Agrupamento de dados com restri����es

Mestrado em Engenharia Inform��tica

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.

Oxorhenium Complexes Bearing the Water-Soluble Tris(pyrazol-1-yl)methanesulfonate, 1,3,5-Triaza-7-phosphaadamantane, or Related Ligands, as Catalysts for Baeyer-Villiger Oxidation of Ketones

New rhenium(VII or III) complexes [ReO3(PTA)(2)][ReO4] (1) (PTA = 1,3,5-triaza-7-phosphaadamantane), [ReO3(mPTA)][ReO4] (2) (mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane cation), [ReO3(HMT)(2)] [ReO4] (3) (HMT = hexamethylenetetramine), [ReO3(eta(2)-Tpm)(PTA)][ReO4] (4) [Tpm = hydrotris(pyrazol-1-yl)methane, HC(pz)(3), pz = pyrazolyl), [ReO3(Hpz)(HMT)][ReO4] (5) (Hpz = pyrazole), [ReO(Tpms)(HMT)] (6) [Tpms = tris(pyrazol-1-yl)methanesulfonate, O3SC(pz)(3)(-)] and [ReCl2{N2C(O)Ph} (PTA)(3)] (7) have been prepared from the Re(VII) oxide Re2O2 (1-6) or, in the case of 7, by ligand exchange from the benzoyldiazenido complex [ReCl2(N2C-(O)Ph}(Hpz)(PPh3)(2)], and characterized by IR and NMR spectroscopies, elemental analysis and electrochemical properties. Theoretical calculations at the density functional theory (DFT) level of theory indicated that the coordination of PTA to both Re(III) and Re(VII) centers by the P atom is preferable compared to the coordination by the N atom. This is interpreted in terms of the Re-PTA bond energy and hard-soft acid-base theory. The oxo-rhenium complexes 1-6 act as selective catalysts for the Baeyer-Villiger oxidation of cyclic and linear ketones (e.g., 2-methylcyclohexanone, 2-methylcyclopentanone, cyclohexanone, cyclopentanone, cyclobutanone, and 3,3-dimethyl-2-butanone or pinacolone) to the corresponding lactones or esters, in the presence of aqueous H2O2. The effects of a variety of factors are studied toward the optimization of the process.

Optimization and validation of organochlorine compounds in adipose tissue by SPE-gas chromatography

Scientific evidence has shown an association between organochlorine compounds (OCC) exposure and human health hazards. Concerning this, OCC detection in human adipose samples has to be considered a public health priority. This study evaluated the efficacy of various solid-phase extraction (SPE) and cleanup methods for OCC determination in human adipose tissue. Octadecylsilyl endcapped (C18-E), benzenesulfonic acid modified silica cation exchanger (SA), poly (styrene-divinylbenzene (EN) and EN/RP18 SPE sorbents were evaluated. The relative sample cleanup provided by these SPE columns was evaluated using gas chromatography with electron capture detection (GC���ECD). The C18-E columns with strong homogenization were found to provide the most effective cleanup, removing the greatest amount of interfering substance, and simultaneously ensuring good analyte recoveries higher than 70%. Recoveries>70% with standard deviations (SD)<15% were obtained for all compounds under the selected conditions. Method detection limits were in the 0.003���0.009 mg/kg range. The positive samples were confirmed by gas chromatography coupled with tandem mass spectrometry (GC-MS/MS). The highest percentage found of the OCC in real samples corresponded to HCB, o,p���-DDT and methoxychlor, which were detected in 80 and 95% of samples analyzed respectively. Copyright �� 2012 John Wiley & Sons, Ltd.

Implementa����o e valida����o de um m��todo anal��tico para a determina����o de surfatantes ani��nicos

Trabalho Final de Mestrado para obten����o do grau de Mestre em Engenharia Qu��mica e Biol��gica

Hyperspectral subspace identification

Signal subspace identification is a crucial first step in many hyperspectral processing algorithms such as target detection, change detection, classification, and unmixing. The identification of this subspace enables a correct dimensionality reduction, yielding gains in algorithm performance and complexity and in data storage. This paper introduces a new minimum mean square error-based approach to infer the signal subspace in hyperspectral imagery. The method, which is termed hyperspectral signal identification by minimum error, is eigen decomposition based, unsupervised, and fully automatic (i.e., it does not depend on any tuning parameters). It first estimates the signal and noise correlation matrices and then selects the subset of eigenvalues that best represents the signal subspace in the least squared error sense. State-of-the-art performance of the proposed method is illustrated by using simulated and real hyperspectral images.

Epigenetic and transcriptional signatures of stable versus plastic differentiation of proinflammatory gd T cell subsets

Two distinct subsets of ���� T cells that produce interleukin 17 (IL-17) (CD27(-) ���� T cells) or interferon-�� (IFN-��) (CD27(+) ���� T cells) develop in the mouse thymus, but the molecular determinants of their functional potential in the periphery remain unknown. Here we conducted a genome-wide characterization of the methylation patterns of histone H3, along with analysis of mRNA encoding transcription factors, to identify the regulatory networks of peripheral IFN-��-producing or IL-17-producing ���� T cell subsets in vivo. We found that CD27(+) ���� T cells were committed to the expression of Ifng but not Il17, whereas CD27(-) ���� T cells displayed permissive chromatin configurations at loci encoding both cytokines and their regulatory transcription factors and differentiated into cells that produced both IL-17 and IFN-�� in a tumor microenvironment.

FIA potentiometric system based on periodate polymeric membrane sensors for the assessment of ascorbic acid in commercial drinks

Ascorbic acid is found in many food samples. Its clinical and technological importance demands an easyto- use, rapid, robust and inexpensive method of analysis. For this purpose, this work proposes a new flow procedure based on the oxidation of ascorbic acid by periodate. A new potentiometric periodate sensor was constructed to monitor this reaction. The selective membranes were of PVC with porphyrin-based sensing systems and a lipophilic cation as additive. The sensor displayed a near-Nernstian response for periodate over 1.0x10-2���6.0x10-6 M, with an anionic slope of 73.9 �� 0.9 mV decade-1. It was pH independent in acidic media and presented good selectivity features towards several inorganic anions. The flow set-up operated in double-channel, carrying a 5.0x10-4 M IO- 4 solution and a suitable buffer; these were mixed in a 50-cm reaction coil. The overall flow rate was 7 ml min-1 and the injection volume 70 ��l. Under these conditions, a linear behaviour against concentration was observed for 17.7���194.0 ��g ml-1, presenting slopes of 0.169 mV (mg/l)-1, a reproducibility of ��1.1 mV (n = 5), and a sampling rate of ~96 samples h-1. The proposed method was applied to the analysis of beverages and pharmaceuticals.

Competitive dynamics for behavior coordination in a joint transportation task

We address the problem of coordinating two non-holonomic mobile robots that move in formation while transporting a long payload. A competitive dynamics is introduced that gradually controls the activation and deactivation of individual behaviors. This process introduces (asymmetrical) hysteresis during behavioral switching. As a result behavioral oscillations, due to noisy information, are eliminated. Results in indoor environments show that if parameter values are chosen within reasonable ranges then, in spite of noise in the robots communi- cation and sensors, the overall robotic system works quite well even in cluttered environments. The robots overt behavior is stable and smooth.

Chemical reaction network of flavylium ions in heterogeneous media

Disserta����o apresentada para a obten����o do Grau de Doutor em Qu��mica, especialidade em Qu��mica-F��sica, pela Universidade Nova de Lisboa, Faculdade de Ci��ncias e Tecnologia

Development of a meso-microscale coupling procedure for site assessment in complex terrain

A procedure for coupling mesoscale and CFD codes is presented, enabling the inclusion of realistic strati���cation ���ow regimes and boundary conditions in CFD simulations of relevance to site and resource assessment studies in complex terrain. Two distinct techniques are derived: (i) in the ���rst one, boundary conditions are extracted from mesoscale results to produce time-varying CFD solutions; (ii) in the second case, a statistical treatment of mesoscale data leads to steady-state ���ow boundary conditions believed to be more representative than the idealised pro���les which are current industry practice. Results are compared with measured data and traditional CFD approaches.

Sistema visual para Ground Truth de sistemas aut��nomos

Este trabalho visa contribuir para o desenvolvimento de um sistema de vis��o multi-c��mara para determina����o da localiza����o, atitude e seguimento de m��ltiplos objectos, para ser utilizado na unidade de rob��tica do INESCTEC, e resulta da necessidade de ter informa����o externa exacta que sirva de refer��ncia no estudo, caracteriza����o e desenvolvimento de algoritmos de localiza����o, navega����o e controlo de v��rios sistemas aut��nomos. Com base na caracteriza����o dos ve��culos aut��nomos existentes na unidade de rob��tica do INESCTEC e na an��lise dos seus cen��rios de opera����o, foi efectuado o levantamento de requisitos para o sistema a desenvolver. Foram estudados os fundamentos te��ricos, necess��rios ao desenvolvimento do sistema, em temas relacionados com vis��o computacional, m��todos de estima����o e associa����o de dados para problemas de seguimento de m��ltiplos objectos . Foi proposta uma arquitectura para o sistema global que endere��a os v��rios requisitos identi cados, permitindo a utiliza����o de m��ltiplas c��maras e suportando o seguimento de m��ltiplos objectos, com ou sem marcadores. Foram implementados e validados componentes da arquitectura proposta e integrados num sistema para valida����o, focando na localiza����o e seguimento de m��ltiplos objectos com marcadores luminosos �� base de Light-Emitting Diodes (LEDs). Nomeadamente, os m��dulos para a identi ca����o dos pontos de interesse na imagem, t��cnicas para agrupar os v��rios pontos de interesse de cada objecto e efectuar a correspond��ncia das medidas obtidas pelas v��rias c��maras, m��todo para a determina����o da posi����o e atitude dos objectos, ltro para seguimento de m��ltiplos objectos. Foram realizados testes para valida����o e a na����o do sistema implementado que demonstram que a solu����o encontrada vai de encontro aos requisitos, e foram identi cadas as linhas de trabalho para a continua����o do desenvolvimento do sistema global.

Avalia����o de realce tardio do mioc��rdio por tomografia computorizada

A distin����o entre mioc��rdio atordoado e danificado tem sido uma preocupa����o relevante, no cen��rio de um enfarte agudo do mioc��rdio (EAM). A avalia����o da viabilidade do mioc��rdio, p��s-enfarte, �� de import��ncia vital, no contexto cl��nico, principalmente numa fase inicial. Actualmente a Resson��ncia Magn��tica Card��aca �� o exame de refer��ncia para a avalia����o de viabilidade do mioc��rdio. No entanto, �� um exame com elevado custo e de dif��cil acesso. Estudos preliminares demonstraram potencial na utiliza����o de imagens por Tomografia Computorizada para avalia����o da ��rea de enfarte, quer em estudos animais quer em humanos. �� objectivo desta tese verificar a utilidade de um protocolo de avalia����o de viabilidade do mioc��rdio, com base em imagens de realce tardio (RT) por Tomografia Computorizada, ap��s um procedimento de interven����o coron��ria percut��nea, no contexto de enfarte agudo do mioc��rdio com eleva����o do segmento ST (STEMI). Pretende-se igualmente contribuir para a an��lise da imagem m��dica do mioc��rdio, proporcionando m��todos de quantifica����o do RT e software de suporte �� decis��o m��dica nesta modalidade de imagem substancialmente recente. S��o avaliados v��rios processos para a quantifica����o do volume de RT, incluindo um m��todo inovador baseado na detec����o autom��tica do mioc��rdio normal. _E ainda proposto um algoritmo para detec����o autom��tica do grau de transmuralidade, por segmento do mioc��rdio, e comparado o seu grau de efici��ncia face ao diagn��stico m��dico dos mesmos exames. Apesar do reduzido n��mero de exames utilizado para valida����o das t��cnicas descritas nesta tese, os resultados s��o bastante promissores e podem constituir uma mais-valia no auxilio �� gest��o do paciente com EAM.

Membrane design and characterisation by incorporation of ionic liquids

Disserta����o apresentada para obten����o do Grau de Doutor em Engenharia Qu��mica, especialidade de Opera����es Unit��rias e Fen��menos de Transfer��ncia, pela Universidade Nova de Lisboa, Faculdade de Ci��ncias e Tecnologia

Seqins: a sequencing tool for educational resources

The teaching-learning process is increasingly focused on the combination of the paradigms ���learning by viewing��� and ���learning by doing.��� In this context, educational resources, either expository or evaluative, play a pivotal role. Both types of resources are interdependent and their sequencing would create a richer educational experience to the end user. However, there is a lack of tools that support sequencing essentially due to the fact that existing speci���cations are complex. The Seqins is a sequencing tool of digital resources that has a fairly simple sequencing model. The tool communicates through the IMS LTI speci���cation with a plethora of e-learning systems such as learning management systems, repositories, authoring and evaluation systems. In order to validate Seqins we integrate it in an e-learning Ensemble framework instance for the computer programming learning.