Cross-linked polyvinyl polymers versus polyureas as designed supports for catalytically active M(0) nanoclusters. Part III. Nanometer scale structure of the cross-linked polyurea support EnCat 30 and of the Pd(II)/EnCat 30 and Pd(0)/EnCat 30NP catalysts.

The cross-linked polyurea support EnCat 30, its related macromolecular complex Pd(II)/EnCat 30 and its related Pd(0)/EnCat 30NP nanocomposite are thoroughly investigated with SEM, TEM, ISEC and ESR in the solid state (SEM and TEM) and swollen state in THF (ISEC and ESR). Pd(II)/EnCat 30 and its related Pd(0)/EnCat 30NP are obtained by microencapsulation of palladium acetate in a polyurea framework, which is formed upon hydrolysis/condensation of mixtures of multi-functional oligo-arylisocyanates in dichloroethane. Most remarkably, both Pd(II)/EnCat and Pd(0)/EnCat 30NP turn out to be far more (nano)porous and swellable materials than the blank polyurea matrix (EnCat 30). It is proposed that there is a strong nanostructural effect exerted by Pd(II) species due to its interaction with functional groups (amines stemming from the hydrolysis of the isocyanato groups or ureido groups belonging to the polymer chains) during the growth of the cross-linked polymer framework. As a consequence, the catalytic species in both Pd(II)/EnCat 30 and Pd(0)/EnCat 30NP are much more accessible to molecules diffusing from liquid phases in contact with the materials and, hence, are better catalysts than expected from the morphology of blank polyurea EnCat 30.

Spin concentration in a possible ESR dosimeter: An electron spin echo study on X-irradiated ammonium tartrate.

Several single crystals and powder samples of ammonium tartrate, recently proposed as a possible ESR dosimeter, have been X-irradiated with different doses. The total radical concentration has been determined by quantitative cw ESR, by comparison with a standard. The samples have been studied by electron spin echo spectroscopy. The two-pulse echo decay has been obtained and simulated by a single exponential function for different values of the microwave power of the pulses and for different pulse lengths. The dependence of the phase memory time TM on the microwave power has been exploited to get information on the contribution of the instantaneous diffusion to spin dephasing. At room temperature in the range of radical concentrations of 10(18)-10(19) spins/cm3 the instantaneous diffusion is the dominant spin dephasing mechanism. The linear dependence of the instantaneous diffusion on the total concentration of the radicals is in agreement with the theory. From the latter result we conclude that the average radical-radical distance corresponds to a random distribution of the radicals in the matrix. A simple method of measuring the radical concentration by the ESE decays in powder samples of irradiated ammonium tartrate is described.