Antisymmetric exchange in [2Fe-2S]1+ clusters: EPR of the Rieske protein from Thermus thermophilus at pH 14

[2Fe-2S] clusters found in the xanthine oxidase family of proteins exhibit an S = 1/2 EPR feature, called signal II, for which one g-value is significantly above g = 2.0. The g-values of signal II cannot be explained with the standard spin coupling model that has been so successful in describing the g = 1.94 signals of [2Fe-2S] ferredoxins. We have studied the EPR spectra of the Rieske protein from Thermus thermophilus at pH 14 and observed a signal II-type EPR spectrum, with g-values at 1.81, 1.94, and 2.14. It is shown that the g-values of signal II can be explained by including an antisymmetric exchange term, d.S1xS2, in the spin Hamiltonian. The presence of this term is sensed by EPR if the isotropic exchange coupling constant J is sufficiently small. For the Rieske protein we determined J = 43 cm-1 which is at least 4 times smaller than the J values reported for [2Fe-2S] clusters that yield standard g = 1.94 signals.     

Relaxation phenomena of hydrolyzed polyvinylamine molecules adsorbed at the silica/water interface III. Interfacial exchange and transfer processes

Surface area exclusion chromatography (SAEC) was employed to determine the stability characteristics of saturated homogeneous layers when interfacial exchange or transfer of molecules was promoted. In these experiments, the first polymer layer was established by elution of a column composed of stacked glass-fiber filters with one polymer. Then, after displacement of the void by water, the second polymer was subsequently injected under the same elution conditions. The experiments combine polymers of equal or different molecular weight and/or hydrolysis grade. Histograms of SAEC experiments demonstrate the great stability of the initially adsorbed layer. Domains of high and low adsorption values were determined to exist along the chromatography column after injection of the first polymer sample. The polymer injected second slightly modifies the initial adsorption histogram and mainly overadsorbs on the low adsorption domain of the first polymer. The major result relates to the relaxation phenomenon affecting or not the second adsorbed polymer when it adsorbs on filters belonging to the low adsorption domain of the polymer first injected. The relaxation is impeded when the relaxation of the first polymer is of great amplitude, whereas it occurs when the relaxation of the first polymer is small.     

Low-power laser deformation of an air-liquid interface

We report on the deformation of an air-water surface with a totally reflected low-power laser beam, inducing a convex mirror effect on the beam propagation. This bending is stronger close to the critical angle and depends on the polarization of the laser light. A model, leading to a simple dependence between the Goos-H?nchen shift and the radius of curvature of the interface, supports these observations. Bendings with radius of curvature as low as 0.10 m are demonstrated.     

Rotational Doppler Effect: A Review

Generally, the linear motion between the source of a wave and an observer leads to a linear Doppler effect. It is associated with the linear momentum of the wave. For electromagnetic beams having a circular polarization or an azimuthal phase distribution, the rotation between the source and the observer results in a less well-known rotational Doppler effect. It is associated with the angular momentum of the wave. This is particularly the case for vortex beams. Here, the various physical insights that are given to explain the origin of the rotational Doppler effect is reviewed. The focus is on different cases where such an effect gives information on the rotational nature of the probed systems, and also on cases where the rotational Doppler effect is useless. Still debated issues and possible applications are then presented.     

Sonochemistry: a systematic study of the maleate-fumarate isomerization in the presence of alkyl bromides

A systematic and quantitative study of diethyl maleate-diethyl fumarate induced isomerization has been performed in CCl₄ using different ‘inert’ gases, different initiators and various experimental conditions. It was shown how changes in the experimental conditions, generally considered as minor in thermochemistry, can have dramatic effects in sonochemistry (for example, the ‘marble effect’).     

Use of a simplex technique and contour diagrams for the determination of the reaction rate constants between glutathione and thiram in the presence of NADPH

The Modified Simplex Method (MSM) coupled with contour diagrams is used to determine the rate constants of a kinetic scheme involving three sequential second order processes. Reaction between glutathione and the dithiocarbamate fungicide tetramethylthiuram disulfide produces the oxidized form of glutathione which is then reduced in the presence of NADPH. The concentration of the reducing agent is monitored as a function of time. In the absence of simplifying assumption a closed form solution of the rate equations does not exist. Computed curves of NADPH concentration versus time were generated using the software SIMULCIN. The rate constant values are optimized by the MSM procedure to obtain the best agreement between calculated and experimental data. The significance, validity limits of the estimated rate constants and the relevance of these in vitro data to previous in vivo studies are discussed.     

Kinetics of adsorption of polyvinylamine on cellulose fibers. I. Adsorption from salt-free solutions

Adsorption of fully hydrolyzed polyvinylamine on cellulose fibers in the short term was investigated by supplying the polymer to the fibers, first instantaneously by pouring the polymer solution into a jar containing the fiber dispersion (jar experiments) and second, at controlled rates (the reactor experiments). In the latter case, the rate of supply of polymer to the fiber dispersion confined in the reactor was monitored by setting the concentration of the solution being injected at a controlled rate. The concentration of the polymer solution exerts a paramount influence on the kinetics of adsorption and on the amount of polymer adsorbed at (or near) fiber surface saturation, while the rate of polymer supply only plays a minor role. The main observation is the emergence of two types of polymer layers corresponding to diffuse and dense layers. The former were characterized by adsorption layers of density smaller than 0.65 mg/g cellulose that are composed of adsorbed polymers having sustained extended flattening in the adsorbed state. The latter reach densities as high as 10 mg/g cellulose when the fiber surface is fully coated, thus indicating that reconformation is limited or even impeded at short terms. The threshold adsorption corresponds more or less to equilibrated layers, since the final coverage determined at adsorption equilibrium did not exceed 0.6 to 0.7 mg/g cellulose.     

Theoretical analysis of the Jahn-Teller distortions in tetrathiolato iron(II) complexes

Crystallographic studies of [Fe(SR)(4)](2-) (R is an alkyl or aryl residue) have shown that the Fe(II)S(4) cores of these complexes have (pseudo) D2d symmetry. Here we analyze the possibility that these structures result from a Jahn-Teller (JT) distortion that arises from the e(3z(2) - r(2), x(2) - y(2)) orbital ground state of Fe(II) in T(d)symmetry. Special attention is paid to the influence of the second-nearest neighbors of Fe, which lowers the symmetry and reduces the full JT effect to a smaller, pseudo JT effect (PJT). To estimate the size of the PJT distortion, we have determined the vibronic parameters and orbital state energies for a number of [Fe(SR)(4)](2-) models using density functional theory (DFT). Subsequently, this information is used for evaluating the adiabatic potential surfaces in the space of the JT-active coordinates of the FeS(4) moiety. The surfaces reveal that the JT effect of Fe(II) is completely quenched by the tetrathiolate coordination.