Studies of the Antiproliferative Activity of Ruthenium (II) Cyclopentadienyl-Derived Complexes with Nitrogen Coordinated Ligands

Four cationic ruthenium(II) complexes with the formula [Ru(eta(5)-C5H5)(PPh3)(2)](+), with L = 5-phenyl-1H-tetrazole (TzH) 1, imidazole (ImH) 2, benzo[1,2-b; 4,3-b'] dithio-phen-2-carbonitrile (Bzt) 3, and [5-(2-thiophen-2-yl)-vinyl]-thiophene-2-carbonitrile] (Tvt) 4 were prepared and characterized in view to evaluate their potentialities as antitumor agents. Studies by Circular Dichroism indicated changes in the secondary structure of ct-DNA. Changes in the tertiary structure of pBR322 plasmid DNA were also observed in gel electrophoresis experiment and the images obtained by atomic force microscopy (AFM) suggest strong interaction with pBR322 plasmid DNA; the observed decreasing of the viscosity with time indicates that the complexes do not intercalate between DNA base pairs. Compounds 1, 2, and 3 showed much higher cytotoxicity than the cisplatin against human leukaemia cancer cells (HL-60 cells).

Studies in 3-oxy-assisted 3-aza Cope rearrangements

On thermolysis appropriately substituted N-silyloxy-N-allyl enamines undergo smooth 3,3-sigmatropic rearrangments to the corresponding N-silyloxy imino ethers.

Educação inclusiva : necessidades de formação de professores do 1º ciclo do ensino básico em meio rural

Este estudo, de natureza qualitativa, visa em primeiro lugar a identificação de necessidades de formação contínua de docentes do 1º ciclo do ensino básico, decorrentes da inclusão de alunos com necessidades educativas especiais (N.E.E.) em escolas de meio rural. Pretende ainda criar linhas orientadoras para a construção de um dispositivo de formação contínua que possa contribuir para o desenvolvimento de capacidades, atitudes e conhecimentos relacionados com a inclusão de alunos com N.E.E. Utilizámos a entrevista semi - directiva, de forma a conhecer a percepção que os professores têm sobre as suas necessidades formativas e recorremos a observações naturalistas, de modo a identificar necessidades decorrentes da prática, através da análise de situações reais de aprendizagem em salas de aula inclusivas. Foram entrevistados 8 professores, tendo sido observadas as aulas de dois desses professores. A partir do cruzamento dos dados obtidos por ambas as técnicas, identificámos um conjunto de preocupações, dificuldades, aspirações/desejos relacionados com a inclusão e ainda carências formativas relacionadas com as N.E.E. As entrevistas permitiram-nos explorar, de uma forma geral, a percepção que os professores tinham das suas necessidades, ou seja as necessidades percebidas, enquanto que as observações nos possibilitaram a identificação das necessidades da prática, necessidades inferidas. No presente estudo, foi possível concluir que as observações constituem um meio privilegiado para a identificação de necessidades de formação, ao nível da prática pedagógica de uma sala de aula, na medida em que os professores, nas entrevistas, não expressaram algumas das dificuldades observadas e não identificaram um conjunto de carências formativas que a análise da observação sugere. Partindo dos resultados obtidos, foi possível enumerar as principais necessidades de formação contínua decorrentes da inclusão e propor um dispositivo de formação contínua, apoiado na observação e supervisão, que julgamos poder dar resposta às necessidades formativas dos professores encontradas no presente estudo.

Structural and Microanalytical Studies of CrO2 Thin Films on c-Sapphire by High Resolution Electron Microscopy Methods

Chromium dioxide (CrO2) has been extensively used in the magnetic recording industry. However, it is its ferromagnetic half-metallic nature that has more recently attracted much attention, primarily for the development of spintronic devices. CrO2 is the only stoichiometric binary oxide theoretically predicted to be fully spin polarized at the Fermi level. It presents a Curie temperature of ∼ 396 K, i.e. well above room temperature, and a magnetic moment of 2 mB per formula unit. However an antiferromagnetic native insulating layer of Cr2O3 is always present on the CrO2 surface which enhances the CrO2 magnetoresistance and might be used as a barrier in magnetic tunnel junctions.

Structural and optical studies of Au doped titanium oxide films

Thin films of TiO2 were doped with Au by ion implantation and in situ during the deposition. The films were grown by reactive magnetron sputtering and deposited in silicon and glass substrates at a temperature around 150 degrees C. The undoped films were implanted with Au fiuences in the range of 5 x 10(15) Au/cm(2)-1 x 10(17) Au/cm(2) with a energy of 150 keV. At a fluence of 5 x 10(16) Au/cm(2) the formation of Au nanoclusters in the films is observed during the implantation at room temperature. The clustering process starts to occur during the implantation where XRD estimates the presence of 3-5 nm precipitates. After annealing in a reducing atmosphere, the small precipitates coalesce into larger ones following an Ostwald ripening mechanism. In situ XRD studies reveal that Au atoms start to coalesce at 350 degrees C, reaching the precipitates dimensions larger than 40 nm at 600 degrees C. Annealing above 700 degrees C promotes drastic changes in the Au profile of in situ doped films with the formation of two Au rich regions at the interface and surface respectively. The optical properties reveal the presence of a broad band centered at 550 nm related to the plasmon resonance of gold particles visible in AFM maps. (C) 2011 Elsevier B.V. All rights reserved.

Coordination Chemistry of the (eta(6)-p-Cymene)ruthenium(II) Fragment with Bis-, Tris-, andTetrakis(pyrazol-1-yl)borate Ligands: Synthesis, Structural, Electrochemical, and CatalyticDiastereoselective Nitroaldol Reaction Studies

Novel [Ru(eta(6)-p-cymene)(kappa(2)-L)X] and [Ru(eta(6)-p-cymene)(kappa(3)-L)]X center dot nH(2)O complexes (L = bis-, tris-, or tetrakis-pyrazolylborate; X = Cl, N-3, PF6, or CF3SO3) are prepared by treatment of [Ru(eta(6)-p-cymene)Cl-2](2) with poly-(pyrazolyl)borate derivatives [M(L)] (L in general; in detail L = Ph(2)Bp = diphenylbis-(pyrazol-1-yl)borate; L = Tp = hydrotris(pyrazol-1-yl)borate; L = pzTp = tetrakis(pyrazol-1-yl)borate; L = Tp(4Bo) = hydrotris(indazol-1-yl)borate, L = T-p4Bo,T-5Me = (5-methylindazol-1-yl)borate; L = Tp(Bn,4Ph) = hydrotris(3-benzyl-4-phenylpyrazol-1-yl)borate; M = Na, K, or TI) and characterized by analytical and spectral data (IR, ESIMS, H-1 and C-13 NMR). The structures of [Ru(eta(6)-p-cymene)(Ph(2)Bp)Cl] (1) and [Ru(eta(6)-p-cymene)(Tp)Cl] (3) have been established by single-crystal X-ray diffraction analysis. Electrochemical studies allowed comparing the electron-donor characters of Tp and related ligands and estimating the corresponding values of the Lever E-L ligand parameter. The complexes [Ru(eta(6)-p-cymene)-(kappa(2)-L)X] and [Ru(eta(6)-p-cymene)(kappa(3)-L)]X center dot nH(2)O act as catalyst precursors for the diastereoselective nitroaldol reaction of benzaldehyde and nitroethane to the corresponding beta-nitroalkanol (up to 82% yield, at room temperature) with diastereoselectivity toward the formation of the threo isomer.

DNA interaction and cytotoxicity studies of new ruthenium(II) cyclopentadienyl derivative complexescontaining heteroaromatic ligands

Four ruthenium(II) complexes with the formula [Ru(eta(5)-C(5)H(5))(PP)L][CF(3)SO(3)], being (PP = two triphenylphosphine molecules), L = 1-benzylimidazole, 1; (PP = two triphenylphosphine molecules), L = 2,2'bipyridine, 2; (PP = two triphenylphosphine molecules), L = 4-Methylpyridine, 3; (PP = 1,2-bis(diphenylphosphine) ethane), L = 4-Methylpyridine, 4, were prepared, in view to evaluate their potentialities as antitumor agents. The compounds were completely characterized by NMR spectroscopy and their crystal and molecular structures were determined by X-ray diffraction. Electrochemical studies were carried out giving for all the compounds quasi-reversible processes. The images obtained by atomic force microscopy (AFM) suggest interaction with pBR322 plasmid DNA. Measurements of the viscosity of solutions of free DNA and DNA incubated with different concentrations of the compounds confirmed this interaction. The cytotoxicity of compounds 1234 was much higher than that of cisplatin against human leukemia cancer cells (HL-60 cells). IC(50) values for all the compounds are in the range of submicromolar amounts. Apoptotic death percentage was also studied resulting similar than that of cisplatin. (C) 2010 Elsevier Inc. All rights reserved.

Representações dos técnicos de intervenção precoce sobre as famílias e práticas de IP em contexto rural e urbano

O presente estudo visou caraterizar as representações que técnicos de intervenção precoce têm sobre famílias que vivem em meio rural e em meio urbano que recebem apoio das equipas. Foram realizadas entrevistas semi-diretivas, os participantes e entrevistados foram dez docentes com intervenção educativa nas equipas, cinco em apoio direto a famílias de meio rural e cinco a realizar intervenções com famílias de meio urbano. Deste estudo resultaram vários dados qualitativos que depois de analisados e discutidos, levaram a diversas conclusões que vem dar respostas às questões e problemática iniciais. As famílias inseridas nestes contextos têm características que as diferenciam; habilitações, recursos, necessidades e comportamentos em comunidade. Tem aspetos culturais que influenciam as suas atitudes, participação e autonomia e são ou não decisivas no desenvolvimento da criança. Em contexto rural as famílias apresentam um maior número de necessidades comparativamente às famílias de meio urbano. As maiores necessidades das famílias em contexto rural situam-se nas questões financeiras, de formação e apoio técnico e especializado. As maiores necessidades das famílias de contexto urbano situam-se ao nível do fraco apoio familiar e das redes sociais. As necessidades comuns situam-se nas necessidades de informação e promoção da autonomia e competências parentais. As visitas e intervenções domiciliares podem permitir melhorar a identificação das necessidades e recursos das famílias e compreender melhor os critérios de referência de algumas crianças. As oportunidades de aprendizagem são maiores nestes encontros em domicílio, estão presentes em muitos casos, elementos da família alargada, que muitas vezes tem um papel fundamental na educação e estimulação destas crianças. Os docentes de IP em intervenção em contexto urbano, comparativamente com os docentes inseridos em contexto rural, apoiam famílias que na generalidade abrangem áreas profissionais mais vantajosas financeiramente. Estas famílias terão á partida melhores condições para aceder a mais recursos e apoios. Nos dois contextos existe uma necessidade comum, falta de informação e alguma autonomia e competências parentais em relação ao crescimento das crianças. A realização de iii encontros de pais ou criação de grupos de pais que tenham por base a partilha de experiencias e informação, estão planeadas mas não são uma realidade nestas equipas. Nas práticas de qualidade, o profissional deve atuar nos contextos naturais como, a família, ou a comunidade, mas pode incluir também rotinas, brincadeiras, festas etc. cenários que facilitem o dia-a-dia. As famílias têm contextos e rotinas próprias que os profissionais devem identificar, os dados que recolhemos indicam essa necessidade de proceder a avaliação mais atenta das necessidades das famílias. As práticas recomendadas e o enquadramento legislativo são tidos em conta pelos docentes e profissionais das equipas, os recursos documentais são na sua maioria comuns, a todas as equipas participantes, seguindo as orientações e documentos/minutas facultadas pela comissão coordenadora do SNIPI (Sistema Nacional de Intervenção Precoce na Infância) Apesar das recomendações teóricas para práticas de qualidade centradas na família, verificamos que estas fazem parte das preocupações destes docentes, mas nem sempre são implementadas. A problemática da criança parece ser ainda o ponto mais importante dos programas e planos de intervenção e mesmo o critério decisivo para delinear a duração e frequência das intervenções, seja em contexto urbano ou rural. - ABSTRACT This study aimed to characterize the families of rural and urban areas that receive support from Early Intervention Teams. It has been proposed yet whether professionals IP suit their practices to the characteristics of these families and communities integrated in different cultural contexts. Interviews were conducted semidirective, participants were ten respondents and teachers with educational intervention teams, five in direct support to families in rural areas and five interventions with families in urban areas. This study resulted in a number of qualitative data that then analyzed and discussed, led to several conclusions that comes to answer the questions and problems early. The families included in these contexts have characteristics that differentiate them; qualifications, resources, needs and behaviors in the community. Has cultural aspects that influence their attitudes, participation and autonomy and are not decisive in the development of the child. In the rural households have a greater number of needs compared to urban families. The greatest needs of families in rural settings are located in financial matters, training and technical support and expertise. The greatest needs of the urban households are located at the level of weak family support and social networks. Common needs lie in information needs and promoting autonomy and parenting skills. The home visits and interventions may allow improved identification of needs and resources of families and understand the benchmarks of some children. Learning opportunities are greater in these meetings at home, are present in many cases, elements of the extended family, which often plays a key role in education and stimulation of these children. Teachers IP intervention in the urban compared with rural teachers placed in context, support families in general include professional areas more financially advantageous. These families will have better starting conditions for access to more resources and support. In both contexts there is a common need, lack of information and some autonomy and parenting skills in relation to the growth of children. The meetings of parents or creating parent groups that are based on the sharing of information and experiences are planned but are not a reality in these teams. In quality practices, the professional must act in natural contexts like the family or the community, but may also include routines, jokes, and parties’ etc. scenarios that v facilitate the day-to-day. Families have their own contexts and routines that professionals should identify, collect the data indicate that the need for more careful assessment of the needs of families. Best practices and legislative environment are taken into account by teachers and professional teams, the documentary resources are mostly common to all participating teams, following the guidelines and documents / drafts provided by the coordinating committee SNIPI (National Intervention Early Childhood) Despite the theoretical recommendations for quality practices family-centered, we see that these are part of the concerns of teachers, but are not always implemented. The issue of child seems to be still the most important programs and plans and even the decisive criterion for delineating the duration and frequency of interventions whether in urban or rural.

Finite element studies of the mechanical behaviour of the diaphragm in normal and pathological cases

The diaphragm is a muscular membrane separating the abdominal and thoracic cavities, and its motion is directly linked to respiration. In this study, using data from a 59-year-old female cadaver obtained from the Visible Human Project, the diaphragm is reconstructed and, from the corresponding solid object, a shell finite element mesh is generated and used in several analyses performed with the ABAQUS 6.7 software. These analyses consider the direction of the muscle fibres and the incompressibility of the tissue. The constitutive model for the isotropic strain energy as well as the passive and active strain energy stored in the fibres is adapted from Humphrey's model for cardiac muscles. Furthermore, numerical results for the diaphragmatic floor under pressure and active contraction in normal and pathological cases are presented.

Image quality of myocardial perfusion-gated studies: effect of ingestion of different fat content in the reduction of extra-myocardial abdominal signal

Myocardial perfusion-gated-SPECT (MP-gated-SPECT) imaging often shows radiotracer uptake in abdominal organs. This accumulation interferes frequently with qualitative and quantitative assessment of the infero-septal region of myocardium. The objective of this study is to evaluate the effect of ingestion of different fat content on the reduction of extra-myocardial uptake and to improve MP-gated-SPECT image quality. In this study, 150 patients (65 ^ 18 years) who were referred for MP-gated-SPECT underwent a 1-day-protocol including imaging after stress (physical or pharmacological) and resting conditions. All patients gave written informed consent. Patients were subdivided into five groups: GI, GII, GIII, GIV and GV. In the first four groups, patients ate two chocolate bars with different fat content. Patients in GV – control group (CG) – had just water. Uptake indices (UI) of myocardium (M)/liver(L) and M/stomach–proximal bowel(S) revealed lower UI of M/S at rest in all groups. Both stress and rest studies using different food intake indicate that patients who ate chocolate with different fat content showed better UI of M/L than the CG. The UI of M/L and M/S of groups obtained under physical stress are clearly superior to that of groups obtained under pharmacological stress. These differences are only significant in patients who ate high-fat chocolate or drank water. The analysis of all stress studies together (GI, GII, GIII and GIV) in comparison with CG shows higher mean ranks of UI of M/L for those who ate high-fat chocolate. After pharmacological stress, the mean ranks of UI of M/L were higher for patients who ate high- and low-fat chocolate. In conclusion, eating food with fat content after radiotracer injection increases, respectively, the UI of M/L after stress and rest in MP-gated-SPECT studies. It is, therefore, recommended that patients eat a chocolate bar after radiotracer injection and before image acquisition.

Study of the influence of count’s number in myocardium in the determination of reproducible functional parameters in Gated-SPECT studies simulated with GATE

Myocardial Perfusion Gated Single Photon Emission Tomography (Gated-SPET) imaging is used for the combined evaluation of myocardial perfusion and left ventricular (LV) function. But standard protocols of the Gated-SPECT studies require long acquisition times for each study. It is therefore important to reduce as much as possible the total duration of image acquisition. However, it is known that this reduction leads to decrease on counts statistics per projection and raises doubts about the validity of the functional parameters determined by Gated-SPECT. Considering that, it’s difficult to carry out this analysis in real patients. For ethical, logistical and economical matters, simulated studies could be required for this analysis. Objective: Evaluate the influence of the total number of counts acquired from myocardium, in the calculation of myocardial functional parameters (LVEF – left ventricular ejection fraction, EDV – end-diastolic volume, ESV – end-sistolic volume) using routine software procedures.

Structural, electrical and magnetic studies of Co:SnO2 and (Co,Mo):SnO2 films prepared by pulsed laser deposition

Here we report on the structural, optical, electrical and magnetic properties of Co-doped and (Co,Mo)-codoped SnO2 thin films deposited on r-cut sapphire substrates by pulsed laser deposition. Substrate temperature during deposition was kept at 500 degrees C. X-ray diffraction analysis showed that the undoped and doped films are crystalline with predominant orientation along the [1 0 1] direction regardless of the doping concentration and doping element. Optical studies revealed that the presence of Mo reverts the blue shift trend observed for the Co-doped films. For the Co and Mo doping concentrations studied, the incorporation of Mo did not contribute to increase the conductivity of the films or to enhance the ferromagnetic order of the Co-doped films. (C) 2012 Elsevier B.V. All rights reserved.

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.

A new fluorescent double-cavity calix[4]arene: synthesis and complexation studies toward nitroanilines

Agência Financiadora: Fundação para a Ciência e a Tecnologia/MCTES (Portugal) - PEst-OE/EQB/UI0702/2012

The influence of count's number in myocardium in the determination of reproducible parameters in Gated-SPECT studies simulated with GATE

Myocardial Perfusion Gated Single Photon Emission Tomography (Gated-SPET) imaging is used for the combined evaluation of myocardial perfusion and left ventricular (LV). The purpose of this study is to evaluate the influence of the total number of counts acquired from myocardium, in the calculation of myocardial functional parameters using routine software procedures. Methods: Gated-SPET studies were simulated using Monte Carlo GATE package and NURBS phantom. Simulated data were reconstructed and processed using the commercial software package Quantitative Gated-SPECT. The Bland-Altman and Mann-Whitney-Wilcoxon tests were used to analyze the influence of the number of total counts in the calculation of LV myocardium functional parameters. Results: In studies simulated with 3MBq in the myocardium there were significant differences in the functional parameters: Left ventricular ejection fraction (LVEF), end-systolic volume (ESV), Motility and Thickness; between studies acquired with 15s/projection and 30s/projection. Simulations with 4.2MBq show significant differences in LVEF, end-diastolic volume (EDV) and Thickness. Meanwhile in the simulations with 5.4MBq and 8.4MBq the differences were statistically significant for Motility and Thickness. Conclusion: The total number of counts per simulation doesn't significantly interfere with the determination of Gated-SPET functional parameters using the administered average activity of 450MBq to 5.4MBq in myocardium.