Driving forces in substitution reactions of octahedral complexes: The influence of the competitive effect

The reaction of cis-[RuCl(2)(P-P)(N-N)] type complexes (P-P = 1,4-bis(diphenylphosphino)butane or (1,1`-diphenylphosphino)ferrocene; N-N = 2,2`-bipyridine or 1,10-phenantroline) with monodentate ligands (L), such as 4-methylpyridine, 4-phenylpyridine and benzonitrile forms [RuCl(L)(P-P)(N-N)](+) species Upon characterization of the isolated compounds by elemental analysis, (31)P{(1)H} NMR and X-ray crystallography it was found out that the type of the L ligand determines its position in relation to the phosphorus atom. While pyridine derivatives like 4-methylpyridine and 4-phenylpyridine coordinate trans to the phosphorus atom, the benzonitrile ligand (bzCN), a good pi acceptor, coordinates trans to the nitrogen atom. A (31)P{(1)H} NMR experiment following the reaction of the precursor cis-[RuCl(2)(dppb)(phen)] with the benzonitrile ligand shows that the final position of the entering ligand in the complex is better defined as a consequence of the competitive effect between the phosphorus atom and the cyano-group from the benzonitrile moiety and not by the trans effect. In this case, the benzonitrile group is stabilized trans to one of the nitrogen atoms of the N-N ligand. A differential pulse voltammetry experiment confirms this statement. In both experiments the [RuCl(bzCN)(dppb)(phen)]PF(6) species with the bzCN ligand positioned trans to a phosphorus atom of the dppb ligand was detected as an intermediate complex. (c) 2009 Elsevier Ltd. All rights reserved.

The soft nucleophilicity of organotellurolates driving the S(N)2-type lactone ring-opening reaction

Lithium and magnesium organotellurolates were reacted with lactones producing the corresponding tellurocarboxylic acids. Treatment of the reaction mixture with lithium aluminum hydride allowed the isolation of the corresponding hydroxytellurides in a one-pot operation. (C) 2009 Published by Elsevier Ltd

Txtng as a replacement for standard written English : an attitude survey based on Age and Gender

Text messaging is a new form of writing, brought about by technological development in the last couple of decades. Mobile phone usage has increased rapidly worldwide and texting is now part of many people's everyday communcation. A large number of users send or receive texts which include some abbreviations and shortenings, commonly referred to as textspeak. This novel linguistic phenomenon is perceived by some with indifference and by others with aggravation. The following study examines attitudes towards this linguistic change from a gender and age perspective. The comparison between two groups show that the most conservative and least positive to change are young women. The analysis and discussion around this focuses on power, prestige and patterns.

”Metcha suki ya nen” : A sociolinguistic attitude survey concerning the Kansai dialect

西日本にある関西弁はたくさん色々な形で標準語と異なる。関西弁は１９７０年代の後に、全国で人気を得た。この社会言語学の研究の目的は現在の関西弁に対する感情を調査することである。これは関西弁の話し手ではなくて日本語の母語話者に配ったアンケートで調査された。質的また量的な分析である。結果は一般的に関西弁に好意的であったが、人気がある理由もいろいろあり、それらをさぐるために歴史的なそして文化的な見方を通して議論する。

Atitude socialmente responsável ou estratégia comercial: o caso do pacto global

The discussion about corporate obligations toward the various stakeholders began in the postindustrial era and developed to culminate in the creation of rules, regulations, programs and projects focusing on the dissemination and promotion of what we know today as corporate social responsibility (CSR). In this context, satisfying this new demand and adopting social policies emerge as a determining factor in defining organizational strategies. Nevertheless, some questions are raised when we examine the subject, such as: To what extent should organizations intervene in society? Is the decision for the organizations to adopt a socially responsible attitude really linked to promoting social well being, or is it only a commercial strategy? How does social marketing relate to CSR projects? The study herein, based on the concept and understanding of CSR theories, stakeholders and social marketing, has sought to find evidence of this relationship, in the light of the Global Compact (GC). It was decided to use the multi-case study methodology, considering the possibility of explaining the reasons why the decisions were taken, how they were implemented and what was the outcome. Interviews, supported by previously prepared scripts, were held with CSR managers, employees from other areas of the organizations, and specialists on the subject. Complementary research studies were made in various sources, such as the website of companies under analysis, their sustainability reports, and the GC websites in Brazil and the United Nations (UN). The results obtained show that the organizations have worked increasingly with CSR projects, but the efforts have not been focused. Special mention is given to the programs that create major impact on the company¿s image and reputation, such as projects competing for prizes and participating in the formation of rankings or socially responsible organizations. From the view of Carroll¿s Pyramid (1991) for CSR, it is found that the projects are predominantly focusing on ethical and philanthropic issues. The driving power of the GC, action based on learning, dialogue and partnership, is not to be found. This factor contributes to the statement that social marketing tools are used to build an ethical and socially responsible image, in detriment to effective action by the organizations to meet the social requirements of their stakeholders. The social marketing has as an objective to transform the way a specific public sees a social question and promotes behavior changes, but what has been seen is the use of marketing tools exclusively to promote the company's image.

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.

Analytical attitude prediction of spin stabilized spacecrafts perturbed by magnetic residual torque

An analytical approach for spin-stabilized spacecraft attitude prediction is presented for the influence of the residual magnetic torques. Assuming an inclined dipole model for the Earth's magnetic field, an analytical averaging method is applied to obtain the mean residual torque every orbital period. The orbit mean anomaly is utilized to compute the average components of residual torque in the spacecraft body frame reference system. The theory is developed for time variations in the orbital elements, and non-circular orbits, giving rise to many curvature integrals. It is observed that the residual magnetic torque does not have component along the spin axis. The inclusion of this torque on the rotational motion differential equations of a spin stabilized spacecraft yields conditions to derive an analytical solution. The solution shows that residual torque does not affect the spin velocity magnitude, contributing only for the precession and the drift of the spin axis of the spacecraft. (c) 2005 COSPAR. Published by Elsevier Ltd. All rights reserved.

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.

Attitude stability of artificial satellites subject to gravity gradient torque

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Spin-Stabilized Spacecrafts: Analytical Attitude Propagation Using Magnetic Torques

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Unscented Kalman Filter Applied to the Spacecraft Attitude Estimation with Euler Angles

The aim of this work is to test an algorithm to estimate, in real time, the attitude of an artificial satellite using real data supplied by attitude sensors that are on board of the CBERS-2 satellite (China Brazil Earth Resources Satellite). The real-time estimator used in this work for attitude determination is the Unscented Kalman Filter. This filter is a new alternative to the extended Kalman filter usually applied to the estimation and control problems of attitude and orbit. This algorithm is capable of carrying out estimation of the states of nonlinear systems, without the necessity of linearization of the nonlinear functions present in the model. This estimation is possible due to a transformation that generates a set of vectors that, suffering a nonlinear transformation, preserves the same mean and covariance of the random variables before the transformation. The performance will be evaluated and analyzed through the comparison between the Unscented Kalman filter and the extended Kalman filter results, by using real onboard data.

Attitude stabilization of a rigid spacecraft in the geomagnetic field

An analytical method is proposed to study the attitude stability of a triaxial spacecraft moving in a circular Keplerian orbit in the geomagnetic field. The method is developed based on the electrodynamics effect of the influence of the Lorentz force acting on the charged spacecraft's surface. We assume that the rigid spacecraft is equipped with an electrostatic charged protective shield, having an intrinsic magnetic moment. The main elements of this shield are an electrostatic charged cylindrical screen surrounding the protected volume of the spacecraft. The rotational motion of the spacecraft about its centre of mass due to torques from gravitational force, as well Lorentz and magnetic forces is investigated. The equilibrium positions of the spacecraft in the orbital coordinate system are obtained. The necessary and sufficient conditions for the stability of the spacecraft's equilibrium positions are constructed using Lyapunov's direct method. The numerical results have shown that the Lorentz force has a significant influence on the stability of the equilibrium positions, which can affect the attitude stabilization of the spacecraft. (C) 2007 COSPAR. Published by Elsevier Ltd. All rights reserved.

Mechanical and electrical driving field induced high-frequency dielectric anomalies in ferroelectric systems

Polycrystalline or single-crystal ferroelectric materials present dielectric dispersion in the frequency range 100 MHz-1 GHz that has been attributed to a dispersive ( relaxation-like) mechanism as well as a resonant mechanism. Particularly in 'normal' ferroelectric materials, a dielectric response that is indistinguishable from dispersion or a resonance has been reported. Nevertheless, the reported results are not conclusive enough to distinguish each mechanism clearly. A detailed study of the dielectric dispersion phenomenon has been carried out in PbTiO3-based ferroelectric ceramics, with the composition Pb1-xLaxTiO3 (x = 0.15), over a wide range of temperatures and frequencies, including microwave frequencies. The dielectric response of La-modified lead titanate ferroelectric ceramics, in 'virgin' and poled states, has been investigated in the temperature and frequency ranges 300-450 K and 1 kHz-2 GHz, respectively. The results revealed that the frequency dependence of the dielectric anomalies, depending on the measuring direction with respect to the orientation of the macroscopic polarization, may be described as a general mechanism related to an 'over-damped' resonant process. Applying either a uniaxial stress along the measurement field direction or a poling electric field parallel and/or perpendicular to the measuring direction, a resonant response of the real and imaginary components of the dielectric constant is observed, in contrast to the dispersion behavior obtained in the absence of the stress, for the 'virgin' samples. Both results, resonance and/or dispersion, can be explained by considering a common mechanism involving a resonant response (damped and/or over-damped) which is strongly affected by a ferroelastic-ferroelectric coupling, contributing to the low-field dielectric constant.

Analytical attitude propagation with non-singular variables and gravity gradient torque for spin stabilized satellite

An analytical approach for the spin stabilized satellite attitude propagation is presented using the non-singular canonical variables to describe the rotational motion. Two sets of variables were introduced for Fukushima in 1994 by a canonical transformation and they are useful when the angle between z-satellite axis of a coordinate system fixed in artificial satellite and the rotational angular momentum vector is zero or when the angle between Z-equatorial axis and rotation angular momentum vector is zero. Analytical solutions for rotational motion equations and torque-free motion are discussed in terms of the elliptic functions and by the application of some simplification to get an approximated solution. These solutions are compared with a numerical solution and the results show a good agreement for many rotation periods. When the mean Hamiltonian associated with the gravity gradient torque is included, an analytical solution is obtained by the application of the successive approximations' method for the satellite in an elliptical orbit. These solutions show that the magnitude of the rotation angular moment is not affected by the gravity gradient torque but this torque causes linear and periodic variations in the angular variables, long and short periodic variations in Z-equatorial component of the rotation angular moment and short periodic variations in x-satellite component of the rotation angular moment. The goal of this analysis is to emphasize the geometrical and physical meaning of the non-singular variables and to validate the approximated analytical solution for the rotational motion without elliptic functions for a non-symmetrical satellite. The analysis can be applied for spin stabilized satellite and in this case the general solution and the approximated solution are coincidence. Then the results can be used in analysis of the space mission of the Brazilian Satellites. (C) 2007 COSPAR. Published by Elsevier Ltd. All rights reserved.