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.

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.

Estudo dos indicadores de qualidade e de risco na interaça o mãe-filho(a)

O presente estudo tem como principal objetivo identificar na interação mãe- bebés de 3 meses, indicadores de risco e de qualidade e, consequentemente, criar um guião que ajude os profissionais a identificar esses mesmos indicadores. Para o efeito observámos 30 díades mãe-filho(a) em jogo livre distribuídas em dois grupos: 1) 12 díades sem condições assinaláveis de risco e 2) 18 díades em risco socioeconómico. O comportamento interativo dos bebés e das mães foi avaliado através do Child-Adult Relashionship Experimental, designado pela autora de CARE-Index (Crittenden, 2003). Os comportamentos maternos e infantis foram cotados de acordo com os 7 aspetos do comportamento diádico: Expressão Facial, Expressão Verbal, Posição e Contato Corporal, Afetividade, Reciprocidade, Diretividade e Escolha da Atividade. Os resultados do nosso estudo revelam que as díades mãe-filho(a) sem condições assinaláveis de risco apresentam interações mais positivas, recíprocas e ajustadas à idade das crianças do que as díades sujeitas a condições de risco e que o comportamento materno sensível e responsivo surge associado ao comportamento cooperativo infantil e negativamente correlacionado com a dificuldade infantil, enquanto que uma postura controladora, diretiva ou punitiva da mãe surge positivamente correlacionada com a submissão e evitamento infantil. Por fim, encontramos associados a comportamentos maternos sensíveis uma variabilidade de comportamentos infantis desde satisfação, coerção, procura de proximidade ou evitamento. Na discussão dos resultados apresentamos um script dos indicadores de qualidade e de risco do comportamento materno. - Abstract This study main goal was to study mother-infant quality of interaction in dyads with 3 months babies. Moreover, our goal was to explore maternal and infant key behaviors that shape the quality of the interaction in order to organize a script that helps professionals to identify these critical interactive behaviors. To this end we observed 30 mother-child dyads (a) in free play interaction divided into two groups: 1) 12 dyads without any known risk condition and 2) 18 dyads at socioeconomic risk. The interactive behavior of infants and mothers was assessed using the Child-Adult Relationship Experimental, designated by the author of CARE-Index (Crittenden, 2003). The maternal and infant behaviors were rated according to seven aspects of dyadic behavior: Facial Expression, Verbal Expression, Position and Contact Body, Affection, Reciprocity, Directivity and Choice of Activity. Findings indicate that mother-child dyads without know risk conditions are more likely to present positive interactions, reciprocal and age-adjusted than dyads at risk. The sensitive and responsive maternal behavior emerges associated with children's cooperative behavior and negatively correlated with infant difficultness, while a controlling or punitive maternal behavior is positively correlated with infant compliance and avoidance. Finally, sensitive maternal behaviors were associated with a variability of child behaviors, from satisfaction, coercion, avoidance or proximity search. In the results discussion we present a script of the quality and risks indicators of maternal behavior.

Avaliação da distribuição de dose em doentes com cancro da mama: cobertura e homogeneidade no volume alvo e dose nos órgãos de risco

Mestrado em Radioterapia

Hyperspectral signal subspace estimation

Given an hyperspectral image, the determination of the number of endmembers and the subspace where they live without any prior knowledge is crucial to the success of hyperspectral image analysis. This paper introduces a new minimum mean squared error based approach to infer the signal subspace in hyperspectral imagery. The method, termed hyperspectral signal identification by minimum error (HySime), is eigendecomposition based and 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. The effectiveness of the proposed method is illustrated using simulated data based on U.S.G.S. laboratory spectra and real hyperspectral data collected by the AVIRIS sensor over Cuprite, Nevada.

Hyperspectral unmixing algorithm via dependent component analysis

This paper introduces a new method to blindly unmix hyperspectral data, termed dependent component analysis (DECA). This method decomposes a hyperspectral images into a collection of reflectance (or radiance) spectra of the materials present in the scene (endmember signatures) and the corresponding abundance fractions at each pixel. DECA assumes that each pixel is a linear mixture of the endmembers signatures weighted by the correspondent abundance fractions. These abudances are modeled as mixtures of Dirichlet densities, thus enforcing the constraints on abundance fractions imposed by the acquisition process, namely non-negativity and constant sum. The mixing matrix is inferred by a generalized expectation-maximization (GEM) type algorithm. This method overcomes the limitations of unmixing methods based on Independent Component Analysis (ICA) and on geometrical based approaches. The effectiveness of the proposed method is illustrated using simulated data based on U.S.G.S. laboratory spectra and real hyperspectral data collected by the AVIRIS sensor over Cuprite, Nevada.