A fluxional (CuN2O2)-N-I core: binding of a keto oxygen atom to Cu-I and Ag-I

[Cu(2-acetylpyridine)(2)]ClO4 (1), characterised here, has a novel Cu'N202 core in the solid state. Variable-temperature H-1 NMR studies show that the two chelate rings open up in solution at room temperature and the keto oxygen atoms dangle freely. As the temperature is lowered, the 0 atoms tend to bind to the metal atom. The corresponding silver(I) complex, [Ag(2-acetylpyridine)2]ClO4 (4), characterised by single-crystal X-ray crystallography, has an (AgN2)-N-I core in the solid state as well as in solution. Thus, while 1 is fluxional, 4 is not. In cyclic voltammetry, complex 1 displays a quasireversible Cu-II/I couple with a half-wave potential of 0.40 V vs. SCE. Complex I is easily oxidised by air and H2O2 in methanol to give rise to a dinuclear copper(II) complex where the ligand framework is not simple acetylpyridine. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).

Tephra fallout hazard assessment for a Plinian eruption scenario at Volcán de Colima (Mexico)

Volcanic ash fallout associated with renewal of explosive activity at Colima, represents a serious threat to the surrounding urbanized area. Here we assess the tephra fallout hazard associated with a Plinian eruption scenario. The eruptive history of Volcán de Colima shows that Plinian eruptions occur approximately every 100 years and the last eruption, the 1913, represents the largest historic eruption of this volcano. We used the last eruption as a reference to discuss volcanic hazard and risk scenarios connected with ash fallout. Tephra fallout deposits are modeled using HAZMAP, a model based on a semi-analytical solution of the advection– diffusion–sedimentation equation for volcanic particles. Based on a statistical study of wind profiles at Colima region, we first reconstructed ash loading maps and then computed ground load probability maps for different seasons. The obtained results show that a Plinian eruptive scenario at Volcán de Colima, could seriously damage more than 10 small towns and ranches, and potentially affect big cities located at tens of kilometers from the eruptive center. The probability maps obtained are aimed to give support to the risk mitigation strategies

Thermal wave scattering by two overlapping and parallel cylinders

In this paper an analytical solution of the temperature of an opaque material containing two overlapping and parallel subsurface cylinders, illuminated by a modulated light beam, is presented. The method is based on the expansion of plane and cylindrical thermal waves in series of Bessel and Hankel functions. This model is addressed to the study of heat propagation in composite materials with interconnection between inclusions, as is the case of inverse opals and fiber reinforced composites. Measurements on calibrated samples using lock-in infrared thermography confirm the validity of the model.

The role of an insulating surface layer on the relaxation time of the ionic redistribution in an electrolytic cell

We analyze the influence of a surface dielectric layer on the transient phenomena related to the ionic redistribution in an electrolytic cell submitted to a step-like external voltage. The adsorption-desorption phenomenon is taken into account in the famework of the Gouy-Chapman approximation, where the ions are assumed dimensionless. In the limit of small amplitude of the applied voltage, where the equations of the problem can be linearized, we obtain an analytical solution for the surface densities of ions, for the electrical potential and for the relaxation time for the transient phenomena. In the general case, when the linearized analysis is no longer valid, the solution of the problem is obtained numerically. The role of the thickness of the dielectric layer on the relaxation time is also discussed.

On exact time averages of a massive Poisson particle

In this work we study, under the Stratonovich definition, the problem of the damped oscillatory massive particle subject to a heterogeneous Poisson noise characterized by a rate of events, lambda(t), and a magnitude, Phi, following an exponential distribution. We tackle the problem by performing exact time averages over the noise in a similar way to previous works analysing the problem of the Brownian particle. From this procedure we obtain the long-term equilibrium distributions of position and velocity as well as analytical asymptotic expressions for the injection and dissipation of energy terms. Considerations on the emergence of stochastic resonance in this type of system are also set forth.

Uma metodologia para adaptação e melhoria de produtos a partir da engenharia reversa

O tema desta dissertação de mestrado é o estudo da Engenharia Reversa como ferramenta de suporte à melhoria e adaptação de produtos. A partir de conceitos teóricos sobre desenvolvimento de produtos e melhoria de processos, propõe-se uma metodologia para adaptação de produtos destinados à exportação. A metodologia proposta consiste de oito passos, contemplando etapas de identificação e priorização das demandas de adaptação de produtos e elencando ferramentas auxiliares no atingimento dos objetivos desejados. A etapa inicial deste trabalho consiste de uma revisão bibliográfica dividida em duas partes: (i) adaptação de produtos através da utilização da Engenharia Reversa e seus habilitadores, e (ii) ferramentas para melhoria de processos. Os tópicos contemplados em (ii) incluem ferramentas para o mapeamento de processos de manufatura e para a sua melhoria. Destaque especial é dado ao Desdobramento da Função Qualidade – QFD (Quality Function Deployment), a Análise de Modos e Efeitos de Falhas (FMEA – Failure Mode and Effect Analysis) e às Cartas de Processos. Na seqüência, apresentam-se os passos da metodologia proposta para a adaptação de produtos às demandas de mercado utilizando a Engenharia Reversa e seus habilitadores. Finalmente, os passos metodológicos são aplicados a um caso prático, cujo objetivo é a adaptação de um pincel, produzido por uma empresa gaúcha, às demandas de um distribuidor alemão de ferramentas manuais.

Otimização de forma aplicando B-splines sob critério integral de tensões

This work proposes a computational methodology to solve problems of optimization in structural design. The application develops, implements and integrates methods for structural analysis, geometric modeling, design sensitivity analysis and optimization. So, the optimum design problem is particularized for plane stress case, with the objective to minimize the structural mass subject to a stress criterion. Notice that, these constraints must be evaluated at a series of discrete points, whose distribution should be dense enough in order to minimize the chance of any significant constraint violation between specified points. Therefore, the local stress constraints are transformed into a global stress measure reducing the computational cost in deriving the optimal shape design. The problem is approximated by Finite Element Method using Lagrangian triangular elements with six nodes, and use a automatic mesh generation with a mesh quality criterion of geometric element. The geometric modeling, i.e., the contour is defined by parametric curves of type B-splines, these curves hold suitable characteristics to implement the Shape Optimization Method, that uses the key points like design variables to determine the solution of minimum problem. A reliable tool for design sensitivity analysis is a prerequisite for performing interactive structural design, synthesis and optimization. General expressions for design sensitivity analysis are derived with respect to key points of B-splines. The method of design sensitivity analysis used is the adjoin approach and the analytical method. The formulation of the optimization problem applies the Augmented Lagrangian Method, which convert an optimization problem constrained problem in an unconstrained. The solution of the Augmented Lagrangian function is achieved by determining the analysis of sensitivity. Therefore, the optimization problem reduces to the solution of a sequence of problems with lateral limits constraints, which is solved by the Memoryless Quasi-Newton Method It is demonstrated by several examples that this new approach of analytical design sensitivity analysis of integrated shape design optimization with a global stress criterion purpose is computationally efficient

Spacecraft's attitude prediction: solar radiation torque and the Earth's shadow

A semi-analytical approach is proposed to study the rotational motion of an artificial satellite, under the influence of torque due to the solar radiation pressure, and taking into account the influence of Earth's shadow. Using Andoyer variables the equations for the rotational motion are presented in extended Hamiltonian form. In order to get a solution for the state variables close to an actual motion, the considered model for the shadow function takes into account physical and geometric factors and three specific regions: shadow, penumbra and full light. A mapping for the shadow function is proposed and a semi-analytical process is applied. When the satellite is totally illuminated or it is inside the penumbra, a known analytical solution is used to compute the satellite's attitude. A numerical simulation shows, when the penumbra region is included, the attenuation of the rotational motion during the transition from the shadow to the illuminate region and vice versa. (c) 2005 Published by Elsevier Ltd on behalf of COSPAR.

Optimal attitude corrections for cylindrical spacecraft

A first order analytical model for optimal small amplitude attitude maneuvers of spacecraft with cylindrical symmetry in an elliptical orbits is presented. The optimization problem is formulated as a Mayer problem with the control torques provided by a power limited propulsion system. The state is defined by Seffet-Andoyer's variables and the control by the components of the propulsive torques. The Pontryagin Maximum Principle is applied to the problem and the optimal torques are given explicitly in Serret-Andoyer's variables and their adjoints. For small amplitude attitude maneuvers, the optimal Hamiltonian function is linearized around a reference attitude. A complete first order analytical solution is obtained by simple quadrature and is expressed through a linear algebraic system involving the initial values of the adjoint variables. A numerical solution is obtained by taking the Euler angles formulation of the problem, solving the two-point boundary problem through the shooting method, and, then, determining the Serret-Andoyer variables through Serret-Andoyer transformation. Numerical results show that the first order solution provides a good approximation to the optimal control law and also that is possible to establish an optimal control law for the artificial satellite's attitude. (C) 2003 COSPAR. Published by Elsevier B.V. Ltd. All rights reserved.

Attitude propagation using non-singular canonical variables

Three sets of non-singular canonical variables for the rotational motion are analyzed. These sets are useful when the angle between z-axis of a coordinate system fixed in artificial satellite ( here defined by the directions of principal moments of inertia of the satellite) and the rotational angular momentum vector is zero or when the angle between Z-inertial axis and rotational angular momentum vector is zero. The goal of this paper is to compare all these sets and to determine the benefits of their uses. With this objective, the dynamical equations of each set were derived, when mean hamiltonian associate with the gravity gradient torque is included. For the torque-free rotational motion, analytical solutions are computed for symmetrical satellite for each set of variables. When the gravity gradient torque is included, an analytical solution is shown for one of the sets and a numerical solution is obtained for one of the other sets. By this analysis we can conclude that: the dynamical equation for the first set is simple but it has neither clear geometrical nor physical meaning; the other sets have geometrical and physical meaning but their dynamical equations are more complex.

Comparison between Two Methods to Calculate the Transition Matrix of Orbit Motion

Two methods to evaluate the state transition matrix are implemented and analyzed to verify the computational cost and the accuracy of both methods. This evaluation represents one of the highest computational costs on the artificial satellite orbit determination task. The first method is an approximation of the Keplerian motion, providing an analytical solution which is then calculated numerically by solving Kepler's equation. The second one is a local numerical approximation that includes the effect of J(2). The analysis is performed comparing these two methods with a reference generated by a numerical integrator. For small intervals of time (1 to 10s) and when one needs more accuracy, it is recommended to use the second method, since the CPU time does not excessively overload the computer during the orbit determination procedure. For larger intervals of time and when one expects more stability on the calculation, it is recommended to use the first method.

Some experiments with high order compact methods using a computer algebra software - Part I

We consider a procedure for obtaining a compact fourth order method to the steady 2D Navier-Stokes equations in the streamfunction formulation using the computer algebra system Maple. The resulting code is short and from it we obtain the Fortran program for the method. To test the procedure we have solved many cavity-type problems which include one with an analytical solution and the results are compared with results obtained by second order central differences to moderate Reynolds numbers. (c) 2005 Elsevier B.V. All rights reserved.

Zeros of Jacobi functions of second kind

The number of zeros in (- 1, 1) of the Jacobi function of second kind Q(n)((alpha, beta)) (x), alpha, beta > - 1, i.e. The second solution of the differential equation(1 - x(2))y (x) + (beta - alpha - (alpha + beta + 2)x)y' (x) + n(n + alpha + beta + 1)y(x) = 0,is determined for every n is an element of N and for all values of the parameters alpha > - 1 and beta > - 1. It turns out that this number depends essentially on alpha and beta as well as on the specific normalization of the function Q(n)((alpha, beta)) (x). Interlacing properties of the zeros are also obtained. As a consequence of the main result, we determine the number of zeros of Laguerre's and Hermite's functions of second kind. (c) 2005 Elsevier B.V. All rights reserved.

Formation of soliton trains in Bose-Einstein condensates as a nonlinear Fresnel diffraction of matter waves

The problem of generation of atomic soliton trains in elongated Bose-Einstein condensates is considered in framework of Whitham theory of modulations of nonlinear waves. Complete analytical solution is presented for the case when the initial density distribution has sharp enough boundaries. In this case the process of soliton train formation can be viewed as a nonlinear Fresnel diffraction of matter waves. Theoretical predictions are compared with results of numerical simulations of one- and three-dimensional Gross-Pitaevskii equation and with experimental data on formation of Bose-Einstein bright solitons in cigar-shaped traps. (C) 2003 Elsevier B.V. All rights reserved.

Fundamental Limits on Wavelength, Efficiency and Yield of the Charge Separation Triad

In an attempt to optimize a high yield, high efficiency artificial photosynthetic protein we have discovered unique energy and spatial architecture limits which apply to all light-activated photosynthetic systems. We have generated an analytical solution for the time behavior of the core three cofactor charge separation element in photosynthesis, the photosynthetic cofactor triad, and explored the functional consequences of its makeup including its architecture, the reduction potentials of its components, and the absorption energy of the light absorbing primary-donor cofactor. Our primary findings are two: First, that a high efficiency, high yield triad will have an absorption frequency more than twice the reorganization energy of the first electron transfer, and second, that the relative distance of the acceptor and the donor from the primary-donor plays an important role in determining the yields, with the highest efficiency, highest yield architecture having the light absorbing cofactor closest to the acceptor. Surprisingly, despite the increased complexity found in natural solar energy conversion proteins, we find that the construction of this central triad in natural systems matches these predictions. Our analysis thus not only suggests explanations for some aspects of the makeup of natural photosynthetic systems, it also provides specific design criteria necessary to create high efficiency, high yield artificial protein-based triads.