Increased ion conduction in dual cation [sodium][tetraalkylammonium] poly[4-styrenesulfonyl(trifluoromethylsulfonyl)imide-co-ethylacrylate] ionomers

© The Royal Society of Chemistry. Solid-state polymer electrolytes, as an alternative to traditional liquid electrolytes, have been intensively investigated for energy conversion and storage devices. The transport rate of single ions is the key to their high performance. For application in emerging sodium batteries, we have developed three dual-cation polymeric ionomers, which contain bulky tetraalkylammonium ions in addition to the sodium ion. The sizes and relative contents of the ammonium ions vary relative to the sodium ion contents. Comparative studies of ion dynamics, thermal properties, phase behaviours and ionic conductivities were carried out, taking advantage of various spectroscopic and thermal chemistry methods. The ion conductivities of the ionomers are greatly enhanced by the introduction of bulky counterions, as a result of the additional free volume and decreased sodium ion association. Raman spectroscopy and thermal analysis as well as the solid-state nuclear magnetic resonance studies are used to probe the conductivity behaviour.

Managing Dual Enrollment Programs: Review of Program Models, Operations, and Outcomes

Universities that offer dual enrollment programs for high school students must manage increasing student demand in the face of changing state legislation. This brief examines how institutions finance their dual enrollment programs, and how they ensure academic rigor as their programs continue to grow. The report also considers how dual enrollment programs ensure that students can transfer credits, and what strategies they use to encourage DE students to matriculate as undergraduates.

Transformação genética em cevada por bombardeamento de partículas

A presente Tese de Doutorado objetivou: (1) definir um método eficiente de transformação genética, por bombardeamento de partículas, para a obtenção de plantas transgênicas de cultivares brasileiras de cevada e (2) identificar gene(s) codificante(s) de quitinase(s) potencialmente capaz(es) de conferir resistência ao fungo patogênico de cevada Bipolaris sorokiniana. Culturas de calos obtidos a partir de escutelos imaturos das cultivares Brasileiras de cevada MN-599 e MN-698 (Cia. de Bebidas das Américas, AMBEV) foram bombardeadas com partículas de tungstênio e avaliadas quanto à expressão do gene repórter gusA através de ensaios histoquímicos de GUS e quanto ao efeito dos bombardeamentos na indução estruturas embriogênicas e regeneração de plantas. As condições de biobalística analisadas incluíram a região promotora regulando a expressão de gusA, tipo e pressão de gás hélio de dois aparelhos de bombardeamento, distância de migração das partículas, número de tiros e a realização de pré e pós-tratamento osmótico dos tecidos-alvo. No presente trabalho foram obtidos um número bastante alto de pontos azuis por calo, a indução de calos embriogênicos e embriões somáticos em uma freqüência de até 58,3% e a regeneração de 60 plantas, sendo 43 de calos bombardeados. As melhores condições observadas foram o promotor e primeiro íntron do gene Adh de milho (plasmídeo pNGI), o aparelho de bombardeamento “ Particle Inflow Gun” (PIG) utilizando-se a distância de migração de partículas de 14,8 cm, dois tiros disparados por placa e a realização de tratamento osmótico dos explantes com 0,2 M de manitol e 0,2 M de sorbitol 4-5 horas antes e 17-19 horas depois dos bombardeamentos. Das 43 plantas obtidas de calos bombardeadas, 3 apresentaram atividade de GUS na base das suas folhas. A utilização de primers sintéticos definidos a partir de genes de quitinases descritos na literatura em PCRs resultou na amplificação de dois fragmentos de aproximadamente 700 e 500 pb a partir de DNA total das cvs. MN-599 e MN-698 de cevada e um fragmento, com aproximadamente 500 pb, a partir do DNA total do isolado A4c de Trichoderma sp. Estes fragmentos foram purificados dos géis de agarose e diretamente seqüenciados de forma manual e automática. Os fragmentos de 700 e 500 pb amplificados do genoma da cultivar MN-599 foram identificados como genes de quitinases de cevada e o fragmento de 500 pb do isolado A4c de Trichoderma sp. não apresentou homologia com seqüências conhecidas de quitinases depositadas no EMBL/GenBank. A utilização de novos pares de primers, representando seqüências conservadas de quitinases do fungo Metarhizium anisopliae, resultou na amplificação de 3 fragmentos a partir do DNA total do isolado A4b de Trichoderma sp., que estão sendo purificados para realização de seqüenciamento.

Price discovery in dual-class shares across multiple markets

We extend the standard price discovery analysis to estimate the information share of dual-class shares across domestic and foreign markets. By examining both common and preferred shares, we aim to extract information not only about the fundamental value of the rm, but also about the dual-class premium. In particular, our interest lies on the price discovery mechanism regulating the prices of common and preferred shares in the BM&FBovespa as well as the prices of their ADR counterparts in the NYSE and in the Arca platform. However, in the presence of contemporaneous correlation between the innovations, the standard information share measure depends heavily on the ordering we attribute to prices in the system. To remain agnostic about which are the leading share class and market, one could for instance compute some weighted average information share across all possible orderings. This is extremely inconvenient given that we are dealing with 2 share prices in Brazil, 4 share prices in the US, plus the exchange rate (and hence over 5,000 permutations!). We thus develop a novel methodology to carry out price discovery analyses that does not impose any ex-ante assumption about which share class or trading platform conveys more information about shocks in the fundamental price. As such, our procedure yields a single measure of information share, which is invariant to the ordering of the variables in the system. Simulations of a simple market microstructure model show that our information share estimator works pretty well in practice. We then employ transactions data to study price discovery in two dual-class Brazilian stocks and their ADRs. We uncover two interesting ndings. First, the foreign market is at least as informative as the home market. Second, shocks in the dual-class premium entail a permanent e ect in normal times, but transitory in periods of nancial distress. We argue that the latter is consistent with the expropriation of preferred shareholders as a class.

Impacto da emissão dual-class na estrutura de capital

A tese propõe que empresas que emitem apenas ações com direitos de voto utilizam mais capitais de terceiros do que empresas que emitem tanto ações votantes quanto não votantes. No desenvolvimento do trabalho, foi demonstrada a relevância de relacionar endividamento ao fato de uma empresa emitir ou não ações sem direito a voto, considerando as principais teorias de estrutura de capital e a realidade brasileira. Como os modelos teóricos que explicam o nível de endividamento das empresas ainda carecem de capacidade explicativa, a busca por novos determinantes está presente na literatura de estrutura de capital. A ocorrência da emissão de ações em classes diferenciadas (dual-class) como fator impactante no nível de endividamento foi analisada sob três prismas: de mercado, dos setores e das empresas que unificaram suas ações. Pelas três investigações ficou evidenciada a perspectiva de que o endividamento seja menor nos casos de emissão de ações preferenciais, considerando o ambiente de negociação e regulamentação do Brasil. A aceitação da tese tem reflexos teóricos na identificação de um fator que deve ser levado em consideração nos modelos de estrutura de capital, bem como suscita a importância de gestores, investidores e credores reconhecerem que o fato de uma empresa ser dual-class impacta não apenas na sua estrutura de controle, mas principalmente em sua estrutura de capital. Entre as considerações da aceitação da tese, estaria o reconhecimento de que empresas que ingressam no Novo Mercado na prática estão, no longo prazo, trocando o uso de ações preferenciais como forma de financiamento pela emissão de dívida.

Dual resource transfers and interruption in external debt service

Externai debt service requires a dual resource transfer. Trade surpluses have to be generated in order to make foreign exchange revenues available for debt repayment. In addition, with developing countries' externai debt being largely a public liability, debt service requires that resources can be effectively transferred from the private to the public sector. This paper derives a statistical model for dealing with dual constraints in the presence of binary dependent variables and applies it to the dual resource transfer problem. The results from the estimation of the model for a sample of 31 middle-income developing countries in the period of 1980 to 1990, strongly support the hypothesis that both externai and fiscal constraints are important in explaining externai debt service disruptions.

Functionalization of dendrimers for improved gene delivery to mesenchymal stem cell

Disease, injury, and age problems compromise human quality of life and continuously motivate the search for new and more efficacious therapeutic approaches. The field of Tissue Regeneration and Engineering has greatly evolved over the last years, mainly due to the combination of the important advances verified in Biomaterials Science and Engineering with those of Cell and Molecular Biology. In particular, a new and promising area arose – Nanomedicine – that takes advantage of the extremely small size and especial chemical and physical properties of Nanomaterials, offering powerful tools for health improvement. Research on Stem Cells, the self-renewing progenitors of body tissues, is also challenging to the medical and scientific communities, being expectable the appearance of new and exciting stem cell-based therapies in the next years. The control of cell behavior (namely, of cell proliferation and differentiation) is of key importance in devising strategies for Tissue Regeneration and Engineering. Cytokines, growth factors, transcription factors and other signaling molecules, most of them proteins, have been identified and found to regulate and support tissue development and regeneration. However, the application of these molecules in long-term regenerative processes requires their continuous presence at high concentrations as they usually present short half-lives at physiological conditions and may be rapidly cleared from the body. Alternatively, genes encoding such proteins can be introduced inside cells and be expressed using cell’s machinery, allowing an extended and more sustained production of the protein of interest (gene therapy). Genetic engineering of stem cells is particularly attractive because of their self-renewal capability and differentiation potential. For Tissue Regeneration and Engineering purposes, the patient’s own stem cells can be genetically engineered in vitro and, after, introduced in the body (with or without a scaffold) where they will not only modulate the behavior of native cells (stem cell-mediated gene therapy), but also directly participate in tissue repair. Cells can be genetically engineered using viral and non-viral systems. Viruses, as a result of millions of years of evolution, are very effective for the delivery of genes in several types of cells, including cells from primary sources. However, the risks associated with their use (like infection and immunogenic reactions) are driving the search for non-viral systems that will efficiently deliver genetic material into cells. Among them, chemical methods that are promising and being investigated use cationic molecules as carriers for DNA. In this case, gene delivery and gene expression level remain relatively low when primary cells are used. The main goal of this thesis was to develop and assess the in vitro potential of polyamidoamine (PAMAM) dendrimers based carriers to deliver genes to mesenchymal stem cells (MSCs). PAMAM dendrimers are monodispersive, hyperbranched and nanospherical molecules presenting unique characteristics that make them very attractive vehicles for both drug and gene delivery. Although they have been explored for gene delivery in a wide range of cell lines, the interaction and the usefulness of these molecules in the delivery of genes to MSCs remains a field to be explored. Adult MSCs were chosen for the studies due to their potential biomedical applications (they are considered multipotent cells) and because they present several advantages over embryonic stem cells, such as easy accessibility and the inexistence of ethical restrictions to their use. This thesis is divided in 5 interconnected chapters. Chapter I provides an overview of the current literature concerning the various non-viral systems investigated for gene delivery in MSCs. Attention is devoted to physical methods, as well as to chemical methods that make use of polymers (natural and synthetic), liposomes, and inorganic nanoparticles as gene delivery vectors. Also, it summarizes the current applications of genetically engineered mesenchymal stem cells using non-viral systems in regenerative medicine, with special focus on bone tissue regeneration. In Chapter II, the potential of native PAMAM dendrimers with amine termini to transfect MSCs is evaluated. The level of transfection achieved with the dendrimers is, in a first step, studied using a plasmid DNA (pDNA) encoding for the β-galactosidase reporter gene. The effect of dendrimer’s generation, cell passage number, and N:P ratio (where N= number of primary amines in the dendrimer; P= number of phosphate groups in the pDNA backbone) on the level of transfection is evaluated, being the values always very low. In a second step, a pDNA encoding for bone morphogenetic protein-2, a protein that is known for its role in MSCs proliferation and differentiation, is used. The BMP-2 content produced by transfected cells is evaluated by an ELISA assay and its effect on the osteogenic markers is analyzed through several classical assays including alkaline phosphatase activity (an early marker of osteogenesis), osteocalcin production, calcium deposition and mineralized nodules formation (late osteogenesis markers). Results show that a low transfection level is enough to induce in vitro osteogenic differentiation in MSCs. Next, from Chapter III to Chapter V, studies are shown where several strategies are adopted to change the interaction of PAMAM dendrimers with MSCs cell membrane and, as a consequence, to enhance the levels of gene delivery. In Chapter III, generations 5 and 6 of PAMAM dendrimers are surface functionalized with arginine-glycine-aspartic acid (RGD) containing peptides – experiments with dendrimers conjugated to 4, 8 and 16 RGD units were performed. The underlying concept is that by including the RGD integrin-binding motif in the design of the vectors and by forming RGD clusters, the level of transfection will increase as MSCs highly express integrins at their surface. Results show that cellular uptake of functionalized dendrimers and gene expression is enhanced in comparison with the native dendrimers. Furthermore, gene expression is dependent on both the electrostatic interaction established between the dendrimer moiety and the cell surface and the nanocluster RGD density. In Chapter IV, a new family of gene delivery vectors is synthesized consisting of a PAMAM dendrimer (generation 5) core randomly linked at the periphery to alkyl hydrophobic chains that vary in length and number. Herein, the idea is to take advantage of both the cationic nature of the dendrimer and the capacity of lipids to interact with biological membranes. These new vectors show a remarkable capacity for internalizing pDNA, being this effect positively correlated with the –CH2– content present in the hydrophobic corona. Gene expression is also greatly enhanced using the new vectors but, in this case, the higher efficiency is shown by the vectors containing the smallest hydrophobic chains. Finally, chapter V reports the synthesis, characterization and evaluation of novel gene delivery vectors based on PAMAM dendrimers (generation 5) conjugated to peptides with high affinity for MSCs membrane binding - for comparison, experiments are also done with a peptide with low affinity binding properties. These systems present low cytotoxicity and transfection efficiencies superior to those of native dendrimers and partially degraded dendrimers (Superfect®, a commercial product). Furthermore, with this biomimetic approach, the process of gene delivery is shown to be cell surface receptor-mediated. Overall, results show the potential of PAMAM dendrimers to be used, as such or modified, in Tissue Regeneration and Engineering. To our knowledge, this is the first time that PAMAM dendrimers are studied as gene delivery vehicles in this context and using, as target, a cell type with clinical relevancy. It is shown that the cationic nature of PAMAM dendrimers with amine termini can be synergistically combined with surface engineering approaches, which will ultimately result in suitable interactions with the cytoplasmic membrane and enhanced pDNA cellular entry and gene expression. Nevertheless, the quantity of pDNA detected inside cell nucleus is always very small when compared with the bigger amount reaching cytoplasm (accumulation of pDNA is evident in the perinuclear region), suggesting that the main barrier to transfection is the nuclear membrane. Future work can then be envisaged based on the versatility of these systems as biomedical molecular materials, such as the conjugation of PAMAM dendrimers to molecules able to bind nuclear membrane receptors and to promote nuclear translocation.

Controlador em modo dual adaptativo robusto - DMARC

The so-called Dual Mode Adaptive Robust Control (DMARC) is proposed. The DMARC is a control strategy which interpolates the Model Reference Adaptive Control (MRAC) and the Variable Structure Model Reference Adaptive Control (VS-MRAC). The main idea is to incorporate the transient performance advantages of the VS-MRAC controller with the smoothness control signal in steady-state of the MRAC controller. Two basic algorithms are developed for the DMARC controller. In the first algorithm the controller's adjustment is made, in real time, through the variation of a parameter in the adaptation law. In the second algorithm the control law is generated, using fuzzy logic with Takagi-Sugeno s model, to obtain a combination of the MRAC and VS-MRAC control laws. In both cases, the combined control structure is shown to be robust to the parametric uncertainties and external disturbances, with a fast transient performance, practically without oscillations, and a smoothness steady-state control signal

Uma abordagem indireta para o Controlador em Modo Dual Adaptativo Robusto

In this work is proposed an indirect approach to the DualMode Adaptive Robust Controller (DMARC), combining the typicals transient and robustness properties of Variable Structure Systems, more specifically of Variable Structure Model Reference Adaptive Controller (VS-MRAC), with a smooth control signal in steady-state, typical of conventional Adaptive Controllers, as Model Reference Adaptive Controller (MRAC). The goal is to provide a more intuitive controller design, based on physical plant parameters, as resistances, inertia moments, capacitances, etc. Furthermore, with the objective to follow the evolutionary line of direct controllers, it will be proposed an indirect version for the Binary Model Reference Adaptive Controller (B-MRAC), that was the first controller attemptting to act as MRAC as well as VS-MRAC, depending on a pre-defined fixed parameter

Mechanism of anticlastogenicity of Agaricus blazei Murill mushroom organic extracts in wild type CHO (K-1) and repair deficient (xrs5) cells by chromosome aberration and sister chromatid exchange assays

Agaricus blazei Murill is a medicinal mushroom native to Brazil. The present work assessed the clastogenic and anticlastogenic potential of organic extracts (ethanol and chloroform/methanol) from the lineage AB97/11 in chinese hamster CHO-K-1 (wild type) and CHO-xrs5 (repair deficient) cells using the chromosome aberration (CA) and sister chromatid exchange (SCE) assays. In these experimental conditions were observed: (a) anticlastogenic effect at concentrations of 0.06 and 0.09% of the EtOH extract and at the 0.03 and 0.06% concentrations of the C/MetOH extract in CHO-K-1; (b) absence of protector effect on CHO-xrs5 cells; and (c) absence of protector effect in the SCE assay. These results indicate that organic extracts of A. blazei lineage AB97/11 present bio-antimutagenic type protective activity. (C) 2003 Elsevier B.V. B.V. All rights reserved.

A influência das injunções de orientação relativa na calibração de um sistema dual de câmeras digitais

Image acquisition systems based on multi-head arrangement of digital frame cameras, such as the commercial systems DMC, UltraCam, besides others, are attractive alternatives enabling larger imaging area when compared to a single frame camera. Considering that in these systems, cameras are tightly attached to an external mount, it is assumed that relative position and orientation between cameras are stable during image acquisition and, consequently, these constraint can be included in the calibration step. This constraint is acceptable because estimates of the relative orientation (RO) parameters between cameras, from previously estimated exterior orientation parameters, present higher and significant deviations than the expected physical variations, due to error propagation. In order to solve this problem, this work presents an approach based on simultaneous calibration of two or more cameras using constraints that state that the relative rotation matrix and the distance between the cameras head are stable. Experiments with images acquired by an arrangement of two Hasselblad H2D cameras were accomplished, without and with the mentioned constraints. The experiments showed that the calibration process with RO constraints allows better results than the approach based on single camera calibration, provided that the estimation has included only images with good target distribution.

Mutagenicity and antimutagenicity of (-)-hinokinin a trypanosomicidal compound measured by Salmonella microsome and comet assays

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

Cheap assays of malate, glycerol and ethanol in fermenting must and food samples

A preparation, enriched with malate dehydrogenase (MDH), alcohol dehydrogenase (ADH), glycerol -3- P dehydrogenase (GPDH) and glycerol kinase (GK), was obtained from dry baker's yeast. This preparation was used to assay glycerol, ethanol and malate measuring the variations in absorbance (NADH formation) at 340 nm. Good degrees of recoveries were obtained when glycerol was added to red wine and fermenting sugar-cane juice and when L-malate was added to commercial apple juice samples. Good results were also obtained when ethanol was assayed in fermented sugar-cane juice and wine samples, using both the partially purified preparation obtained from dry yeast and a purified commercial alcohol dehydrogenase.

Um método primal-dual aplicado na resolução do problema de fluxo de potência ótimo

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

A modified Primal-Dual Logarithmic-Barrier Method for solving the Optimal Power Flow problem with discrete and continuous control variables

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