955 resultados para hydroxyl-terminated polybutadiene
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Polysaccharide natural seed coat from the tree Magonia pubescens, in the form of hydrogel was used to remove metals in aqueous solution. Swelling tests indicate that seed coat presents hydrogel behavior, with maximum water absorption of 292 g water/g. Adsorption experiments performed using Na(+), Mg(2+), K(+), Ca(2+), Cr(3+), Fe(3+) and Zn(2+) demonstrated that the polysaccharide structure has a high capacity to extract these ions from the aqueous solution. Scanning electron microscopy revealed significant morphological changes of the material before and after water contact. Differential scanning calorimetry measurements indicate a signal shift of the water evaporation temperature in the material with adsorbed zinc. X-ray photoelectron spectroscopy analysis combined with theoretical studies by the density functional theory and on Hartree-Fock (HF) level evidence that the metallic ions were adsorbed through coordination with hydroxyl groups of polysaccharide. In the case of Zn(2+) the lowest HF energy was observed for the tetracoordination mode, where Zn(2+) is coordinated by two hydroxyl groups and two water molecules.
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CD and EPR were used to characterize interactions of oxindole-Schiff base copper(II) complexes with human serum albumin (HSA). These imine ligands form very stable complexes with copper, and can efficiently compete for this metal ion towards the specific N-terminal binding site of the protein, consisting of the amino acid sequence Asp-Ala-His. Relative stability constants for the corresponding complexes were estimated from CD data, using the protein as competitive ligand, with values of log K(CuL) in the range 15.7-18.1, very close to that of [Cu(HSA)] itself, with log K(CuHSA) 16.2. Some of the complexes are also able to interfere in the a-helix structure of the protein, while others seem not to affect it. EPR spectra corroborate those results, indicating at least two different metal species in solution, depending on the imine ligand. Oxidative damage to the protein after incubation with these copper(II) complexes, particularly in the presence of hydrogen peroxide, was monitored by carbonyl groups formation, and was observed to be more severe when conformational features of the protein were modified. Complementary EPR spin-trapping data indicated significant formation of hydroxyl and carbon centered radicals, consistent with an oxidative mechanism. Theoretical calculations at density functional theory (DFT) level were employed to evaluate Cu(II)-L binding energies, L -> Cu(II) donation, and Cu(II) -> L back-donation, by considering the Schiff bases and the N-terminal site of HSA as ligands. These results complement previous studies on cytotoxicity, nuclease and pro-apoptotic properties of this kind of copper(II) complexes, providing additional information about their possibilities of transport and disposition in blood plasma. (C) 2009 Elsevier Inc. All rights reserved.
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This work describes the partial oxypropylation of filter paper cellulose fibers, employing two different basic catalyst, viz., potassium hydroxide and 1,4-diazabicyclo [2.2.2] octane, to activate the hydroxyl groups of the polysaccharide and thus provide the anionic initiation sites for the ""grafting-from"" polymerization of propylene oxide. The success of this chemical modification was assessed by FTIR spectroscopy, X-ray diffraction, scanning electron microscopy, differential scanning calorimetry, thermogravimetric analysis and contact angle measurements. The study of the role of the catalyst employed on the extent of the modification and on the mechanical properties of the ensuing composites, after hot pressing, showed that both the Bronsted and the Lewis base gave satisfactory results, without any marked difference.
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Reactions of N-[N`,N`-diethylamino(thiocarbonyl)]benzimidoyl chloride with 4,4-dialkylthiosemicarbazides give a novel class of thiosemicarbazides/thiosemicarbazones, H(2)L, which causes a remarkable reduction of cell growth in in vitro experiments. These strong antiproliferative effects are also observed for oxorhenium(V) complexes of the general composition [ReOCl(L)], which are formed by reactions of the potentially tridentate ligands with (NBu(4))[ReOCl(4)]. A systematic substitution of the alkyl groups in the thiosemicarbazone building blocks of the ligands do not significantly influence the biological activity of the metal complexes, while the replacement of the chloro ligand by a PPh(3) ligand (by the replacement of the oxo unit by a nitrido ligand) completely terminated the cytotoxicity of the metal complexes.
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In this paper the behavior of matter waves in suddenly terminated potential structures is investigated numerically. It is shown that there is no difference between a fully quantum mechanical treatment and a semiclassical one with regards to energy redistribution. For the quantum case it is demonstrated that there can be substantial reflection at the termination. The neglect of backscattering by the semiclassical method brings about major differences in the case of low kinetic energies. A simple phenomenological model is shown to partially explain the observed backscattering using dynamics of reduced dimensionality.
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Amostras de borracha natural foram reticuladas por meio de radiação gama (doses de 2, 4, 6 e 8 MRad) e intumescidas: a) em n-octano, ciclo-hexano e esqualeno; b) em polibutadieno líquido (Mn=1830 g/mol; alto teor 1,4- cis) a 45°C; C) em solução de polibutadieno de baixo peso molecular (M,= 1830 g/mol; alto teor 1,4-cis) em n-octano e ciclo-hexano; d) em solução de polibutadieno de alto peso molecular (Mn= 175.000 g/rnol; alto teor 1,4-cis) emn-octano e ciclo-hexano ; e) em solução de borracha natural (Mn=779.000 g/mol) em ciclo- hexano, a 25°C. Amostras de polibutadieno (alto teor 1,4-cis) foram reticuladas por meio de radiação gama (doses de 1,s; 18 e 25 MRad) e intumescidas: a) em n-octano, ciclo-hexano e esquaieno. Salvo quando mencionado em contrário, as amostras de borracha natural e de polibutadieno foram intumescidas nas temperaturas de 25, 35 e 45°C. A partir dos ensaios de intumescirnento acima mencionados, foram determinadas as solubilidades de borracha natural e de polibutadieno em n-octano, ciclo-hexano e esqualeno através dos parâmetros de Flory-Huggins, calculados com o emprego da equação de Flory-Rehner. Verificou-se a influência da temperatura e da concentração de polimero no gel sobre o valor do parâmetro de Flory-Huggins. Também através desse parâmetro procurou-se determinar a compatibilidade entre borracha natural e polibutadieno. Foi demonstrado que cadeias lineares de baixo peso molecular de polibutadieno conseguem penetrar em amostras reticuladas de borracha natural, quando o peso molecular das cadeias lineares for bem inferior ao do arco de rede Mc das amostras reticuladas. Cadeias lineares de polibutadieno e de borracha natural com peso molecular superior ao do arco de rede da borracha natural reticulada, entretanto, não conseguem penetrar no retículo. Quranto mais alta a concentração da solução externa em moléculas de alto peso molecular, tanto menor é o grau de intumescimento da amostra reticulada.
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o serviço móvel celular apresentou, nos últimos anos, mudanças significativas em termos de evolução tecnológica e dos produtos e serviços oferecidos ao cliente. O ambiente de prestação do serviço evoluiu a partir de um monopólio estatal para um regime de duopólio regional privado. A introdução da competição trouxe benefícios aos clientes, dentre os quais podem ser citados a redução dos preços de aquisição e das tarifas de uso do serviço e o aumento da oferta de linhas celulares, antes em falta no mercado. A introdução do serviço pré-pago, em 1999, representou um marco na história do Serviço Móvel Celular no Brasil. O produto, adequado para usuários que querem controlar seus gastos com telefonia celular, permitiu o acesso das classes econômicas C e D ao serviço. O pré-pago trouxe vantagens e desvantagens para clientes e prestadores de serviço. Uma de suas limitações, quando lançado, era a impossibilidade de utilização do servIço fora da área de atuação da operadora ("roaming"). O problema técnico que impedia o oferecimento de roammg para chamadas terminadas foi resolvido e as empresas prestadoras adotaram estratégias distintas em relação a isso. Algumas ofereceram o serviço para todos os clientes pré-pago, indistintamente; outras segmentaram o mercado pré-pago, criando produtos novos com a facilidade de roaming e mantendo os produtos já lançados no mercado sem a facilidade de roaming. A Americel, empresa operadora do Serviço Móvel Celular na região Centro Oeste e parte da região Norte, possui dois produtos pré-pago: o primeiro, chamado Legal, não permite o roaming de chamadas terminadas. Foi criado também o Legal Pacas que oferecia, entre outras novas funcionalidades, a possibilidade de roaming de chamadas terminadas. Os dois produtos possuem outras características diferentes e planos de tarifa próprios. O objetivo da pesquisa é avaliar como o cliente pré-pago da Americel percebe a funcionalidade de roaming de chamadas terminadas. A pesquisa pretende avaliar a importância do serviço para o cliente, como ele avalia o serviço prestado pela empresa e como essa funcionalidade é classificada (básica, de desempenho ou de encantamento). A partir da compreensão da percepção do cliente quanto ao roaming, será avaliada a estratégia de marketing de segmentar o mercado pré-pago por meio dessa funcionalidade. VI A metodologia empregada utiliza-se de ferramentas de medição da satisfação dos clientes. A Americel realiza mensalmente uma pesquisa de satisfação com uma amostra de 400 clientes que são entrevistados por telefone. O questionário de pesquisa possui 50 perguntas sobre vários aspectos relacionados à prestação do serviço. Os resultados anteriores dessa pesquisa apontam a cobertura como sendo a característica mais importante do serviço do ponto de vista do cliente e, ao mesmo tempo, uma característica mal avaliada por ele. A pesquisa também demonstra uma confusão do cliente que, quando questionado sobre onde necessita de cobertura, indica regiões onde a empresa não atua e, portanto, não poderia oferecer cobertura, mas roaming. Para uma parte dos clientes, roaming e cobertura são o mesmo atributo. Foram acrescentadas ao questionário padrão perguntas relacionadas ao roaming. As perguntas foram elaboradas para avaliar a freqüência com que os clientes viajam, a importância atribuída ao roaming, a avaliação do serviço de roaming e a avaliação geral da Americel. Os resultados permitem concluir que, apesar do usuário do serviço pré-pago não viajar freqüentemente, ele considera a funcionalidade de roaming como importante ou muito importante. A avaliação do serviço é ruim, o que implica na necessidade de priorizar ações no sentido de melhorar o serviço de roaming para os clientes pré-pago. Isso pode ser feito através da extensão do oferecimento do roaming a todos os clientes pré-pago. O resultado da análise penalidade-recompensa foi de que a funcionalidade de roaming é uma funcionalidade de desempenho do Serviço Móvel Celular. Isso significa que sua ausência causa insatisfação do cliente, enquanto sua presença aumenta a sua satisfação. Sendo assim, mais uma vez é confirmada a necessidade de oferecimento dessa facilidade a toda a base de clientes pré-pago. A pesquisa permite, então, concluir que a estratégia de marketing de segmentar o mercado de clientes pré-pago por meio do uso da facilidade de roaming tem como conseqüência final a insatisfação do cliente, uma vez que, de acordo com sua percepção, o roaming é uma funcionalidade importante do serviço móvel celular, que deve ser oferecido para toda a base de clientes. As características do serviço que devem ser usadas para segmentação devem ser aquelas que, quando ausentes, não causam insatisfação nos clientes, mas, quando presentes, o encantam.
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O processo de globalização e o grande fluxo de mão de obra levaram à edição da lei 7064/1982 (“Mendes Junior”) responsável por regular os direitos dos trabalhadores transferidos temporariamente para o exterior. De acordo com essa norma, àqueles empregados transferidos para outros países é assegurado o recolhimento de FGTS e INSS, além do pagamento de outras verbas trabalhistas dispostas na lei. Contudo, a essa legislação editada em 1982 se tornou inócua e desatualizada diante das novas relações de trabalho que lhe foram apresentadas. O presente trabalho pretende analisar o âmbito de aplicação da Lei Mendes Junior através do estudo de caso, onde o empregado é transferido para o exterior sem animus de volta e em caráter definitivo e, em virtude dessa transferência, tem o seu contrato de trabalho rescindido com a empresa brasileira e é admitido por uma empresa estrangeira, integrante do mesmo grupo econômico da sua empregadora original. Através de uma análise sistemática dos dispositivos da lei, é possível observar que a Lei Mendes Junior foi proposta com o objetivo principal de proteger os empregados que foram transferidos para o exterior com a expectativa de retorno para o Brasil. A interpretação da lei confirma a assertiva acima de que a legislação não foi criada para as transferências definitivas. Por fim, o trabalho em epígrafe oferece uma proposta legislativa para dirimir a lacuna da lei.
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Este estudo tem o objetivo de verificar o tratamento dado aos contratos de Locação Comercial de Devedor Locatário em Recuperação Judicial. A lei 11.101/2005 determina, em seus artigos 117 e 119,VII, que os contratos bilaterais não se resolvem pela falência e que na falência do locatário, o administrador judicial pode, a qualquer tempo, denunciar o contrato. Porém, a lei é lacônica a respeito do processo de Recuperação Judicial. Então, o estudo pretende verificar a aplicabilidade dos artigos pertinentes à falência, aos contratos de Devedor submetido ao processo de Recuperação Judicial. Com o intuito de realizar interpretação congruente com a eficiência que se espera da legislação em comento, a metodologia utilizada no trabalho é a da Análise Econômica do Direito, segundo os contornos conferidos pelo autor THOMAS H. JACKSON. Assim, o trabalho aproveita os conceitos do common pool assets e dos executory contracts para auxiliar na compreensão da função dos contratos de locação no Processo de Recuperação Judicial. Nesse sentido, o estudo é importante, pois estabelece parâmetros de interpretação teleológica da legislação concursal, considerando-se as tensões entre o Direito Material e Concursal aplicáveis a hipótese aqui formulada. Então, constatou-se que o tema gera divergência de entendimentos perante a jurisprudência brasileira, no que se refere a possibilidade, ou não, de despejar locatário Devedor em Recuperação Judicial. A controvérsia ronda, principalmente, em torno de duas questões: (a) a aplicação do principio da preservação da empresa, presente no art. 47. da L.11.101/2005 (b) (i)liquidez da ação de despejo por falta de pagamento para fins do artigo 6 da mesma lei. Por fim, o estudo avalia forma pela qual a jurisprudência trata do tema e a sua compatibilidade com a metodologia de Análise Econômica Aplicável ao Direito Concursal.
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Gene therapy, which involves the transfer of nucleic acid into target cells in patients, has become one of the most important and widely explored strategies to treat a variety of diseases, such as cancer, infectious diseases and genetic disorders. Relative to viral vectors that have high immunogenicity, toxicity and oncogenicity, non-viral vectors have gained a lot of interest in recent years. This is largely due to their ability to mimic viral vector features including the capacity to overcome extra- and intra-cellular barriers and to enhance transfection efficiency. Polyethyleneimine (PEI) has been extensively investigated as a non-viral vector. This cationic polymer, which is able to compact nucleic acid through electrostatic interactions and to transport it across the negatively charged cell membranes, has been shown to effectively transfect nucleic acid into different cell lines. Moreover, entrapment of gold nanoparticles (Au NPs) into such an amine-terminated polymer template has been shown to significantly enhance gene transfection efficiency. In this work, a novel non-viral nucleic acid vector system for enhanced and targeted nucleic acid delivery applications was developed. The system was based on the functionalization of PEI with folic acid (FA; for targeted delivery to cancer cells overexpressing FA receptors on their surface) using polyethylene glycol (PEG) as a linker molecule. This was followed by the preparation of PEI-entrapped Au NPs (Au PENPs; for enhancement of transfection efficiency). In the synthesis process, the primary amines of PEI were first partially modified with fluorescein isothiocyanate (FI) using a molar ratio of 1:7. The formed PEI-FI conjugate was then further modified with either PEG or PEGylated FA using a molar ratio of 1:1. This process was finally followed by entrapment of Au NPs into the modified polymers. The resulting conjugates and Au PENPs were characterized by several techniques, namely Nuclear Magnetic Resonance, Dynamic Light Scattering and Ultraviolet-Visible Spectroscopy, to assess their physicochemical properties. In the cell biology studies, the synthesized conjugates and their respective Au PENPs were shown to be non-toxic towards A2780 human ovarian carcinoma cells. The role of these materials as gene delivery agents was lastly evaluated. In the gene delivery studies, the A2780 cells were successfully transfected with plasmid DNA using the different vector systems. However, FA-modification and Au NPs entrapment were not determinant factors for improved transfection efficiency. In the gene silencing studies, on the other hand, the Au PENPs were shown to effectively deliver small interfering RNA, thereby reducing the expression of the B-cell lymphoma 2 protein. Based on these results, we can say that the systems synthesized in this work show potential for enhanced and targeted gene therapy applications.
Low generation triazine-based dendrimers-synthesis, characterzation and in vitro biological activity
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In the present study, two low generation triazine-based dendrimers, G1.0(Cl)4 dendrimer and G1.5(OH)8 dendrimer, were synthesized and their cytotoxicity were tested by using the NIH 3T3 and the A2780 cell lines. In the synthesis process of the G1.0(Cl)4 dendrimer, cyanuric chloride (CAC) which has high reactivity chlorine atom was connected to the terminal of triethylene glycol (TEG) via nucleophilic substitution by controlling temperature. The prepared G1.0(Cl)4 dendrimer was purified by silica gel column chromatography. Then the four chlorine atoms in the G1.0(Cl)4 dendrimer were substituted by diethanolamine (DEA) to give dendrimer with the hydroxyl terminal group G1.5(OH)8. The starting materials, CAC, G1.0(Cl)4 dendrimer and G1.5(OH)8 dendrimer were analyzed by one-dimensional NMR, FTIR and MS techniques. The two dendrimers, G1.0(Cl)4 and G1.5(OH)8, showed perfect stability in the air environment at room temperature. However, G1.0(Cl)4 is not soluble in water while the G1.5(OH)8 dendrimer is a water soluble compound. Furthermore, cell biological evaluation at the studied concentrations showed that the CAC, as well as the prepared G1.0(Cl)4 and G1.5(OH)8 dendrimers, have no cytotoxicity towards the NIH 3T3 and A2780 cell lines.
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ALVES, Ana paula Melo. Vermiculitas tratadas quimicamente na obtenção de sólidos microporosos como precursores para híbridos inorgânico-orgânicos com aplicações adsortivas. 2009. 124 f. Tese (Doutorado em Quimica) - Centro de Ciências Exatas e da Natureza, Universidade Federal da Paraíba, João Pessoa, PB, 2009.
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Studies made with polysaccharides of seaweed have demonstrated that these present important biological and pharmacological activities. These composites had presented "scavenging" activity of free radicals, which is important in the mediation of the inflammatory process and in the pathology of diverse disease. Recently, this "scavenging" property has taken some researches to evaluate the antioxidant capacity from various polysaccharides. Considering the limited research with polysaccharides and knowing its largely employed by the pharmaceutical and foodstuffs industries, we have objective to verify the actions from fucans and galactans as antioxidants. The fucans are found in brown seaweed and the galactans (carrageenans) in red seaweed. The fucans were obtained from seaweed Padina gymnospora (F0.5 e F1.1 fractions), common to our coastline and one another fucan, fucoidan, was of origin commercial and extracted from seaweed Fucus vesiculosus. The λ, κ e ι carrageenans were also of origin commercial. The antioxidant activities were tested in superoxide and hydroxyl systems to generated free radicals and for the inhibition of the lipid peroxidation. The results obtained to inhibition of formation the superoxide radicals demonstrated that all polysaccharides presented scavenging activity of superoxide radicals. The fucoidan, F0.5 and F1.1 fractions presented IC50 of 0.058; 0.243 and 0.243 mg/mL, respectively, while IC50 of the λ, κ and ι carrageenans were 0.046; 0.112 and 0.332 mg/mL, respectively. The results to inhibition of formation the hydroxyl radicals demonstrated that all sample had low effect in the inhibition of the formation of these radicals, except the F0.5. For these radicals the IC50 were 0.157 and 0.353 mg/mL to the fucoidan and F1.1, respectively and 0.357; 0.335 and 0.281 mg/mL to λ, κ and ι carrageenans, respectively. All the samples were capacity to inhibition the peroxidation, it present the IC50 of 1.250; 2.753 and 2.341 mg/mL to fucoidan, F0.5 and F1.1, respectively. Already the λ, κ and ι carrageenans presented the IC50 of 2.697; 0.323 and 0.830 mg/mL, respectively. With these findings, we conclude that polysaccharides used in this study presented activity antioxidant, and that fucoidan and the λ carrageenan show a significant "scavenging" activity for the radicals superoxide and the κ carrageenan a significant inhibitory activity for the lipid peroxidation
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Sulfated polysaccharides (PS) are biomolecules with a great biotechnological potential. There are few data about PS from high plants. In addition, pharmacological activities of PS from plants have not been carrying out. The aim of this work was extract PS from the angiosperm Halodule wrightii and study their anticoagulant and antioxidant activities. Histological analysis showed the presence of the PS manly in the roots. A polysaccharide-rich extract was obtained from H. wrightii by proteolysis followed by methanol and TCA precipitation. Chemical, infra-red analysis and agarose gel electrophoresis in 1.3 diaminopropane acetate buffer confirmed the presence of sulfated polysaccharides made by glucose, galactose, xylose and sulfate residues in the proportion 1: 0,9: 1: 1. In addition polyacrilamide electrophoresis have shown that extract is mainly compose by 11kDa sulfated polysaccharides. Pharmacological analysis have shown total antioxidant capacity (CAT) that resulted in 15,21 μg for equivalent of ascorbic acid, scavenging activity of the DPPH radical with 41,36 % of scavenging, activity of reducing power with the maximum of 0,290 nm (50 % of vitamin C activity) and scavenging activity superoxide radical (O2-) with a maximum of 32,23 %. Chelating activity of metal less than 4% and scavenging activity of the radical hydroxyl (OH-) less than 2%. Time of activated partial tromboplastin (aPTT) doubling the time of coagulation from 20μg of and protrombin time (PT) was not present. The data indicate that PS from Halodule wrightii could be considered for future applications in medicine, food production or cosmetic industry
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In recent years, sulfated polysaccharides (SP) from marine algae have emerged as an important class of natural biopolymers with potential pharmacology applications. Among these, SP isolated from the cell walls of red algae have been study due to their anticoagulant,antithrombotic and anti-inflammatory activities. In the present study, three sulfated polysaccharides fractions denominated F1.5v, F2.0v and F3.0v were obtained from seaweed G. caudate by proteolysis followed to acetone fractionation. Gel electrophoresis using 0.05 M 1,3-diaminopropane-acetate buffer, pH 9,0, stained with 0.1% toluidine blue, showed the presence of SP in all fractions. The chemical analysis demonstrated that all the fractions are composed mainly of galactose. These compounds were evaluated in anticoagulant, antioxidant and antiproliferative activities. In anticoagulant activity evaluated through aPTT and PT tests, no one fractions presented anticoagulant activity at tested concentrations (0.1 mg/mL; 1.0 mg/mL; 2.0 mg/mL).The antioxidant activities of the three fractions were evaluated by the following in vitro systems: Total antioxidant capacity, superoxide and hydroxyl radical scavenging, ferrous chelating activity and reducing power. The fractions were found to have different levels of antioxidant activity in the systems tested. F1.5v shows the highest activity, especially in the ferrous chelating system, with 70% of ferrous inhibiting at 1.0 mg.mL-1. Finally, all the fractions showed dose-dependent antiproliferative activity against HeLa cells. The fractions F1.5v and F2.0v presented the highest antiproliferative activity at 2.0 mg/mL with 42.7% and 37.0% of inhibition, respectively. Ours results suggests that the sulfated polysaccharides from seaweed G. caudata are promising compounds in antioxidant and/or antitumor therapy