Evaluation of water properties in HEA–HEMA hydrogels swollen in aqueous-PEG solutions using thermoanalytical techniques

Hydrogels are polymeric materials used in many pharmaceutical and biomedical applications due to their ability to form 3D hydrophilic polymeric networks, which can absorb large amounts of water. In the present work, polyethylene glycols (PEG) were introduced into the hydrogel liquid phase in order to improve the mechanical properties of hydrogels composed of 2-hydroxyethylacrylate and 2-hydroxyethylmethacrylate (HEA–HEMA) synthesized with different co-monomer compositions and equilibrated in water or in 20 % water–PEG 400 and 600 solutions. The thermoanalytical techniques [differential scanning calorimetry (DSC) and thermogravimetry (TG)] were used to evaluate the amount and properties of free and bound water in HEA–HEMA hydrogels. The internal structure and the mechanical properties of hydrogels were studied using scanning electron microscopy and friability assay. TG “loss-on-drying” experiments were applied to study the water-retention properties of hydrogels, whereas the combination of TG and DSC allowed estimating the total amount of freezable and non-freezing water in hydrogels. The results show that the addition of viscous co-solvent (PEG) to the liquid medium results in significant improvement of the mechanical properties of HEA–HEMA hydrogels and also slightly retards the water loss from the hydrogels. A redistribution of free and bound water in the hydrogels equilibrated in mixed solutions containing 20 vol% of PEGs takes place.

A Bayesian model for estimating the malaria transition probabilities considering individuals lost to follow-up

It is known that patients may cease participating in a longitudinal study and become lost to follow-up. The objective of this article is to present a Bayesian model to estimate the malaria transition probabilities considering individuals lost to follow-up. We consider a homogeneous population, and it is assumed that the considered period of time is small enough to avoid two or more transitions from one state of health to another. The proposed model is based on a Gibbs sampling algorithm that uses information of lost to follow-up at the end of the longitudinal study. To simulate the unknown number of individuals with positive and negative states of malaria at the end of the study and lost to follow-up, two latent variables were introduced in the model. We used a real data set and a simulated data to illustrate the application of the methodology. The proposed model showed a good fit to these data sets, and the algorithm did not show problems of convergence or lack of identifiability. We conclude that the proposed model is a good alternative to estimate probabilities of transitions from one state of health to the other in studies with low adherence to follow-up.

Transfer reactions in the investigation of light-nuclei nucleosynthesis

Cross sections for the (6)Li(p,gamma)(7)Be, (7)Li(n,gamma)(8)Li (8)Li(n,gamma)(9)Li and (8)Li(p,gamma)(9)Be capture reactions have been investigated in the framework of the potential model. The main ingredients of the potential model are the potentials used to generate the continuum and bound-state wave functions and spectroscopic factors of the corresponding bound systems. The spectroscopic factors for the (7)Li circle times n=(8)Li(gs), (8)Li circle times n=(9)Li(gs) bound systems were obtained from a FR-DWBA analysis of neutron transfer reactions induced by (8)Li radioactive beam on a (9)Be target, while spetroscopic factor for the (8)Li circle times n=(9)Be(gs) bound system were obained from a proton transfer reaction. From the obtained capture reaction cross section, reaction rate for the (8)Li(n,gamma)(9)Li and (8)Li(p,gamma)(9)Be direct neutron and proton capture were determined and compared with other experimental and calculated values.

Near threshold vibrational excitation of molecules by positron impact: A projection operator approach

We report vibrational excitation (v(i) = 0 -> v(f) = 1) cross-sections for positron scattering by H(2) and model calculations for the (v(i) = 0 -> v(f) = 1) excitation of the C-C symmetric stretch mode of C(2)H(2). The Feshbach projection operator formalism was employed to vibrationally resolve the fixed-nuclei phase shifts obtained with the Schwinger multichannel method. The near threshold behavior of H(2) and C(2)H(2) significantly differ in the sense that no low lying singularity (either virtual or bound state) was found for the former, while a e(+)-acetylene virtual state was found at the equilibrium geometry (this virtual state becomes a bound state upon stretching the molecule). For C(2)H(2), we also performed model calculations comparing excitation cross-sections arising from virtual (-i kappa(0)) and bound (+i kappa(0)) states symmetrically located around the origin of the complex momentum plane (i.e. having the same kappa(0)). The virtual state is seen to significantly couple to vibrations, and similar cross-sections were obtained for shallow bound and virtual states. (c) 2007 Elsevier B.V. All rights reserved.

Nonlinear spectrum effect on the coherent control of molecular systems

This work demonstrates that the detuning of the fs-laser spectrum from the two-photon absorption band of organic materials can be used to reach further control of the two-photon absorption by pulse spectral phase manipulation. We investigate the coherent control of the two-photon absorption in imidazole-thiophene core compounds presenting distinct two-photon absorption spectra. The coherent control, performed using pulse phase shaping and genetic algorithm, exhibited different growth rates for each sample. Such distinct trends were explained by calculating the two-photon absorption probability considering the intrapulse interference mechanism, taking into account the two-photon absorption spectrum of the samples. Our results indicate that tuning the relative position between the nonlinear absorption and the pulse spectrum can be used as a novel strategy to optimize the two-photon absorption in broadband molecular systems. (C) 2011 Elsevier B.V. All rights reserved.

qtl.outbred: Interfacing outbred line cross data with the R/qtl mapping software

Background qtl.outbred is an extendible interface in the statistical environment, R, for combining quantitative trait loci (QTL) mapping tools. It is built as an umbrella package that enables outbred genotype probabilities to be calculated and/or imported into the software package R/qtl. Findings Using qtl.outbred, the genotype probabilities from outbred line cross data can be calculated by interfacing with a new and efficient algorithm developed for analyzing arbitrarily large datasets (included in the package) or imported from other sources such as the web-based tool, GridQTL. Conclusion qtl.outbred will improve the speed for calculating probabilities and the ability to analyse large future datasets. This package enables the user to analyse outbred line cross data accurately, but with similar effort than inbred line cross data.

Genetic heterogeneity of residual variance : estimation of variance components using double hierarchical generalized linear models

Background: The sensitivity to microenvironmental changes varies among animals and may be under genetic control. It is essential to take this element into account when aiming at breeding robust farm animals. Here, linear mixed models with genetic effects in the residual variance part of the model can be used. Such models have previously been fitted using EM and MCMC algorithms. Results: We propose the use of double hierarchical generalized linear models (DHGLM), where the squared residuals are assumed to be gamma distributed and the residual variance is fitted using a generalized linear model. The algorithm iterates between two sets of mixed model equations, one on the level of observations and one on the level of variances. The method was validated using simulations and also by re-analyzing a data set on pig litter size that was previously analyzed using a Bayesian approach. The pig litter size data contained 10,060 records from 4,149 sows. The DHGLM was implemented using the ASReml software and the algorithm converged within three minutes on a Linux server. The estimates were similar to those previously obtained using Bayesian methodology, especially the variance components in the residual variance part of the model. Conclusions: We have shown that variance components in the residual variance part of a linear mixed model can be estimated using a DHGLM approach. The method enables analyses of animal models with large numbers of observations. An important future development of the DHGLM methodology is to include the genetic correlation between the random effects in the mean and residual variance parts of the model as a parameter of the DHGLM.

A consensualidade e a administração pública em juízo

Com o aumento da pressão social sobre a qualidade do serviço prestado pelo Poder Judiciário, há necessidade de se perseguir maior eficiência por estes órgãos. Neste contexto, vem ganhando força a idéia da consensualidade, de modo a permitir à Administração, por meio da interação com o cidadão, promover acordos e obter resultados mais efetivos para todos. O foco deste estudo é a identificação de aspectos práticos que reduzem e, em alguns casos, inviabilizam a materialização de pontos de consenso entre o cidadão e a Administração Pública, para reverter esse quadro.

Evolução dos conceitos em orientação vocacional - de uma visão estática a uma visão dinâmica

O presente trabalho discute a fundamentação teórica da Orientação Vocacional buscando em sua história, a compreensão da relação de uma problemática com o pensamento dominante na época e questionando em que medida ações e atitudes ou métodos apresentados foram uma superação dos anteriores.Teve como objetivos: 1) retraçar a evolução das teorias em Orientação Vocacional, apontando a diversificação das infra-estruturas teóricas e confrontando-as com as respectivas diretrizes pragmáticas; 2) discutir os limites do crescimento pessoal e da manipulação exercida sobre o orientando no processo de Orientação Vocacional; 3) demonstrar que, dentre os determinantes de um impasse teórico em Orientação Vocacional, encontramos a superposição de problemáticas distintas que representam concepções e formas de orientação distintas. Neste estudo foram abordadas as teorias da Orientação Vocacional, desde o seu início com Parsons até nossos dias destacando-se as duas grandes teorias da década de 70: o Enfoque Operatório de Pelletier, Noiseux e Bujold como expoente desenvolvimentista e a Estratégia Clínica de Bohoslavsky no enfoque psicodinâmico. Estas teorias foram analisadas nas suas principais contribuições e limitações. Com apoio nas considerações teóricas desenvolvidas foram apresentadas sugestões quanto á prática da Orientação Vocacional quer nas suas modalidades estrutural e maturacional quer nas suas formas periódica e contínua.

Acesso à justiça: como os balcões de justiça e cidadania contribuem oara garantir o acesso à ordem jurídica justa

Esse trabalho cuida, em linhas gerais, do acesso à Justiça, na perspectiva de acesso à ordem jurídica justa, a compreender tanto o acesso à orientação jurídica quanto o acesso ao sistema judicial, a partir da revisão teórica e da observação empírica dos Balcões de Justiça e Cidadania (BJC), instalados pelo Tribunal de Justiça do Estado da Bahia na cidade de Salvador. A proposta é proceder a uma análise profunda dos BJC para verificar de que forma colaboram para a inclusão no sistema de justiça de parte da população da Capital do Estado que não teria como obter informações sobre seus direitos e/ou resolverem seus conflitos. Para tanto, elaborei uma hipótese: a de que os Balcões de Justiça e Cidadania contribuem para dar acesso à população que procura orientação quanto aos seus direitos, ou tem conflitos cuja solução ainda não foi formalizada judicialmente. Em seguida, defini alguns parâmetros para conduzir a investigação: a) natureza da demanda dos serviços jurídicos - o número de atendimentos dos BJC de Salvador, desde aqueles atendimentos que se referiam a orientação jurídica até os que diziam respeito a conflitos de interesse; b) número de acordos realizados nos BJC de Salvador; c) natureza do conflito levado aos BJC; d) características dos locais em que estão situados os BJC; e) perfil dos usuários dos serviços dos BJC; f) satisfação dos usuários dos serviços prestados nos BJC de Salvador. O objetivo é sumariar alguns insights oriundos da pesquisa desenvolvida nos BJC da cidade de Salvador, por acreditar que poderá ter alguma utilidade para o desenvolvimento da prática e para se pensar uma política pública efetiva de acesso à Justiça, customizada aos contornos da cidade de Salvador.

Os desafios da integração entre os instrumentos de planejamento orçamentário: PPA, LDO e LOA : estudo de caso do município de Nilópolis/RJ

A presente pesquisa tem o objetivo de identificar e entender em que medida a integração entre os instrumentos orçamentários é afetada no âmbito do município de Nilópolis / RJ. Para isso, foram estudados os principais conceitos relacionados ao assunto, bem como diversos documentos, e diversas entrevistas com atores (stakeholders) do Poder Legislativo e do Poder Executivo. O Referencial teórico apresenta o orçamento como um instrumento multifacetado que pode ser entendido em três dimensões: Política, Jurídica e Econômica. Tal referencial teórico foi utilizado na presente pesquisa a fim de identificar as questões e fatores que afetam a integração dos instrumentos orçamentários (PPA, LDO e LOA) no município de Nilópolis / RJ, dando desta forma, uma perspectiva ao leitor sobre o assunto em foco. Verificou-se que os fatores identificados pelos entrevistados, não são diretamente responsáveis por um falta de integração entre o PPA, LDO e LOA. Foi concluído que os principais fatores, indicados na pesquisa, são conseqüências de causas externas ao município de Nilópolis.

Nanocatalysts for sustainable industrial processses

In Chapter 1, rhodium nanoparticles were supported on multiwalled carbon nanotubes (MWCNTs) and bound to the magnetic core-shell system Fe3O4@TiO2. The composite Fe3O4@TiO2-Rh-MWCNT and the intermediates were characterized by SEM, EDS and TEM. Their catalytic activity was studied using i) the hydrogenation transfer of nitroarenes and cyclohexene in the presence of hydrazine hydrate; ii) the reduction of 2-nitrophenol with NaBH4; and iii) the decoloration of pigments in the presence of hydrogen peroxide. The results were monitored by gas chromatography (i) and UV Visible (ii and iii). In the second chapter, the catalytic activity of six oxidovanadium(V) aroylhydrazone complexes, viz. [VOL1(OEt)][VOL1(OEt)(EtOH)] (1), [VOL2(OEt)] (2), [Et3NH][VO2L1] (3), [VO2(H2L2)]2·EtOH (4), [VOL1(µ -O)VOL1] (5) and [VOL2(µ -O)VOL2] (6) (H2L1 = 3,5-di-tert-butyl-2-hydroxybenzylidene)-2hydroxybenzohydrazide and H2L2 = 3,5-di-tert-butyl-2-hydroxybenzylidene)-2 aminobenzohydrazide), anchored on nanodiamonds with different treatments, was studied towards the microwave-assisted partial oxidation of 1-phenylethanol to acetophenone in the presence of tert-butyl hydroperoxide (TBHP) as oxidant. A high selectivity for acetophenone was achieved for the optimized conditions. The possibility of recycling and reuse the heterogeneous catalysts was also investigated. In chapter 3, the catalytic activity of gold nanoparticles supported at different metal oxides, such as Fe2O3, Al2O3 ZnO or TiO2, was studied for the above reaction. The effect of the support, quantity of the catalyst and temperature was investigated. The recyclability of the gold catalysts was also studied. In the last chapter, a new copper nanocomposite with functionalized mutiwalled carbon nanotubes (Cu-MWCNT) was synthesized using a microwave assisted polyol method. The characterization was performed using XRD and SEM. The catalytic activity of Cu-MWCNT was studied through the degradation of pigments, such as amaranth, brilliant blue, indigo, tartrazine and methylene blue.

Análise da Expressão de APE1 após Estresse Oxidativo Induzido em Células Proficientes e Deficientes na Via de Reparo por Excisão de Nucleotídeos

Riboflavin is a vitamin very important in aerobic organisms, as a precursor of many coenzymes involved in the electron transporter chain. However, after photosensitization of riboflavin with UV or visible light, it generates reactive oxygen species (ROS), which can oxidize the DNA. The repair of oxidative lesions on DNA occurs through the base excision repair pathway (BER), where APE1 endonuclease plays a central role. On the other hand, the nucleotide excision repair pathway (NER) repairs helix-distorting lesions. Recently, it was described the participation of NERproteins in the repair of oxidative damage and in stimulation of repair function fromAPE1. The aim of this research was to evaluate the cytotoxic effects of photosensitized riboflavin (RF*) in cells proficient and deficient in NER, correlating with APE1 expression. For this propose, the cells were treated with RF* and it was performed the cell viability assay, extraction of whole proteins, cells fractionation, immunoblotting, indirect immunofluorescence and analysis of polymorphisms of BER gens. The results evidenced that cells deficient in XPA and CSB proteins were more sensitive to RF*. However, XPC-deficient cells presented similar resistance to MRC5- SV cells, which is proficient in NER. These results indicate that XPA and CSB proteins have an important role on repair of oxidative lesions induced by RF*. Additionally, it was evidenced that single nucleotide polymorphisms (SNPs) in BER enzymes may influence in sensitivity of NER-deficient cell lines. Concerning the APE1 expression, the results showed that expression of this protein after treatment with RF* only changed in XPC-deficient cells. Though, it was observed that APE1 is recruited and is bound to chromatin in MRC5-SV and XPA cells after treatment with RF*. The results also showed the induction of DNA damage after treatment with RF*, through the analysis of-H2AX, since the treatment promoted an increase of endogenous levels of this phosphorylated protein, which acts signaling double strand-break on DNA. On the other hand, in XPC-deficient cells, regardless of resistance of RF*, the endogenous levels of APE1 are extremely reduced when compared with other cell lines and APE1 is not bound to chromatin after treatment with RF*. These results conclude that RF* was able to induce cell death in NERdeficient cells, where XPA and CSB cells were more sensitive when compared with MRC5-SV and XPC-deficient cells. This last result is potentially very interesting, since XPC-deficient cell line presents low levels of APE1. Additionally, the results evidenced that APE1 protein can be involved in the repair of oxidative damage induced by RF*, because APE1 is recruited and bound strongly to chromatin after treatment.

Propagação de Camellia sinensis: efeito do genótipo, estaca, substrato, recipiente e ácido indolbutírico

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Estimativa do número de frutos por amostragem de parte da copa em laranjeiras

Estudou-se um método objetivo para a estimativa do número de frutos em pomares de laranja baseado na contagem dos frutos em ramos de 5 cm de diâmetro. Foram realizados levantamentos em laranjeiras durante três safras, obtendo-se o número de frutos produzidos em um ramo terminal, tomado ao acaso, bem como o número total na árvore. Consideraram-se nove estratos, constituídos pelas cultivares de laranja-doce, Hamlin, Pêra, Natal e Valência (as duas últimas analisadas conjuntamente) e três faixas etárias (três a cinco, seis a 10 e mais que 10 anos de idade). Foram ajustados modelos de regressão linear para o número total de frutos da árvore em função do número de frutos no ramo, obtendo-se coeficientes de determinação variando de 0,79 a 0,94. Com exceção da cultivar Hamlin, verificou-se coincidência entre as curvas das faixas etárias correspondentes. Esses resultados permitem estimar a produção média de frutos em um pomar de laranja, com base em amostragem de ramos com tamanho fixo, com precisão satisfatória, sem o uso de métodos de amostragem mais laboriosos e onerosos.