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.     

Systematic studies of positron production in heavy-ion collisions near the Coulomb barrier

We present the results obtained from systematic studies of positron creation for a series of heavy-collision systems, with united chargeZ _u =Z ₁ +Z ₂ ranging fromZ _u =164 (Pb + Pb) toZ _u =184 (U+U) at bombarding energies close to the Coulomb barrier, using the Orangeβ-spectrometer at GSI. For each collision system studied, the dominating continuous distributions due to quasiatomic and nuclear positron emission are determined accurately. This is essential in obtaining the characteristics of the still unexplained monoenergetic positron lines which appear in the energy range between 200 keV and 400 keV. Our results are compared with coupled-channels calculations for quasi-atomic positron creation. The latter describe quite well the global features of the measured spectra, but overestimate systematically their absolute values. From the comparison, a common normalization factor of about 0.75 can be established for the calculated spectra. In particular, the dependence onZ _u of the measured emission probabilities was found to follow a power law (∝Z _u ^195±1), in fair agreement with the theoretical prediction.     

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.     

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.     

Synthesis of the insect antifeedant CDE molecular fragment of 12-ketoepoxyazadiradione and related compounds

A diastereoselective synthesis of the model insect antifeedant 29 a CDE molecular fragment of 12-ketoepoxyazadiradione has been achieved in ten steps from indenone 9 in 44% overall yield. Several of the compounds obtained along the synthesis related to model compound 29 show significant antifeedant activity against Spodoptera littoralis and Spodoptera frugiperda.     

Synthesis and biological evaluation of 6-oxa-nor-tropane glycomimetics as glycosidase inhibitors

The preparation of polyhydroxylated 6-oxa-nor-tropane glycomimetics structurally related to the glycosidase inhibitor family of the calystegines is reported. The synthetic strategy involves the furanose→piperidine rearrangement of 5-deoxy-5-ureido-l-idose precursors, followed by intramolecular glycosylation involving the primary hydroxyl group. Inversion of the configuration at C-3 in the resulting 6-oxa-(+)-calystegine B₂ analogue allows accessing the elusive 3-epi-6-oxa-(+)-calystegine B₂ skeleton. Acid-catalyzed opening of the nor-tropane bicycle was observed, however, which could be avoided by careful neutralization of the reaction mixture. The inhibition results suggest that (+)-calystegine B₂ derivatives and the corresponding C-3 epimers can be seen as glucomimetics and galactomimetics, respectively, pointing to a 1-azasugar mode of action for this family of alkaloids.