Cobalt and Zinc Compounds Bearing 1,10-Phenanthroline-5,6-dione or 1,3,5-Triaza-7-phosphaadamantane Derivatives - Synthesis, Characterization, Cytotoxicity, and Cell Selectivity Studies

The compounds [mPTA][CoCl4] (1, mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane cation), [CoCl(H2O)(DION)(2)][BF4] (2, DION = 1,10-phenanthroline-5,6-dione), [Zn(DION)(2)]Cl-2 (3) and [ZnCl(O-PTA=O)(DION)][BF4] (4) were synthesized by reaction of CoCl2 with [mPTA]I or DION and ZnCl2 with DION or 1,3,5-triaza-7-phosphaadamantane-7-oxide (PTA=O) and DION, respectively. All complexes are water soluble and have been characterized by IR, far-IR, H-1, C-13 and P-31{H-1} NMR spectroscopy, ESI-MS, elemental analyses and single-crystal X-ray diffraction structural analysis (for 1). They were screened against the human tumour cell lines HCT116, HepG2 and MCF7. Complexes 2 and 3 exhibit the highest in vitro cytotoxicity and show lower cytotoxic activities in normal human fibroblast cell line than in HCT116 tumour cell line, which demonstrates their slight specificity for this type of tumour cell.

Insights into the mechanims underlyng the antiproliferative potential of a Co(II) coordination compound bearing 1,10-Phenanthroline-5,6-Dione: DNA and protein interaction studies

The very high antiproliferative activity of [Co(Cl)(H2O)(phendione)(2)][BF4] (phendione is 1,10-phenanthroline-5,6-dione) against three human tumor cell lines (half-maximal inhibitory concentration below 1 mu M) and its slight selectivity for the colorectal tumor cell line compared with healthy human fibroblasts led us to explore the mechanisms of action underlying this promising antitumor potential. As previously shown by our group, this complex induces cell cycle arrest in S phase and subsequent cell death by apoptosis and it also reduces the expression of proteins typically upregulated in tumors. In the present work, we demonstrate that [Co(Cl)(phendione)(2)(H2O)][BF4] (1) does not reduce the viability of nontumorigenic breast epithelial cells by more than 85 % at 1 mu M, (2) promotes the upregulation of proapoptotic Bax and cell-cycle-related p21, and (3) induces release of lactate dehydrogenase, which is partially reversed by ursodeoxycholic acid. DNA interaction studies were performed to uncover the genotoxicity of the complex and demonstrate that even though it displays K (b) (+/- A standard error of the mean) of (3.48 +/- A 0.03) x 10(5) M-1 and is able to produce double-strand breaks in a concentration-dependent manner, it does not exert any clastogenic effect ex vivo, ruling out DNA as a major cellular target for the complex. Steady-state and time-resolved fluorescence spectroscopy studies are indicative of a strong and specific interaction of the complex with human serum albumin, involving one binding site, at a distance of approximately 1.5 nm for the Trp214 indole side chain with log K (b) similar to 4.7, thus suggesting that this complex can be efficiently transported by albumin in the blood plasma.

Copper-organic frameworks assembled from in situ generated 5-(4-pyridyl) tetrazole building blocks: synthesis, structural features, topological analysis and catalytic oxidation of alcohols

Two new metal- organic compounds {[Cu-3(mu(3)-4-(p)tz)(4)(mu(2)-N-3)(2)(DMF)(2)](DMF)(2)}(n) (1) and {[Cu(4ptz) (2)(H2O)(2)]}(n) (2) {4-ptz = 5-(4-pyridyl)tetrazolate} with 3D and 2D coordination networks, respectively, have been synthesized while studying the effect of reaction conditions on the coordination modes of 4-pytz by employing the [2 + 3] cycloaddition as a tool for generating in situ the 5-substituted tetrazole ligands from 4-pyridinecarbonitrile and NaN3 in the presence of a copper(II) salt. The obtained compounds have been structurally characterized and the topological analysis of 1 discloses a topologically unique trinodal 3,5,6-connected 3D network which, upon further simplification, results in a uninodal 8-connected underlying net with the bcu (body centred cubic) topology driven by the [Cu-3(mu(2)-N-3)(2)] cluster nodes and mu(3)-4-ptz linkers. In contrast, the 2D metal-organic network in 2 has been classified as a uninodal 4-connected underlying net with the sql [Shubnikov tetragonal plane net] topology assembled from the Cu nodes and mu(2)-4-ptz linkers. The catalytic investigations disclosed that 1 and 2 act as active catalyst precursors towards the microwave-assisted homogeneous oxidation of secondary alcohols (1-phenylethanol, cyclohexanol, 2-hexanol, 3-hexanol, 2-octanol and 3-octanol) with tert-butylhydroperoxide, leading to the yields of the corresponding ketones up to 86% (TOF = 430 h(-1)) and 58% (TOF = 290 h(-1)) in the oxidation of 1-phenylethanol and cyclohexanol, respectively, after 1 h under low power ( 10 W) microwave irradiation, and in the absence of any added solvent or additive.

Aspectos psicossociais associados à percepção da dor pós-operatória em indivíduos submetidos a cirurgia coronária

Objectivo: Identificar os factores psicossociais que influenciam a percepção da dor pós-operatória em doentes submetidos a cirurgia de revascularização do miocárdio (CRM). Material e Métodos: Estudo exploratório correlacional de 91 doentes (71 homens e 20 mulheres) submetidos a CRM (pontagem aortocoronária) por esternotomia). A idade média era de 63,8 ± 9,6 anos (entre 39 e 84). Foram utilizados os seguintes instrumentos: Escala Analógica Visual às 24, 48 e 96 horas do pós-operatório; Questionário de Caracterização Demográfica; Mental Health Inventory de 5 itens; Percepção de Saúde Geral (SF-36); Escala de Expectativas de Dor; Escala de Percepção de Apoio; Escala de Expectativas de Auto-eficácia; Satisfação com o tratamento, médicos e enfermeiros (American Pain Society Questionnaire) aplicados às 96 horas após a cirurgia. Resultados: Os doentes que apresentaram expectativas elevadas de dor, percepcionaram maior apoio, apresentaram níveis elevados de auto-eficácia para lidar com a dor ou, se pertenciam ao sexo masculino, sentiram menos dor. De igual modo, os doentes que apresentaram melhor saúde mental, percepcionaram a sua saúde como boa e os doentes que expressaram maior satisfação com o tratamento sentiram menos dor. A dor não foi influenciada pela idade, grau de escolaridade ou pela satisfação com a conduta de médicos e enfermeiros. Conclusão: Após as primeiras 48 horas do pós-operatório, a experiência de dor é influenciada por factores psicossociais, em oarticular pela expectativa de dor, expectativa de auto-eficácia, apoio percebido, percepção da saúde geral, percepção de saúde mental e satisfação com o tratamento para a dor. Perante os resultados, evidencia-se a necessidade de conjugar conhecimentos no sentido de dar respostas mais alargadas e de carácter multidisciplinar no tratamento da dor pós-operatória em CRM devendo, a par de outros aspectos, focar-se na gestão das expectativas dos doentes. ABSTRACT - Objective: To identify the psychological factors that influence post-surgery pain perception in patients undergoing coronary artery bypass graft surgery (CABG). Methods: This was an exploratory correlational study of 91 patients (71 men and 20 women) who underwent CABG (aortocoronary anastomosis) by sternotomy. Mean age was 63.8 ± 9.6 years (between 39 and 84). The following instruments were used: visual analogical scales at 24, 48 and 96 hours of post-surgery; demographic characteristics survey; pain expectations scale; perceived support scale; self-efficacy scale, Mental Inventory (5 items); health perception scale; and satisfaction with treatment, doctors and nurses (American Pain Society questionnaire) at 96 hours after surgery. Results: Patients who had presented high expectations of pain, perceived more support, presented high levels of self-efficacy to deal with pain or were male, felt less pain. Furthermore, patients who presented better mental health, perceived their general health as being good, or expressed greater satisfaction with treatment, felt less pain. Pain was not influenced by age, level of education or satisfaction with doctors and nurses. Conclusion: After the first 48 hours following surgery, the pain experience is influenced by psychosocial factors, in particular by expectation of pain and of self-efficacy, perceived support, perception of general and mental health, and satisfaction with pain treatment. The results confirm the need to bring together different kinds of knowledge for a broad, multidisciplinary approach to postoperative CABG pain treatment, focusing, along with other aspects, on management of patients’ expectations.

Superprodução, purificação e caracterização parcial de complexos proteína-polissacáridos inovadores a partir de estirpes de basidiomicetos

O presente trabalho teve como objectivo o estudo de meios de cultura, tendo em vista a superprodução de complexos proteína-polissacáridos, intracelulares e extracelulares, a partir dos basidiomicetos Pleurotus ostreatus e Lentinula edodes. O meio de cultura suplementado com soro de leite apresentou diversas vantagens para a obtenção dessas macromoléculas biológicas, face aos restantes meios analisados, pelo que foi seleccionado para a produção em fermentador de laboratório em regime descontínuo. O crescimento da cultura foi efectuado a 28°C, 200 rpm e durante 10 dias, e as produtividades de complexos proteína-polissacáridos obtidas para o Pleurotus ostreatus foram de 0,008 ± 8,12 x 10-5 g/(L.dia) e de 0,324 ± 0,005 g/(L.dia), para os complexos precipitados a partir da biomassa e do caldo de fermentação, respectivamente. Posteriormente, os complexos intracelulares e extracelulares foram purificados por cromatografia de filtração em gel e parcialmente caracterizados, revelando concentrações de polissacáridos superiores à concentração proteica, pseudo-actividade de superóxido dismutase, e valores de Mr entre 64 e 9 000kDa. As amostras de complexos proteína-polissacáridos foram caracterizadas por HPLC e apresentaram picos de UV e IR com tempos de retenção de aproximadamente 6 e 12 minutos, respectivamente. Após hidrólise ácida, os complexos heteropolissacáridos obtidos apresentaram na sua constituição glucose, ramnose e arabinose. Adicionalmente, a análise dos complexos proteína-polissacáridos por FT-IR revelou bandas de absorção características destas macromoleculas biológicas, designadamente, a 846,5; 1032,3; 1186,4; 1471,0; 1648,8; 2739,6 e 3419,3 cm-1 para o Pleurotus ostreatus e 862,3; 1044,1; 1474,9; 1644,8; 2372,0; 2992,5; e 3415,4 cm-1 para Lentinula edodes.

Aeroporto de Lisboa: acessibilidades à estação de metro "Aeroporto"

O presente relatório enquadra-se no âmbito do Trabalho Final de Mestrado inserido no Mestrado em Engenharia Civil, do perfil de Estruturas, no Instituto Superior de Engenharia de Lisboa (ISEL). Para tal, foi realizado um estágio curricular com a duração de 23 semanas pela empresa BRITALAR – Sociedade de Construções S.A. na obra pública designada por AEROPORTO DE LISBOA – Acessibilidades à Estação do Metro “Aeroporto”, cujo promotor é a ANA – Aeroportos de Portugal S.A., e tendo como grande objectivo a ligação do metropolitano ao aeroporto. Sendo a área de especialização Estruturas, foi definido como meta para o relatório, abordar duas das grandes vertentes da Engenharia Civil, o Dimensionamento e a Construção. Na fase inicial do relatório, mais precisamente no capítulo 2, será feito um enquadramento geral da obra, no qual serão expostos os traços gerais da mesma. No que diz respeito ao Dimensionamento, no capítulo 3 serão apresentados todos os aspectos que serviram de base para efectuar o projecto, como Acções, Combinações de Acções e Materiais, para posteriormente realizar-se a Modelação Estrutural e consequente Dimensionamento Estrutural desenvolvido no capítulo 4. Relativamente à Construção, nos capítulos 5, 6 e 7 será feita uma comparação a vários níveis entre estacas e micro-estacas, abordar-se-á a evolução construtiva ao longo de todo o período do estágio, assim como as problemáticas que assumiram especial relevância no decorrer da execução da obra. Para terminar, o capítulo 8, expõe as principais actividades realizadas enquanto membro estagiário.

Solubility of red 153 and blue 1 in supercritical carbon dioxide

Solubilities of red 153, (3-[[4-[[5,6(or 6,7)-dichloro-2-benzothiazolyl]azo]phenyl]ethylamino]propanenitrile), an azo compound, and disperse blue1 (1,4,5,8-tetraaminoantraquinone) in supercritical carbon dioxide (SC CO(2)) were measured at T = (333.2 to 393.2) K over the pressure range (12.0 to 40.0) MPa by a flow type apparatus. The solubility of red 153 (0.985. 10(-6) to 37.2. 10(-6)) in the overall region of measurements is found to be significantly higher than that of disperse blue 1 (1.12.10(-7) to 4.89.10(-7)). The solubility behavior of disperse red 153 follows the general solubility trend displayed by disperse dyes with a crossover pressure at about 20 MPa. On the other hand, blue 1, which is a disperse anthraquinone dye, exhibits unexpected behavior not recorded previously there is no crossover pressure at the temperature and pressure ranges studied, and the dye's solubility at T = 333.2 K practically does not increase with pressure. To the best of our knowledge, there are no previous measurements of blue 1 solubility in SC CO(2) reported in the literature. The experimental data were correlated by using the Soave Redlich Kwong equation of state (EoS) with the one-fluid van der Waals mixing rule, and an acceptable correlation of the solubility data for both dyes was obtained.

Comparison of Py-GC/FID and Wet Chemistry Analysis for Lignin Determination in Wood and Pulps from Eucalyptus globulus

The kraft pulps produced from heartwood and sapwood of Eucalyptus globulus at 130 degrees C, 150 degrees C, and 170 degrees C were characterized by wet chemistry (total lignin as sum of Klason and soluble lignin fractions) and pyrolysis (total lignin denoted as py-lignin). The total lignin content obtained with both methods was similar. In the course of delignification, the py-lignin values were higher (by 2 to 5%) compared to Klason values, which is in line with the importance of soluble lignin for total lignin determination. Pyrolysis analysis presents advantages over wet chemical procedures, and it can be applied to wood and pulps to determine lignin contents at different stages of the delignification process. The py-lignin values were used for kinetic modelling of delignification, with very high predictive value and results similar to those of modelling using wet chemical determinations.

Monte Carlo simulation of the basic features of the GE Millennium MG single photon emission computed tomography gamma camera

Objective - To describe and validate the simulation of the basic features of GE Millennium MG gamma camera using the GATE Monte Carlo platform. Material and methods - Crystal size and thickness, parallel-hole collimation and a realistic energy acquisition window were simulated in the GATE platform. GATE results were compared to experimental data in the following imaging conditions: a point source of 99mTc at different positions during static imaging and tomographic acquisitions using two different energy windows. The accuracy between the events expected and detected by simulation was obtained with the Mann–Whitney–Wilcoxon test. Comparisons were made regarding the measurement of sensitivity and spatial resolution, static and tomographic. Simulated and experimental spatial resolutions for tomographic data were compared with the Kruskal–Wallis test to assess simulation accuracy for this parameter. Results - There was good agreement between simulated and experimental data. The number of decays expected when compared with the number of decays registered, showed small deviation (≤0.007%). The sensitivity comparisons between static acquisitions for different distances from source to collimator (1, 5, 10, 20, 30cm) with energy windows of 126–154 keV and 130–158 keV showed differences of 4.4%, 5.5%, 4.2%, 5.5%, 4.5% and 5.4%, 6.3%, 6.3%, 5.8%, 5.3%, respectively. For the tomographic acquisitions, the mean differences were 7.5% and 9.8% for the energy window 126–154 keV and 130–158 keV. Comparison of simulated and experimental spatial resolutions for tomographic data showed no statistically significant differences with 95% confidence interval. Conclusions - Adequate simulation of the system basic features using GATE Monte Carlo simulation platform was achieved and validated.

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

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.

New RuII(arene) complexes with halogen-substituted bis- and tris(pyrazol-1-YL)borate ligands

[RuCl(arene)(-Cl)](2) dimers were treated in a 1:2 molar ratio with sodium or thallium salts of bis- and tris(pyrazolyl)borate ligands [Na(BpBr3)], [Tl(TpBr3)], and [Tl(Tp(iPr,4Br))]. Mononuclear neutral complexes [RuCl(arene)((2)-BpBr3)] (1: arene=p-cymene (cym); 2: arene=hexamethylbenzene (hmb); 3: arene=benzene (bz)), [RuCl(arene)((2)-TpBr3)] (4: arene=cym; 6: arene=bz), and [RuCl(arene)((2)-Tp(iPr,4Br))] (7: arene=cym, 8: arene=hmb, 9: arene=bz) have been always obtained with the exception of the ionic [Ru-2(hmb)(2)(-Cl)(3)][TpBr3] (5), which formed independently of the ratio of reactants and reaction conditions employed. The ionic [Ru(CH3OH)(cym)((2)-BpBr3)][X] (10: X=PF6, 12: X=O3SCF3) and the neutral [Ru(O2CCF3)(cym)((2)-BpBr3)] (11) have been obtained by a metathesis reaction with corresponding silver salts. All complexes 1-12 have been characterized by analytical and spectroscopic data (IR, ESI-MS, H-1 and (CNMR)-C-13 spectroscopy). The structures of the thallium and calcium derivatives of ligand TpBr3, [Tl(TpBr3)] and [Ca(dmso)(6)][TpBr3](2)2DMSO, of the complexes 1, 4, 5, 6, 11, and of the decomposition product [RuCl(cym)(Hpz(iPr,4Br))(2)][Cl] (7) have been confirmed by using single-crystal X-ray diffraction. Electrochemical studies showed that 1-9 and 11 undergo a single-electron (RuRuIII)-Ru-II oxidation at a potential, measured by cyclic voltammetry, which allows comparison of the electron-donor characters of the bis- and tris(pyrazol-1-yl)borate and arene ligands, and to estimate, for the first time, the values of the Lever E-L ligand parameter for BpBr3, TpBr3, and Tp(iPr,4Br). Theoretical calculations at the DFT level indicated that both oxidation and reduction of the Ru complexes under study are mostly metal-centered with some involvement of the chloride ligand in the former case, and also demonstrated that the experimental isolation of the (3)-binuclear complex 5 (instead of the mononuclear 5) is accounted for by the low thermodynamic stability of the latter species due to steric reasons.