A synthesis has been developed that allows the isolation of four-coordinate [(tpy)Ni-Br](1, tpy = terpyridine) in high yield. Complex 1 has been structurally characterized, and the X-ray data reveal a square-planar geometry, unlike the known [(tpy')Ni-I](tpy'= 4,4',4''-tri-tert-butyl-terpyridine) but similar to [(tpy)Ni-CH(3)]. In the solid-state, EPR spectroscopy indicates, however, that unlike [(tpy)Ni-CH(3)], the electronic structure of 1 is a metal-centered, not a ligand-centered radical. Density functional theory (DFT) analyses support this assignment. The preparation of 1 also facilitated the analysis of the redox potentials of a series of terpyridine nickel derivatives. It was found that the overall ligand sphere (one vs two coordinated terpyridine ligands) plays more of a role in determining the redox potentials of these derivatives than do the formal oxidation states of the nickel ions in the solution phase.

A new macrocyclic bolaamphiphile with thiocytosine fragments in the molecule (B1) has been synthesized and advanced as perspective platform for the design of soft supramolecular systems. Strong concentration-dependent structural behavior is observed in the water-DMF (20% vol) solution of B1 as revealed by methods of tensiometry, conductometry, dynamic light scattering, and atomic force microscopy. Two breakpoints are observed in the surface tension isotherms. The first one, around 0.002 M, is identified as a critical micelle concentration (cmc), whereas the second critical concentration of 0.01 M is a turning point between the two models of the association involved. Large aggregates of ca. 200 nm are mostly formed beyond the cmc, whereas small micelle-like aggregates exist above 0.01 M. The growth of aggregates between these critical points occurs, resulting in a gel-like behavior. An unusual decrease in the solution pH with concentration takes place, which is assumed to originate from the steric hindrance around the B1 head groups. Because of controllable structural behavior, B1 is assumed to be a candidate for the development of biomimetic catalysts, nanocontainers, drug and gene carriers, etc.

Electron spin resonance (ESR) spectroscopy was used to detect and identify radicals formed by UV irradiation of Nafion and Dow perfluorinated membranes partially or fully neutralized by Cu(II), Fe(II), and Fe(III). This method allowed the monitoring of ESR signals from the paramagnetic counterions together with the appearance of membrane-derived radical species. The most surprising aspect of this study was the formation of membrane-derived radical species only in the neutralized membranes, and even in the absence of H(2)O(2) in the case of Nafion/Cu(II) and Nafion/Fe(III). In Nafion/Cu(II), ESR spectra from radicals exhibiting hyperfine interactions with three equivalent (19)F nuclei (the "quartet") and with four equivalent (19)F nuclei (the "quintet") were detected. In Nafion/Fe(II) exposed to H(2)O(2) solutions, the formation of Fe(III) was detected. Upon UV irradiation, strong signals from the chain-end radical ROCF(2)CF(2)(*) were detected first, followed by the appearance, upon annealing above 200 K, of the quartet signal observed in Nafion/Cu(II). In subsequent experiments with Nafion and Dow membranes neutralized by Fe(III), the ROCF(2)CF(2)(*) radicals were formed even in the absence of H(2)O(2), indicating that the role of H(2)O(2) is oxidation of Fe(II) to Fe(III); moreover, in these systems small amounts of the chain-end radicals were detected even without UV irradiation. This result validates the method used to form the radicals: the role of UV irradiation is to accelerate the formation of a signal that is produced, albeit slowly, even in the dark, and possibly during fuel cell operation. The major conclusion is that cations are involved in degradation processes; the point of attack appears to be at or near the pendant chain of the ionomer. Therefore when studying membrane stability, it is important to consider not only the formation of oxygen radicals, such as HO(*), HOO(*), and O(2)(*-), that can attack the membrane but also the specific reactivity of counterions.

The authors studied fluctuations of the memory volume on the basis of the original method of the memory analysis using 50 series which consist of 10 words following each other in every 30 seconds. Three groups included normals, schizophrenic patients (paranoid form, the initial stage of remission) and patients with posttraumatical psychosis in the period of recovery. It was demonstrated that the level of the memory volume fluctuations was over and with a greater swing in the patients than in the normals. The lowest memory level was found in the patients with traumatical pscyhoses.