The surface-localized hyperthermia of gold nanoparticles under microwave irradiation was examined. Gold nanoparticles with a hydrodynamic diameter of ∼6 nm stabilized by polymeric “thermometers” were used to gather information on the extent of heating as well as its spatial confinements. Reversible addition–fragmentation chain transfer polymerization was employed to synthesize well-defined, functional polymers of predetermined molecular weights, allowing for estimation of the distance between the nanoparticle surface and the polymer chain end. The polymers were conjugated with a fluorescent dye separated by a thermally-labile azo linkage, and these polymeric ligands were bound to gold nanoparticles via gold–thiolate bonds. Conventional heating experiments elucidated the relationship between temperature and the extent of dye release from the gold nanoparticle using fluorescence spectroscopy. The local temperature increase experienced under microwave irradiation was calculated using the same methodology. This approach indicated the temperature near the surface of the nanoparticle was nearly 70 °C higher than the bulk solution temperature, but decreased rapidly with distance, with no noticeable temperature increase when the azo linkage was approximately 2 nm away.
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