Concerted and stepwise proton-coupled electron transfers in aquo/hydroxo complex couples in water: oxidative electrochemistry of [Os(II)(bpy)(2)(py)(OH(2))](2+)

Successive oxidation of transition metal(II) aqua complexes (M(II)OH(2) to M(III)OH) is a domain in which proton-coupled electron transfer reactions are extremely common. The mechanism of these PCET reactions-concerted or stepwise-is an important issue in the understanding and design of natural or artificial systems catalyzing the formation of dioxygen by four-electron oxidation of water. Concerted proton-coupled electron transfer from an aqua metal(II) to a hydroxo metal(III) complex requires the close proximity of a proton-accepting group with a pK value between those of the aqua complexes. Otherwise, stepwise electron-proton or proton-electron pathways involving high-energy intermediates are followed. Concerted proton-electron pathways involving water as proton-acceptor or proton-donor group are inefficient. Cyclic voltammetry of the title complex in buffered aqueous solution and re-examination of previous results for the same complex attached to an electrode surface are used to establish these conclusions, which provide a starting point on the route to higher degrees of oxidation, such as those involved in the catalysis of water oxidation.     

Ultrathin (CoFe/Pt)n multilayers with tuned magnetic properties

Perpendicular magnetic anisotropy (PMA) has been investigated in ultrathin (CoFe [0.2] nm/Pt [0.2] nm)_n multilayers. The Pt layers show an fcc crystal structure with a preferred [111] orientation. The multilayers with n=3, 4 show PMA in the as-grown state, which can be enhanced by thermal annealing. However, no PMA is observed in the as-grown state with higher repetitions (n>&=5), although it is observed after thermal annealing. For 1=&<n=&<8, the anisotropy energy is around 10⁵ J/m³ for all (CoFe [0.2]/Pt [0.2])_n stacks. The perpendicular anisotropy is related to layer thickness and interface roughness.     

Mössbauer spectra and magnetic properties of iron nitrides

The iron nitrides Fe₃N, Fe₄N and Fe₈N (impure) have been prepared by treating iron in NH₃/H₂ gas mixtures followed by appropriate heat treatment. Fe₈N has also been prepared by mechanical alloying. Mössbauer spectra are analysed in terms of iron sites with different nitrogen environments, and results are compared with magnetization measurements and band-structure calculations. Moments and hyperfine fields on sites with nitrogen neighbours are reduced by p-d hybridization, whereas the sites farthest from nitrogen have the lowest charge and the highest moments. There is no evidence of an exceptionally high magnetization in any of these compounds.     

In Vivo EPR For Dosimetry

As a result of terrorism, accident, or war, populations potentially can be exposed to doses of ionizing radiation that could cause direct clinical effects within days or weeks. There is a critical need to determine the magnitude of the exposure to individuals so that those with significant risk have appropriate procedures initiated immediately, while those without a significant probability of acute effects can be reassured and removed from the need for further consideration in the medical/emergency system. In many of the plausible scenarios there is an urgent need to make the determination very soon after the event and while the subject is still present. In vivo EPR measurements of radiation-induced changes in the enamel of teeth is a method, perhaps the only such method, which can differentiate among doses sufficiently for classifying individuals into categories for treatment with sufficient accuracy to facilitate decisions on medical treatment. In its current state, the in vivo EPR dosimeter can provide estimates of absorbed dose with an error approximately +/- 50 cGy over the range of interest for acute biological effects of radiation, assuming repeated measurements of the tooth in the mouth of the subject. The time required for acquisition, the lower limit, and the precision are expected to improve, with improvements in the resonator and the algorithm for acquiring and calculating the dose. The magnet system that is currently used, while potentially deployable, is somewhat large and heavy, requiring that it be mounted on a small truck or trailer. Several smaller magnets, including an intraoral magnet are under development, which would extend the ease of use of this technique.     

Mössbauer studies of interstitial rare earth-iron intermetallics

Two series of interstitial rare earth-iron intermetallics, R₂Fe₁₇N_3-σ and R₂Fe₁₇C_3-σ have been prepared by gas phase reaction from the R₂Fe₁₇ parent compounds (R=Ce, Pr, Nd, ... Lu and Y). The interstitials raise the Curie temperature of the compounds by 390 K in the case of N and 330 K in the case of C. Mössbauer spectra at 15 K and 293 K, and data as a function of temperature for R=Er and Tm are analysed to yield hyperfine interactions at the four sites, and information on the local magnetization and its orientation. The change in hyperfine field is not proportional to the change in magnetization produced by the interstitials, being much greater in the nitrides than the carbides. Likewise for the isomer shifts. These effects are discussed in terms of the differences in electronic structure of the nitrides and carbides.