On the interactions of free radicals with gold nanoparticles

Electron paramagnetic resonance (EPR) spectroscopy was used to study the interactions between stable free radicals and gold nanoparticles. The nitroxyl free radicals used were TEMPO, TEMPAMINE, and TEMPONE. Two sizes of Au particles, 15 and 2.5 nm in diameter, were synthesized to investigate the interactions with the metallic particles. We find that the EPR signal is reduced upon adsorption of the radicals onto the 15 nm Au particle surface. Despite the strong adsorption of TEMPAMINE on the particles, the signal intensity recovers upon the introduction of a high concentration of ethanolamine to the solution. The signal reduction was proportional to the concentration of Au particles, and the signal totally disappeared at high concentrations of Au particles. Possible explanations of the signal reduction are discussed in this Article. We propose that the reduction in signal intensity arises from exchange interactions between the unpaired electrons of the adsorbed radicals and conduction-band electrons of the metallic particles. In addition, in the presence of oxygen, the adsorbed TEMPAMINE radicals are catalytically oxidized to the carbonyl derivative, TEMPONE. A mechanism for this unexpected catalytic reaction is proposed.