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A series of Au nanoparticles functionalised with nitroxide spin labels has been prepared and studied by EPR spectroscopy. Samples with low coverage of the spin label were used to investigate the dynamics of the surface-attached labels at different distances from the Au surface. The rotational correlation times of spin labels vary from 10(-10) s to more than 3 x 10(-9) s, depending on the chain length of the label and the surrounding ligand. The samples with higher coverage of the spin label show an increasing contribution of the exchange interaction between nitroxides adsorbed in a close proximity to each other on the same nanoparticle. Quantitative analysis of the EPR spectra of these samples suggests the presence of non-equivalent binding sites on the surface of Au nanoparticles. Additionally, EPR signals of isolated radical pairs were observed at intermediate coverage.

The structure and bonding of the azo dye Orange II (Acid Orange 7) in parent and reduced forms have been studied using NMR, infrared, Raman, UV-visible, and electron paramagnetic resonance (EPR) spectroscopy, allied with density functional theory (DFT) calculations on three hydrazone models (no sulfonate, anionic sulfonate, and protonated sulfonate) and one azo model (protonated sulfonate). The calculated structures of the three hydrazone models are similar to each other and that of the model without a sulfonate group (Solvent Yellow 14) closely matches its reported crystal structure. The 1H and 13C NMR resonances of Orange II, assigned directly from 1D and 2D experimental data, indicate that it is present as > or = 95% hydrazone in aqueous solution, and as a ca. 70:30 hydrazone:azo mixture in dimethyl sulfoxide at 300 K. Overall, the experimental data from Orange II are matched well by calculations on the hydrazone model with a protonated sulfonate group; the IR, Raman, and UV-visible spectra of Orange II are assigned to specific vibrational modes and electronic transitions calculated for this model. The EPR spectrum obtained on one-electron reduction of Orange II by the 2-hydroxy-2-propyl radical (*CMe2OH) at pH 4 is attributed to the hydrazyl radical produced on protonation of the radical anion. Calculations on reduced forms of the model dyes support this assignment, with electron spin density on the two nitrogen atoms and the naphthyl ring; in addition, they provide estimates of the structures, vibrational spectra, and electronic transitions of the radicals.

Complementary hydroxylation assays and stopped-flow e.s.r. techniques have been employed in the investigation of the effect of various iron chelators (of chemical, biological and clinical importance) on hydroxyl-radical generation via the Haber-Weiss cycle and the ascorbate-driven Fenton reaction. Chelators have been identified which selectively promote or inhibit various reactions involved in hydroxyl-radical generation (for example, NTA and EDTA promote all the reactions of both the Haber-Weiss cycle and the ascorbate-driven Fenton reaction, whereas DTPA and phytate inhibit the recycling of iron in these reactions). The biological chelators succinate and citrate are shown to be relatively poor catalysts of the Haber-Weiss cycle, whereas they are found to be effective catalysts of .OH generation in the ascorbate-driven Fenton reaction. It is also suggested that continuous redox-cycling reactions between iron, oxygen and ascorbate may represent an important mechanism of cell death in biological systems.

The chlorine atom (C1') has been generated in aqueous solution by reaction of C1with SO;and H,PO;, obtained by metal-catalysed decomposition of the appropriate peroxides. E.s.r. experiments in conjunction with a fast-flow method establish that C1' is highly reactive, readily undergoing rapid addition, hydrogen-abstraction and electron-transfer reactions (k % 108-109 dm3 mol-' s-'). The factors which influence the observed selectivity (energetics and polar effects) are discussed.

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EPR experiments confirm that reaction of qinghaosu and some related endoperoxides with Fe2+ in aqueous acetonitrile leads to the production of carbon-centred radicals derived by rapid rearrangement of first-formed cyclic alkoxyl radicals. Signals obtained from qinghaosu itself with spin-traps DMPO and DBNBS are assigned to the adducts (15) and (16), a finding which accounts for the formation of the major products (11) and (14).

The mechanism of a place-exchange reaction of ligand-protected Au nanoparticles was investigated using diradical disulfide spin labels. Analysis of reaction mixtures using a combination of GPC and EPR allowed us to determine concentration profile and propose a kinetic model for the reaction. In this model, only one branch of the disulfide ligand is adsorbed on the Au surface during exchange; the other branch forms mixed disulfide with the outgoing ligand. The two branches of the disulfide ligand therefore do not adsorb in adjacent positions on the surface of Au nanoparticles; this was ultimately proven by the powder EPR spectra of frozen exchange reaction mixtures. Our data also suggest the presence of different binding sites with different reactivity in the exchange reaction. The most-active sites are likely to be nanoparticle surface defects.