Adsorption Behavior of 5-Fluorouracil on Au(111): An In Situ STM Study

The biological effects of chemical substitution of DNA bases triggered several investigations of their physicochemical properties This paper studies the adsorption behavior of a halogenated uracil, 5-fluorouracil (5FU). at the electrochemical interface of Au(111) and sulfuric acid solution. Upon modulation of the electric field across the interface, four distinct phases could be inferred by means of cyclic voltammetry (CV) At negative potentials relative to the SCE electrode, limited by the threshold of hydrogen evolution, no molecular species could be detected by scanning tunneling microscopy (STM) at the reconstructed Au(111)-(23 x root 3) surface, indicating that any physisorbed molecules are randomly distributed Incursion into more positive potentials increases the surface population but doer not form any two-dimensional (2D) physisorbed ordered structure Instead, we observed metastable structures that are only detectable. on surfaces with high defect density At sufficiently high positive potentials. limited by gold oxidation, the molecules are chemisorbed in a (3 x 2 root 3) ordered structure. with the aromatic ring perpendicular to the surface We report the densest chemisorbed monolayer for pyrimidine-derivative molecules (area per molecule 0 14 +/- 0 04 nm(2)). A comparison of the adsorption behavior of uracil derivatives has been made based on recent results of chemical substitution and solvent effects. We propose that pi-stacking is enhanced when halogens are incorporated in the uracil structure, in a similar fashion to what is observed in then crystal structure

Classical and fragment-based hologram structure-activity relationships for a series of analgesic cyclic imides

Cyclic imides have been widely employed in drug design research due to their multiple pharmacological and biological properties. In the present study, two-dimensional quantitative structure-activity relationship (2D QSAR) studies were conducted on a series of potent analgesic cyclic imides using both classical and hologram QSAR (HQSAR) methods, yielding significant statistical models (classical QSAR, q(2) = 0.80; HQSAR, q(2) = 0.84). The models were then used to evaluate an external data test, and the predicted values were in good agreement with the experimental results, indicating their consistency for untested compounds.

Structure-activity relationships for a class of selective inhibitors of the major cysteine protease from Trypanosoma cruzi

Chagas` disease is a parasitic infection widely distributed throughout Latin America, with devastating consequences in terms of human morbidity and mortality. Cruzain, the major cysteine protease from Trypanosoma cruzi, is an attractive target for antitrypanosomal chemotherapy. In the present work, classical two-dimensional quantitative structure-activity relationships (2D QSAR) and hologram QSAR (HQSAR) studies were performed on a training set of 45 thiosemicarbazone and semicarbazone derivatives as inhibitors of T. cruzi cruzain. Significant statistical models (HQSAR, q2=0.75 and r2=0.96; classical QSAR, q2=0.72 and r2=0.83) were obtained, indicating their consistency for untested compounds. The models were then used to evaluate an external test set containing 10 compounds which were not included in the training set, and the predicted values were in good agreement with the experimental results (HQSAR, [image omitted]=0.95; classical QSAR, [image omitted]=0.91), indicating the existence of complementary between the two ligand-based drug design techniques.

Nuclear Magnetic Resonance Study of Hydrated Bentonite

Impedance spectroscopy and nuclear magnetic resonance (NMR) were used to investigate the mobility of water molecules located in the interlayer space of H(+) - exchanged bentonite clay. The conductivity obtained by ac measurements was 1.25 x 10(-4) S/cm at 298 K. Proton ((1)H) lineshapes and spin-lattice relaxation times were measured as a function of temperature over the temperature range 130-320 K. The NMR experiments exhibit the qualitative features associated with the proton motion, namely the presence of a (1)H NMR line narrowing and a well-defined spin-lattice relaxation rate maximum. The temperature dependence of the proton spin-lattice relaxation rates was analyzed with the spectral density function appropriate for proton dynamics in a two-dimensional system. The self-diffusion coefficient estimated from our NMR data, D similar to 2 x 10(-7) cm(2)/s at 300 K, is consistent with those reported for exchanged montmorillonite clay hydrates studied by NMR and quasi-elastic neutron scattering (QNS).

Design of novel antituberculosis compounds using graph-theoretical and substructural approaches

The increasing resistance of Mycobacterium tuberculosis to the existing drugs has alarmed the worldwide scientific community. In an attempt to overcome this problem, two models for the design and prediction of new antituberculosis agents were obtained. The first used a mixed approach, containing descriptors based on fragments and the topological substructural molecular design approach (TOPS-MODE) descriptors. The other model used a combination of two-dimensional (2D) and three-dimensional (3D) descriptors. A data set of 167 compounds with great structural variability, 72 of them antituberculosis agents and 95 compounds belonging to other pharmaceutical categories, was analyzed. The first model showed sensitivity, specificity, and accuracy values above 80% and the second one showed values higher than 75% for these statistical indices. Subsequently, 12 structures of imidazoles not included in this study were designed, taking into account the two models. In both cases accuracy was 100%, showing that the methodology in silico developed by us is promising for the rational design of antituberculosis drugs.

Electrochemical Control of the Time-Dependent Intensity Fluctuations in Surface-Enhanced Raman Scattering (SERS)

Time-dependent fluctuations in surface-enhanced Raman scattering (SERS) intensities were recorded from a roughened silver electrode immersed in diluted solutions of rhodamine 6G (R6G) and congo red (CR). These fluctuations were attributed to a small number of SERS-active molecules probing regions of extremely high electromagnetic field (hot spots) at the nanostructured surface. The time-dependent distribution of SERS intensities followed a tailed statistics at certain applied potentials, which has been linked to single-molecule dynamics. The shape of the distribution was reversibly tuned by the applied voltage. Mixtures of both dyes, R6G and CR, at low concentrations were also investigated. Since R6G is a cationic dye and CR is an anionic dye, the statistics of the SERS intensity distribution of either dye in a mixture were independently controlled by adjusting the applied potential. The potential-controlled distribution of SERS intensities was interpreted by considering the modulation of the surface coverage of the adsorbed dye by the interfacial electric field. This interpretation was supported by a two-dimensional Monte Carlo simulation that took into account the time evolution of the surface configuration of the adsorbed species and their probability to populate a hypothetical hot spot. The potential-controlled SERS dynamics reported here is a first step toward the spectroelectrochemical investigation of redox processes at the single-molecule level by SERS.

Study of Proteinuria: Isolation of Proteins from the Nephrotic Syndrome

One of the most puzzling phenomena of abnormal renal physiology is the occurrence of the nephrotic syndrome. The syndrome has been defined by a collection of clinical and pathological symptoms, but there is no correlation between the clinical and pathological symptoms nor is the etiology of the syndrome known. Proteinuria is probably the most distinguishing feature in the nephrotic syndrome, and there are two possible explanations for its occurrence: (1) the excessive amounts of protein found in nephrotic urine could be due to an increased basement membrane permeability in the glomerulus of the kidney or (2) dysproteinemia. An attempt has been made to evaluate the theory of dysproteinemia in connection with the syndrome. The albumin fractions of nephrotic urine have been studied for their amino acid composition by separating them from the urine by paper electrophoresis, hydrolyzing them, and identifying the amino acids present by two-dimensional chromatography. There seem to be no variations in the qualitative makeup of nephrotic albumin from that of normal albumin, but the literature shows that there are some slight variations in the quantitative amino acid composition of nephrotic albumin compared with normal albumin. More extensive and highly developed experimentation along the lines of protein structure and composition must be done before it can conclusively be stated that dysproteinemia is of importance in the nephrotic syndrome.

Respostas dinâmicas em sistemas distribuídos e decomposição forçada da superfície livre para um modelo acoplado Oceano-Atmosfera

O objetivo deste trabalho é a introdução e desenvolvimento de uma metodologia analítico-simbólica para a obtenção de respostas dinâmicas e forçadas (soluções homogêneas e não homogêneas) de sistemas distribuídos, em domínios ilimitados e limitados, através do uso da base dinâmica gerada a partir da resposta impulso. Em domínios limitados, a resposta impulso foi formulada pelo método espectral. Foram considerados sistemas com condições de contorno homogêneas e não homogêneas. Para sistemas de natureza estável, a resposta forçada é decomposta na soma de uma resposta particular e de uma resposta livre induzida pelos valores iniciais da resposta particular. As respostas particulares, para entradas oscilatórias no tempo, foram calculadas com o uso da fun»c~ao de Green espacial. A teoria é desenvolvida de maneira geral permitindo que diferentes sis- temas evolutivos de ordem arbitrária possam ser tratados sistematicamente de uma forma compacta e simples. Realizou-se simulações simbólicas para a obtenção de respostas dinâmicas e respostas for»cadas com equações do tipo parabólico e hiperbólico em 1D,2D e 3D. O cálculo das respostas forçadas foi realizado com a determinação das respostas livres transientes em termos dos valores iniciais das respostas permanentes. Foi simulada a decomposição da resposta forçada da superfície livre de um modelo acoplado oceano-atmosfera bidimensional, através da resolução de uma equação de Klein-Gordon 2D com termo não-homogêneo de natureza dinâmica, devido a tensão de cisalhamento na superfície do oceano pela ação do vento.

Proteome of the phytopathogen Xanthomonas citri subsp citri: a global expression profile

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

Um método para determinação da profundidade combinando visão estéreo e autocalibração para aplicação em robótica móvel

This work proposes a method to determine the depth of objects in a scene using a combination between stereo vision and self-calibration techniques. Determining the rel- ative distance between visualized objects and a robot, with a stereo head, it is possible to navigate in unknown environments. Stereo vision techniques supply a depth measure by the combination of two or more images from the same scene. To achieve a depth estimates of the in scene objects a reconstruction of this scene geometry is necessary. For such reconstruction the relationship between the three-dimensional world coordi- nates and the two-dimensional images coordinates is necessary. Through the achievement of the cameras intrinsic parameters it is possible to make this coordinates systems relationship. These parameters can be gotten through geometric camera calibration, which, generally is made by a correlation between image characteristics of a calibration pattern with know dimensions. The cameras self-calibration allows the achievement of their intrinsic parameters without using a known calibration pattern, being possible their calculation and alteration during the displacement of the robot in an unknown environment. In this work a self-calibration method based in the three-dimensional polar coordinates to represent image features is presented. This representation is determined by the relationship between images features and horizontal and vertical opening cameras angles. Using the polar coordinates it is possible to geometrically reconstruct the scene. Through the proposed techniques combination it is possible to calculate a scene objects depth estimate, allowing the robot navigation in an unknown environment

Enolase from Paracoccidioides brasiliensis: isolation and identification as a fibronectin-binding protein

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

Propagação de danos em sistemas cooperativos: propriedades termodinâmicas

High-precision calculations of the correlation functions and order parameters were performed in order to investigate the critical properties of several two-dimensional ferro- magnetic systems: (i) the q-state Potts model; (ii) the Ashkin-Teller isotropic model; (iii) the spin-1 Ising model. We deduced exact relations connecting specific damages (the difference between two microscopic configurations of a model) and the above mentioned thermodynamic quanti- ties which permit its numerical calculation, by computer simulation and using any ergodic dynamics. The results obtained (critical temperature and exponents) reproduced all the known values, with an agreement up to several significant figures; of particular relevance were the estimates along the Baxter critical line (Ashkin-Teller model) where the exponents have a continuous variation. We also showed that this approach is less sensitive to the finite-size effects than the standard Monte-Carlo method. This analysis shows that the present approach produces equal or more accurate results, as compared to the usual Monte Carlo simulation, and can be useful to investigate these models in circumstances for which their behavior is not yet fully understood

A combination of implicit and adaptative upwind tools for the numerical solution of incompressible free surface flows

This paper is concerned with the numerical solutions of time dependent two-dimensional incompressible flows. By using the primitive variables of velocity and pressure, the Navier-Stokes and mass conservation equations are solved by a semi-implicit finite difference projection method. A new bounded higher order upwind convection scheme is employed to deal with the non-linear (advective) terms. The procedure is an adaptation of the GENSMAC (J. Comput. Phys. 1994; 110: 171-186) methodology for calculating confined and free surface fluid flows at both low and high Reynolds numbers. The calculations were performed by using the 2D version of the Freeflow simulation system (J. Comp. Visual. Science 2000; 2:199-210). In order to demonstrate the capabilities of the numerical method, various test cases are presented. These are the fully developed flow in a channel, the flow over a backward facing step, the die-swell problem, the broken dam flow, and an impinging jet onto a flat plate. The numerical results compare favourably with the experimental data and the analytical solutions. Copyright (c) 2006 John Wiley & Sons, Ltd.

Two field BPS solutions for generalized Lorentz breaking models

In this work we present nonlinear models in two-dimensional space-time of two interacting scalar fields in the Lorentz and CPT violating scenarios. We discuss the soliton solutions for these models as well as the question of stability for them. This is done by generalizing a model recently published by Barreto and collaborators and also by getting new solutions for the model introduced by them.

Análises estratigráfica e estrutural da Seção Rifte (Valanginiano ao Barremiano) na área do levantamento sísmico 3D de baixo vermelho, Bacia Potiguar emersa

Baixo Vermelho area, situated on the northern portion of Umbuzeiro Graben (onshore Potiguar Basin), represents a typical example of a rift basin, characterized, in subsurface, by the sedimentary rift sequence, correlated to Pendência Formation (Valanginian-Barremian), and by the Carnaubais fault system. In this context, two main goals, the stratigraphic and the structural analysis, had guided the research. For this purpose, it was used the 3D seismic volume and eight wells located in the study area and adjacencies. The stratigraphic analysis of the Valanginian-Barremian interval was carried through in two distinct phases, 1D and 2D, in which the basic concepts of the sequence stratigraphy had been adapted. In these phases, the individual analysis of each well and the correlation between them, allowed to recognize the main lithofacies, to interpret the effective depositional systems and to identify the genetic units and key-surfaces of chronostratigraphic character. The analyzed lithofacies are represented predominantly by conglomerates, sandstones, siltites and shales, with carbonate rocks and marls occurring subordinately. According to these lithofacies associations, it is possible to interpret the following depositional systems: alluvial fan, fluvio-deltaic and lacustrine depositional systems. The alluvial fan system is mainly composed by conglomerates deposits, which had developed, preferentially in the south portion of the area, being directly associated to Carnaubais fault system. The fluvial-deltaic system, in turn, was mainly developed in the northwest portion of the area, at the flexural edge, being characterized by coarse sandstones with shales and siltites intercalated. On the other hand, the lacustrine system, the most dominant one in the study area, is formed mainly by shales that could occur intercalated with thin layers of fine to very fine sandstones, interpreted as turbidite deposits. The recognized sequence stratigraphy units in the wells are represented by parasequence sets, systems tracts and depositional sequences. The parasequence sets, which are progradational or retrogradational, had been grouped and related to the systems tracts. The predominance of the progradation parasequence sets (general trend with coarsening-upward) characterizes the Regressive Systems Tract, while the occurrence, more frequently, of the retrogradation parasequence sets (general trend with finning-upward) represents the Transgressive System Tract. In the seismic stratigraphic analysis, the lithofacies described in the wells had been related to chaotic, progradational and parallel/subparallel seismic facies, which are associated, frequently, to the alluvial fans, fluvial-deltaic and lacustrine depositional systems, respectively. In this analysis, it was possible to recognize fifteen seismic horizons that correspond to sequence boundaries and to maximum flooding surfaces, which separates Transgressive to Regressive systems tracts. The recognition of transgressive-regressive cycles allowed to identify nine, possibly, 3a order deposicional sequences, related to the tectonic-sedimentary cycles. The structural analysis, in turn, was done at Baixo Vermelho seismic volume, which shows, clearly, the structural complexity printed in the area, mainly related to Carnaubais fault system, acting as an important fault system of the rift edge. This fault system is characterized by a main arrangement of normal faults with trend NE-SO, where Carnaubais Fault represents the maximum expression of these lineations. Carnaubais Fault corresponds to a fault with typically listric geometry, with general trend N70°E, dipping to northwest. It is observed, throughout all the seismic volume, with variations in its surface, which had conditioned, in its evolutive stages, the formation of innumerable structural features that normally are identified in Pendencia Formation. In this unit, part of these features is related to the formation of longitudinal foldings (rollover structures and distentional folding associated), originated by the displacement of the main fault plan, propitiating variations in geometry and thickness of the adjacent layers, which had been deposited at the same time. Other structural features are related to the secondary faultings, which could be synthetic or antithetic to Carnaubais Fault. In a general way, these faults have limited lateral continuity, with listric planar format and, apparently, they play the role of the accomodation of the distentional deformation printed in the area. Thus, the interaction between the stratigraphic and structural analysis, based on an excellent quality of the used data, allowed to get one better agreement on the tectonicsedimentary evolution of the Valanginian-Barremian interval (Pendência Formation) in the studied area