Evidence of a Photo‐Radical Pathway Responsible of the Rearrangement of a Manganese(III)‐Schiff Base Complex in Solution

A new Mn^III‐Schiff base complex, [MnL(OH₂)](ClO₄) ( 1 ) (H₂L = N, N′‐bis‐(3‐Br‐5‐Cl‐salicylidene)‐1, 2‐diimino‐2‐methylethane), an inorganic model of the catalytic center (OEC, Oxygen Evolving Complex) in photosystem II (PSII), has been synthesized and characterized by elemental analysis, IR and EPR spectroscopy, mass spectrometry, magnetic susceptibility measurement and the study of its redox properties by cyclic and normal pulse voltammetry. This complex mimics reactivity (showing a relevant photolytic activity), and also some structural characteristics (parallel‐mode Mn^III EPR signal from partially assembled OEC cluster) of the natural OEC. The complex 1 was found to rearrange in solution into a crystallographically solved square‐pyramidal complex, [MnLL′] ( 2 ) (HL′ = 6‐bromo‐4‐chloro‐2‐cyanophenol), through a process, which probably liberates radical species (detected by EPR), and provokes a C—N bond cleavage in the ligand. A photo‐radical mechanism is discussed to explain this rearrangement.     

Continuation of travelling‐wave solutions of the Navier–Stokes equations

An efficient way of obtaining travelling waves in a periodic fluid system is described and tested. We search for steady states in a reference frame travelling at the wave phase velocity using a first‐order pseudospectral semi‐implicit time scheme adapted to carry out the Newton's iterations. The method is compared to a standard Newton–Raphson solver and is shown to be highly efficient in performing this task, even when high‐resolution grids are used. This method is well suited to three‐dimensional calculations in cylindrical or spherical geometries. Copyright © 2006 John Wiley & Sons, Ltd.     

A delta white noise functional

The additive renormalization% MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXafv3ySLgzGmvETj2BSbqefm0B1jxALjhiov2D% aebbfv3ySLgzGueE0jxyaibaiGc9yrFr0xXdbba91rFfpec8Eeeu0x% Xdbba9frFj0-OqFfea0dXdd9vqaq-JfrVkFHe9pgea0dXdar-Jb9hs% 0dXdbPYxe9vr0-vr0-vqpWqaaeaabiGaciaacaqabeaadaqaaqGaaO% qaaiaabs7adaWgaaWcbaGaaeySdiaab6cacaqG0bqefeKCPfgBaGqb% diaa-bcaaeqaaOGaeyypa0Jaa8hiaiaacIcacaaIYaGaeqiWdaNaai% ykamaaCaaaleqabaGaeyOeI0IaaGymaiaac+cacaaIYaaaaGqadOGa% a4hiaiGacwgacaGG4bGaaiiCaiaacIcacqGHsislcaqGXoWaaWbaaS% qabeaacaqGYaaaaOGaai4laiaaikdacaGGPaGaa4hiaiaacQdaciGG% LbGaaiiEaiaacchacqGHXcqSdaWadiqaaiabgkHiTiaadkeacaGGNa% GaaiikaiaadshacaGGPaWaaWbaaSqabeaacaaIYaaaaOGaai4laiaa% ikdacaGFGaGaey4kaSIaa4hiaiaabg7acaWGcbGaai4jaiaacIcaca% WG0bGaaiykaaGaay5waiaaw2faaiaacQdaaaa!6C5C!\[{\rm{\delta }}_{{\rm{\alpha }}{\rm{.t}} } = (2\pi )^{ - 1/2} \exp ( - {\rm{\alpha }}^{\rm{2}} /2) :\exp \pm \left[ { - B'(t)^2 /2 + {\rm{\alpha }}B'(t)} \right]:\]is shown to be a generalized Brownian functional. Some of its properties are derived. is shown to be a generalized Brownian functional. Some of its properties are derived.On leave from Universidade do Minho, Area de Matematica, Largo Carlos Amarante, P-4700 Braga, Portugal.     

On gravitational radiation and the energy flux of matter

A suitable derivative of Einstein's equations in the framework of the teleparallel equivalent of general relativity (TEGR) yields a continuity equation for the gravitational energy‐momentum. In particular, the time derivative of the total gravitational energy is given by the sum of the total fluxes of gravitational and matter fields energy. We carry out a detailed analysis of the continuity equation in the context of Bondi and Vaidya's metrics. In the former space‐time the flux of gravitational energy is given by the well known expression in terms of the square of the news function. It is known that the energy definition in the realm of the TEGR yields the ADM (Arnowitt‐Deser‐Misner) energy for appropriate boundary conditions. Here we show that the same energy definition also describes the Bondi energy. The analysis of the continuity equation in Vaidya's space‐time shows that the variation of the total gravitational energy is determined by the energy flux of matter only.     

Comparison of the Kerr effect and X-ray pole figure methods for determining crystallographic texture in PrFeB magnets

In this study, magnetic domains in Pr₁₆Fe₇₆B₈ sintered magnets have been observed by Kerr effect and a histogram of the angular distribution of domain orientations has been used to determine the magnetic texture (cos Φ). The degree of easy-axis alignment of Pr₂Fe₁₄B matrix grains in these magnets has been also determined by X-ray pole figure analysis using the (0 0 4) reflection. The (0 0 4) pole figure measurements were carried out by the Schultz's reflection method. The (0 0 4) normalized intensity data has been fitted for a Gaussian distribution and the degree of crystal alignment, cos Θ, has been calculated using the Stoner–Wohlfarth model. Comparison of these methods has been carried out. It has been shown that in magnets with medium and high degrees of crystallographic alignment, the pole figure values are higher than that obtained by the Kerr effect method. Conversely, in magnets with low degrees of alignment, cos Θ is lower than cos Φ.     

High-order harmonic generation with a strong laser field and an attosecond-pulse train: The Dirac-Delta comb and monochromatic limits

In recent publications, it has been shown that high-order harmonic generation can be manipulated by employing a time delayed attosecond-pulse train superposed to a strong, near-infrared laser field. It is an open question, however, which is the most adequate way to approximate the attosecond-pulse train in a semianalytic framework. Employing the strong-field approximation and saddle-point methods, we make a detailed assessment of the spectra obtained by modeling the attosecond-pulse train by either a monochromatic wave or a Dirac-Delta comb. These are the two extreme limits of a real train, which is composed by a finite set of harmonics. Specifically, in the monochromatic limit, we find the downhill and uphill sets of orbits reported in the literature, and analyze their influence on the high-harmonic spectra. We show that, in principle, the downhill trajectories lead to stronger harmonics, and pronounced enhancements in the low plateau region. These features are analyzed in terms of quantum interference effects between pairs of quantum orbits, and compared to those obtained in the Dirac-Delta limit.     

Physical aging of a polyetherimide: Creep and DSC measurements

Creep and differential scanning calorimetry (DSC) measurements have been used to study the physical aging behavior of a polyetherimide. Isothermal aging temperatures ranged from 160°C to T_g with aging times ranging from 10 min to 8 days. The only measurable effect of physical aging on the short-time creep curves is a shift of the creep compliance to longer times. Andrade plots of the compliance versus the cube root of time are linear at short times with the slope β decreasing with increasing aging time to a constant value once equilibrium is reached. Log β³ is related directly to the degree to which the creep curves shift to longer times with physical aging, and is used in this work as a measure of physical aging. A reduced curve of log β³ versus log aging time is obtained for the aging temperatures investigated by appropriate vertical and horizontal shifts. The enthalpy change during aging increases linearly with the logarithm of the aging time, t_a, leveling off at equilibrium at values which increase with decreasing aging temperature. Hence, both nonequilibrium and equilibrium temperature shift factors can be calculated from the DSC data. Good agreement is observed between the equilibrium temperature shift factors obtained from the creep and DSC data. The temperature dependence of the nonequilibrium temperature shift factors is found to be an order of magnitude smaller than that of the equilibrium shift factors. The time scales to reach equilibrium for enthalpy and for mechanical measurements are found to be the same within experimental error. © 1995 John Wiley & Sons, Inc.     

Immobilized polysiloxanes as stationary phases for high-performance liquid chromatography and solid phase extraction

Polysiloxanes immobilized onto the surfaces of porous silica particles have proven to be good stationary phases for the separation of multiresidues of pesticides and their metabolic/degradation products by reversed-phase high-performance liquid chromatography (RP-HPLC). Similar materials have proven effective for pre-concentration and clean-up procedures using solid phase extraction. The present paper describes the preparation and some applications of several of these packing materials.