Combined (13)C NMR and DFT/GIAO studies of the polyketides Aurasperone A and Fonsecinone A

Structural characterization by NMR spectroscopy and DFT calculations was performed for two dimeric naptho-gamma-pyrones, the polyketides Aurasperone A and Fonsecinone A. Experimental data ((13)C NMR chemical shifts and interatomic geometries) were found to be in reasonable agreement with theoretical ones, obtained at B3LYP level for three different basis sets (6-31G/6-31G(d)/6-31G(d,p)). Additionally, the dipolar moments calculation allowed explaining the different solubility for these molecules. The (13)C NMR theoretical chemical shifts were calculated with the GIAO method and the solvent effects were taken into account by means of the PCM approximation. In this work, the DFT/GIAO methodology shows to be a reliable tool in the assignment of experimental NMR chemical shifts of similar molecules. (C) 2008 Wiley Periodicals, Inc. Int J Quantum Chem 108: 2408-2416, 2008.

Theoretical study on the reaction mechanism of VO2+ with propyne in gas phase

Possible molecular mechanisms of the gas-phase ion/molecule reaction of VO2+ in its lowest singlet and triplet states ((1)A(1)/(3)A '') with propyne have been investigated theoretically by density functional theory (DFT) methods. The geometries, energetic values, and bonding features of all stationary and intersystem crossing points involved in the five different reaction pathways (paths 1-5), in both high-spin (triplet) and low-spin (singlet) surfaces, are reported and analyzed. The oxidation reaction starts by a hydrogen transfer from propyne molecule to the vanadyl complex, followed by oxygen migration to the hydrocarbon moiety. A hydride transfer process to the vanadium atom opens four different reaction courses, paths 1-4, while path 5 arises from a hydrogen transfer process to the hydroxyl group. Five crossing points between high- and low-spin states are found: one of them takes place before the first branching point, while the others occur along path 1. Four different exit channels are found: elimination of hydrogen molecule to yield propynaldehyde and VO+ ((1)Sigma/(3)Sigma); formation of propynaldehyde and the moiety V-(OH2)(+); and two elimination processes of water molecule to yield cationic products, Prod-fc(+) and Prod-dc(+) where the vanadium atom adopts a four- and di-coordinate structure, respectively.

Resolving power of 2D pion interferometry

A χ2 analysis is performed to test the resolving power of two-dimensional pion interferometry using for illustration the preliminary E802 data on Si+Au at 14.6 A GeV/c. We find that the resolving power to distinguish two decoupling geometries of different dynamical models is enhanced by studying the variation of the mean χ2 per degrees of freedom with respect to the range of the analysis in the qT, qL plane. The preliminary data seem to rule out dynamical models with significant ω, η resonance formation yields.

A steady-state model for heat pipes of circular or rectangular cross-sections

The objective of this paper is to present a generalized analytical-numerical model of the internal flow in heat pipes. The model formulation is based on two-dimensional formulation of the energy and momentum equations in the vapour and liquid regions and also in the metallic tube. The numerical solution of the model is obtained by using the descretization scheme LOAD and the SIMPLE numerical code. The flow fields, as well as the pressure fields, for different geometries were obtained and discussed. Copyright © 1996 Elsevier Science Ltd.

Gravitational Lorentz force and the description of the gravitational interaction

In the context of a gauge theory for the translation group, we have obtained, for a spinless particle, a gravitational analogue of the Lorentz force. Then, we have shown that this force equation can be rewritten in terms of magnitudes related to either the teleparallel or the Riemannian structures induced in spacetime by the presence of the gravitational field. In the first case, it gives a force equation, with torsion playing the role of force. In the second, it gives the usual geodesic equation of general relativity. The main conclusion is that scalar matter is able to feel any one of the above spacetime geometries, the teleparallel and the metric ones. Furthermore, both descriptions are found to be completely equivalent in the sense that they give the same physical trajectory for a spinless particle in a gravitational field.

Comportamento fractal de tracos de fraturas na borda sul do macico granitico de itu, estado de Sao Paulo

Fractal geometry is relevant to understand and explain many natural complex geometries. Using the fractal set concept (fig. 1) many authors have shown that shorelines, landscapes and fractures follow a fractal behaviour. These authors have developed many methods, including the Cantor's Dust Method (CDM) (VELDE et al., 1992), a linear method of analysis adapted for the determination of two-dimensional phenomena. The Itu Granitic Complex (IGC) is a wide granitic body that that crops out at northwest of Cabreuva City, Sao Paulo State (fig. 2) and was affected in its south border by dextral Itu-Jundiuvira Shear Zone (IJSZ) that produced fractures and alignment of feldspars crystals. The different types of fractures (compression, distension and shear) was discriminated from the relationship between them and medium stress ellipsoid of IJSZ (fig. 3). A modified version of CDM was used to study a possible fractal behaviour of the fracture traces in the south border of IGC. The main modification was the use only one direction of analysis (NE/SW). Four parallel profiles were traced with lengths between 9.75km and 12.75km, each one them was divided into six classes of segments (x) with 375m, 500m, 750m, 1.000m, 1.250m and 1.500m. The parameter (N) is provided by he rate between profile length and choiced segment. For each x the number of intervals is counted with at least one event (fracture intersection) which supplied the parameter(n). The n/N rate provide the parameter (p) that represents the relationship between frequency of events and x. And finally the parameters p and x were plotted in a logarithmic graphics (fig. 4) that provide a line with such a declivity (1) which is related to effective dimension (De). In theory, granitics bodies are isotropics and they would have a same fractal dimension in all segments, but the logarithmic graphics (fig. 4) show that fracture traces of IGC has a fractal behaviour in a restrict interval. This fact probably occurs from the passage of a ductil-brittle deformation condition to a more brittle deformation condition of IGC.

Riemannian and teleparallel descriptions of the scalar field gravitational interaction

A comparative study between the metric and the teleparallel descriptions of gravitation is made for the case of a scalar field. In contrast to the current belief that only spin matter could detect the teleparallel geometry, scalar matter being able to feel the metric geometry only, we show that a scalar field is able not only to feel anyone of these geometries, but also to produce torsion. Furthermore, both descriptions are found to be completely equivalent, which means that in fact, besides coupling to curvature, a scalar field couples also to torsion.

A low-voltage programmable-gain CMOS amplifier with very-low temperature-drift

A new topology for a LVLP variable-gain CMOS amplifier is presented. Input- and load-stage are built around triode-transconductors so that voltage-gain is fully defined by a linear relationship involving only device-geometries and biases. Excellent gain-accuracy, temperature-insensitivity; and wide range of programmability, are thus achieved. Moreover, adaptative biasing improves the common-mode voltage stability upon gain-adjusting. As an example, a 0-40dB programmablegain audio-amplifier is designed. Its performance is supported by a range of simulations. For VDD=1.8V and 20dB-nominal gain, one has Av=19.97dB, f3db=770KHz and quiescent dissipation of 378μW. Over temperatures from -25°C to 125°C, the 0. ldB-bandwidth is 52KHz. Dynamic-range is optimized to 57.2dB and 42.6dB for gains of 20dB and 40dB, respectively. THD figures correspond to -60.6dB@Vout= 1Vpp and -79.7dB@Vout= 0.5 Vpp. A nearly constant bandwidth for different gains is also attained.

Effect of anharmonicities in the critical number of trapped condensed atoms with an attractive two-body interaction

The quantitative effect in the maximum number of particles and other static observables was determined. A deviation in the harmonic trap potential that is effective only outside the central part of the potential, with the addition of a term that is proportional to a cubic or quartic power of the distance was considered. Results showed that this study could be easily transferred to other trap geometries to estimate anharmonic effects.

Influência da geometria do martelo na determinação da força durante o ensaio de impacto Charpy-V

The instrumentation applied to the Charpy test machine allows the accompaniment of the specimen answer front the impact load, in form of a sign characteristically dynamic representative of the deformation process and it fractures of material tested. The main advantages of the rehearsal conventional Charpy: low cost, manufacturing sample facilities and simple handle the machine. With the instrumentation, the number of information regarding the process of fracture of the specimen increases. In this work discusses the influence of the hammer geometry in determination of the force during the process of specimen fracture submitted to the instrumented impact test Charpy-V. The purpose is obtaining a hammer, in conformity with Norma ISO 14.556, with great sensibility to register the force during the impact. Two geometries different from hammers were instrumented and rehearsed with material of low tenacity, in this case the steel ABNT 4140 in the condition of having normalized. It could be proven as larger the sensibility of the hammer, adult will be the effects of the shock waves in the strain gages of the transducer.

Caracterização morfológica da corrosão por pite da liga AL2024 em soluções contendo cloretos e molibdatos

A very new method application for digital image processing and analysis to classify shape and evaluate size and morphology parameters of pit corrosion is used in this paper. This method seems to be very effective to analysis surfaces with low or high degree of pitting formation. Pits formed on 2024 alloy surface by chloride and by chloride + molibdate anions have similar mean area, are found to be widther than deeper and exhibit predominantly conical or near-conical and irregular geometries.

Synthesis and spectroscopic characterization of new metal(II) complexes with methionine sulfoxide

Methionine sulfoxide complexes of iron(II) and copper(II) were synthesized and characterized by chemical and spectroscopic techniques. Elemental and atomic absorption analyses fit the compositions K2[Fe(metSO) 2]SO4 · H2O and [Cu(metSO)2] · H2O. Electronic absorption spectra of the complexes are typical of octahedral geometries. Infrared spectroscopy suggests coordination of the ligand to the metal through the carboxylate and sulfoxide groups. An EPR spectrum of the Cu(II) complex indicates tetragonal distortion of its octahedral symmetry. 57Fe Mössbauer parameters are also consistent with octahedral stereochemistry for the iron(II) complex. The complexes are very soluble in water.

Thermally developing forced convection of non-Newtonian fluids inside elliptical ducts

Laminar-forced convection inside tubes of various cross-section shapes is of interest in the design of a low Reynolds number heat exchanger apparatus. Heat transfer to thermally developing, hydrodynamically developed forced convection inside tubes of simple geometries such as a circular tube, parallel plate, or annular duct has been well studied in the literature and documented in various books, but for elliptical duct there are not much work done. The main assumptions used in this work are a non-Newtonian fluid, laminar flow, constant physical properties, and negligible axial heat diffusion (high Peclet number). Most of the previous research in elliptical ducts deal mainly with aspects of fully developed laminar flow forced convection, such as velocity profile, maximum velocity, pressure drop, and heat transfer quantities. In this work, we examine heat transfer in a hydrodynamically developed, thermally developing laminar forced convection flow of fluid inside an elliptical tube under a second kind of a boundary condition. To solve the thermally developing problem, we use the generalized integral transform technique (GITT), also known as Sturm-Liouville transform. Actually, such an integral transform is a generalization of the finite Fourier transform, where the sine and cosine functions are replaced by more general sets of orthogonal functions. The axes are algebraically transformed from the Cartesian coordinate system to the elliptical coordinate system in order to avoid the irregular shape of the elliptical duct wall. The GITT is then applied to transform and solve the problem and to obtain the once unknown temperature field. Afterward, it is possible to compute and present the quantities of practical interest, such as the bulk fluid temperature, the local Nusselt number, and the average Nusselt number for various cross-section aspect ratios.

Influence of the tool edge geometry on specific cutting energy at high-speed cutting

This paper presents specific cutting energy measurements as a function of the cutting speed and tool cutting edge geometry. The experimental work was carried out on a vertical CNC machining center with 7,500 rpm spindle rotation and 7.5 kW power. Hardened steels ASTM H13 (50 HRC) were machined at conventional cutting speed and high-speed cutting (HSC). TiN coated carbides with seven different geometries of chip breaker were applied on dry tests. A special milling tool holder with only one cutting edge was developed and the machining forces needed to calculate the specific cutting energy were recorded using a piezoelectric 4-component dynamometer. Workpiece roughness and chip formation process were also evaluated. The results showed that the specific cutting energy decreased 15.5% when cutting speed was increased up to 700%. An increase of 1 °in tool chip breaker chamfer angle lead to a reduction in the specific cutting energy about 13.7% and 28.6% when machining at HSC and conventional cutting speed respectively. Furthermore the workpiece roughness values evaluated in all test conditions were very low, closer to those of typical grinding operations (∼0.20 μm). Probable adiabatic shear occurred on chip segmentation at HSC Copyright © 2007 by ABCM.

Simulation of needle-type corona electrodes by the finite element method

This paper describes a software tool, called LEVSOFT, suitable for the electric field simulations of corona electrodes by the Finite Element Method (FEM). Special attention was paid to the user friendly construction of geometries with corners and sharp points, and to the fast generation of highly refined triangular meshes and field maps. The execution of self-adaptive meshes was also implemented. These customized features make the code attractive for the simulation of needle-type corona electrodes. Some case examples involving needle type electrodes are presented.