Factors which affect the catalytic activity of iron(III) meso tetrakis(2,6-dichlorophenyl)porphyrin chloride in homogeneous system

An optimization study of the reaction conditions of Fe(TDCPP)Cl when it is used as catalyst in the hydroxylation of cyclohexane by iodosylbenzene (PhIO) has been carried out, It was found that Fe(TDCPP)Cl follows the classical PhIO mechanism described for Fe(TPP)Cl, which involves the monomeric active species Fe-IV(O)P-+. (I). In the optimized condition ([Fe(TDCPP) = 3.0 X 10(-4) mol l(-1) in 1,2-dichloroethane (DCE); ultrasound stirring at 0 degrees C; PhIO/FeP molar ratio = 100), this FeP led to a yield of cyclohexanol (C-ol) of 96% and a turnover number of 96, Therefore, Fe(TDCPP)Cl may be considered a good biomimetic model and a very stable, resistant and selective catalyst, which yields C-ol as the sole product. DCE showed to be a better solvent than dichloromethane (DCM), 1 DCE:1 MeOH mixture or acetonitrile (ACN). Since the Fe-IV(O)P-+. is capable of abstracting hydrogen atom from DCM, MeOH or ACN, the solvent competes with the substrate. Presence of O-2 lowers the yield of C-ol, as it can further oxidize this alcohol to carboxylic acid in the presence of radicals, Presence of H2O also causes a decrease in the yield, since it converts the active species I into Fe-IV(OH)P, which cannot oxidize cyclohexane. Addition of excess imidazole or OH- to the system results in a decrease in the yield of C-ol, due to the formation of the hexacoordinated complexes Fe(TDCPP)Im(2)(+) (low-spin, beta(2) = 2.5 X 10(8) mol(-2) l(2)) and Fe(TDCPP)(OH)(2)(-) (high-spin, beta(2) = 6.3 X 10(7) mol(-2) l(2)), the formation of both Fe(TDCPP)Im(2)(+) and Fe(TDCPP)(OH)(2)(-) complexes were confirmed by EPR studies. The catalytic activities of Fe(TDCPP)C and Fe(TFPP)Cl were compared, the unusually high yields of C-ol with Fe(TFPP)Cl obtained when ultrasound, DCM and O-2 atmosphere were used, suggest that a parallel mechanism involving the mu-oxo dimer form, O-2 and radicals may also be occurring with this FeP, besides the PhIO mechanism.

On the existence of infinite heteroclinic cycles in polynomial systems and its dynamic consequences

In this work we consider the dynamic consequences of the existence of infinite heteroclinic cycle in planar polynomial vector fields, which is a trajectory connecting two saddle points at infinity. It is stated that, although the saddles which form the cycle belong to infinity, for certain types of nonautonomous perturbations the perturbed system may present a complex dynamic behavior of the solutions in a finite part of the phase plane, due to the existence of tangencies and transversal intersections of their stable and unstable manifolds. This phenomenon might be called the chaos arising from infinity. The global study at infinity is made via the Poincare Compactification and the argument used to prove the statement is the Birkhoff-Smale Theorem. (c) 2004 WILEY-NCH Verlag GmbH & Co. KGaA, Weinheim.

On the number of critical periods for planar polynomial systems

In this paper we get some lower bounds for the number of critical periods of families of centers which are perturbations of the linear one. We give a method which lets us prove that there are planar polynomial centers of degree l with at least 2[(l - 2)/2] critical periods as well as study concrete families of potential, reversible and Lienard centers. This last case is studied in more detail and we prove that the number of critical periods obtained with our approach does not. increases with the order of the perturbation. (C) 2007 Elsevier Ltd. All rights reserved.

Pre-weighted homogeneous map germs finite determinacy and topological triviality

In this paper we introduce the notion of G-pre-weighted homogeneous map germ, (G is one of Mather's groups A or K.) and show that any G-pre-weighted homogeneous map germ is G-finitely determined. We also give an explicit order, based on the Newton polyhedron of a pre-weighted homogeneous germ of function, such that the topological structure is preserved after perturbations by terms of higher order.

An extremal nonnegative sine polynomial

For any positive integer n, the sine polynomials that are nonnegative in [0, π] and which have the maximal derivative at the origin are determined in an explicit form. Associated cosine polynomials Kn (θ) are constructed in such a way that {Kn(θ)} is a summability kernel. Thus, for each Pi 1 ≤ P ≤ ∞ and for any 27π-periodic function f ∈ Lp [-π, π], the sequence of convolutions Kn * f is proved to converge to f in Lp[-ππ]. The pointwise and almost everywhere convergences are also consequences of our construction.

Landau and Kolmogoroff type polynomial inequalities II

Let 0 < j < m ≤ n. Kolmogoroff type inequalities of the form ∥f(j)∥2 ≤ A∥f(m)∥ 2 + B∥f∥2 which hold for algebraic polynomials of degree n are established. Here the norm is defined by ∫ f2(x)dμ(x), where dμ(x) is any distribution associated with the Jacobi, Laguerre or Bessel orthogonal polynomials. In particular we characterize completely the positive constants A and B, for which the Landau weighted polynomial inequalities ∥f′∥ 2 ≤ A∥f″∥2 + B∥f∥ 2 hold. © Dynamic Publishers, Inc.

Fractional polynomial response surface models

Second-order polynomial models have been used extensively to approximate the relationship between a response variable and several continuous factors. However, sometimes polynomial models do not adequately describe the important features of the response surface. This article describes the use of fractional polynomial models. It is shown how the models can be fitted, an appropriate model selected, and inference conducted. Polynomial and fractional polynomial models are fitted to two published datasets, illustrating that sometimes the fractional polynomial can give as good a fit to the data and much more plausible behavior between the design points than the polynomial model. © 2005 American Statistical Association and the International Biometric Society.

Estimates of covariance functions for growth of Nelore cattle applying a parametric correlation structure to model within-animal correlations

A total of 20,065 weights recorded on 3016 Nelore animals were used to estimate covariance functions for growth from birth to 630 days of age, assuming a parametric correlation structure to model within-animal correlations. The model of analysis included fixed effects of contemporary groups and age of dam as quadratic covariable. Mean trends were taken into account by a cubic regression on orthogonal polynomials of animal age. Genetic effects of the animal and its dam and maternal permanent environmental effects were modelled by random regressions on Legendre polynomials of age at recording. Changes in direct permanent environmental effect variances were modelled by a polynomial variance function, together with a parametric correlation function to account for correlations between ages. Stationary and nonstationary models were used to model within-animal correlations between different ages. Residual variances were considered homogeneous or heterogeneous, with changes modelled by a step or polynomial function of age at recording. Based on Bayesian information criterion, a model with a cubic variance function combined with a nonstationary correlation function for permanent environmental effects, with 49 parameters to be estimated, fitted best. Modelling within-animal correlations through a parametric correlation structure can describe the variation pattern adequately. Moreover, the number of parameters to be estimated can be decreased substantially compared to a model fitting random regression on Legendre polynomial of age. © 2004 Elsevier B.V. All rights reserved.

A tool to simplify the management of homogeneous and heterogeneous grids

To simplify computer management, several system administrators are adopting advanced techniques to manage software configuration on grids, but the tight coupling between hardware and software makes every PC an individual managed entity, lowering the scalability and increasing the costs to manage hundreds or thousands of PCs. This paper discusses the feasibility of a distributed virtual machine environment, named Flexlab: a new approach for computer management that combines virtualization and distributed system architectures as the basis of a management system. Flexlab is able to extend the coverage of a computer management solution beyond client operating system limitations and also offers a convenient hardware abstraction, decoupling software and hardware, simplifying computer management. The results obtained in this work indicate that FlexLab is able to overcome the limitations imposed by the coupling between software and hardware, simplifying the management of homogeneous and heterogeneous grids. © 2009 IEEE.

Monte Carlo and analytical calculation of lateral deflection of proton beams in homogeneous targets

Proton radiation therapy is a precise form of radiation therapy, but the avoidance of damage to critical normal tissues and the prevention of geographical tumor misses require accurate knowledge of the dose delivered to the patient and the verification of his position demand a precise imaging technique. In proton therapy facilities, the X-ray Computed Tomography (xCT) is the preferred technique for the planning treatment of patients. This situation has been changing nowadays with the development of proton accelerators for health care and the increase in the number of treated patients. In fact, protons could be more efficient than xCT for this task. One essential difficulty in pCT image reconstruction systems came from the scattering of the protons inside the target due to the numerous small-angle deflections by nuclear Coulomb fields. The purpose of this study is the comparison of an analytical formulation for the determination of beam lateral deflection, based on Molière's theory and Rutherford scattering with Monte Carlo calculations by SRIM 2008 and MCNPX codes. © 2010 American Institute of Physics.

Encoding through generalized polynomial codes

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

Stable singularities of co-rank one quasi homogeneous map germs from (ℂn+1, 0) to (ℂn, 0), n = 2, 3

In this article, we investigate the geometry of quasi homogeneous corank one finitely determined map germs from (ℂn+1, 0) to (ℂn, 0) with n = 2, 3. We give a complete description, in terms of the weights and degrees, of the invariants that are associated to all stable singularities which appear in the discriminant of such map germs. The first class of invariants which we study are the isolated singularities, called 0-stable singularities because they are the 0-dimensional singularities. First, we give a formula to compute the number of An points which appear in any stable deformation of a quasi homogeneous co-rank one map germ from (ℂn+1, 0) to (ℂn, 0) with n = 2, 3. To get such a formula, we apply the Hilbert's syzygy theorem to determine the graded free resolution given by the syzygy modules of the associated iterated Jacobian ideal. Then we show how to obtain the other 0-stable singularities, these isolated singularities are formed by multiple points and here we use the relation among them and the Fitting ideals of the discriminant. For n = 2, there exists only the germ of double points set and for n = 3 there are the triple points, named points A1,1,1 and the normal crossing between a germ of a cuspidal edge and a germ of a plane, named A2,1. For n = 3, there appear also the one-dimensional singularities, which are of two types: germs of cuspidal edges or germs of double points curves. For these singularities, we show how to compute the polar multiplicities and also the local Euler obstruction at the origin in terms of the weights and degrees. © 2013 Pushpa Publishing House.

Classification of masses in mammographic image using wavelet domain features and polynomial classifier

Breast cancer is the most common cancer among women. In CAD systems, several studies have investigated the use of wavelet transform as a multiresolution analysis tool for texture analysis and could be interpreted as inputs to a classifier. In classification, polynomial classifier has been used due to the advantages of providing only one model for optimal separation of classes and to consider this as the solution of the problem. In this paper, a system is proposed for texture analysis and classification of lesions in mammographic images. Multiresolution analysis features were extracted from the region of interest of a given image. These features were computed based on three different wavelet functions, Daubechies 8, Symlet 8 and bi-orthogonal 3.7. For classification, we used the polynomial classification algorithm to define the mammogram images as normal or abnormal. We also made a comparison with other artificial intelligence algorithms (Decision Tree, SVM, K-NN). A Receiver Operating Characteristics (ROC) curve is used to evaluate the performance of the proposed system. Our system is evaluated using 360 digitized mammograms from DDSM database and the result shows that the algorithm has an area under the ROC curve Az of 0.98 ± 0.03. The performance of the polynomial classifier has proved to be better in comparison to other classification algorithms. © 2013 Elsevier Ltd. All rights reserved.

Study of the threshold line between macroscopic and bulk behaviors for homogeneous type II superconductors

In this work we solved the time dependent Ginzburg-Landau equations to simulate homogeneous superconducting samples with square geometry for several lateral sizes. As a result of such simulations we notice that in the Meissner state, when the vortices do not penetrate the superconductor, the response of small samples are not coincident with that expected for the bulk ones, i.e., 4. πM=. -. H. Thus, we focused our analyzes on the way which the M(. H) curves approximate from the characteristic curve of bulk superconductors. With such study, we built a diagram of the size of the sample as a function of the temperature which indicates a threshold line between macroscopic and bulk behaviors. © 2013 Elsevier B.V.