Triplet Electron Exchange in Carbon Nanodots‐assisted Long‐persistent near‐infrared Chemiluminescence for Oncology Synergistic Imaging and Therapy

In classical photodynamic therapy, tumor cells are killed by the cytotoxic species via type-I/II photochemical reactions, seriously limited by the external photoexcitation and hypoxia. Herein, the electron transfer mechanism between fluorophores and peroxalate-H₂O₂ reaction is investigated and the singlet/triplet electron exchange is utilized to achieve long-persistent chemiluminescence imaging and synergistic type-I/II/III photodynamic therapy. As a proof-of-concept, the photosensitizers of carbon nanodots (CDs)-loaded chlorin e6 (CDs-Ce6) are designed and integrated with the peroxalate molecules, and the as-prepare polymer carbon nanodots (p-CDs) exhibit novel tumor microenvironment (TME)-responsive long-persistent near-infrared CL and photochemical reactions, evoking the in vivo imaging and synergistic dynamic therapy in tumor tissue. Mechanistically, the excess reactive oxygen species in TME can trigger the chemically initiated singlet/triplet electron exchange between the hydrophobic CDs-Ce6 and peroxalate-derived 1,2-dioxetanes and thus the excess excited singlet/triplet electron of the CDs-Ce6 can ensure the long-persistent near-infrared CL, type I/II photochemical production of hydroxyl radicals, superoxide radical and singlet oxygen, and type III photochemical damage of maladjusted biomacromolecules, enabling the long-persistent near-infrared biological imaging and enhanced cancer therapy. These results shed a new sight into the energy transfer mechanism in chemiluminescence and pave a new sight into the architecture of multifunctional theragnostic nanoplatforms.