DNA-Templated Silver Nanocluster/Porphyrin/MnO₂ Platform for Label-Free Intracellular Zn²⁺ Imaging and Fluorescence-/Magnetic Resonance Imaging-Guided Photodynamic Therapy

Abstract

Developing a theranostic platform that integrates diagnosis and treatment in one single nanostructure is necessary for efficient tumor treatment. Here, we presented a novel theranostic nanoprobe for nonlabeled fluorescence imaging of Zn²⁺ and 635 nm red light-triggered photodynamic therapy (PDT) by a multifunctional DNA-templated silver nanocluster/porphyrin/MnO₂ nanoplatform. MnO₂ nanosheets adsorbed hairpin DNA-silver nanoclusters (AgNCs) and porphyrin (P) by facile physisorption, which accelerate the transfection of nanoprobes and P into tumor cells. After entering the cells, the biodegradation of MnO₂ nanosheets by glutathione and acidic hydrogen peroxide released AgNCs for label-free Zn²⁺ fluorescence imaging by the hairpin DNA-fueled dynamic self-assembly of three-way DNA junction architectures, and the released Mn²⁺ could act as an effective magnetic resonance imaging (MRI) contrast agent. In addition, MnO₂ was decomposed in the acidic H₂O₂-ample environment and produced O₂ to overbear hypoxia-related PDT resistance, highly efficient PDT was obtained by excess singlet oxygen (¹O₂) release of P-AgNCs-MnO₂ nanoprobes under light irradiation compared with free P. In vitro and in vivo studies confirmed that P-AgNCs-MnO₂ exhibited high fluorescence specificity, excellent PDT effect, and good biocompatibility and could be used as a contrast agent for MRI. This theranostic platform provided a new avenue for the fluorescence and MRI diagnosis of tumors and efficient tumor treatment.