The role of energy deposition on the luminescence sensitization in porphyrin-functionalized SiO2/ZnO nanoparticles under X-ray excitation.

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Hybrid nanoscintillators, which feature a heavy inorganic nanoparticle conjugated with an organic emitter, represent a promising avenue for advancements in diverse fields, including high-energy physics, homeland security, and biomedicine. Many research studies have shown the suitability of hybrid nanoscintillators for radiation oncology, showing potential to improve therapeutic results compared to traditional protocols. In this work, we studied SiO2/ZnO nanoparticles functionalized with porphyrin as a photosensitizer, capable of producing cancer cytotoxic reactive oxygen species for possible use in radio-oncological therapeutics. Radioluminescence measurements under increasing energy of the ionizing radiation beam up to 10 keV show sensitization of porphyrin moieties on SiO2/ZnO. This can be attributed to an increase in energy deposition promoted by the ZnO nanoparticles, which have a higher density and atomic number. This assumption was confirmed by computational simulations of energy deposition after the first interaction of ionizing radiation with SiO2, ZnO, and air. Indeed, Monte Carlo simulations evidence that, despite a decrease in the absolute number of X-rays interacting within the system while increasing the energy of the beam, at 10 keV, the presence of ZnO is dominant to enhance energy deposition. Hence, these experimental and computational studies evidence the importance of each hybrid nanosystem component in the scintillation process. This work shows how an appropriate choice of constituents, in terms of physicochemical properties and architecture, can favour energy deposition mechanisms under X-ray irradiation and thus can boost the hybrid nanosystems' performance for diverse biomedical scintillation-based applications.