Gold Nanorod/Titanium Dioxide Hybrid Nanoparticles for Plasmon-Enhanced Near-Infrared Photoproduction of Hydroxyl Radicals and Photodynamic Therapy

Gold nanoparticles, such as nanorods (AuNRs), present exceptionally high absorption cross sections that can be tuned to the near-infrared (NIR), the optimal window for light penetration in biological tissues. This makes them valuable photosensitizers for the treatment of cancer using photothermal therapy, where absorbed light energy is converted into heat. In addition, there is a strong interest in using hot electron carriers generated in AuNRs by NIR irradiation to produce cytotoxic radical oxygen species in order to enhance the efficiency of the phototherapy. Here, we show that hybrid nanoparticles composed of AuNRs with TiO₂ deposited at their extremities are efficient sensitizers to produce hydroxyl radical species under NIR irradiation. We attribute this phenomenon to the transfer of hot electrons generated from the plasmon excitation in AuNR to the TiO₂ tips, followed by reduction of dioxygen. We then functionalize these hybrid AuNR/TiO₂ nanoparticles with block poly(ethylene glycol)-phosphonate polymer ligands to stabilize them in a physiological medium. We finally demonstrate that the photodynamic effect induces cell death upon irradiation with a greater efficiency than the photothermal effect alone.