Carbon chars have been synthesized in our laboratory from a variety of starting materials, by means of a highly controlled pyrolysis technique. These chars exhibit electron paramagnetic resonance (EPR) line shapes which change with the local oxygen concentration in a reproducible and stable fashion; they can be calibrated and used for oximetry. Biological stability and low toxicity make chars good sensors for in vivo measurements. Scalar and dipolar interactions of water protons at the surfaces of chars may be utilized to produce dynamic nuclear polarization (DNP) of the 1H nuclear spin population in conjunction with electron Zeeman pumping. Low-frequency EPR, DNP and DNP-enhanced MRI all show promise as oximetry methods when used with carbon chars.

No abstract

Nitric oxide is implicated in a wide range of biological functions and in many processes of ecological importance. The formation of iron–nitrosyl complexes is fairly well documented, although the oxidation state of the iron atom is not adequately elucidated: the metal ion is in the formal +1 oxidation state forming low‐ and high‐spin d7 complexes. Owing to the documented evidence that iron–NO compounds are involved in bioregulatory mechanisms and immune responses, and to the biological relevance of these processes and of related structures, the EPR and NMR features of these complexes were reconsidered and combined EPR and NMR analysis was carried out to obtain information on binding sites and coordination behaviour. © 1997 John Wiley & Sons, Ltd.

Vanadium uptake by whole cells and isolated cell walls of the yeast Saccharomyces cerevisiae was studied. When orthovanadate was added to wild-type S. cerevisiae cells growing in rich medium, growth was inhibited as a function of the VO4(3-) concentration and the growth was completely arrested at a concentration of 20 mM of VO4(3-) in YEPD. Electron paramagnetic resonance (EPR) spectroscopy was used to obtain structural and dynamic information about the cell-associated paramagnetic vanadyl ion. The presence of EPR signals indicated that vanadate was reduced by whole cells to the vanadyl ion. On the contrary, no EPR signals were detected after interaction of vanadate with isolated cell walls. A 'mobile' and an 'immobile' species associated in cells with small chelates and with macromolecular sites, respectively, were identified. The value of rational correlation time tau r indicated the relative motional freedom at the macromolecular site. A strongly 'immobilized' vanadyl species bound to polar sites mainly through coulombic attractions was detected after interaction of VO2+ ions with isolated cell walls.

No abstract