Dual Sensitization via Electron and Energy Harvesting in a Nanohybrid for Improvement of Therapeutic Efficacy

We demonstrate experimental evidence of the effect of surface plasmon resonance of noble metal nanoparticles (NPs) on the activity of a well-known biomedicinal drug in the proximity of a semiconductor having a wide band gap for enhanced photodynamic therapy (PDT) efficacy. We have chosen riboflavin (Rf) (or vitamin B2) as a model photosensitizer, attached with ZnO NPs and further attached with gold (Au) NP-decorated ZnO to increase the efficiency. The synthesized nanohybrids are characterized with the help of different microscopic, optical spectroscopic, and density functional theory (DFT)-based techniques. The DFT and time-dependent DFT-based calculations validate the experimental findings. A detailed ultrafast spectroscopic study has been carried out further to study the excited-state charge dynamics in the interface of the nanohybrids. The occurrence of a Förster resonance energy transfer (FRET) between Rf and Au has been found to be the key reason for the increased efficiency in the Rf–ZnO–Au nanohybrid over the Rf–ZnO one. The dipolar coupling between Au and Rf in the Rf–ZnO–Au nanohybrid further facilitates the generation of reactive oxygen species (ROS) in comparison to Rf–ZnO under blue-light irradiation. The greater efficiency in ROS generation by the Rf–ZnO–Au nanohybrid has been utilized for antimicrobial action against methicillin-resistant S. aureus (MRSA). Overall, the present study highlights the dual sensitization for achieving enhanced electron injection efficiency in the Rf–ZnO–Au nanohybrid in order to use it as an antibacterial agent that could be translated in PDT.