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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 It remains a challenge to obtain biocompatible afterglow materials with long emission wavelengths, durable lifetimes, and good water solubility. Herein we develop a photooxidation strategy to construct near-infrared afterglow carbon nanodots with an extra-long lifetime of up to 5.9 h, comparable to that of the well-known rare-earth or organic long-persistent luminescent materials. Intriguingly, size-dependent afterglow lifetime evolution from 3.4 to 5.9 h has been observed from the carbon nanodots systems in aqueous solution. With structural/ultrafast dynamics analysis and density functional theory simulations, we reveal that the persistent luminescence in carbon nanodots is activated by a photooxidation-induced dioxetane intermediate, which can slowly release and convert energy into luminous emission via the steric hindrance effect of nanoparticles. With the persistent near-infrared luminescence, tissue penetration depth of 20 mm can be achieved. Thanks to the high signal-to-background ratio, biological safety and cancer-specific targeting ability of carbon nanodots, ultralong-afterglow guided surgery has been successfully performed on mice model to remove tumor tissues accurately, demonstrating potential clinical applications. These results may facilitate the development of long-lasting luminescent materials for precision tumor resection.

Abstract Physical unclonable functions (PUFs) have emerged as a promising encryption technology, utilizing intrinsic physical identifiers that offer enhanced security and tamper resistance. Multi‐level PUFs boost system complexity, thereby improving system reliability and fault tolerance. However, crosstalk‐free multi‐level PUFs remain a persistent challenge. In this study, a hierarchical PUF system that harnesses the spontaneous phase separation of silk fibroin /PVA blend and the random distribution of silicon‐vacancy diamonds within the blend is presented. The thermodynamic instability of phase separation and inherent unpredictability of diamond dispersion gives rise to intricate random patterns at two distinct scales, enabling time‐efficient hierarchical authentication for cryptographic keys. These patterns are complementary yet independent, inherently resistant to replication and damage thus affording robust security and reliability to the proposed system. Furthermore, customized authentication algorithms are constructed: visual PUFs authentication utilizes neural network combined structural similarity index measure, while spectral PUFs authentication employs Hamming distance and cross‐correlation bit operation. This hierarchical PUF system attains a high recognition rate without interscale crosstalk. Additionally, the coding capacity is exponentially enhanced using M‐ary encoding to reinforce multi‐level encryption. Hierarchical PUFs hold significant potential for immediate application, offering unprecedented data protection and cryptographic key authentication capabilities.

Abstract Carbon nanodots (CDs) have emerged as an alternative option for traditional nanocrystals due to their excellent optical properties and low toxicity. Nevertheless, high emission efficiency is a long‐lasting pursuit for CDs. Herein, CDs with near‐unity emission efficiency are prepared via atomic condensation of doped pyrrolic nitrogen, which can highly localize the excited states thus lead to the formation of bound excitons and the symmetry break of the π–electron conjugation. The short radiative lifetimes (

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 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.