namely A2780, A2780cisR, MCF7, MDAMB231, HT29, PC3 and V79 non-tumorigenic cells and compared with the reference drug cisplatin. TM85 cytotoxic effect was reduced in the presence of endocytosis modulators at low temperatures, suggesting an energy-dependent mechanism consistent with endocytosis. Ultrastructural analysis by transmission electron microscopy (TEM) revealed that TM85 targets the endomembranar system disrupting the Golgi and also affects the mitochondria. Disruption of plasma membrane observed by flow cytometry could lead to cellular damage and cell death. On the whole, the biological activity evaluated herein combined with the water solubility property suggests that complex TM85 could be a promising anticancer agent. (C) 2013 Elsevier Inc. All rights reserved.