Summary: | Photodynamic therapy (PDT) has been reported as a possible pathway for the treatment of tumors. The exploration for promising PDT systems thus attracts continuous research efforts. This work focused on an ordered core–shell structure encapsulated by mesoporous SiO<sub>2</sub> with the upconverting emission property following a surfactant-assisted sol–gel technique. The mesoporous silica shell possessed a high surface area-to-volume ratio and uniform distribution in pore size, favoring photosensitizer (rose bengal) loading. Simultaneously, upconverting nanocrystals were synthesized and used as the core. After modification via hydrophobic silica, the hydrophobic upconverting nanocrystals became hydrophilic ones. Under near-infrared (NIR) light irradiation, the nanomaterials exhibited strong green upconverting luminescence so that rose bengal could be excited to produce singlet oxygen. The photodynamic therapy (PDT) feature was evaluated using a <sup>1</sup>O<sub>2</sub> fluorescent indicator. It was found that this core–shell structure generates <sup>1</sup>O<sub>2</sub> efficiently. The novelty of this core–shell structure was the combination of upconverting nanocrystals with a mesoporous SiO<sub>2</sub> shell so that photosensitizer rose bengal could be effectively adsorbed in the SiO<sub>2</sub> shell and then excited by the upconverting core.
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