Excited-State Dynamics in fac-[Re(CO)(3)(Me(4)phen)(L)](+)

Excited-state dynamics in fac-[Re(CO)(3)(Me(4)phen)(cis-L)](+) (Me(4)phen = 3,4,7,8-tetramethyl-1,10-phenanthroline, L = 4-styrylpyridine (stpy) or 1,2-bis(4-pyridyl)ethylene (bpe)) were investigated by steady-state and time-resolved techniques. A complex equilibrium among three closely lying excited states, 3IL(cis-L), (3)MLCT(Re -> me4phen), and (3)IL(Me4phen), has been established. Under UV irradiation, cis-to-trans isomerization of coordinated cis-L is observed with a quantum yield of 0.15 in acetonitrile solutions. This photoreaction competes with radiative decay from (3)MLCT(Re -> Me4phen) and (3)IL(Me4phen) excited states, leading to a decrease in the emission quantum yield relative to the nonisomerizable complex fac-[Re(CO)(3)(Me(4)phen)(bpa)](+) (bpa = 1,2-bis(4-pyridyl)ethane). From temperature-dependent time-resolved emission measurements in solution and in poly(methyl methacrylate) (PMMA) films, energy barriers (Delta E(a)) for interconversion between (3)MLCT(Re -> me4Phen) and (3)IL(Me4phen) emitting states were determined. For L = cis-stpy, Delta E(a) = 11 (920 cm(-1)) and 15 kJ mol(-1) (1254 cm(-1)) in 5:4 propionitrile/butyronitrile and PMMA, respectively. For L = cis-bpe, Delta E(a) = 13 kJ mol(-1) (1087 cm(-1)) in 5:4 propionitrile/butyronitrile. These energy barriers are sufficient to decrease the rate constant for internal conversion from higher-lying (3)IL(me4phen) state to (3)MLCT(Re -> Me4phen), k(i) congruent to 10(6) s(-1). The decrease in rate allows for the observation of intraligand phosphorescence, even in fluid medium at room temperature. Our results provide additional insight into the role of energy gap and excited-state dynamics on the photochemical and photophysical properties of Re(I) polypyridyl complexes.

Structural studies of prephenate dehydratase from Mycobacterium tuberculosis H37Rv by SAXS, ultracentrifugation, and computational analysis

Tuberculosis (TB) is one of the most common infectious diseases known to man and responsible for millions of human deaths in the world. The increasing incidence of TB in developing countries, the proliferation of multidrug resistant strains, and the absence of resources for treatment have highlighted the need of developing new drugs against TB. The shikimate pathway leads to the biosynthesis of chorismate, a precursor of aromatic amino acids. This pathway is absent from mammals and shown to be essential for the survival of Mycobacterium tuberculosis, the causative agent of TB. Accordingly, enzymes of aromatic amino acid biosynthesis pathway represent promising targets for structure-based drug design. The first reaction in phenylalanine biosynthesis involves the conversion of chorismate to prephenate, catalyzed by chorismate mutase. The second reaction is catalyzed by prephenate dehydratase (PDT) and involves decarboxylation and dehydratation of prephenate to form phenylpyruvate, the precursor of phenylalanine. Here, we describe utilization of different techniques to infer the structure of M. tuberculosis PDT (MtbPDT) in solution. Small angle X-ray scattering and ultracentrifugation analysis showed that the protein oligomeric state is a tetramer and MtbPDT is a flat disk protein. Bioinformatics tools were used to infer the structure of MtbPDT A molecular model for MtbPDT is presented and molecular dynamics simulations indicate that MtbPDT i.s stable. Experimental and molecular modeling results were in agreement and provide evidence for a tetrameric state of MtbPDT in solution.

Simulação computacional da interação fluido-estrutura em bombas de cavidades progressivas

The pumping through progressing cavities system has been more and more employed in the petroleum industry. This occurs because of its capacity of elevation of highly viscous oils or fluids with great concentration of sand or other solid particles. A Progressing Cavity Pump (PCP) consists, basically, of a rotor - a metallic device similar to an eccentric screw, and a stator - a steel tube internally covered by a double helix, which may be rigid or deformable/elastomeric. In general, it is submitted to a combination of well pressure with the pressure generated by the pumping process itself. In elastomeric PCPs, this combined effort compresses the stator and generates, or enlarges, the clearance existing between the rotor and the stator, thus reducing the closing effect between their cavities. Such opening of the sealing region produces what is known as fluid slip or slippage, reducing the efficiency of the PCP pumping system. Therefore, this research aims to develop a transient three-dimensional computational model that, based on single-lobe PCP kinematics, is able to simulate the fluid-structure interaction that occurs in the interior of metallic and elastomeric PCPs. The main goal is to evaluate the dynamic characteristics of PCP s efficiency based on detailed and instantaneous information of velocity, pressure and deformation fields in their interior. To reach these goals (development and use of the model), it was also necessary the development of a methodology for generation of dynamic, mobile and deformable, computational meshes representing fluid and structural regions of a PCP. This additional intermediary step has been characterized as the biggest challenge for the elaboration and running of the computational model due to the complex kinematic and critical geometry of this type of pump (different helix angles between rotor and stator as well as large length scale aspect ratios). The processes of dynamic generation of meshes and of simultaneous evaluation of the deformations suffered by the elastomer are fulfilled through subroutines written in Fortan 90 language that dynamically interact with the CFX/ANSYS fluid dynamic software. Since a structural elastic linear model is employed to evaluate elastomer deformations, it is not necessary to use any CAE package for structural analysis. However, an initial proposal for dynamic simulation using hyperelastic models through ANSYS software is also presented in this research. Validation of the results produced with the present methodology (mesh generation, flow simulation in metallic PCPs and simulation of fluid-structure interaction in elastomeric PCPs) is obtained through comparison with experimental results reported by the literature. It is expected that the development and application of such a computational model may provide better details of the dynamics of the flow within metallic and elastomeric PCPs, so that better control systems may be implemented in the artificial elevation area by PCP

Dynamics of inter-modality re-weighting during human postural control

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Numerical analysis of refrigerant flow along non-adiabatic capillary tubes using a two-fluid model

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

Influence of corn processing provided in the diet on the ruminal dynamics of dairy steer

Objetivou-se com este trabalho avaliar a dinâmica ruminal de novilhos leiteiros recebendo dietas contendo grão de milho inteiro, milho moído na forma de quirera ou milho inteiro tratado com ureia. Para isso, foram mantidos em regime de confinamento seis animais fistulados no rúmen alimentados com dietas com teores semelhantes de energia e proteína. A dieta foi formulada com relação volumoso:concentrado de 40:60 na matéria seca e continha silagem de sorgo como volumoso. O delineamento utilizado foi na forma de um quadrado latino 3 × 3, com três animais e três períodos, e foi repetido duas ou quatro vezes conforme o parâmetro estudado, totalizando seis ou 12 repetições por dieta. O tratamento do grão de milho não influenciou o pH do líquido ruminal nem a degradabilidade ruminal da matéria seca, fibra em detergente ácido e celulose. Todas as dietas propiciaram concentração de N-amoniacal adequada para o crescimento microbiano ruminal; todavia, nos animais alimentados com grão de milho inteiro tratado com ureia, essa concentração foi significativamente menor. A atividade bacteriana é menor em animais alimentados com dietas contendo milho moído e não difere entre os animais alimentados com grão de milho inteiro ou grão de milho inteiro tratado com ureia.

Structural studies of prephenate dehydratase from Mycobacterium tuberculosis H37Rv by SAXS, ultracentrifugation, and computational analysis

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

A mass-transportation approach to a one dimensional fluid mechanics model with nonlocal velocity

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

Solitary waves on a free surface of a heated Maxwell fluid

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

On Nonlinear Dynamics and an Optimal Control Design to a Longitudinal Flight

In this work, we analyzed a bifurcational behavior of a longitudinal flight nonlinear dynamics, taking as an example the F-8 aircraft Crusader. We deal with an analysis of high angles of attack in order to stabilize the oscillations; those were close to the critical angle of the aircraft, in the flight conditions, established. We proposed a linear optimal control design applied to the considered nonlinear aircraft model below angle of stall, taking into account regions of Hopf and saddled noddle bifurcations.

Optimal pest control problem in population dynamics

One of the main goals of the pest control is to maintain the density of the pest population in the equilibrium level below economic damages. For reaching this goal, the optimal pest control problem was divided in two parts. In the first part, the two optimal control functions were considered. These functions move the ecosystem pest-natural enemy at an equilibrium state below the economic injury level. In the second part, the one optimal control function stabilizes the ecosystem in this level, minimizing the functional that characterizes quadratic deviations of this level. The first problem was resolved through the application of the Maximum Principle of Pontryagin. The Dynamic Programming was used for the resolution of the second optimal pest control problem.

Wavelet-Galerkin method for one-dimensional elastoplasticity and damage problems: Constitutive modeling and computational aspects

This work presents an analysis of the wavelet-Galerkin method for one-dimensional elastoplastic-damage problems. Time-stepping algorithm for non-linear dynamics is presented. Numerical treatment of the constitutive models is developed by the use of return-mapping algorithm. For spacial discretization we can use wavelet-Galerkin method instead of standard finite element method. This approach allows to locate singularities. The discrete formulation developed can be applied to the simulation of one-dimensional problems for elastic-plastic-damage models. (C) 2007 Elsevier B.V. All rights reserved.

Nonlinear Dynamics and Control of an Ideal/Nonideal Load Transportation System With Periodic Coefficients

In this paper, a loads transportation system in platforms or suspended by cables is considered. It is a monorail device and is modeled as an inverted pendulum built on a car driven by a dc motor the governing equations of motion were derived via Lagrange's equations. In the mathematical model we consider the interaction between the dc motor and the dynamical system, that is, we have a so called nonideal periodic problem. The problem is analyzed, qualitatively, through the comparison of the stability diagrams, numerically obtained, for several motor torque constants. Furthermore, we also analyze the problem quantitatively using the Floquet multipliers technique. Finally, we devise a control for the studied nonideal problem. The method that was used for analysis and control of this nonideal periodic system is based on the Chebyshev polynomial exponsion, the Picard iterative method, and the Lyapunov-Floquet transformation (L-F transformation). We call it Sinha's theory.

Exact dynamics of single-qubit-gate fidelities under the measurement-based quantum computation scheme

Measurement-based quantum computation is an efficient model to perform universal computation. Nevertheless, theoretical questions have been raised, mainly with respect to realistic noise conditions. In order to shed some light on this issue, we evaluate the exact dynamics of some single-qubit-gate fidelities using the measurement-based quantum computation scheme when the qubits which are used as a resource interact with a common dephasing environment. We report a necessary condition for the fidelity dynamics of a general pure N-qubit state, interacting with this type of error channel, to present an oscillatory behavior, and we show that for the initial canonical cluster state, the fidelity oscillates as a function of time. This state fidelity oscillatory behavior brings significant variations to the values of the computational results of a generic gate acting on that state depending on the instants we choose to apply our set of projective measurements. As we shall see, considering some specific gates that are frequently found in the literature, the fast application of the set of projective measurements does not necessarily imply high gate fidelity, and likewise the slow application thereof does not necessarily imply low gate fidelity. Our condition for the occurrence of the fidelity oscillatory behavior shows that the oscillation presented by the cluster state is due exclusively to its initial geometry. Other states that can be used as resources for measurement-based quantum computation can present the same initial geometrical condition. Therefore, it is very important for the present scheme to know when the fidelity of a particular resource state will oscillate in time and, if this is the case, what are the best times to perform the measurements.