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.     

Direction of magnetization and domain wall mobility in (Dy,Y)Fe2

Magnetization measurements in the (Dy _x Y_1−x )Fe₂ intermetallic compounds show evidence of blocking of domain wall motion. This effect is a function of concentrationx. The direction of magnetization is also dependent on the Dy concentration. We have used the Mossbauer spectroscopy of⁵⁷Fe to verify the direction of magnetization in the series as a function ofx and temperature. The results show that this change in easy direction occurs at higher temperatures than those where the blocking is detected through DC magnetization measurements. supported by RHAE/SCT.     

Immobilization of catalase on membranes of poly(ethylene)-g-co-acrylic acid and poly(tetrafluoroethylene)-g-co-acrylic acid and their application in hydrogen peroxide electrochemical sensors

The immobilization of catalase on grafted membranes of poly(ethylene)-g-co-acrylic acid and poly(tetrafluoroethylene)-g-co-acrylic acid and their application in hydrogen peroxide electrochemical sensors is described. The introduction of carboxylic acid groups onto a hydrophobic support provides a good environment for subsequent enzyme immobilization. This single membrane, hydrogen peroxide sensor showed significant improvement with respect to the double membrane versions. The response is very rapid, the linear range being from 10 μM up to 6 mM, with a detection limit of 4.7 μM, and a lifetime of more than 4 months.     

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.     

Extended X-ray absorption fine structure studies of thulium doped GaN epilayers

The local structure of Tm³⁺ ions incorporated into GaN epilayers was studied by means of Extended X-ray Absorption Fine Structure. The samples were doped either in situ during growth by Molecular Beam Epitaxy or by ion implantation of layers grown by Metal Organic Chemical Vapour Deposition. The implantation was done at ion energy of 300 keV and different nominal fluences of 3×10¹⁵, 4×10¹⁵ cm⁻² and 5×10¹⁵ cm⁻². The concentration of Tm in the samples studied was measured by Wavelength Dispersive X-ray analysis. For the in situ doped sample with concentration of 0.5%, and for all of the implanted samples, Tm was found on the Ga site in GaN. The ion implanted sample and an in situ doped sample with a similar concentration of Tm showed the same local structure, which suggests that the lattice site occupied by Tm does not depend on the doping method. When the average Tm concentration for in situ doped samples is increased to 1.2% and 2.0%, Tm is found to occupy the Ga substitutional site and the presence of a substantial number of Tm ions in the second coordination sphere indicates dopant clustering in the films. The formation of pure TmN clusters was found in an in situ doped sample with a dopant concentration of 3.4%.     

Scaling impacted structures

Summary The problem of non-scalability of structures under impact loads caused by strain-rate effects is solved in this article by properly correcting the impact velocity. The technique relies on the use of an alternative dimensionless basis, together with a mathematical model which allows the calculation of a correction factor for the impact velocity. This new velocity, when applied to the model, makes it to assure the satisfaction of the scaling laws. The indirect similitude method detailed here is applied to two strain-rate sensitive structures, a double plate under in-plane impact and a beam subjected to a blast load. The results show a very good agreement so that the model and a prototype made from strain rate sensitive materials behave the same.accepted for publication 3 March 2004     

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.     

Comparison of Several Calibration Procedures for Glass Electrodes in Proton Concentration

Several reported procedures for calibrating glass electrodes in proton concentration are compared. Some recommendations for non-experts are also given. The examined procedures can be classified into two broad categories, namely: those based on direct potential difference measurements of solutions of known proton concentration and those that use one or several pH standards to calibrate the electrode and subsequently measure the pH of solutions containing known proton concentrations. With a single buffer, the two types of procedures lead to equivalent results. However, if two pH buffers are used, the slope of the calibration graph in proton concentration will differ from the real electrode slope to an extent proportional to the difference between the liquid junction potentials of the two buffers. Therefore, any other method is preferable under these circumstances.