Novel Cleavage of Propargylamines by Reaction with Organolithium Compounds

Treatment of secondary aliphatic 2-bromoallylamines with an excess of an organolithium compound led to saturated amines in which the organic group of the organolithium compound is incorporated at the alpha carbon. On the other hand, the successive reaction of the former amines with BuLi and t-BuLi between -80 degrees C and rt gave 1,3-diamines or hexahydropyrimidines depending on the reaction time. The formation of these unexpected products involves initial generation of lithium propargylamides, which subsequently undergo cleavage of the C propargylic-C acetylenic bond induced by the organolithium present in each case in the reaction medium. A mechanism which takes into account all the different reaction products has been proposed and additionally supported by successful trapping of dilithium acetylide.     

Thermal Cyclodimerization of Aliphatic Secondary C,N-Dilithioallylamine Derivatives

beta-Nitrogen-functionalized vinylic organolithium compounds derived from secondary aliphatic allylamines have been found to undergo upon heating (reflux of THF) either a dimerization or a regio- and stereoselective cyclodimerization reaction affording diamino 1,4-dienes or cis-2,3-disubstituted 4-methylenepyrrolidines, respectively, according to reaction time. In contrast, the corresponding dianions derived from aromatic allylamines underwent protonation by the solvent under analogous thermal treatment. A mechanism accounting for all these results has been proposed, which involves a spontaneous beta-elimination of lithium hydride and an intramolecular nucleophilic cyclization by addition of a lithium amide to an alkene group as critical steps. In addition, experimental evidence is provided about the formation of 3-lithio-1-aza 1,3-dienes as intermediates in these unusual thermal transformations.     

Gravitational energy-momentum density in teleparallel gravity

In the context of a gauge theory for the translation group, a conserved energy-momentum gauge current for the gravitational field is obtained. It is a true spacetime and gauge tensor, and transforms covariantly under global Lorentz transformations. By rewriting the gauge gravitational field equation in a purely spacetime form, it becomes the teleparallel equivalent of Einstein's equation, and the gauge current reduces to the Moller's canonical energy-momentum density of the gravitational field.     

Antioxidant capacity and in vitro prevention of dental plaque formation by extracts and condensed tannins of Paullinia cupana

Chemical evaluation of the semi-purified fraction from the seeds of guaraná, Paullinia cupana H.B.K. var. sorbilis (Mart.) Ducke, yielded the following compounds: caffeine, catechin, epicatechin, ent-epicatechin, and procyanidins B1, B2, B3, B4, A2, and C1. Measurement of the antioxidant activity by reduction of the DPPH radical confirmed the anti-radical properties of the aqueous (AqE) and crude (EBPC) extracts and semi-purified (EPA and EPB) fractions. The EPA fraction showed radical-scavenging activity (RSA) and protected DPPH from discoloration at 5.23 +/- 0.08 (RSD% = 1.49) microg/mL, and for the phosphomolybdenum complex showed a higher Relative Antioxidant Capacity (RAC) at 0.75 +/- 0.01 (1.75). The EPA fraction had a total polyphenolics content of 65.80% +/- 0.62 (RSD% = 0.93). The plant drug showed 5.47% +/- 0.19 (RSD% = 3.51) and 6.19% +/- 0.08 (RSD% = 1.29) for total polyphenolics and methylxanthines, respectively. In vitro assessment of the antibacterial potential of the Paullinia cupana extracts against Streptococcus mutans showed that these could be used in the prevention of bacterial dental plaque.     

Nonlinear compression of optical solitons

In this paper, we consider nonlinear Schrödinger (NLS) equations, both in the anomalous and normal dispersive regimes, which govern the propagation of a single field in a fiber medium with phase modulation and fibre gain (or loss). The integrability conditions are arrived from linear eigen value problem. The variable transformations which connect the integrable form of modified NLS equations are presented. We succeed in Hirota bilinearzing the equations and on solving, exact bright and dark soliton solutions are obtained. From the results, we show that the soliton is alive, i.e. pulse area can be conserved by the inclusion of gain (or loss) and phase modulation effects.     

Microwave absorption studies of MgB2 superconductor

Microwave absorption studies have been carried out on MgB₂ superconductor using a standard X-band EPR spectrometer. The modulated low-field microwave absorption signals recorded for polycrystalline (grain size ∼ 10 μm) samples suggested the absence of weak-link character. The field dependent direct microwave absorption has been found to obey a ✓H dependence with two different slopes, which indicated a transition from strongly pinned lattice to flux flow regime.     

Effect of substrate temperature on electrical and magnetic properties of epitaxial La1−x Pb x MnO3 films

Epitaxial La_1−x Pb _x MnO₃ (LPMO) thin films, grown on (100) SrTiO₃ substrates by laser ablation technique at different temperatures between 600 and 850°C, have been characterized for electrical and magnetic properties. The temperature dependence of resistivity showed that the metal-insulator transition temperature (T _MI) decreases with increasing substrate temperature, which has been attributed to decrease in Pb content in the filsm. The YBa₂Cu₃O _x /La_1−x MnO₃ heterostructures, exhibiting both superconductivity and ferromagnetism, have been fabricated.     

Influence of the Matrix Type on the Mode I Fracture of Carbon-Epoxy Composites Under Dynamic Delamination

The delamination energy and fracture behaviour under static and dynamic mode I loading of two composites, made of the same unidirectional carbon reinforcement embedded in two different matrices, one tough and the other brittle, was investigated with the aim of analyzing the influence of the employed resin on the fatigue delamination behaviour of both composites. In the case of dynamic loading, the number of cycles necessary for the onset of delamination was determined for a given elastic energy release rate and crack growth rate for different critical energy rates. The double cantilever beam (DCB) test was found to be suitable for promoting the initial delamination. The experimental results confirm the enhanced performance of the tough resin both in terms of crack initiation and growth rate.     

Cross-phase modulational instability in an elliptical birefringent fiber with higher order nonlinearity and dispersion

We obtain conditions for the occurrence of cross-phase modulational instability in the normal dispersion regime for the coupled higher order nonlinear Schrödinger equation with higher order dispersion and nonlinear terms.     

On exact and approximated formulations for scaling-mode shapes in operational modal analysis by mass and stiffness change

When operational modal analysis (OMA) is used to estimate modal parameters, mode shapes cannot be mass normalized. In the past few years, some equations have been proposed to scale mode shapes using the mass-change method, which consists of repeating modal testing after changing the mass at different points of the structure where the mode shapes are known. In this paper, the structural-dynamic-modification theory is used to derive a set of equations, from which all the existing formulations can be derived. It is shown that the known equations can be divided into two types, the exact and the approximated equations, where the former type does in fact fulfill the equations derived from the theory of structural modification, whereas the remaining equations do not, mainly because the change of the mode shapes of the modified structure is not properly taken into account. By simulations, the paper illustrates the large difference in accuracy between the approximate and the exact formulations. The paper provides two new exact formulations for the scaling factors, one for the non-modified structure and – for the first time in the literature – one for the modified structure. The simulations indicate the influence of errors from the measured natural frequencies and mode shapes on the estimation of the scaling factors using the two exact formulations from the literature and the new exact formulation proposed in this paper. In addition, the paper illustrates statistics of the errors on mode-shape scaling. All simulations were carried out using a plate with closely spaced modes.