To address the limitations of traditional methods in detecting 3-chloro-1,2-propanediol (3-MCPD) in food contact materials (FCMs)—notably complex operations, prolonged detection cycles, and low sensitivity—this study introduces a novel Molecularly Imprinted Polymer-based Nano-Analytical System (MNAS). This integrated system enables rapid, in situ, and derivatization-free detection of 3-MCPD in paper-based FCMs. The MNAS innovatively combines molecularly imprinted polymers (MIPs) with a quartz crystal microbalance (QCM) sensing mechanism. Guided by density functional theory (DFT), a “pre-organized recognition” strategy was employed to design highly selective imprinting interfaces through precise monomer-template hydrogen bonding configurations. Further insights into the hydrogen bond-driven recognition mechanism were obtained using variable-temperature infrared spectroscopy and multimodal interference validation. This synergistic approach of interfacial molecular configuration control and enhanced mass response mechanisms endows the system with exceptional selectivity and anti-interference capabilities in complex matrices. The detection limit achieved is 0.006 µM, significantly surpassing that of traditional GC-MS methods (2.2 µM). Moreover, the overall detection process time is reduced by over 75%, eliminating the need for organic extraction and derivatization steps inherent in conventional methods, thereby greatly enhancing operational simplicity and practicality. The MNAS system not only broadens the application scope of MIPs in detecting non-intentionally added substances but also offers a novel strategy for high-throughput, on-site rapid screening of chlorinated contaminants in paper-based materials. This advancement holds significant implications for early warning systems and risk assessment in food safety.
Lysosomes are essential organelles for cells that act as the “recycling center” for decomposing biomolecules and clearing out damaged organelles. The status of lysosomes is tightly regulated by cells to maintain normal homeostasis. To monitor subcellular lysosomal status, super-resolution imaging has emerged as a promising technology that surpasses conventional imaging limitations, offering extraordinary visualization capability. However, existing fluorescent probes for super-resolution imaging still suffer from significant drawbacks, such as complex synthesis, poor intracellular stability, and the lack of near-infrared (NIR) imaging capability. Besides, to quantitatively analyze fluorescence images, traditional human-driven image interpretation is time-consuming and prone to information loss and human error. To tackle these challenges, we first developed a quinolinium-based fluorescent probe, PA-2, for NIR super-resolution imaging of lysosomes with low cytotoxicity and stable fluorescence. Harnessing PA-2's strong resistance to photobleaching, the lysosomal dynamic statuses, encompassing autophagy, mitochondria-lysosome contacts, and mitophagy, were successfully visualized. Building on this, we next demonstrate a novel approach leveraging a large multimodal model (LMM), an advanced artificial intelligence (AI) tool, for automated analysis of super-resolution images. The LMM accurately interprets images of PA-2 and predicts lysosomal status under various drug treatments with remarkable speed, precision, and explainability, significantly outperforming human experts in image analysis. To sum up, this work highlights the strong potential of combining advanced fluorescent probe design with AI-assisted image interpretation to drive revolutionary innovation in bioimaging and beyond.
We present GED-CRN, a 3D convolutional residual network that achieves quantum-chemical accuracy (MAE =7.6×10−4 bohr−3) in predicting electron densities for AIE-active systems using only 19 training molecules—overcoming the data scarcity bottleneck via spatial cube sampling (2×2×2 bohr3) of pro-molecular densities and nuclear potentials. The model demonstrates 1500× faster computation than MP2 while preserving AIE-critical features (<0.1 Å vdW surface error), enabling high-throughput screening of π-conjugated materials with 50% lower error than conventional organic systems, as validated on QM9 and ASBase datasets. This few-shot learning paradigm bridges data-efficient quantum ML with functional luminescent material design.
Conductive hydrogels show great promise in the field of flexible bioelectronics, but their complex synthesis process and insufficient safety limit practical applications. Starch, as a natural polysaccharide, is an ideal candidate for bio-based conductive materials due to its processability, biocompatibility, and degradability. This review summarizes the research progress of starch-based conductive materials, elucidates their synthesis mechanisms, and elaborates on the methods for imparting conductivity to starch and their application advancements in the conductive materials. Especially, the review emphasizes the high compatibility between starch-based materials and biological tissues and focuses on different design methods of starch-based conductive hydrogels, highlighting their respective advantages and disadvantages. Then, the properties and applications of starch-based conductive hydrogels in wearable sensors, supercapacitors, batteries, and other biomedical-related devices were summarized emphatically. Meanwhile, this review also objectively examined the current challenges, focusing on the difficulties in enhancing the performance of starch-based conductive hydrogels, reducing production costs, and scaling up manufacturing. Overall, these analyses were conducted to guide the further development of conductive hydrogels toward greener and more sustainable practices.
Organic small-molecule luminophores (SMLs) with low photoluminescence quantum yield (PLQY, ΦPL < 0.1) are commonly found in the field of optical research. However, existing strategies fail to induce their afterglow emission, as the excited-state energy of these molecules is almost dissipated through non-radiative transitions, which severely limits their practical applications. Here, we report a breakthrough strategy for converting non-emissive SMLs into highly efficient delayed emitters. By constructing efficient energy transfer between low-PLQY SMLs (acceptors) and energy donors within a thermoplastic polymer matrix, we achieve the first demonstration of delayed emission in such materials, with a delayed quantum yield of 28.9% and a delayed lifetime of 534 ms. In addition, the doped films offer distinct advantages in flat-panel display applications, successfully achieving large-area, high luminescence, and uniform ultraviolet projection display. This work marks a significant breakthrough in low-PLQY molecular afterglow materials, laying a crucial material foundation and technical support for emerging applications, such as new display devices and ultraviolet projection technologies.
Biopolymer-driven supramolecular chirality in aqueous media has gained significant advancements in hierarchical chiral nanostructures. However, researches on the aqueous circularly polarized luminescence (CPL) induced by supramolecular self-assembly and its mechanism have been rarely reported. Herein, we explore the hierarchical chirality transfer in self-assembled fluorescent homopolypeptide systems showing aqueous CPL, and unveil an α-helix-dominated CPL regulation mechanism. A relationship is established between molecular structure (degree of polymerization, DP), supramolecular assembly (self-assembly temperature, TSA), and resulting CPL properties. The stabilization for the homopolypeptide α-helix by increasing DP and decreasing TSA enables efficient chirality transfer from the polypeptide backbone to its terminal chromophore, thereby improving CPL properties. Our work elucidates the critical role of α-helix control in aqueous CPL systems, providing insights for designing biocompatible and tunable CPL-active nanomaterials.
Materials exhibiting time-dependent phosphorescence color (TDPC) are attractive, but generally suffer from complex preparation processes and low-color contrast. Herein, molecular aggregation regulation of 1-pyrenecarboxylic acid (PyC) in the konjac glucomannan (KGM) matrix is proposed to realize high-contrast TDPC. The steric hindrance of KGM enables isolated state, carboxyl dimer, and π-stacking-induced multimers of PyC with different phosphorescence wavelengths and lifetimes to coexist, leading to a typical TDPC evolution from red to blue-green. The TDPC shows remarkable phosphorescence wavelength shift up to 182 nm and phosphorescence lifetime up to 788.43 ms, readily recognized by the naked eye. In addition, KGM, an edible natural polysaccharide, displays decent rheological properties suitable for screen printing, film casting, and 3D printing, making PyC-KGM an eco-friendly tool for multi-dimensional information security applications. The work provides a simple yet efficient method for high-contrast TDPC materials and affords a promising material for high-level dynamic information encryption and anti-counterfeiting.
Rare earth-activated nanophosphors (NPs) have attracted significant attention due to their promising applications in compact and portable optoelectronic devices. However, limited by inherent nanoscale effects, achieving stable and efficient luminescence remains a long-standing challenge. Herein, we developed microwave-facilitated Ce sensitization engineering to obtain desirable green-emitting NaSrY(PO4)2 (NSYP):Tb NPs. Compared to NSYP:Tb, benefiting from highly efficient Ce–Tb energy transfer, NSYP:Ce,Tb exhibits a 45.8-fold enhancement in green emission intensity, along with exceptional internal quantum efficiency (IQE) of 82.2% and outstanding thermostability (93% intensity retention at 423 K). For health lighting, the NSYP:Ce,Tb NPs enable a high-quality white lighting source with remarkable color rendering index of 94. For multimodal non-contact thermometry, it can realize superior relative sensitivities across broad temperature ranges (2.28% K−1 at 473 K and 2.20% K−1 at 298 K). For X-ray imaging, it reaches a spatial resolution of up to 18.1 lp/mm, which surpasses commercially mainstream scintillators by above 70%. This study provides a microwave-facilitated sensitization route for multifunctional nanomaterials with high performance.
Antibiotic resistance is a major challenge in the clinical treatment of bacterial infectious diseases. Herein, we constructed a multifunctional DNA nanoplatform as a versatile carrier for bacteria-specific delivery of clinical antibiotic ciprofloxacin (CIP) and classic nanoantibiotic silver nanoparticles (AgNP). In our rational design, CIP was efficiently loaded in the self-assembly double-bundle DNA tetrahedron through intercalation with DNA duplex, and single-strand DNA-modified AgNP was embedded in the cavity of the DNA tetrahedron through hybridization. With the site-specific assembly of targeting aptamer in the well-defined DNA tetrahedron, the bacteria-specific dual-antibiotic delivery system exhibited excellent combined bactericidal properties. With enhanced antibiotic accumulation through breaking the out membrane of bacteria, the antibiotic delivery system effectively inhibited biofilm formation and promoted the healing of infected wounds in vivo. This DNA-based antibiotic delivery system provides a promising strategy for the treatment of antibiotic-resistant infections.
The development of affordable and user-friendly diagnostic tools for early warning and monitoring progression of chronic kidney disease (CKD) is crucial to reducing CKD-related morbidity and mortality. This study reports on (1) a protein-templated AIEgen, Ir@BSA, which emits intense green phosphorescence with a quantum yield up to 69.40% and a lifetime up to 1839.40 ns in aqueous solution; (2) a straightforward protocol for Cys C quantitation, which employs Ir@BSA as the phosphorescent signal indicator and papain as the biomolecular recognition element, respectively; and (3) a smartphone-based portable phosphorescence reader (termed as SAPD), which can stably excite and accurately collect phosphorescence signals from the paper-based arrays. Quantitation of Cys C in clinical serum samples using SAPD integrated with the paper-based arrays highlights its remarkable advantages including high sensitivity (0.36 µg mL−1) and specificity, cost-effectiveness (∼$67.5 per set), portability (∼450 g), good precision (RSD ≤ 8.25 %), good accuracy (comparable to clinical standard latex immune-turbidimetric method), and high throughput (16 samples per experiment). More importantly, this study reveals the significant potential of Cys C as an early warning marker of CKD progression. The reported method enables Cys C quantitation anywhere, anytime, by anyone, and is ideally suited for mass screening for CKD and home monitoring of CKD progression, facilitating early diagnosis and proactive management of CKD.
Fluorescent lateral flow immunoassay (LFIA) has emerged as a critical point-of-care (POC) diagnostic platform for in vitro diagnosis. However, the analytical sensitivity of conventional fluorescent LFIA is constrained by the suboptimal quantum yield (QY) and photostability of conventional fluorophores. Here, we developed a class of fluorescent nanoparticles by encapsulating butterfly-shaped aggregation-induced emission (AIE) luminogens with polystyrene microspheres, achieving a remarkable QYs of 91%—representing a 2.2-fold enhancement compared to previous AIEgens (42% QY). In addition, the broad emission spectrum characteristic of AIE fluorophores enables significant improvements in detection sensitivity and system stability of LFIAs through strategic optimization of optical filter configurations. Comparative performance evaluation revealed that the optimized 30 nm filter-AIE LFIAs platform presents outstanding performance relative to conventional, in which 85-folds and 43-folds improvements in detection limits for cardiac troponin I is achieved with excellent reproducibility (coefficient of variation < 15%). Overall, the synergistic combination of high-manufacturing efficiency, high sensitivity, and good biocompatibility of the developed AIE-RNPs enables it as an efficiency and broadly applicable signal amplifier for LFIA applications, which is expected to extend the application of LFIA for trace and quantitative detection, paving the way for more reliable POC testing in clinical and resource-limited setting.
Organic electrochemical transistors (OECTs) represent a promising platform for neuromorphic computing, owing to their unique ability to achieve non-volatile memory under low-voltage operation. The achievement of biologically relevant synaptic functionalities within OECTs remains challenging due to uncontrolled ionic-electronic coupling, limited device stability, and fabrication complexity. Herein, we report synaptic OECTs based on polymer blends of the ion-permeable semiconductor (Pg2T-T) and the ion-blocking polymers (PMMA, PS), which are designed to modulate ionic diffusion within the transistor channel. Morphological and electrochemical characterizations demonstrate that the incorporation of these blocking polymers induces nanofibrous phase separation, resulting in continuous Pg2T-T nanofibers that facilitate electronic transport, interspersed with PMMA-rich domains serving as physical barriers to ion migration. Based on the systematic evaluation of OECT transistor and synapse performances, we identified an optimal Pg2T-T to PMMA composition ratio of 1:2, which yields significantly enhanced synaptic behaviors, including excitatory postsynaptic current (EPSC), tunable paired-pulse facilitation and depression (PPF/PPD), as well as stable long-term potentiation and depression (LTP/LTD) across multiple writing/erasing cycles. Moreover, by integrating the device into a neuromorphic system based on the Fashion-MNIST dataset, achieving a classification accuracy of 80.41%, which surpassed the ideal synapse baseline, attributed to the beneficial stochasticity of physical weight updates. These results highlight a scalable material strategy for high-robust synaptic emulation in OECTs, offering a promising foundation for future bioinspired neuromorphic hardware.
The escalating threats of antimicrobial resistance and monkeypox virus infections pose a significant challenge to public health, necessitating innovative therapeutic approaches. Developing materials with balanced photodynamic and photothermal effects for the elimination of broad-spectrum drug-resistant bacteria and inactivation of the monkeypox virus remains a formidable task. Herein, we prepared a series of Nile Red derivatives by a donor rotation and charge transfer enhancement strategy, identifying 5-(dicyanomethylene)-9-[4-(bis(4-methoxyphenyl)amino)phenyl]-7a,12a-dihydro-5H-benzo[a]phenoxazine (TPAOMCN)-featuring alkoxy-triphenylamine and malononitrile, as the optimal candidate. TPAOMCN demonstrated extended near-infrared absorption, enhanced intersystem crossing (ISC) efficiency, and intense molecular motions, enabling dual-modal phototherapy. Electrospun TPAOMCN nanofibers (NFs) with submicron-scale diameter achieved >50°C temperature elevation and excellent reactive oxygen species (ROS) generation under irradiation. In methicillin-resistant S. aureus (MRSA)-induced wound infection and vaccinia virus-mediated tail-scarred models, TPAOMCN NFs effectively eliminated MRSA colonies and reduced viral load through physical disruption of pathogen membranes, thermal denaturation of viral capsids, and ROS-mediated oxidation of biomolecules, while suppressing inflammation and accelerating angiogenesis-mediated tissue repair. This study not only established a molecular engineering strategy for Nile Red to achieve prime PDT-PTT performance but also provided a paradigm for advancing dual-functional phototherapeutic platforms against emerging antimicrobial threats and monkeypox virus infections.
Tau protein aggregation is a hallmark of a diverse group of neurodegenerative disorders known as tauopathies, including Alzheimer's disease, Pick's disease, and progressive supranuclear palsy. These disorders are characterized by the misfolding of tau into β-sheet-rich fibrils, disrupting neuronal function and contributing to disease progression. This review presents a comprehensive overview of the advances in molecular imaging that have deepened our understanding of tau pathology. We begin by examining tau's domain architecture, isoform diversity, and aggregation mechanisms, highlighting the central role of the microtubule-binding region in fibril formation. The review then explores the structural polymorphism of tau fibrils across tauopathies, emphasizing the significance of cryo-electron microscopy in resolving disease-specific conformers. We discuss the fluorescence and radioimaging as powerful tools for detecting tau aggregates at the nanoscale. Particular focus is given to the development of tau-selective fluorescent probes and positron emission tomography tracers, detailing their design strategies, binding mechanisms, and diagnostic potential. Emerging approaches such as super-resolution imaging and sensor arrays are also considered for their ability to enhance sensitivity and specificity. By integrating insights from structural biology, chemical imaging, and molecular neuroscience, this review provides a multiscale framework for understanding tau aggregation and its implications for diagnosis and therapeutic intervention.
Borate-based hybrids offer an excellent platform for advanced materials design, yet integrating multiple functional units remains challenged by competing structural requirements. Here, we presented a rationally designed hybrid system that first achieves synergistic coupling between π-conjugated malonate and polymerized boro-oxygen units through precise coordination chemistry control. We synthesized eight new malonate-borate hybrids comprising two structural types: series I ([B3O7(OH)]-based) and series II ([H3BO3]-based). Starting from three centrosymmetric series I compounds, controlled variation of stoichiometry and reaction pathways yielded four non-centrosymmetric series II hybrids and one centrosymmetric series II phase, enabling tailored structural symmetry. The series II system exhibits diverse functional properties across the material series, including a high birefringence (Δn = 0.203@546 nm) with a short cutoff edge of 200 nm, strong second-harmonic generation responses rivaling KH2PO4 (KDP), and high ionic conductivity. This work establishes a new paradigm for functional crystal engineering by elucidating fundamental design principles for balancing competing property requirements through controlled structural evolution.
Tau oligomers are recognized for their critical role in causing neuronal toxicity and synaptic dysfunction in a diverse array of neurodegenerative diseases collectively referred to as tauopathies. However, the discovery of drugs that specifically target tau oligomers has been impeded by the absence of appropriate screening methods. Here, we suggest a drug screening platform based on tau amyloid corona-shelled nanoparticles (TACONs) to assess the efficacy of tau oligomer-degrading agents through aggregation-induced colorimetric responses of TACONs. TACONs were engineered via the encapsulation of gold nanoparticles (AuNPs) with homogeneous tau oligomers by leveraging heparin as a co-factor. Our TACON-based strategy harnesses two primary functions of AuNPs: (i) catalytic activators for the selective isolation of tau oligomers and (ii) optical reporters for quantifying colorimetric responses induced by tau oligomer-degrading agents. To validate this approach, we employed proteases that can degrade tau oligomers (protease XIV and plasmin) along with various small molecules known to aid in the treatment of tauopathies. Furthermore, we significantly enhanced screening efficiency by integrating a time-series deep learning architecture, enabling rapid identification of effective agents within 1 h. These results highlight the great potential of a deep learning-assisted TACON-based drug screening platform as a powerful strategy for streamlining drug discovery in tauopathies.
X-ray scintillators play a critical role in medical diagnostics and industrial applications by converting ionizing radiation into low-energy photons. Among various scintillators, metal clusters are promising due to advantages such as atom-precise structures, high heavy-atom density, strong luminescence intensity, and low usage cost. Those exhibiting temperature-inert radioluminescence properties show broad application potential in extreme environments and have attracted considerable attention. In this work, a comprehensive strategy incorporating triplet exciton recycling and fluoride-bridge-induced carrier traps was introduced in the design of a temperature-inert cluster scintillator (Tb16). The introduction of rare earth elements facilitated high-efficiency triplet exciton recycling during the radioluminescence process, endowing Tb16 with a high light yield of 41380 ± 950 photons MeV−1. Meanwhile, the presence of fluoride-bridges in Tb16 induced abundant carrier traps, and the charge carriers captured by these traps could be thermally released back to the excited state at high temperatures, effectively compensating for emission loss. As a result, the radioluminescence intensity of Tb16 remains nearly unchanged over a temperature range from 300 to 540 K, demonstrating its strong application potential in variable-temperature X-ray imaging.
Organic host–guest systems exhibiting room-temperature phosphorescence (RTP) hold great promise for sensing, encryption, and bioimaging. However, achieving both long lifetimes and high efficiency remains challenging, as enhanced spin–orbit coupling (SOC) often competes with efficient intersystem crossing (ISC). We report an isotope-engineering strategy that overcomes the lifetime–efficiency trade-off in classical carbazole (Cz) host–guest systems. Doping just 0.5 wt% of deuterated 1H-benzo[f]indole (BdD8) into Cz extends the RTP lifetime from 0.485 to 1.771 s, a 3.65-fold enhancement without compromising the phosphorescence quantum yield. Replacing the N–H group in BdD8 with a CD3 moiety (BdD8CD3) and using a methylated host (CzCH3) further extends the RTP lifetime to 1.870 s. This improvement arises from isotope-induced suppression of non-radiative decay and enhancement of ISC, as evidenced by a reduction in the non-radiative rate from 2.01 to 0.51 s−1 and an increase in the ISC rate from 4.91 × 107 s−1 to 6.21 × 107 s−1. Building on this success, we applied the strategy to benzo[b]carbazole (BCz) derivatives, which similarly exhibited enhanced RTP performance. Finally, we demonstrate time-resolved multi-information encoding enabled by this ultralong afterglow system.
Reversible self-assembly of nanoparticles remains challenging due to limited molecular mobility. Moreover, reported successful examples typically rely on inorganic-core nanoparticles that require surface pre-functionalization with specific stimuli-responsive ligands. Here, we demonstrate reversible self-assembly of organic nanoparticles through the selective self-modulation of aliphatic chains, without the need for prior modification with external stimuli-responsive ligands. D-glucose 11-octadecylthioundecanoate (D-Glc-C11S18E) self-assembles into microspheres (3–6 µm) comprising nanospheres (100–300 nm). Within these nanospheres, octadecylthioundecanoyl (C29) groups form interior crystalline domains (C29 lamella) while octadecyl (C18) chains organize at nanosphere interfaces (C18 lamella). Thermal triggering enables selective reversibility: at 50°C, the C18 lamella dissociates into disordered structures while the C29 lamella remains intact; cooling to 20°C regenerates the C18 lamella. In methanol, this process drives reversible microsphere-nanosphere morphological transitions (validated by scanning electron microscopy/dynamic light scattering), accompanied by a reversible fluorescence modulation. Both structural and optical modulations exhibit no apparent fatigue over 10 consecutive cycles. Energy decomposition analysis reveals stronger C29 binding energy (ΔEint = –29.80 kcal/mol vs. C18's –19.90 kcal/mol), explaining selective reversibility. Density functional theory calculations confirm the distinct highest occupied molecular orbital-lowest unoccupied molecular orbital gaps correlating with emission wavelengths. Leveraging the temperature/wavelength-dependent fluorescence, we constructed a multi-input logic gate. This work establishes a new insight for reversible assembly and enables smart and fatigue-resistant optoelectronic applications.
The future of precision oncology hinges on tools capable of revealing the invisible and treating the intractable. Aggregation-induced emission (AIE) nanoparticles, uniquely characterized by intensified luminescence upon aggregation, have emerged as intelligent, immune-compatible platforms precisely suited for this dual mandate. These systems redefine how light interacts with matter and how therapy interfaces with immunity, offering unprecedented opportunities for real-time tumor detection, targeted therapy, and immunomodulation. This perspective outlines the conceptual foundations, engineering principles, and translational promise of AIE nanoparticles in precision cancer theranostics. By illuminating the unseen and enabling intervention where conventional strategies fail, AIE nanotechnology is poised to fundamentally reshape the landscape of cancer diagnosis and treatment.
The development and fabrication of cucurbit[7]uril (Q[7])-based host‒guest supramolecular polymers remain challenging due to the limited cavity size of Q[7]. Herein, we designed and synthesized three thiophene-pyridinium guests and investigated their binding interactions with Q[7]. NMR, ESI-MS spectroscopy, and DFT calculations revealed that Q[7] can encapsulate one or two thiophene groups of the guests to form supramolecular complexes, including discrete inclusion complexes and supramolecular polymers. Importantly, all supramolecular complexes demonstrated reversible photochromism in the solid state, which is attributed to viologen radical generation, as confirmed by UV-vis-NIR, ESR, and DFT studies. Due to the aggregation caused quenching (ACQ) effect induced by the intermolecular π⋯π stacking interaction of thiophene groups within the Q[7] cavity, the Q[7]-based supramolecular polymers remained fluorescence-silent, whereas the discrete inclusion complexes showed enhanced fluorescence compared to their thiophene-pyridinium guests. The dual photochromic and fluorescence properties of the Q[7]-based supramolecular complexes render them suitable for applications in erasable inkless printing, multi-level anti-counterfeiting, and advanced information encryption. This study provides a strategy for constructing dual-functional supramolecular polymers using Q[7]-based host‒guest interactions.
The report combines experimental data and linear extrapolation structure calculation results to simulate the changes in intermolecular interactions energy in crystals using dimers, accurately locating the energy storage positions of bis(acetylacetonate) copper (II) [CuL12] and two other single crystals ([CuL22] and [CuL32]) under elastic stress and revealing the origin of elastic recovery force.
The aggregation state modification of graphene, including nanographene molecules, is essential for optimizing their performance in various applications. However, the current understanding of how to regulate the structures and features of nanographene aggregates primarily relies on non-covalent bonding interactions, while achieving exact control remains a significant challenge. Herein, we describe unique occurrence in which a σ-bond is reversibly constructed and subsequently broken to produce dimeric nanographene and monomeric analogues. These molecules are fused with azulene unit(s) at the edge. The acid-driven transformation occurs with a radical mechanism. Moreover, the manipulation of the chemical employed to terminate the reaction can regulate the selective creation of dimer and monomer. As compared to the monomer, the dimer with a helical structure exhibited a substantial rise in the molar absorbance coefficient (ɛ), fluorescence emission, a greater range of electrochemical characteristics, and much enhanced chirality stability. This study presents an unprecedented strategy that can precisely control and modulate the structures of aggregation state and characteristics of nanographene by regulating covalent bond cleavage and formation.
Overcoming drug resistance remains a central challenge in cancer therapy, particularly in hepatocellular carcinoma (HCC), where elevated intracellular glutathione (GSH) levels suppress ferroptosis and limit therapeutic efficacy. Here, we report a natural polyphenol–metal supramolecular nanocomplex (bm–Cur–NC), assembled from bisdemethylcurcumin and Cu(II), with its successful formation and structural features confirmed by high-resolution mass spectrometry (HR-MS), 1H NMR, UV–vis spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and high-resolution transmission electron microscopy (HR-TEM). This nanocomplex simultaneously disrupts cytoplasmic and mitochondrial redox homeostasis to induce ferroptosis in cisplatin-resistant HCC (HepG2/DDP) cells. The nanocomplex depletes GSH through a multifaceted “three-stones-for-one-bird” strategy: inhibiting GSH biosynthesis via downregulation of the system Xc− transporter component SLC7A11, and directly consuming GSH through Cu(II) redox cycling and Michael addition reactions. This coordinated GSH depletion resensitizes drug-resistant HCC cells (HepG2/DDP) and triggers ferroptotic cell death in both the cytoplasm and mitochondria, accompanied by downregulation of key ferroptosis regulators, including glutathione peroxidase 4 (GPX4) and SLC7A11. Notably, bm–Cur–NC (10–20 µg mL−1) demonstrates potent antitumor efficacy in vivo with minimal systemic toxicity, while simultaneously suppressing ferroptosis- and resistance-related proteins such as GPX4, SLC7A11, P-glycoprotein (P-gp), and glutathione S-transferases (GSTs) in a nude mouse model. This study presents a supramolecular nanomaterial platform derived from biocompatible herbal components for redox-based ferroptosis activation, offering a promising strategy to combat drug-resistant cancers.
Clear cell renal cell carcinoma (ccRCC) is the most prevalent and aggressive subtype of kidney cancer, demanding rapid and precise diagnostic tools to guide clinical decision-making. Current methods, such as immunohistochemistry (IHC) and frozen section analysis, face limitations in speed, sensitivity, and workflow complexity. To address these challenges, we developed a tetrahedral DNA nanostructure (TDN)-enhanced quadrivalent hybridization chain reaction (qHCR) platform targeting carbonic anhydrase IX (CAIX), a highly specific biomarker for ccRCC. This system integrates aptamer-based molecular recognition with enzyme-free signal amplification, leveraging the spatial confinement and multivalent effects of TDNs to achieve ultrasensitive detection. The qHCR platform demonstrated remarkable performance, with a reaction rate 95 times faster than traditional HCR and sustained signal stability in serum for over 36 h. In clinical validation using 40 ccRCC tissue samples, the platform enabled Precision Tumor Recognition within 25 min for frozen sections, yielding a tumor-to-normal tissue signal ratio of 3.35:1, and completed molecular profiling within 2.5 h for formalin-fixed, paraffin-embedded (FFPE) samples, showing full concordance with histopathological diagnoses. Its modular design allows seamless target switching by replacing aptamer sequences, as confirmed by successful detection of protein tyrosine kinase (PTK7) in an acute lymphoblastic leukemia model. With its cost-effectiveness ($0.15 per test), streamlined workflow, and compatibility with both intraoperative margin assessment and postoperative pathological analysis, the qHCR platform represents a transformative advancement in molecular diagnostics for ccRCC management, offering a robust solution for precision oncology and time-critical surgical decision-making.
Flexible UV-sensitive photodetectors and optoelectronic synapses are highly desired in numerous sensing areas and neuromorphic computations. Herein, the large-size, flat, and continuous sheet of polyamic acid (PAA), a two-dimensional (2D) porous organic polymer (POP), was synthesized at the liquid/liquid interface. Combining with graphene (G), the hybrids demonstrate efficient UV-selective photodetection. On the soft substrate of polyethylene glycol terephthalate (PET), the UV-selective detecting ability is retained even under 90° bending and after 20,000 bending cycles, indicating the remarkable flexibilities. And our PAA/G/PET devices exhibit self-healing capability via a simple thermal annealing at 45°C. The remarkable flexibilities can be attributed to the high mechanical strength of 2D covalent-bonded backbones of PAA and G, the adaptive porous connections, and reversible broken/reformation of the large number of hydrogen bonds in PAA. Furthermore, the PAA/G/PET devices can mimic the functions of biosynapse very well, including paired-pulse facilitation, short-term plasticity (STP) and long-term plasticity (LTP), transition of STP to LTP, spike time, number, and intensity-dependent plasticity. With this optoelectronic synapse, the human brain-like process and wireless communications are realized. The memory time can achieve 10,000 s after 45 s learning. And the synaptic functions persist at the bending angle of 90°. The results in this work provide valuable support for developing flexible wavelength-selective photodetectors and artificial synapses with 2D POPs and their hybrid films.