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Multifunctional Gadolinium‐Doped Mesoporous TiO2 Nanobeads: Photoluminescence,Enhanced Spin Relaxation,and Reactive Oxygen Species Photogeneration,Beneficial for Cancer Diagnosis and Treatment
Authors:Roghayeh Imani  Ralf Dillert  Detlef W Bahnemann  Meysam Pazoki  Toma? Apih  Veno Kononenko  Ne?a Repar  Veronika Kralj‐Igli?  Gerrit Boschloo  Damjana Drobne  Tomas Edvinsson  Ale? Igli?
Affiliation:1. Institut fuer Technische Chemie, Gottfried Wilhelm Leibniz Universitaet Hannover, Hannover, Germany;2. Department of Chemistry–Physical Chemistry Division, ?ngstr?m Laboratory, Uppsala University, Uppsala, Sweden;3. Faculty of Electrical Engineering, Biophysics Laboratory, University of Ljubljana, Slovenia;4. Laboratory of Nano and Quantum Engineering, University of Hannover, Hannover, Germany;5. Laboratory “Photoactive Nanocomposite Materials”, Saint‐Petersburg State University, Saint‐Petersburg, Russia;6. Department of Chemistry–Structural Chemistry Division, ?ngstr?m Laboratory, Uppsala University, Uppsala, Sweden;7. Jo?ef Stefan Institute, Ljubljana, Slovenia;8. Biotechnical Faculty, Department of Biology, University of Ljubljana, Ljubljana, Slovenia;9. Faculty of Health Sciences, Biophysics Laboratory, University of Ljubljana, Ljubljana, Slovenia;10. Department of Engineering Sciences–Solid State Physics Division, Uppsala University, Uppsala, Sweden
Abstract:Materials with controllable multifunctional abilities for optical imaging (OI) and magnetic resonant imaging (MRI) that also can be used in photodynamic therapy are very interesting for future applications. Mesoporous TiO2 sub‐micrometer particles are doped with gadolinium to improve photoluminescence functionality and spin relaxation for MRI, with the added benefit of enhanced generation of reactive oxygen species (ROS). The Gd‐doped TiO2 exhibits red emission at 637 nm that is beneficial for OI and significantly improves MRI relaxation times, with a beneficial decrease in spin–lattice and spin–spin relaxation times. Density functional theory calculations show that Gd3+ ions introduce impurity energy levels inside the bandgap of anatase TiO2, and also create dipoles that are beneficial for charge separation and decreased electron–hole recombination in the doped lattice. The Gd‐doped TiO2 nanobeads (NBs) show enhanced ability for ROS monitored via ?OH radical photogeneration, in comparison with undoped TiO2 nanobeads and TiO2 P25, for Gd‐doping up to 10%. Cellular internalization and biocompatibility of TiO2@x Gd NBs are tested in vitro on MG‐63 human osteosarcoma cells, showing full biocompatibility. After photoactivation of the particles, anticancer trace by means of ROS photogeneration is observed just after 3 min irradiation.
Keywords:cancer treatment  gadolinium  photocatalysis  reactive oxygen species  TiO2
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