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Abstract
Oxygen vacancy (OV) engineering in semiconductors can greatly enhance the separation of photo-induced electron-hole pairs, thereby enhancing the photocatalytic activity. Taking inspiration from this, we prepared a novel BiOBr-H/Rub2d composite by functionalizing OV-rich BiOBr (named BiOBr-H) with a carboxyl functionalized ruthenium photosensitizer (Ru(bpy)2C-pyCl2, abbreviated as Rub2d), which was then successfully applied for photodynamic therapy (PDT). Density functional theory (DFT) calculations confirmed efficient electron transfer from the Rub2d complex to the intermediate energy level of BiOBr-H under visible light irradiation. In vitro and in vivo studies demonstrated that BiOBr-H/Rub2d was a superior agent for photodynamic therapy compared with the free ruthenium complex. The theoretical and experimental data presented thus reveal for the first time that abundant OVs in BiOBr-H can significantly improve the photocatalytic activity of a photosensitizer, resulting in the generation of more reactive oxygen species to enhance PDT. The findings of this study thus offer a new strategy for the development of highly efficient cancer therapies.
Highlights
The theoretical and experimental data presented reveal for the first time that abundant Oxygen vacancy (OV) in BiOBr–H can significantly improve the photocatalytic activity of a photosensitizer, resulting in the generation of more reactive oxygen species to enhance photodynamic therapy (PDT)
Edge Article the Electronic supplementary information (ESI).† Compared with the Rub2d complex alone, the BiOBr– H/Rub2d agent can considerably improve the production of reactive oxygen species (ROS) under light irradiation, which can be veri ed by both Electron Spin Resonance (ESR) data and the Density functional theory (DFT) calculation
Ru(bpy)2C-pyCl2 was prepared via a two-step reaction of ruthenium chloride with 2,20-bipyridine and 2,20-bipyridine-4,40-dicarboxylic acid, the molecular structure of which is shown in Fig. S1.† BiOBr–H/Rub2d and BiOBr/Rub2d were synthesized via the electrostatic attraction between positively charged BiOBr–H and negatively charged Ru(bpy)2CpyCl2
Summary
Cancer has always been one of the most common diseases in humans, which has been a threat to human beings.[1,2] Photodynamic therapy (PDT) has been widely applied in cancer treatment due to its non-invasive properties, few side effects, easy procedure and short treatment time relative to surgery or chemotherapy.[3,4] In the PDT system, the mechanism is driven via the excitation of a photosensitizer (PS) to its triplet state, from which energy is transferred to triplet oxygen, leading to the production of singlet oxygen (1O2).[5,6,7] Over the past decade, researchers have developed various PSs for PDT, including indocyanine green (ICG),[8] chlorin e6 (Ce6),[9,10,11,12] zinc phthalocyanine (ZnPc),[13] and ruthenium complexes.[14,15] traditional PSs suffer from photo-bleaching under irradiation, resulting in the recombination of electron–hole pairs, leading to low production rates of singlet oxygen.[16]it is highly desirable to realize the reaction mechanism and discover a method that can prevent the recombination of electron–hole pairs and improve the PDT therapeutic effect. The theoretical and experimental data presented reveal for the first time that abundant OVs in BiOBr–H can significantly improve the photocatalytic activity of a photosensitizer, resulting in the generation of more reactive oxygen species to enhance PDT.
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