Porphyrin functionalized ZnO/SiO2 hybrid nanoparticles as scintillator agent

The coupling of ZnO-based nanomaterials with organic photosensitizers (PS) is potentially interesting for cancer treatment under X-ray. In these conditions, ZnO nanoparticles (NPs) convert the X-ray into UV-Vis emission, promoting the PS excitation and producing reactive oxygen species (ROS). Main advantages for in vivo applications are ZnO photostability and biocompatibility, even if its efficient coupling with different PS (typically porphyrin) is still a controversial issue, as both a high ZnO luminescence yield and a good overlapping of ZnO emission-PS absorption spectra are necessary, along with a suitable energy transfer between ZnO and PS. In this perspective, the aim is the investigation of the optical properties of an ad-hoc system composed of porphyrin functionalized ZnO NPs anchored on SiO2 NPs (ZnO/SiO2). The goal is the understanding of the optimal conditions for a good energy transfer efficiency of ZnO-porphyrin structures, including the role of ZnO-PS proximity, to promote their application in anti-cancer therapies and imaging with ionizing radiations. First, amorphous ZnO NPs of 5-6 nm were anchored onto SiO2 NPs (~80 nm); then, ZnO/SiO2 was functionalized with different porphyrin contents (tetrakis(4-carboxyphenyl)porphyrin, TCPP, 0.3 – 3.0 wt%) by exploiting a silane grafting agent (3-aminopropyl)triethoxysilane. The structural characterization demonstrated that increasing TCPP amounts were bonded to SiO2 depending on the TCPP loading. The optical properties were preliminary tested in dimethylformamide, used as solvent reaction for TCPP anchoring on SiO2. The Photoluminescence Analysis (PL) revealed a high luminescence of ZnO NPs and the occurrence of a radiative energy transfer between ZnO and TCPP, that was not visible in a mechanical mixing of ZnO and TCCP, highlighting their optical interaction upon functionalization. Besides, TCPP emission was hugely enhanced under X-ray in the Radioluminescence (RL), whereas no enhancement was detectable in the mechanical mixing, that could be generated by both re-absorption of ZnO emitted photons and by ionizing radiation energy deposition in the porphyrin surroundings, whose efficiency depend on the TCPP arrangement and spatial distribution. In conclusion, this work paves the way to the deeper understanding of the correlation between the synthesis and the optical interactions of ZnO scintillator coupled with organic moieties to improve their luminescence performances.