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Abstract 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.

Abstract Optical multiplexing attracts considerable attention in the field of information encryption, optical probe, and time‐resolved bioimaging. However, the optical multiplexing based on rare‐earth nanoparticles suffers from heavy metal elements and relatively short lifetimes; sophisticated facilities are thus needed. Herein, time division duplexing based on eco‐friendly carbon nanodots (CNDs) with manipulative luminescence lifetimes is demonstrated. In a single green color emission channel, the luminescence lifetimes of the CNDs can be manipulated from nanosecond level to second level by introducing water, while the lifetime of the CNDs confined by a silica shell stays. Time division duplexing based on the CNDs and CNDs@silica with distinct lifetimes is realized and spatio‐temporal overlapping information is thus resolved. High‐level information encryption using the time division duplexing technology is realized. This work may promise the potential applications of CNDs in multi‐lifetime channels biological imaging, high‐density information storage, and anti‐counterfeiting.

Abstract Reactive oxygen species (ROS) are generated in the body and related to many pathophysiological processes. Hence, detection of ROS is indispensable in understanding, diagnosis, and treatment of many diseases. Here, near‐infrared (NIR) chemiluminescent (CL) carbon nanodots (CDs) are fabricated for the first time and their CL quantum yield can reach 9.98 × 10−3 einstein mol−1, which is the highest value ever reported for CDs until now. Nanointegration of NIR CDs and peroxalate (P‐CDs) through the bridging effect of amphiphilic triblock copolymer can serve as turn‐on probes for the detection and imaging of hydrogen peroxide (H2O2). Considering high efficiency and large penetration depth of NIR photons, the P‐CDs are employed in bioimaging H2O2 in vitro and in vivo, and the detection limit can reach 5 × 10−9 m, among the best reported of CDs‐based sensors. Moreover, imaging of inflammatory H2O2 in a mouse model of peritonitis is achieved by employing the P‐CDs as sensors. The results may provide a clue for the diagnosis and treatment of inflammation or cancers employing CL CDs as sensors.

Abstract Hydrogen peroxide (H2O2) is an important product of oxidase-based enzymatic reactions, such as glucose/glucose oxidase (GOD) reaction. Therefore, the probing of generated H2O2 for achieving the detection of various carbohydrates and their oxidases is very significative. Herein, we report one kind of dual-emission carbon nanodots (CDs) that can serve as novel dual-mode nanosensors with both fluorometric and colorimetric output for the selective detection of H2O2. The dual-model nanosensors are established only by the undecorated dual-emission CDs, where significant fluorometric and colorimetric changes are observed with the addition of different concentrations of H2O2 in the CD solution, which benefit to the achievement of the naked-eye detection for H2O2. The mechanism of the nanosensors can be attributed to the fact that the external chemical stimuli like hydroxyl radicals from H2O2 bring about the change of surface properties and the aggregation of CDs, which dominate the emission and absorption of CDs. The constructed dual-mode nanosensors exhibit good biocompatibility and high selectivity toward H2O2 with a linear detection range spanning from 0.05 to 0.5 M and allow the detection of H2O2 as low as 14 mM.

Abstract Red/near‐infrared (NIR) emissive carbon nanodots (CNDs) with photoluminescence (PL) quantum yield (QY) of 57% are prepared via an in situ solvent‐free carbonization strategy for the first time. 1‐Photon and 2‐photon cellular imaging is demonstrated by using the CNDs as red/NIR fluorescence agent due to the high PL QY and low biotoxicity. Further study shows that the red/NIR CNDs exhibit multiphoton excited (MPE) upconversion fluorescence under excitation of 800–2000 nm, which involves three NIR windows (NIR‐I, 650–950 nm; NIR‐II, 1100–1350; NIR‐III, 1600–1870 nm). 2‐Photon, 3‐photon, and 4‐photon excited fluorescence of the CNDs under excitation of different wavelengths is achieved. This study develops an in situ solvent‐free carbonization method for efficient red/NIR emissive CNDs with MPE upconversion fluorescence, which may push forward the application of the CNDs in bioimaging.

Abstract The various luminescent properties of carbon nanodots (CDs) reveal fascinating applications in several areas. Here, bright and multicolor chemiluminescence (CL) is realized from CDs, whose CL quantum yield can be optimized by adjusting the energy level alignment between the CDs and 1,2‐dioxetanedione intermediate generated from the reaction of peroxalate and hydrogen peroxide. A CL quantum yield of 9.32 × 10−3 Einsteins mol−1, maximal luminance of 3.28 cd m−2, and lifetime of 186.4 s are achieved in red CDs, all of which are the best values ever reported for CDs. As a proof‐of‐concept prototype, a high‐quality information encryption strategy is established via CD based CL imaging techniques by virtue of the high brightness and multicolor CL.