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| - EPR Study of Dialkyl Nitroxides as Probes to Investigate theExchange of Solutes between the Ligand Shell of Monolayersof Protected Gold Nanoparticles and Aqueous Solutions
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| - EPR spectroscopy has been used to study the interaction of para-substituted benzyl hydroxyalkylnitroxides with the monolayer of water-soluble protected gold cluster made by a short alkyl chain and atriethylene glycol monomethyl ether unit. The inclusion of nitroxide probes in the more hydrophobicenvironment of the monolayer gave rise to a reduction of the value of both nitrogen and β-proton hyperfinesplittings. The spectra also showed selective line broadening attributed to modulation of the spectroscopicparameters as the result of exchange between free and complexed nitroxide. The rate constants wereobtained by analyzing the EPR line shape variations as functions of nanoparticle concentration andtemperature. This represents, to the best of our knowledge, the first determination of rate constants for thesolubilization of organic substrates in a monolayer-protected cluster.
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