The Crystal Complex of Phosphofructokinase-2 of Escherichia coli with Fructose-6-phosphate KINETIC AND STRUCTURAL ANALYSIS OF THE ALLOSTERIC ATP INHIBITION

Substrate inhibition by ATP is a regulatory feature of the phosphofructokinases isoenzymes from Escherichia coli (Pfk-1 and Pfk-2). Under gluconeogenic conditions, the loss of this regulation in Pfk-2 causes substrate cycling of fructose-6-phosphate (fructose-6-P) and futile consumption of ATP delaying growth. In the present work, we have broached the mechanism of ATP-induced inhibition of Pfk-2 from both structural and kinetic perspectives. The crystal structure of Pfk-2 in complex with fructose-6-P is reported to a resolution of 2 angstrom. The comparison of this structure with the previously reported inhibited form of the enzyme suggests a negative interplay between fructose-6-P binding and allosteric binding of MgATP. Initial velocity experiments show a linear increase of the apparent K(0.5) for fructose-6-P and a decrease in the apparent k(cat) as a function of MgATP concentration. These effects occur simultaneously with the induction of a sigmoidal kinetic behavior (n(H) of approximately 2). Differences and resemblances in the patterns of fructose-6-P binding and the mechanism of inhibition are discussed for Pfk-1 and Pfk-2, as an example of evolutionary convergence, because these enzymes do not share a common ancestor.

The Mobility of Chondroitin Sulfate in Articular and Artificial Cartilage Characterized by (13)C Magic-Angle Spinning NMR Spectroscopy

We have studied the molecular dynamics of one of the major macromolecules in articular cartilage, chondroitin sulfate. Applying (13)C high-resolution magic-angle spinning NMR techniques, the NMR signals of all rigid macromolecules in cartilage can be suppressed, allowing the exclusive detection of the highly mobile chondroitin sulfate. The technique is also used to detect the chondroitin sulfate in artificial tissue-engineered cartilage. The tissue-engineered material that is based on matrix producing chondrocytes cultured in a collagen gel should provide properties as close as possible to those of the natural cartilage. Nuclear relaxation times of the chondroitin sulfate were determined for both tissues. Although T(1) relaxation times are rather similar, the T(2) relaxation in tissue-engineered cartilage is significantly shorter. This suggests that the motions of chondroitin sulfate in data:rat and artificial cartilage different. The nuclear relaxation times of chondroitin sulfate in natural and tissue-engineered cartilage were modeled using a broad distribution function for the motional correlation times. Although the description of the microscopic molecular dynamics of the chondroitin sulfate in natural and artificial cartilage required the identical broad distribution functions for the correlation times of motion, significant differences in the correlation times of motion that are extracted from the model indicate that the artificial tissue does not fully meet the standards of the natural ideal. This could also be confirmed by macroscopic biomechanical elasticity measurements. Nevertheless, these results suggest that NMR is a useful tool for the investigation of the quality of artificially engineered tissue. (C) 2010 Wiley Periodicals, Inc. Biopolymers 93: 520-532, 2010.

Major shear zones of southern Brazil and Uruguay: escape tectonics in the eastern border of Rio de La plata and Paranapanema cratons during the Western Gondwana amalgamation

The Mantiqueira Province represents a series of supracrustal segments of the South-American counterpart formed during the Gondwana Supercontinent agglutination. In this crustal domain, the process of escape tectonics played a conspicuous role, generating important NE-N-S-trending lineaments. The oblique component of the motions of the colliding tectonic blocks defined the transpressional character of the main suture zones: Lancinha-Itariri, Cubato-Arcadia-Areal, Serrinha-Rio Palmital in the Ribeira Belt and Sierra Ballena-Major Gercino in the Dom Feliciano Belt. The process as a whole lasted for ca. 60 Ma, since the initial collision phase until the lateral escape phase predominantly marked by dextral and subordinate sinistral transpressional shear zones. In the Dom Feliciano Belt, southern Brazil and Uruguay, transpressional event at 630-600 Ma is recognized and in the Ribeira Belt, despite less coevally, the transpressional event occurred between 590 and 560 Ma in its northern-central portion and between ca. 625 and 595 Ma in its central-southern portion. The kinematics of several shear zones with simultaneous movement in opposite directions at their terminations is explained by the sinuosity of these lineaments in relation to a predominantly continuous westward compression.

Minimal Lagrangian surfaces in the tangent bundle of a Riemannian surface

Given an oriented Riemannian surface (Sigma, g), its tangent bundle T Sigma enjoys a natural pseudo-Kahler structure, that is the combination of a complex structure 2, a pseudo-metric G with neutral signature and a symplectic structure Omega. We give a local classification of those surfaces of T Sigma which are both Lagrangian with respect to Omega and minimal with respect to G. We first show that if g is non-flat, the only such surfaces are affine normal bundles over geodesics. In the flat case there is, in contrast, a large set of Lagrangian minimal surfaces, which is described explicitly. As an application, we show that motions of surfaces in R(3) or R(1)(3) induce Hamiltonian motions of their normal congruences, which are Lagrangian surfaces in TS(2) or TH(2) respectively. We relate the area of the congruence to a second-order functional F = f root H(2) - K dA on the original surface. (C) 2010 Elsevier B.V. All rights reserved.

Structure, Dynamics, and RNA Interaction Analysis of the Human SBDS Protein

Shwachman-Bodian-Diamond syndrome is an autosomal recessive genetic syndrome with pleiotropic phenotypes, including pancreatic deficiencies, bone marrow dysfunctions with increased risk of myelodysplasia or leukemia, and skeletal abnormalities. This syndrome has been associated with mutations in the SBDS gene, which encodes a conserved protein showing orthologs in Archaea and eukaryotes. The Shwachman-Bodian-Diamond syndrome pleiotropic phenotypes may be an indication of different cell type requirements for a fully functional SBDS protein. RNA-binding activity has been predicted for archaeal and yeast SBDS orthologs, with the latter also being implicated in ribosome biogenesis. However, full-length SBDS orthologs function in a species-specific manner, indicating that the knowledge obtained from model systems may be of limited use in understanding major unresolved issues regarding SBDS function, namely, the effect of mutations in human SBDS on its biochemical function and the specificity of RNA interaction. We determined the solution structure and backbone dynamics of the human SBDS protein and describe its RNA binding site using NMR spectroscopy. Similarly to the crystal structures of Archaea, the overall structure of human SBDS comprises three well-folded domains. However, significant conformational exchange was observed in NMR dynamics experiments for the flexible linker between the N-terminal domain and the central domain, and these experiments also reflect the relative motions of the domains. RNA titrations monitored by heteronuclear correlation experiments and chemical shift mapping analysis identified a classic RNA binding site at the N-terminal FYSH (fungal, Yhr087wp, Shwachman) domain that concentrates most of the mutations described for the human SBDS. (C) 2010 Elsevier Ltd. All rights reserved.

Structural Investigation of MFe(2)O(4) (M = Fe, Co) Magnetic Fluids

Ferrites of the type M(II)Fe(2)O(4) (M = Fe and Co) have been prepared by the traditional coprecipitation method. These ferrites were modified by the adsorption of fatty acids derived from soybean and castor oil and were then dispersed in cyclohexane, providing very stable magnetic fluids, readily usable in nonpolar media. The structural properties of the ferrites and modified ferrites as well as the magnetic fluids were characterized by XRD (X-ray powder diffraction), TEM (transmission electron microscopy), DRIFTS (diffusion reflectance infrared Fourier transform spectroscopy), FTMR (Fourier transform near-infrared), UV-vis, normal Raman spectroscopy, and surface-enhanced Raman scattering (SERS). XRD and TEM analysis have shown that the magnetic nanoparticles (nonmodified and modified) present diameters in the range of 10-15 nm. DRIFTS measurements have shown that the carboxylate groups of soybean and castor oil fatty acids adsorb on the ferrite surface, forming three different structures: a bridging bidentate, a bridging monodentate, and a bidentate chelate structure. The FTIR and Raman spectra of nonmodified Fe(3)O(4) and CoFe(2)O(4) nanoparticles have shown that the number of observed phonons is not compatible with the expected O(h)(7) symmetry, since IR-only active phonons were observed. in the Raman spectra and vice versa. SERS measurements of a CoFe(2)O(4) thin film on a SERS-active gold electrode at different applied potentials made possible the assignment of the signals near 550 and 630 cm(-1) to Co-O motions and the signals near 470 and 680 cm(-1) to Fe-O motions.

Azo-hydrazone tautomerism in protonated aminoazobenzenes: Resonance Raman spectroscopy and quantum-chemical calculations

The protonation effect on the vibrational and electronic spectra of 4-aminoazobenzene and 4-(dimethylamino)azobenzene was investigated by resonance Raman spectroscopy, and the results were discussed on the basis of quantum-chemical calculations. Although this class of molecular systems has been investigated in the past concerning the azo-hydrazone tautomerism, the present work is the first to use CASSCF/CASPT2 calculations to unveil the structure of both tautomers as well the nature of the molecular orbitals involved in chromophoric moieties responsible for the resonance Raman enhancement patterns. More specifically both the resonance Raman and theoretical results show clearly that in the neutral species, the charge transfer transition involves mainly the azo moiety, whereas in the protonated forms there is a great difference, depending on the tautomer. In fact, for the azo tautomer the transition is similar to that observed in the corresponding neutral species, whereas in the hydrazone tautomer such a transition is much more delocalized due to the contribution of the quinoid structure. The characterization of protonated species and the understanding of the tautomerization mechanism are crucial for controlling molecular properties depending on the polarity and pH of the medium.

Os avanços da arbitragem no Brasil e uma análise crítica a respeito dos posicionamentos existentes na Doutrina Nacional sobre o cabimento de ação anulatória contra sentença arbitral que tenha violado a ordem pública

O presente trabalho tem como objetivo o estudo sobre o cabimento da ação anulatória - prevista no artigo 32 da Lei de Arbitragem - contra uma sentença arbitral doméstica que tenha violado a ordem pública. A relevância do tema encontra-se no fato de que o legislador, ao elencar as hipóteses pelas quais poderá ser declarada a invalidade de uma decisão arbitral, excluiu, propositalmente, a violação à ordem pública como uma delas. O Poder Judiciário ainda não teve a oportunidade de analisar o assunto. A preocupação, quando elaborada a Lei de Arbitragem em 1996, era a de que, caso o artigo 32 previsse expressamente a violação à ordem pública, todos os procedimentos arbitrais desembocariam no Judiciário, tendo em vista a indeterminação do conceito. Somava-se a isso o elevado preconceito que o instituto sofria no Brasil, além de seu pouco uso. O debate ganha ainda maior proporção quando se analisa as causas pelas quais o Poder Judiciário poderá negar homologação a uma sentença arbitral estrangeira. Quis o legislador, e o fez de modo expresso, que a violação à ordem pública fosse causa de negativa de homologação, mas nada disse com relação às sentenças domésticas. Analisarei, neste trabalho, todos os avanços pelos quais a arbitragem passou no Brasil, tudo para concluir, na primeira parte do trabalho, que a preocupação do legislador não mais subsiste. Além disso, analisarei os posicionamentos existentes na doutrina nacional para responder a principal pergunta desse trabalho: É possível ajuizar uma ação anulatória contra uma sentença arbitral doméstica que tenha violado a ordem pública, mesmo sem que o artigo 32 da Lei de Arbitragem a preveja, expressamente, como uma das causas de anulabilidade? Finalmente, no último capítulo do trabalho, exporei o meu entendimento sobre o assunto, no sentido de ser possível o ajuizamento de ação anulatória com base na combinação dos artigos 32, IV, com o artigo 2º, § 1º, ambos da Lei de Arbitragem.

Imaginário radical e educação física: trajetória esportiva de corredores de longa distância

Cette étude propose une lecture du sport d endurance, prenant comme perspective théorique l imaginaire radical et considérant les dimensions socio-historiques e subjectives de la pratique de courses de longue distance. D abord, l échantillon la recherche a été composé de huit sujets-atlètes du groupe de courreurs de rue Sport Vida. Ainsi, em même temps que nous faisons une analyse socio-historique de cette pratique sportive, nous considérons l ensemble des aspects sócio-culturels et poursuivons la recherche avec comme objectif de comprendre les sens qui lui sont attribués par les sjuets-atlètes, au-delá de l aspect économique et de la consommation. Nous observons que, même si l altétismo qui est pratiqué a des aspects competitifs (economiques), les atlètes créent d autres sens pour continuer a pratiquer ce sport, comme les amitiés, être ensemble avec les amis. Ils rompent avec la logique déterministe du sport dépasser la limite du corps, vaincre à n importe quel prix, dépasser les collègues -, en cherchant des moments de solidarité, un sport sans violence et affectif. Nous percevons néanmoins des contradictions dans le discours de quelques atlètes quand confessent que le plus important est l amour du sport, les amitiés, mais réclament du manque de sponsorts et d appui pour pouvoir s entrainer tranquillement. Cette recherche a aussi montré que dans la pratique de ce sport, les atlètes construisent une obstination, sachant le sacrifice qu il impose au corps, mais cela se transforme en plaisir, excitation et recherche d émotions fortes. Valeurs éthiques sont aussi construites et valorisées dans l atlétisme, ce qui est observé lorsque que les sujets-atlètes critiquent avec véemence a propos de l usage de substances chimiques par les sportifs. En choisissant l imaginaire radical comme principale inspiration théorique pour cette recherche, il devient évident que le sport peut être ressignifié, à partir du moment que cet imaginaire est potencialisé dans l enseignement de l éducation physique, porvocant chez les élèves une réflexion critique sur la société et sur le sport, qui passe à être redimensionné vers la solidarité, avec démocratie et autonomie. Enfin, l étude a révélé que le sport d endurance est capable de créer des liens sociaux et structurer des relations à partir de cette pratique

Por uma educação ambiental corporalizada :a emoção em trilhas interpretativas

Prétendant contribuer au progrès sur le champ épistémologique de l éducation environnementale, nous avons défini l objetif principal de cette recherche visant construire et évaluer initialement des structures éco-vécues appliquées aux sentiers écologiques interprétatifs dans des zones de protection environnementale. Pour conduire la tâche de l investigation écophénoménologique, l objectif présent a été déplié spécifiquement de la façon suivante: 1. Approfondir la discussion sur le rôle de l émotion et du sentiment dans l éducation. 2. Démarquer un trajet de sentier écologique du Parque das Dunas en identifiant des aires éco-sensorielles pour le développement du vécu écologique. 3. Construire des structures des vécus écologiques pour les environnements préalablement définis dans un sentier du Parque das Dunas. 4. Vivre l expérience des structures éco-vécues en tant qu éducateurs, visant leur validation méthodologique. 5. Présenter la conception de l éducation environnementale corpororalisée qui valorise les émotions et les sentiments dans les structures des éco-vécus. Pour orienter notre investigation écophénoménologique à fin de construire et évaluer des structures des éco-vécues appliquées aux sentiers écologiques interprétatifs, quelques présupposés ont été définis pour agir comme une boussole pendant toute notre promenade écologique: Du point de vue biologique, l amour est l émotion qui constitue le domaine des actions dans lequel l autre est accepté comme il est dans le présent, sans attente par rapport aux conséquences de l intimité, même si c est légitime de les attendre (Maturana e Verden-Zöller, 2004). Éduquer dans la biologie de l amour est s occuper du développement, de la pensée et des intelligences et, au même temps, éduquer l écoute du sentiment et l ouverture du coeur (Moraes, 2003). La corporéité est le siège radiant, le premier et le principal le critère éducationnel (Assmann, 1995). Les activités qui fluent, proportionnent la sensation de découverte, un sentiment créatif qui transpose l individu vers une nouvelle réalité (Csikszntmihalyi, 1992). Ressentir le sentiment fait exalter la portée des émotions (Damásio, 2004). L ethnographie et l écophénoménologie ont été les approches méthodologiques utilisées dans l étude. Onze éducateurs ont participé du processus de l expérience vécue et de l évaluation des structures éco-vécues construites dans la perspective d une Education Environnementale Corporalisée. Le développement de la conception d une Education Environnementale Corporalisée à partir du vécu sur les sentiers écologiques du Parque das Dunas, à Natal-RN, nous a amenés à structurer un système autopoïétique pour proposer des propriétés ou des principes configurant les intentions fondamentales d une Éducation Environnementale Corporalisée. Telle conception considère la métaphore de la Toile de la Corporéité vécue dans la Base de Recherche Corporéité et Éducation BACOR/UFRN et le phénomène de la ludopoïèse capable de faire émerger la joie de vivre la vie avec le sens de luminescence humaine. Associés à la Biologie de l amour, nous espérons pouvoir contribuer à la présence des émotions et des sentiments pour une perspective transdisciplinaire et corporalisée pour l Education Environnementale. Nous présentons cinq principes de guidage pour la concrétisation d une Education Environnementale Corporalisée: Ecopréservation, Ecoterritorialité, Ecoconectivité, Ecovaleur, Ecojouissance

A natureza da alma e o clinamen: ação e liberdade em Lucrécio

The concept of freedom and his presupposition, the free will or libera voluntas in Lucretius relies on the notion of clinamen (declination), an occasional and random motion of atoms, inaccessible to experience. It is endowed with a complex movement provided by spontaneity, without the need for mechanical causes. The action of perceiving (sensus) is selfconsciousness, according to which this will, illuminated by previous experiences (sensory, intellectual or emotional) of the soul, takes advantage of the freedom and own spontaneity of atomic motions to drive them to a perceived direction and chosen. On the other hand, if we consider that the declination has a predominant role for the acts of will, we are facing other problems and questions. There is always the choice of a determined action and, therefore, even if the individual is facing a need to act, is possible choose to do not continue finish this action. Thereby, the will is related to conditions that are originate, ultimately, from the images formed randomly in space and impress the soul: the simulacra of desire and pleasure. The declination itself is a very important notion in this research, in order to emphasize the relationship between the freedom and the kinetic of elements. The approach developed in this work had as main objective to investigate the philosophy of nature and the soul in Lucretius, their constituents and movement, as well as demonstrating how the notion of clinamen articulates with the concepts of image, desire and pleasure, proposing a possible interpretation for the declination as an indeterminate and ethical foundation of freedom

Lítio e parâmetros orbitais em sistemas binários com componentes evoluídas

One of the best established properties of the single late type evolved stars is that their rotational velocity and lithium content decrease with effective temperature and age. Nevertheless, the root cause of this property, as well as the link between rotation and lithium abundance and, in particular, the effects of binarity on rotation and lithium content in binary systems with evolved component, are not yet completely established. How does the gravitational tides, in binary systems, affects rotational evolution and lithium dilution? Trying to answer these questions, we have carried out an observational survey, in the lithium region centered at the lithium I line A6707.81A, for a large sample of about 100 binary systems with evolved component along the spectral range F, G and K, with the CES spectrometer mounted at the CAT 1.44 m Telescope of the ESO, La Silla, Chile. By combining the abundances of lithium issued from these observations with rotational velocity and orbital parameters, we have found a number of important results. First of all, we confirm that in this class of binary systems rotation is effectively affected by tidal effects. Binary systems with orbital period lower than about 100 days and circular or nearly circular orbits, present rotational velocity enhanced in relation to the single giant stars and to the binary systems with an orbital period larger than 100 days. This is clearly the result of the synchonization between the rotational and orbital motions due to tidal effects. In addition, we have found that lithium abundances in binary systems with giant components present the same gradual decreasing with effective temperature, observed in the single giants of same luminosity class and spectral types. We have found no lithium-rich binary systems, in contrast with single giants. A remarkable result from the present study is the one showing that synchronized binary systems with giant component retains more of their original lithium than the unsynchronized systems. In fact, we have found a possible "inhibited zone", in which synchronized binary systems with giant component having lithium abundance lower than a threshold level should be unusual. Finally, the present study also shows that the binary systems with giant component presenting the highest lithium contents are those with the highest rotation rates

Artificial satellites orbits in 2:1 resonance: GPS constellation

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

A Model Coupling Vibrational and Rotational Motion for the DNA Molecule

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

Thermodynamic analysis of a non linear lattice

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