Study of the phenanthroline-Mn-imidazole bonding in Mn(I) triscarbonyl complex: A X-ray and DFT computational analysis

355 nm light irradiation of fac-[Mn(CO)(3)(phen)(imH)](+) (fac-1) produces the mer-1 isomer and a long lived radical which can be efficiently trapped by electron acceptor molecules. EPR experiments shows that when excited, the manganese(I) complex can be readily oxidized by one-electron process to produce Mn(II) and phen(.-). In the present study, DFT calculations have been used to investigated the photochemical isomerization of the parent Mn(I) complex and to characterize the electronic structures of the long lived radical. The theoretical calculations have been performed on both the fac-1 and mer-1 species as well as on their one electron oxidized species fac-1+ and mer-1+ for the lowest spin configurations (S = 1/2) and fac-6 and mer-6 (S = 5/2) for the highest one to characterize these complexes. In particular, we used a charge decomposition analysis (CDA) and a natural bonding orbital (NBO) to have a better understanding of the chemical bonding in terms of the nature of electronic interactions. The observed variations in geometry and bond energies with an increasing oxidation state in the central metal ion are interpreted in terms of changes in the nature of metal-ligand bonding interactions. The X-ray structure of fac-1 is also described. (C) 2011 Elsevier B.V. All rights reserved.

FT-Raman, FTIR and density functional theory studies of a hydrogen-bonded formamide: pyridine complex

Raman and IR experiments have been carried out on formamide (FA) and pyridine (Py) mixtures at different compositions. The appearance of a new Raman band at 996 cm(-1) (nu(1) region of Py), whose intensity depends on the FA concentration, is assigned to an FA: Py adduct and this result is in excellent agreement with those of other authors who employed noisy light-based coherent Raman scattering spectroscopy (I((2)) CARS). Another band at 1587 cm(-1) (nu(8) region of Py) has been observed for the first time by using Raman and IR spectroscopies. Its intensity shows the same dependence on the FA concentration and this fact allows us to also attribute it to an FA: Py adduct. The good relationship between the Raman and IR data demonstrates the potential of the vibrational spectroscopy for this kind of study. Owing to higher absolute Raman scattering cross section, the nu(1) region of Py has been chosen for the quantitative analysis and a stoichiometry of 1 : 1 FA: Py is reported. The experimental data are very well supported by the density functional theory (OFT) calculation, which was employed for the first time to the present system. Furthermore, the actual investigation shows an excellent agreement with those reported from computational calculations for similar systems. A comparison with our previous studies confirms that: the solvent dielectric constant determines the stoichiometry of a given Lewis acid-base adduct in the infinite dilution limit. Copyright (C) 2009 John Wiley & Sons, Ltd.

Oxindole-Schiff base copper(II) complexes interactions with human serum albumin: Spectroscopic, oxidative damage, and computational studies

CD and EPR were used to characterize interactions of oxindole-Schiff base copper(II) complexes with human serum albumin (HSA). These imine ligands form very stable complexes with copper, and can efficiently compete for this metal ion towards the specific N-terminal binding site of the protein, consisting of the amino acid sequence Asp-Ala-His. Relative stability constants for the corresponding complexes were estimated from CD data, using the protein as competitive ligand, with values of log K(CuL) in the range 15.7-18.1, very close to that of [Cu(HSA)] itself, with log K(CuHSA) 16.2. Some of the complexes are also able to interfere in the a-helix structure of the protein, while others seem not to affect it. EPR spectra corroborate those results, indicating at least two different metal species in solution, depending on the imine ligand. Oxidative damage to the protein after incubation with these copper(II) complexes, particularly in the presence of hydrogen peroxide, was monitored by carbonyl groups formation, and was observed to be more severe when conformational features of the protein were modified. Complementary EPR spin-trapping data indicated significant formation of hydroxyl and carbon centered radicals, consistent with an oxidative mechanism. Theoretical calculations at density functional theory (DFT) level were employed to evaluate Cu(II)-L binding energies, L -> Cu(II) donation, and Cu(II) -> L back-donation, by considering the Schiff bases and the N-terminal site of HSA as ligands. These results complement previous studies on cytotoxicity, nuclease and pro-apoptotic properties of this kind of copper(II) complexes, providing additional information about their possibilities of transport and disposition in blood plasma. (C) 2009 Elsevier Inc. All rights reserved.

Neural network based on adaptive resonance theory with continuous training for multi-configuration transient stability analysis of electric power systems

This work presents a methodology to analyze electric power systems transient stability for first swing using a neural network based on adaptive resonance theory (ART) architecture, called Euclidean ARTMAP neural network. The ART architectures present plasticity and stability characteristics, which are very important for the training and to execute the analysis in a fast way. The Euclidean ARTMAP version provides more accurate and faster solutions, when compared to the fuzzy ARTMAP configuration. Three steps are necessary for the network working, training, analysis and continuous training. The training step requires much effort (processing) while the analysis is effectuated almost without computational effort. The proposed network allows approaching several topologies of the electric system at the same time; therefore it is an alternative for real time transient stability of electric power systems. To illustrate the proposed neural network an application is presented for a multi-machine electric power systems composed of 10 synchronous machines, 45 buses and 73 transmission lines. (C) 2010 Elsevier B.V. All rights reserved.

Linear analysis of building floor structures by a BEM formulation based on Reissner's theory

In this work, the plate bending formulation of the boundary element method (BEM) based on the Reissner's hypothesis is extended to the analysis of zoned plates in order to model a building floor structure. In the proposed formulation each sub-region defines a beam or a slab and depending on the way the sub-regions are represented, one can have two different types of analysis. In the simple bending problem all sub-regions are defined by their middle surface. on the other hand, for the coupled stretching-bending problem all sub-regions are referred to a chosen reference surface, therefore eccentricity effects are taken into account. Equilibrium and compatibility conditions are automatically imposed by the integral equations, which treat this composed structure as a single body. The bending and stretching values defined on the interfaces are approximated along the beam width, reducing therefore the number of degrees of freedom. Then, in the proposed model the set of equations is written in terms of the problem values on the beam axis and on the external boundary without beams. Finally some numerical examples are presented to show the accuracy of the proposed model.

A joint computational and experimental study of a novel dioxomolybdenum(VI) complex bearing chiral N,N-dimethyllactamide ligand

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

A BEM formulation based on Reissner's theory to perform simple bending analysis of plates reinforced by rectangular beams

In this work, the plate bending formulation of the boundary element method (BEM), based on the Reissner's hypothesis, is extended to the analysis of plates reinforced by rectangular beams. This composed structure is modelled by a zoned plate, being the beams represented by narrow sub-regions with larger thickness. The integral equations are derived by applying the weighted residual method to each sub-region, and summing them to get the equation for the whole plate. Equilibrium and compatibility conditions are automatically imposed by the integral equations, which treat this composed structure as a single body. In order to decrease the number of degrees of freedom, some approximations are considered for both displacements and tractions along the beam width. The accuracy of the proposed model is illustrated by simple examples whose exact solution are known as well as by more complex examples whose numerical results are compared with a well-known finite element code.

Methodology analysis of a computational tool used in electronic circuit design

This paper considers the importance of using a top-down methodology and suitable CAD tools in the development of electronic circuits. The paper presents an evaluation of the methodology used in a computational tool created to support the synthesis of digital to analog converter models by translating between different tools used in a wide variety of applications. This tool is named MS 2SV and works directly with the following two commercial tools: MATLAB/Simulink and SystemVision. Model translation of an electronic circuit is achieved by translating a mixed-signal block diagram developed in Simulink into a lower level of abstraction in VHDL-AMS and the simulation project support structure in SystemVision. The method validation was performed by analyzing the power spectral of the signal obtained by the discrete Fourier transform of a digital to analog converter simulation model. © 2011 IEEE.

Simplified computational routine to correct the modal decoupling in transmission lines and power systems modelling

Modal analysis is widely approached in the classic theory of power systems modelling. This technique is also applied to model multiconductor transmission lines and their self and mutual electrical parameters. However, this methodology has some particularities and inaccuracies for specific applications, which are not clearly described in the technical literature. This study provides a brief review on modal decoupling applied in transmission line digital models and thereafter a novel and simplified computational routine is proposed to overcome the possible errors embedded by the modal decoupling in the simulation/ modelling computational algorithm. © The Institution of Engineering and Technology 2013.

A multiple intelligences theory-based 3D virtual lab environment for digital systems teaching.

This paper describes a 3D virtual lab environment that was developed using OpenSim software integrated into Moodle. Virtuald software tool was used to provide pedagogical support to the lab by enabling to create online texts and delivering them to the students. The courses taught in this virtual lab are methodologically in conformity to theory of multiple intelligences. Some results are presented.

Capacitance spectroscopy and density functional theory

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

Generalizing the dynamic field theory of spatial cognition across real and developmental time scales

Within cognitive neuroscience, computational models are designed to provide insights into the organization of behavior while adhering to neural principles. These models should provide sufficient specificity to generate novel predictions while maintaining the generality needed to capture behavior across tasks and/or time scales. This paper presents one such model, the Dynamic Field Theory (DFT) of spatial cognition, showing new simulations that provide a demonstration proof that the theory generalizes across developmental changes in performance in four tasks—the Piagetian A-not-B task, a sandbox version of the A-not-B task, a canonical spatial recall task, and a position discrimination task. Model simulations demonstrate that the DFT can accomplish both specificity—generating novel, testable predictions—and generality—spanning multiple tasks across development with a relatively simple developmental hypothesis. Critically, the DFT achieves generality across tasks and time scales with no modification to its basic structure and with a strong commitment to neural principles. The only change necessary to capture development in the model was an increase in the precision of the tuning of receptive fields as well as an increase in the precision of local excitatory interactions among neurons in the model. These small quantitative changes were sufficient to move the model through a set of quantitative and qualitative behavioral changes that span the age range from 8 months to 6 years and into adulthood. We conclude by considering how the DFT is positioned in the literature, the challenges on the horizon for our framework, and how a dynamic field approach can yield new insights into development from a computational cognitive neuroscience perspective.

A review and evaluation on constructive heuristics to optimise product mix based on the Theory of Constraints

In this paper, we address the problem of defining the product mix in order to maximise a system's throughput. This problem is well known for being NP-Complete and therefore, most contributions to the topic focus on developing heuristics that are able to obtain good solutions for the problem in a short CPU time. In particular, constructive heuristics are available for the problem such as that by Fredendall and Lea, and by Aryanezhad and Komijan. We propose a new constructive heuristic based on the Theory of Constraints and the Knapsack Problem. The computational results indicate that the proposed heuristic yields better results than the existing heuristic.

Computation of (3)J(HH) coupling constants with a combination of density functional theory and semiempirical calculations. Application to complex molecules

This work evaluates the efficiency of economic levels of theory for the prediction of (3)J(HH) spin-spin coupling constants, to be used when robust electronic structure methods are prohibitive. To that purpose, DFT methods like mPW1PW91. B3LYP and PBEPBE were used to obtain coupling constants for a test set whose coupling constants are well known. Satisfactory results were obtained in most of cases, with the mPW1PW91/6-31G(d,p)//B3LYP/6-31G(d,p) leading the set. In a second step. B3LYP was replaced by the semiempirical methods PM6 and RM1 in the geometry optimizations. Coupling constants calculated with these latter structures were at least as good as the ones obtained by pure DFT methods. This is a promising result, because some of the main objectives of computational chemistry - low computational cost and time, allied to high performance and precision - were attained together. (C) 2012 Elsevier B.V. All rights reserved.