Exploitation of a pulsed neutron source for the structural study of anisotropic polymer films

A novel but simple time-of-flight neutron scattering geometry which allows structural anisotropy to be probed directly, simultaneously and thus unambiguously in polymeric and other materials is described. A particular advantage of the simultaneous data collection when coupled to the large area of the beam is that it enables thin films (< 10 μm < 10 mg) to be studied with relative ease. The utility of the technique is illustrated by studies on both deformed poly(styrene) glasses and on thin films of electrical conducting polymers. In the latter case, the power of isotopic substitution is illustrated to great effect. The development of these procedures for use in other areas of materials science is briefly discussed.

Application of cylindrical distribution functions to wide-angle X-ray scattering from oriented polymers

A systematic approach is presented for obtaining cylindrical distribution functions (CDF's) of noncrystalline polymers which have been oriented by extension. The scattering patterns and CDF's are also sharpened by the method proposed by Deas and by Ruland. Data from atactic poly(methyl methacrylate) and polystyrene are analysed by these techniques. The methods could also be usefully applied to liquid crystals.

Optimizing layer-by-layer deposition of interpolymer complexes on solid substrates using Biacore

The layer-by-layer deposition of polymers onto surfaces allows the fabrication of multilayered materials for a wide range of applications, from drug delivery to biosensors. This work describes the analysis of complex formation between poly(acrylic acid) and methylcellulose in aqueous solutions using Biacore, a surface plasmon resonance analytical technique, traditionally used to examine biological interactions. This technique characterized the layer-by-layer deposition of these polymers on the surface of a Biacore sensor chip. The results were subsequently used to optimize the experimental conditions for sequential layer deposition on glass slides. The role of the solution pH and poly(acrylic acid) molecular weight on the formation of interpolymer multilayered coatings was researched, and showed that the optimal deposition of the polymer complexes was achieved at pHs ≤2.5 with a poly(acrylic acid) molecular weight of 450 kDa.

Polyhydroxyalkanoates production by actinobacteria isolated from soil

Polyhydroxyalkanoates (PHAs) are biodegradable and renewable polymers produced by a wide range of bacterial groups. New microbial bioprospection approaches have become an important way to find new PHA producers and new synthesized polymers. Over the past years, bacteria belonging to actinomycetes group have become known as PHA producers, such as Nocardia and Rhodococcus species, Kineosphaera limosa Liu et a]. 2002, and, more recently, Streptomyces species. In this paper, we disclose that there are more actinobacteria PHA producers in addition to the genera cited. Some unusual genera, such as Streptoalloteichus, and some genera frequently present in soil, such as Streptacidiphilus, have been found. Thirty-four isolates were able to accumulate poly(3-hydroxybutyrate) and a number of these have traces of poly(3-hydroxyvalerate) when cultivated on glucose or glucose and casein as carbon source. Furthermore, some strains showed traces of medium chain length PHA. Transmission electron microscopy demonstrated that the PHA accumulation occurs in hyphae and spores.

Caldensinic acid, a prenylated benzoic acid from Piper caldense

The CH(2)Cl(2) and MeOH extracts from leaves of Piper caldense were subjected to chromatographic separation procedures to afford the new prenylated benzoic acid, caldensinic acid (3-[(2`E,6`E,10`E)-11`-carboxy-3`,7`,15`-trimethylhexadeca-2`,6`,10`,14`-tetraenyl]-4,5-dihydroxybenzoic acid) whose structure was determined by spectral analysis, mainly NMR ((1)H, (13)C, HSQC, HMBC) and ESI-MS. The natural compound and derivatives displayed antifungal activity against the phytopathogenic fungi Cladosporium cladosporioides and C. sphaerospermum by direct bioautography. (C) 2009 Phytochemical Society of Europe. Published by Elsevier B.V. All rights reserved.

Development of Highly Selective Enzymatic Devices Based on Deposition of Permselective Membranes on Aligned Nanowires

We describe a simple and efficient strategy to fabricate enzymatic devices based on the deposition of glucose oxidase on aligned and highly oriented CoNiMo metallic nanowires. CoNiMo nanowires with an average diameter of 200 nm and length of 50 mu m were electrodeposited on Au-covered alumina substrates via electrodeposition, using alumina membranes as templates. Enzyme-modified electrodes were fabricated via enzyme immobilization using a cross-linker. To minimize nonspecific reactions in the presence of interfering agents, a permselective membrane composed of poly(vinylsulfonic acid) and polyamidoamine dendrimer was deposited via electrostatic interaction. The formation of hydrogen peroxide as a product of the enzymatic reaction was monitored at low overpotential, 0.0 V (vs Ag/AgCl). The detection limit was estimated at 22 mu M under an applied potential of 0.0 V. The apparent Michaelis-Menten constant determined from the Lineweaver-Burke plot was 2 mM.

A three-state model for the photophysics of guanine

The nonadiabatic photochemistry of the guanine molecule (2-amino-6-oxopurine) and some of its tautomers has been studied by means of the high-level theoretical ab initio quantum chemistry methods CASSCF and CASPT2. Accurate computations, based by the first time on minimum energy reaction paths, states minima, transition states, reaction barriers, and conical intersections on the potential energy hypersurfaces of the molecules lead to interpret the photochemistry of guanine and derivatives within a three-state model. As in the other purine DNA nucleobase, adenine, the ultrafast subpicosecond fluorescence decay measured in guanine is attributed to the barrierless character of the path leading from the initially populated (1)(pi pi* L-a) spectroscopic state of the molecule toward the low-lying methanamine-like conical intersection (gs/pi pi* L-a)(CI). On the contrary, other tautomers are shown to have a reaction energy barrier along the main relaxation profile. A second, slower decay is attributed to a path involving switches toward two other states, (1)(pi pi* L-b) and, in particular, (1)(n(o)pi*), ultimately leading to conical intersections with the ground state. A common framework for the ultrafast relaxation of the natural nucleobases is obtained in which the predominant role of a pi pi*-type state is confirmed.

Human endogenous RNAs: Implications for the immunomodulation of Toll-like receptor 3

Toll-like receptors (TLRs), a family of mammalian receptors, are able to recognize nucleic acids. TLR3 recognizes double-stranded (ds)RNA, a product of the replication of certain viruses. Polyinosinic-polycytidylic acid, referred to as poly(I:C), an analog of viral dsRNA, interacts with TLR3 thereby eliciting immunoinflammatory responses characteristic of viral infection or down-regulating the expression of chemokine receptor CXCR4. It is known that dsRNA also directly activates interferon (IFN)-induced enzymes, such as the RNA-dependent protein kinase (PKR). In the present study, the mRNA expression of TLR3, CXCR4, IFN gamma and PKR was investigated in a culture of peripheral blood mononuclear cells (PBMCs) stimulated with poly(I:C) and endogenous RNA from human PBMCs. No cytotoxic effect on the cells or on the proliferation of CD3(+), CD4(+) and CD8(+) cells was observed. TLR3 expression in the PBMCs in the presence of poly(I:C) was up-regulated 9.5-fold, and TLR3 expression in the PBMCs treated with endogenous RNA was down-regulated 1.8-fold (p=0.002). The same trend was observed for IFN gamma where in the presence of poly(I:C) an 8.7-fold increase was noted and in the presence of endogenous RNA a 3.1-fold decrease was observed. In the culture activated with poly(1:C), mRNA expression of CXCR4 increased 8.0-fold and expression of PKR increased 33.0-fold. Expression of these genes decreased in the culture treated with endogenous RNA when compared to the culture without stimulus. Thus, high expression of mRNA for TLR3, IFN gamma, CXCR4 and PKR was observed in the presence of poly(I:C) and low expression was observed in the cells cultured with endogenous RNA. In conclusion, TLR3 may play major physiological roles that are not in the context of viral infection. It is possible that RNA released from cells could contain enough double-stranded structures to regulate cell activation. The involvement of endogenous RNA in endogenous gene expression and its implications in the regulation thereof, are still being studied, and will have significant implications in the future.

O posicionamento dos tribunais perante os contratos de distribuição (1980-1999)

Esta pesquisa tem por objeto a análise sistemática da jurisprudência brasileira sobre os contratos de distribuição entre os anos de 1.980 e 2.000, procurando identificar qual a posição dos nossos Tribunais face a esses contratos. Nessa linha, constatou-se que os casos (acórdãos) abrem-se em cinco grandes blocos, quais sejam: (1) atribuição/divisão territorial; (2) questões possessórias; (3) renovatória de locação; (4) rescisão dos contratos de distribuição. Este grupo divide-se (i) naqueles contratos sujeitos à Lei Ferrari, (ii) naqueles referentes ao setor de combustíveis e derivados e (iii) naqueles não subsumíveis a tal diploma; (5) questões processuais relevantes, dividido em (i) litisconsórcio necessário e (ii) título executivo extrajudicial. Além disso, por se tratar de uma avenca atípica na maioria dos casos, a pesquisa procurou extrair de cada um dos casos qual o conceito de contrato de distribuição adotado.

Vantagens e desvantagens do modelo dinâmico de Nelson-Siegel : aplicação ao mercado brasileiro

A modelagem da estrutura a termo da taxa juros tem grande relevância para o mercado financeiro, isso se deve ao fato de ser utilizada na precificação de títulos de crédito e derivativos, ser componente fundamental nas políticas econômicas e auxiliar a criação de estratégias trading. A classe de modelos criada por Nelson-Siegel (1987), foi estendida por diversos autores e atualmente é largamente utilizada por diversos bancos centrais ao redor do mundo. Nesse trabalho utilizaremos a extensão proposta por Diebold e Li (2006) aplicada para o mercado brasileiro, os parâmetros serão calibrados através do Filtro de Kalman e do Filtro de Kalman Estendido, sendo que o último método permitirá estimar com dinamismo os quatros parâmetros do modelo. Como mencionado por Durbin e Koopman (2012), as fórmulas envolvidas no filtro de Kalman e em sua versão estendida não impõe condições de dimensão constante do vetor de observações. Partindo desse conceito, a implementação dos filtros foi feita de forma a possibilitar sua aplicação independentemente do número de observações da curva de juros em cada instante de tempo, dispensando a necessidade de interpolar os dados antes da calibração. Isso ajuda a refletir mais fielmente a realidade do mercado e relaxar as hipóteses assumidas ao interpolar previamente para obter vértices fixos. Também será testada uma nova proposta de adaptação do modelo de Nelson-Siegel, nela o parâmetro de nível será condicionado aos títulos terem vencimento antes ou depois da próxima reunião do Copom. O objetivo é comparar qualidade da predição entre os métodos, pontuando quais são as vantagens e desvantagens encontradas em cada um deles.

Determinantes de intervenção do Banco Central do Brasil no mercado de câmbio: uma abordagem empírica por regressão logística e redes neurais

Em economias com regimes de metas de inflação é comum que Bancos Centrais intervenham para reduzir os níveis de volatilidade do dólar, sendo estas intervenções mais comuns em países não desenvolvidos. No caso do Brasil, estas intervenções acontecem diretamente no mercado à vista, via mercado de derivativos (através de swaps cambiais) ou ainda com operações a termo, linhas de liquidez e via empréstimos. Neste trabalho mantemos o foco nas intervenções no mercado à vista e de derivativos pois estas representam o maior volume financeiro relacionado à este tipo de atuação oficial. Existem diversos trabalhos que avaliam o impacto das intervenções e seus graus de sucesso ou fracasso mas relativamente poucos que abordam o que levaria o Banco Central do Brasil (BCB) a intervir no mercado. Tentamos preencher esta lacuna avaliando as variáveis que podem se relacionar às intervenções do BCB no mercado de câmbio e adicionalmente verificando se essas variáveis se relacionam diferentemente com as intervenções de venda e compra de dólares. Para tal, além de utilizarmos regressões logísticas, como na maioria dos trabalhos sobre o tema, empregamos também a técnica de redes neurais, até onde sabemos inédita para o assunto. O período de estudo vai de 2005 a 2012, onde o BCB interveio no mercado de câmbio sob demanda e não de forma continuada por longos períodos de tempo, como nos anos mais recentes. Os resultados indicam que algumas variáveis são mais relevantes para o processo de intervenção vendendo ou comprando dólares, com destaque para a volatilidade implícita do câmbio nas intervenções que envolvem venda de dólares, resultado este alinhado com outros trabalhos sobre o tema.

Aplicação de termogravimetria acoplada à espectrometria de massas para caracterização de petróleo e determinação da curva de evolução de gás sulfídrico

With the new discoveries of oil and gas, the exploration of fields in various geological basins, imports of other oils and the development of alternative fuels, more and more research labs have evaluated and characterized new types of petroleum and derivatives. Therefore the investment in new techniques and equipment in the samples analysis to determine their physical and chemical properties, their composition, possible contaminants, especification of products, among others, have multiplied in last years, so development of techniques for rapid and efficient characterization is extremely important for a better economic recovery of oil. Based on this context, this work has two main objectives. The first one is to characterize the oil by thermogravimetry coupled with mass spectrometry (TG-MS), and correlate these results with from other types of characterizations data previously informed. The second is to use the technique to develop a methodology to obtain the curve of evaluation of hydrogen sulfide gas in oil. Thus, four samples were analyzed by TG-MS, and X-ray fluorescence spectrometry (XRF). TG results can be used to indicate the nature of oil, its tendency in coke formation, temperatures of distillation and cracking, and other features. It was observed in MS evaluations the behavior of oil main compounds with temperature, the points where the volatilized certain fractions and the evaluation gas analysis of sulfide hydrogen that is compared with the evaluation curve obtained by Petrobras with another methodology

Caracterização e quantificação de marcadores químicos do extrato hidroetanólico das folhas de Kalanchoe brasiliensis Cambess

Kalanchoe brasiliensis Cambess (Crassulaceae), commonly known as saião , coirama branca , folha grossa , is originally from Brazil and commonly found in São Paulo to Bahia, mainly in the coastal zone. Regarding of biological activities, most preclinical studies were found in the literature, mainly about the anti-inflammatory activity of extracts obtained from leaves and / or aerial parts of K. brasiliensis. As regards the chemical constitution, it has been reported mainly the presence of flavonoids in the leaves of the species, but until this moment did not knows which are the active compounds. Although it is a species widely used in traditional medicine in Brazil, there is no monograph about the quality parameters of the plant drug. In this context, this study aims to characterize and quantify the chemical markers of hydroethanolic extract (HE) from the leaves of K. brasiliensis, which can be used in quality control of plant drug and derivatives obtained from this species. The methodology was divided into two parts: i. Phytochemical study: to fractionate, isolate and characterizate of the chemical (s) marker (s) of the HE from the leaves of K. brasiliensis; ii. To Developed validate of analytical method by High Performance Liquid Chromatography (HPLC)-diode array detector (DAD) to quantify the chemical (s) marker (s) of the EH. i. The EH 50% was prepared by turbo extraction method. It was then submitted to liquid-liquid partition, obtaining dichloromethane, n-butanol and ethyl acetate (AcOEt) fractions. The AcOEt fraction was selected to continue the fractionation process, because it has a chemical profile rich in flavonoids. The acOEt fraction was submitted to column chromatography using different systems for obtaining the compound Kb1. To identify this compound, it was submitted to UV analysis ii. For quantitative analysis, the EH was analyzed by HPLC, using different methods. After selecting the most appropriate method, which showed satisfactory resolution and symmetrical peaks, it was validated according to parameters in the RE 899/2003. As result, it was obtained from the AcOEt fraction the compound Kb1 (2.7 mg). Until this moment, the basic nucleus was characterized by UV analysis using shift reagents. The partial chemical structure of the compound Kb1 was identified as a flavonol, containing hydroxyls in 3 , 4 position (ring A), 5 and 7 free (ring B) and a replacement of the C3 hydroxyl by a sugar. As the analysis were performed in the HPLC coupled to a DAD, we observed that the UV spectrum of the major peaks of EH from K. brasiliensis shown similar UV spectrum. According to the literature, it has been reported the presence of patuletin glycosydes derivatives in the leaves of this species. Therefore, it is suggested that the compound Kb1 is glycosylated patuletin derivative. Probably the sugar (s) unit(s) are linked in the C3 in the C ring. . Regarding the development of HPLC analytical method, the system used consists of phase A: water: formic acid (99,7:0,3, v / v) and phase B: methanol: formic acid (99,7:0,3, v / v), elution gradient of 40% B - 58% B in 50 minutes, ccolumn (Hichrom ®) C18 (250x4, 0 mm, 5 μm), flow rate 0.8 mL / min, UV detection at 370 nm, temperature 25 ° C. In the analysis performed with the co-injection of thecompound Kb1 + HE of K. brasiliensis was observed that it is one of the major compounds with a retention time of 12.47 minutes and had a content of 15.3% in EH of leaves from K. brasiliensis. The method proved to be linear, precise, accurate and reproducible. According to these results, it was observed that compound Kb1 can be used as a chemical marker of EH from leaves of K. brasiliensis, to assist in quality control of drug plant and its derivatives

Novas fronteiras petrolíferas no Brasil : uma análise da necessidade de nova regulamentação da área do pré-sal sob a ótica constitucional

The Oil industry in Brazil has gone through several stages during the economical, political and social historical process. However, the significative changes have happened in the last fifteen years, due to market opening arising from the relaxation of the state monopoly over the Oil deposits and its derivatives. The edition of the Constitutional Amendment #9, changing the first paragraph of the 177th item of the Federal Constitution, marked the end of a stiffness about the monopoly that the Brazilian state kept in relation to the exploration and research of Oil and Gas. The economical order was fundamental to actualize the idea contained in the #9 Amendment, since its contents has the power to set up measures to be adopted by public power in order to organize the economical relations from a social viewpoint. The new brazilian Oil scenery, called pre-salt, presents itself in a way to amaze the economical markets, in addition to creating a new perspective to the social sector. This work will identify, in this new scenario, the need for change in the legal system. Nevertheless, this subject must not be treated in a thoughtless way: being an exhaustible good, we shall not forget that the future generations also must benefit from the exploration of natural resources recently discovered. The settlement of a new regulatory mark, including the change in the concession contract model to production and sharing is one of the suggested solutions as a bill in the National Congress, in an attempt to ensure the sovereignty of the nation. The constitutionality of a new regulatory mark is questioned, starting from an analysis of the state monopoly, grounding the comprehnsions in the brazilian constitutions, the relevance of the creation of Petrobras for self-assertion of the state about the monopoly of Oil and derivatives, and its posture after the Constitutional Amendment nº 9 (1995), when a company stops having control of the state monopoly, beginning to compete in a fairly way with other companies. The market opening and private initiative are emphasized from the viewpoint of the Constitutional Principles of the Economical and Social Order. The relaxation of the monopoly regarding the exploratory activity in the Federal Constitution doesn't deprive from the Union the ownerships of underground goods, enabling to this federal entity to contract, directly or by concession of exploration of goods, to state-owned or private companies. The existing oil in the pre-salt layer transforms the scenario from very high risk to low risk, which gives the Union the possibility of defining another way of exploring this resources in the best interests of the Public Administration

Controlled Drug Release from Ureasil-Polyether Hybrid Materials

Flexible, transparent, and insoluble urea-cross-linked polyether-siloxane hybrids presenting a tunable drug delivery pattern were prepared using the sol-gel method from PEO (poly(ethylene oxide)) and PPO (poly(propylene oxide)) functionalized at both chain ends with triethoxysilane. Different polyether chain lengths were used to control the urea/siloxane (named ureasil) node density, flexibility, and swellability of the hybrid network. We herein demonstrate that the drug release from swellable hydrophilic ureasil-PEO hybrids can be sustained for some days, whereas that from the unswellable ureasil-PPO hybrids can be sustained for some weeks. This outstanding feature conjugated with the biomedically safe formulation of the ureasil cross-linked polyether-siloxane hybrid widens their scope of application to include the domain of soft and implantable drug delivery devices.