Thermally responsive elastomeric supramolecular polymers featuring flexible aliphatic hydrogen-bonding end-groups

The present paper details the synthesis, characterization, and preliminary physical analyses of a series of polyisobutylene derivatives featuring urethane and urea end-groups that enable supramolecular network formation to occur via hydrogen bonding. These polymers are readily accessible from relatively inexpensive and commercially available starting materials using a simple two-step synthetic approach. In the bulk, these supramolecular networks were found to possess thermoreversible and elastomeric characteristics as determined by temperature-dependent rheological analysis. These thermoreversible and elastomeric properties make these supramolecular materials potentially very useful in applications such as adhesives and healable surface coatings.

Effects of hydrocolloid addition and high pressure processing on the rheological properties and microstructure of a commercial ostrich meat product "Yor" (Thai sausage)

"Yor" is a traditional sausage like product widely consumed in Thailand. Its textures are usually set by steaming, in this experiment ultra-high pressure was used to modify the product. Three types of hydrocolloid; carboxymethylcellulose (CMC), locust bean gum (LBG) and xanthan gum, were added to minced ostrich meat batter at concentration of 0-1% and subjected to high pressure 600 Mpa, 50 degrees C, 40 min. The treated samples were analysed for storage (G) and loss (G '') moduli by dynamic oscillatory testing as well as creep compliance for control stress measurement. Their microstructures using confocal microscopy were also examined. Hydrocolloid addition caused a significant (P < 0.05) decrease in both the G' and G '' moduli. However the loss tangent of all samples remained unchanged. Addition of hydrocolloids led to decreases in the gel network formation but appears to function as surfactant materials during the initial mixing stage as shown by the microstructure. Confocal microscopy suggested that the size of the fat droplets decreased with gum addition. The fat droplets were smallest on the addition of xanthan gum and increased in the order CMC, LBG and no added gum, respectively. Creep parameters of ostrich yors with four levels of xanthan gum addition (0.50%, 0.75%, 1.00% and 1.25%) showed an increase in the instantaneous compliance (J(0)), the retarded compliance (J(1)) and retardation time (lambda(1)) but a decrease in the viscosity (eta(0)) with increasing levels of addition. The results also suggested that the larger deformations used during creep testing might be more helpful in assessing the mechanical properties of the product than the small deformations used in oscillatory rheology. (c) 2007 Elsevier Ltd. All rights reserved.

A single director switching mode for monodomain liquid crystal elastomer

We report rotation of a single director in a nematic monodomain, acrylate based side-chain elastomer which was subjected to mechanical fields applied at angles in the range to the director, , present at the time of network formation. Time and spatially resolving wide angle X-ray scattering, together with polarised light microscopy measurements revealed a pronounced, almost discontinuous switching mode at a critical extension as the strain was applied at angles approaching to , whereas a more continuous rotation was seen when the strain was applied at more acute angles. This director reorientation was more or less uniform across the complete sample and was accompanied by a modest decrease in orientation parameter . At strains sufficient to induce switching there was some continuous distribution of director orientations with fluctuations of 10 although there was no evidence for any localised director inhomogenities such as domain formation. The observed deformation behaviour of these acrylate-based nematic monodomains was in accord with the predictions of a theory developed by Bladon et al., in that the complete set of data could be accounted for through a single parameter describing the chain anisotropy. The experimentally deduced chain anisotropy parameter was in broad agreement with that obtained from small-angle neutron scattering procedures, but was somewhat greater than that obtained by spontaneous shape changes at the nematic-isotropic transition.

Side-chain liquid crystalline elastomers: the relationship between the orientational ordering of the polymer backbone and the length of the coupling chain

The influence of cross-linking on the phase behaviour of a series of side-chain liquid crystalline elastomers has been studied. For samples cross-linked in the temperature range corresponding to the nematic phase, the phase transition was shifted compared to that observed when an identical sample was cross-linked in the isotropic phase. This shift represented a stabilisation of the nematic phase in the former case, in line with theoretical expectations. By utilising a novel, slow cross-linking method, which allows the polymer backbone to take up an equilibrium conformation prior to network formation, it proved possible to monitor the shifts in phase transition temperature as a function of the length of the methylene chain coupling the mesogenic units to the polymer backbone. The results obtained are related to the backbone anisotropy and indicate that the level of orientational order of the polymer in the nematic phase backbone increases with a reduction in the length of the coupling chain.

Conditional transgenic expression of fibroblast growth factor 9 in the adult mouse heart reduces heart failure mortality after myocardial infarction

BACKGROUND: Fibroblast growth factor 9 (FGF9) is secreted from bone marrow cells, which have been shown to improve systolic function after myocardial infarction (MI) in a clinical trial. FGF9 promotes cardiac vascularization during embryonic development but is only weakly expressed in the adult heart. METHODS AND RESULTS: We used a tetracycline-responsive binary transgene system based on the α-myosin heavy chain promoter to test whether conditional expression of FGF9 in the adult myocardium supports adaptation after MI. In sham-operated mice, transgenic FGF9 stimulated left ventricular hypertrophy with microvessel expansion and preserved systolic and diastolic function. After coronary artery ligation, transgenic FGF9 enhanced hypertrophy of the noninfarcted left ventricular myocardium with increased microvessel density, reduced interstitial fibrosis, attenuated fetal gene expression, and improved systolic function. Heart failure mortality after MI was markedly reduced by transgenic FGF9, whereas rupture rates were not affected. Adenoviral FGF9 gene transfer after MI similarly promoted left ventricular hypertrophy with improved systolic function and reduced heart failure mortality. Mechanistically, FGF9 stimulated proliferation and network formation of endothelial cells but induced no direct hypertrophic effects in neonatal or adult rat cardiomyocytes in vitro. FGF9-stimulated endothelial cell supernatants, however, induced cardiomyocyte hypertrophy via paracrine release of bone morphogenetic protein 6. In accord with this observation, expression of bone morphogenetic protein 6 and phosphorylation of its downstream targets SMAD1/5 were increased in the myocardium of FGF9 transgenic mice. CONCLUSIONS: Conditional expression of FGF9 promotes myocardial vascularization and hypertrophy with enhanced systolic function and reduced heart failure mortality after MI. These observations suggest a previously unrecognized therapeutic potential for FGF9 after MI.

Supramolecular materials for inkjet printing: self-assembling polymer networks

Electronically complementary, low molecular weight polymers that self-assemble through tuneable π-π stacking interactions to form extended supramolecular polymer networks have been developed for inkjet printing applications and successfully deposited using three different printing techniques. Sequential overprinting of the complementary components results in supramolecular network formation through complexation of π-electron rich pyrenyl or perylenyl chain-ends in one component with π-electron deficient naphthalene diimide residues in a chain-folding polyimide. The complementary π-π stacked polymer blends generate strongly coloured materials as a result of charge-transfer absorptions in the visible spectrum, potentially negating the need for pigments or dyes in the ink formulation. Indeed, the final colour of the deposited material can be tailored by changing varying the end-groups of the π electron rich polymer component. Piezoelectric printing techniques were employed in a proof of concept study to allow characterisation of the materials deposited, and a thermal inkjet printer adapted with imaging software enabled a detailed analysis of the ink-drops as they formed, and of their physical properties. Finally, continuous inkjet printing allowed greater volumes of material to be deposited, on a variety of different substrate surfaces, and demonstrated the utility and versatility of this novel type of ink for industrial applications.

Contágio no modelo de Allen e Gale com infraestrutura bancária endógena

Neste trabalho investigamos a formação de network considerando agentes cautelosos. O modelo consiste em duas regiões com (n/2) bancos em cada, onde a interligação entre eles ocorre através e depósitos interbancários. Cada banco está sujeito a corrida bancária, ou devido a um choque negativo de agentes impacientes, ou devido a contaminação da corrida de um banco pertencente a infraestrutura bancária. Os bancos podem tentar eliminar a possibilidade de contágio ao fazer um número alto de inter-ligações. Para isso, é necessário uma coordenação entre todos os bancos. Se um banco não se prevenir de um contágio, ele impõe a todos os outros a possibilidade de contágio no pior cenário. Há duas regiões bem definidas de equilíbrio de nash simétrico com network estável, uma na qual todos os bancos se previnem do cenário de contágio no pior cenário e a outra na qual nenhum banco se previne. Devido ao problema de coordenação, o equilíbrio com contágio no pior cenário pode ocorrer mesmo sendo pareto dominado pelo equilíbrio sem contágio. Sob certas condições, o equilíbrio com contágio ocorre com um network pareto eficiente. Neste caso o network eficiente é diferente do network mais resiliente ao contágio.

The consumer litigation industry: chasing dragon kings in lawyer-client networks

The community of lawyers and their clients form a scale-free bipartite network that develops naturally as the outcome of the recommendation process through which lawyers form their client base. This process is an example of preferential attachment where lawyers with more clients are more likely to be recommended to new clients. Consumer litigation is an important market for lawyers. In large consumer societies, there always a signi cant amount of consumption disputes that escalate to court. In this paper we analyze a dataset of thousands of lawsuits, reconstructing the lawyer-client network embedded in the data. Analyzing the degree distribution of this network we noticed that it follows that of a scale-free network built by preferential attachment, but for a few lawyers with much larger client base than could be expected by preferential attachment. Incidentally, most of these also gured on a list put together by the judiciary of Lawyers which openly advertised the bene ts of consumer litigation. According to the code of ethics of their profession, lawyers should not stimulate clients into litigation, but it is not strictly illegal. From a network formation point of view, this stimulation can be seen as a separate growth mechanism than preferential attachment alone. In this paper we nd that this composite growth can be detected by a simple statistical test, as simulations show that lawyers which use both mechanisms quickly become the \Dragon-Kings" of the distribution of the number of clients per lawyer.

A organização social e o acesso à cultura: o caso das bibliotecas parque do Estado do Rio de Janeiro

Esta dissertação procura analisar qual a contribuição das Organizações Sociais para o acesso a direitos culturais, a partir da experiência das Bibliotecas Parque do Estado do Rio de Janeiro, em especial a de Manguinhos e a da Rocinha. Ciente de que as formas de cooperação para a efetivação de direitos culturais são múltiplas e que precisam ser pensadas a partir da inter-relação de vários atores e aspectos, todas invariavelmente necessitam desaguar em molduras de gestão viabilizadoras do acesso à cultura. A pesquisa adota o método do estudo de caso, valendo-se de pesquisas bibliográfica, documental e de campo. Apresenta o cenário de construção dos direitos culturais, em larga expansão no Brasil, e destaca que, para materializá-los, torna-se necessário estudar, avaliar e adotar modelos organizacionais alternativos aos tradicionais que caracterizam a administração pública direta e indireta. Aborda o campo da gestão e dos direitos culturais no contexto das três principais reformas do aparelho do Estado Republicano, ocorridas nas décadas de 30, 60 e 90, com ênfase na última, que incorpora a teoria da Nova Gestão Pública, base desta dissertação. Focaliza a Organização Social como modelo opcional à gestão de instituições ou programas culturais, a partir da realidade existente, das motivações, das vantagens e das perspectivas e aduz uma narrativa acerca do processo de concepção da legislação do estado do Rio de Janeiro. Verifica como surgiram esses equipamentos culturais e como se deu a formação da rede de Bibliotecas Parque. Descreve o processo de implantação das Organizações Sociais de Cultura no estado e apresenta o gestor das bibliotecas e sua relação com a secretaria de Cultura. Conclui que há necessidade de aperfeiçoamento de mecanismos de gestão, a fim de que o modelo possa, de fato, oferecer contribuição para o acesso a direitos culturais.

Influence of root-surface conditioning with acid and chelating agents on clot stabilization

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Synthesis and Structural Studies of Er3+ Containing Lead Cadmium Fluoroborate Glasses and Glass-Ceramics

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

Structural studies on TeO2-PbO glasses

Binary tellurite-based glasses in the TeO2-PbO system were prepared and its structure investigated by means of Raman Scattering and X-ray Absorption Spectroscopy. Both spectroscopies indicate strong modifications of the first coordination shell around tellurium atoms when the PbO content increases revealing for lead its glassy network modifier role. Also, Pb L-3-edge EXAFS measurements reveal this structural role played by lead atoms, but the presence of a medium range order contribution indicates that lead also participates to the glassy network formation. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

Electrical percolation during gelation of lithium doped siloxane-poly(oxyethylene) hybrids

Gelation mechanisms of lithium-doped Siloxane-Poly(oxyethylene) (PEO) hybrids containing polymer of two different molecular weight (500 and 1900 g/mol) were investigated through the evolution of the electrical properties during the solgel transition. The results of electrical measurements, performed by in-situ complex impedance spectroscopy, were correlated with the coordination and the dynamical properties of the lithium ions during the process as shown by Li-7 NMR measurements. For both hybrids sols, a decrease of the conductivity is observed at the initial gelation stage, due to the existence of an inverted percolation process consisting of the progressive separation of solvent molecules containing conducting species in isolated islands during the solid network formation. An increase of conductivity occurs at more advanced stages of gelation and aging, attributed to the increasing connectivity between PEO chains promoted by the formation of crosslinks of siloxane particles at their extremities, favoring hopping motions of lithium ions along the chains.

Redes dinâmicas de sensores sem fio ZigBee para aplicações de monitoramento e controle

Pós-graduação em Engenharia Elétrica - FEB

RHEOLOGICAL EVALUATION OF THE STRUCTURE OF ICE CREAM MIXES VARYING FAT BASE

This paper discusses the influence of fat type in the structure of ice cream, during its production by means of rheo-optical analysis. Fat plays an important part in the ice cream structure formation. It's responsible for the air stabilization, flavor release, texture and melting properties. The objective of this study was to use a rheological method to predict the fat network formation in ice cream with three types of fats (hydrogenated, low trans and palm fat). The three formulations were produced using the same methodology and ratio of ingredients. Rheo-optical measurements were taken before and after the ageing process, and the maximum compression force, overrun and melting profile were calculated in the finished product. The rheological analysis showed a better response from the ageing process from the hydrogenated fat, followed by the low trans fat. The formulation with palm fat showed greater differences between the three, where through the rheological tests a weaker destabilization of the fat globule membrane by the emulsifier was suggested. The overrun, texture measurements and meltdown profile has shown the distinction on the structure formation by the hydrogenated fat from the other fats.