Ternary Heteronanocrystals with Dual-Heterojunction for Boosting Near-Infrared-Triggered Photo-Chemodynamic Therapy

• Published in: Journal of the American Chemical Society 2024-12, Vol.146 (51), p.35493-35503
• Main Authors: Kou, Yufang, Liu, Minchao, Hou, Mengmeng, Zhao, Tiancong, Chen, Liang, Jia, Jia, Zhan, Yating, Yan, Kui, Wang, Boya, Zhang, Fan, Zhao, Dongyuan, Li, Xiaomin
• Format: Article
• Language: English
• Subjects: Animals; Antineoplastic Agents - chemical synthesis; Antineoplastic Agents - chemistry; Antineoplastic Agents - pharmacology; Cell Line, Tumor; Fluorides - chemistry; Fluorides - radiation effects; Fluorine - chemistry; Gadolinium; Humans; Infrared Rays; Mice; Nanocomposites - chemistry; Nanocomposites - radiation effects; Thulium - chemistry; Titanium - chemistry; Titanium - pharmacology; Ytterbium - chemistry; Ytterbium - radiation effects
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/jacs.4c15819

Strongly coupled interfaces in the epitaxial growth heteronanocrystals (HNCs) provide advanced functionalities regarding interface connection, electron transfer, and carrier separation. However, the majority of current nanocomposites primarily focus on a single heterojunction involving only two subunits, which hinders the achievement of optimized synergy energy transfer among more than two components. Herein, ternary NaGdF4:Yb,Tm-TiO2:F-Fe3O4 HNCs with dual-heterojunction were synthesized based on the crystal plane epitaxial growth strategy for boosting near-infrared (NIR)-triggered photo-chemodynamic therapy (PCDT). Fluorine is doped into TiO2 (TiO2:F), which not only enhances the exposure of the (001) facet of TiO2 for Fe3O4 subunit growth but also promotes the growth of the NaGdF4:Yb,Tm upconversion nanocrystal (UCNC) subunit, enabling an epitaxial combination of all three components. Upon NIR irradiation, the UCNC subunit transfers the light energy of the absorbed NIR light to the TiO2:F subunit, thereby facilitating the generation of electron–hole pairs within TiO2:F. Due to different work functions between TiO2:F and Fe3O4 in the ternary HNCs, electrons tend to transfer from TiO2:F into Fe3O4, resulting in a reduction of inactive Fe3+ into active Fe2+ and further enhancing the Fenton-catalysis performance. Simultaneously, the efficient separation of electrons and holes improves the photocatalytic oxidation property induced by TiO2:F. Based on ternary UCNC-TiO2:F-Fe3O4 HNCs boosting Fenton catalysis and photocatalysis at the single particle level, as a proof of concept, we propose a NIR light-triggered PCDT (NIR-PCDT) synergistically enhanced tumor treatment strategy. In vitro and in vivo experiments demonstrate that this NIR-PCDT agent exhibits a pronounced ability to generate reactive oxygen species, effectively inducing apoptosis in tumor cells.