Synthesis of novel hyperbranched polymers featuring oxazoline linear units and their application in fast-drying solvent-borne coating formulations

Novel acid-terminated hyperbranched polymers (HBPs) containing adipic acid and oxazoline monomers derived from oleic and linoleic acid have been synthesized via a bulk polymerization procedure. Branching was achieved as a consequence of an acid-catalyzed opening of the oxazoline ring to produce a trifunctional monomer in situ which delivered branching levels of >45% as determined by 1H and 13C NMR spectroscopy. The HBPs were soluble in common solvents, such as CHCl3, acetone, tetrahydrofuran, dimethylformamide, and dimethyl sulfoxide and were further functionalized by addition of citronellol to afford white-spirit soluble materials that could be used in coating formulations. During end group modification, a reduction in branching levels of the HBPs (down to 12–24%) was observed, predominantly on account of oxazoline ring reformation and trans-esterification processes under the reaction conditions used. In comparison to commercial alkyd resin paint coatings, formulations of the citronellol-functionalized hyperbranched materials blended with a commercial alkyd resin exhibited dramatic decreases of the blend viscosity when the HBP content was increased. The curing characteristics of the HBP/alkyd blend formulations were studied by dynamic mechanical analysis which revealed that the new coatings cured more quickly and produced tougher materials than otherwise identical coatings prepared from only the commercial alkyd resins.

Amygdala functional connectivity with medial prefrontal cortex at rest predicts the positivity effect in older adults’ memory

As people get older, they tend to remember more positive than negative information. This age-by-valence interaction has been called “positivity effect.” The current study addressed the hypotheses that baseline functional connectivity at rest is predictive of older adults' brain activity when learning emotional information and their positivity effect in memory. Using fMRI, we examined the relationship among resting-state functional connectivity, subsequent brain activity when learning emotional faces, and individual differences in the positivity effect (the relative tendency to remember faces expressing positive vs. negative emotions). Consistent with our hypothesis, older adults with a stronger positivity effect had increased functional coupling between amygdala and medial PFC (MPFC) during rest. In contrast, younger adults did not show the association between resting connectivity and memory positivity. A similar age-by-memory positivity interaction was also found when learning emotional faces. That is, memory positivity in older adults was associated with (a) enhanced MPFC activity when learning emotional faces and (b) increased negative functional coupling between amygdala and MPFC when learning negative faces. In contrast, memory positivity in younger adults was related to neither enhanced MPFC activity to emotional faces, nor MPFC–amygdala connectivity to negative faces. Furthermore, stronger MPFC–amygdala connectivity during rest was predictive of subsequent greater MPFC activity when learning emotional faces. Thus, emotion–memory interaction in older adults depends not only on the task-related brain activity but also on the baseline functional connectivity.

Subdiffraction fluorescence imaging of biomolecular structure and distributions with quantum dots

We introduce semiconductor quantum dot-based fluorescence imaging with approximately 2-fold increased optical resolution in three dimensions as a method that allows both studying cellular structures and spatial organization of biomolecules in membranes and subcellular organelles. Target biomolecules are labelled with quantum dots via immunocytochemistry. The resolution enhancement is achieved by three-photon absorption of quantum dots and subsequent fluorescence emission from a higher-order excitonic state. Different from conventional multiphoton microscopy, this approach can be realized on any confocal microscope without the need for pulsed excitation light. We demonstrate quantum dot triexciton imaging (QDTI) of the microtubule network of U373 cells, 3D imaging of TNF receptor 2 on the plasma membrane of HeLa cells, and multicolor 3D imaging of mitochondrial cytochrome c oxidase and actin in COS-7 cells.

Transition metal atoms encapsulated in adamantane molecules

We performed a first principles total energy investigation on the structural, electronic, and magnetic properties of 3d-transition metal-encapsulated adamantane molecules (TM@C(10)H(16). with TM = Cr, Mn, Fe, Co, and Ni). We find that the C-C interactions are strong enough to maintain the molecular rigidity upon TM incorporation, although outward relaxations and formation energies are large. We built a microscopic model that explains the electronic structure of those molecules. (C) 2011 Elsevier B.V. All rights reserved.

Lojalitet eller kriminalitet? : Ransoneringsbrottsligheten i Sandviken/Högbo under åren 1939-1949.

Syftet med uppsatsen är att undersöka omfattningen av och karaktären på ransoneringsbrottsligheten i Sandviken/Högbo under åren 1939-1949 samt myndigheternas försök att stävja denna brottslighet. Det ska främst uppnås genom att studera den rannsakade ransonerings-brottsligheten som det framkommer i domböckerna.Materialet som använts i undersökningen är domböcker för Gästriklands östra domsaga, protokoll från Högbo kommuns och Sandvikens köpings kristidsnämnd, ett klipparkiv med pressklipp från lokaltidningarna samt ett brottmålsdiarium för Sandvikens distrikt.Resultatet är att det föll 119 st fällande domar för ransoneringsbrott i Sandviken/Högbo under de undersökta åren, de flesta sakfällda brotten begicks under åren 1944-45. Den övervägande delen av brotten handlade om olika varubrott, i regel olaga försäljning/köp av ransonerade varor. De varor som framförallt drabbades av olika brott var olika former av livsmedel, främst smör. De som framförallt begick ransoneringsbrotten var personer som på något sätt hanterade ransonerade varor eller ransoneringskuponger i sitt yrke. Påföljderna för ransoneringsbrotten var i regel dagsböter, vilka oftast låg på två normala dagslöner, varvid det märktes att myndigheterna försökte stävja denna brottslighet. Endast fem personer dömdes till fängelse eller straffarbete under de undersökta åren. Karaktären på brottsligheten var att den främst verkade drivas av vinstintressen eller bekvämlighet.

Heterocyclic acetals in Madeira wines

The maturation of Madeira wines usually involves exposure to relatively high temperatures which affect the aroma and flavour composition leading to the formation of the typical and characteristic bouquet of these wines. The formation of heterocyclic acetals (1,3-dioxanes and 1,3-dioxolanes) was investigated in order to determine levels and for possible use as indicators of wine age. The results show a linear correlation of the investigated acetals with wine age but suggest that the acetalization reaction is not particularly affected by the drastic oxidative conditions observed during maturation.

Morfologia de frutos e sementes de espécies arbóreas do gênero Solanum L.

O objetivo do trabalho foi caracterizar a morfologia do fruto e da semente de três espécies florestais nativas do Brasil, Solanum granuloso-leprosum Dunal, S. lycocarpum A.St.-Hil. e S. pseudoquina A.St.-Hil., recomendadas para plantações destinadas à recuperação de áreas degradadas. Os frutos são indeiscentes, carnosos, do tipo baga, globosos, polispérmicos e constituídos por dois ou mais lóculos. As sementes são estenospérmicas, campilótropas, elipsóides, comprimidas, apresentando seção longitudinal largo-ovalada ou achatado-ovalada e seção transversal elíptica. Hilo mediano-marginal localizado em uma depressão e micrópila arredondada. Sementes albuminosas, com endosperma abundante, periférico, carnoso-firme, semitransparente e de coloração esbranquiçada. Embrião axial, linear, contínuo e curvado. em Solanum lycocarpum e S. pseudoquina o embrião é circinado e em S. granuloso-leprosum é espiralado.

Balancing guava nutrition with liming and fertilization

A resposta da goiabeira à calagem e à adubação pode ser monitorada por análises de tecido vegetal. O perfil nutricional é definido em relação a padrões de teores de nutrientes. No entanto, os teores de nutrientes-padrão são constantemente criticados por não considerarem as interações que ocorrem entre nutrientes e por gerarem tendências numéricas, decorrentes da redundância dos dados, da dependência de escala e da distribuição não normal. As técnicas de análise composicional de dados podem controlar esses dados tendenciosos, equilibrando os grupos de nutrientes, tais como os envolvidos na calagem e na adubação. A utilização das relações log isométricas (ilr) ortonormais, sequencialmente dispostas, evita tendências numéricas inerentes aos dados de composição. Os objetivos do trabalho foram relacionar o balanço de nutrientes dos tecidos vegetais com a produção de goiabeiras em pomares de 'Paluma' diferentemente corrigidos e adubados, e ajustar os atuais padrões de nutrientes com a faixa de equilíbrio das goiabeiras mais produtivas. Um experimento de calagem de sete anos e três, experimentos de três anos com doses de N, P2O5 e K2O, foram conduzidos em pomares de goiabeiras 'Paluma' em um Latossolo Vermelho-Amarelo. Os teores de N, P, K, Ca e Mg na planta foram monitorados anualmente. Selecionaram-se os balanços [N, P, K | Ca, Mg], [N, P | K], [N | P] e [Ca | Mg] para separar os efeitos da calagem (Ca-Mg) e dos fertilizantes (N-K) nos balanços de macronutrientes. Os balanços foram mais influenciados pela calagem do que pela fertilização. A produtividade das goiabeiras e seu balanço nutricional permitiram a definição de faixas de equilíbrio de nutrientes e sua validação com as faixas de concentrações críticas atualmente utilizadas no Brasil e combinadas em coordenadas ilr.

Evaluation of the use of vinasse as a biostimulation agent for the biodegradation of oily sludge in soil

Este trabalho objetivou estudar o efeito da vinhaça na biodegradação em solo da borra oleosa proveniente da refinaria de petróleo Replan-Petrobras. Foi utilizado o método respirométrico de Bartha para verificar a eficiência de tratamentos constituídos de solo, borra oleosa nas concentrações 7 e 14 % (m/m) e ajuste da umidade do solo com e sem vinhaça (0,11 mL/g solo seco) durante 121 dias. Embora a adição da vinhaça tenha proporcionado um aumento da população microbiana nos tratamentos, esta não se mostrou adequada para aumentar a eficiência de biodegradação da borra oleosa em solo, uma vez que não houve diferença entre o CO2 produzido nos tratamentos com ou sem vinhaça após o consumo total da vinhaça. Assim, o uso da vinhaça como agente estimulante em processos de biodegradação mostrou-se ineficiente nas condições estudadas.

Occurrence and geochemistry of metamafic rocks from the Forquilha Eclogite Zone, central Ceara (NE Brazil): geodynamic implications

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)