Organic room-temperature phosphorescent (RTP) materials, characterized by their prolonged emission durations, cost-effectiveness and environmental sustainability, present substantial potential for utilization in optoelectronic devices and information encryption, thereby garnering considerable research attention. Nevertheless, the intrinsically weak spin-orbit coupling (SOC) in organic molecules hampers efficient intersystem crossing (ISC) between singlet and triplet states, thereby shortening the lifetime (τ) of RTP. Achieving room-temperature phosphorescence in organic molecules hinges on overcoming two fundamental challenges: promoting efficient ISC between singlet and triplet states and suppressing non-radiative decay through rigid microenvironmental confinement. This review summarizes recent advances in pure organic RTP from the perspective of multicomponent systems, highlighting emerging strategies for modulating exciton dynamics and rigidifying the local environment of emissive molecules. Approaches such as supramolecular self-assembly, guest-host doping, eutectic formation and exciplex engineering are discussed as effective means to suppress non-radiative deactivation and realize ultralong RTP (emission lifetime of over 100 ms). The underlying design principles and representative applications of these systems are delineated, and future directions for constructing high-performance pure organic RTP materials are outlined. Our goal is to foster interdisciplinary collaboration and innovation to fully exploit the potential of RTP materials in organic optoelectronics and biomedicine. This review aims to delineate a coherent research trajectory and offer forward-looking insights into emerging opportunities in this rapidly evolving field. By promoting cross-disciplinary dialogue to catalyze new ideas and applications that harness the unique photophysical characteristics of RTP materials for transformative technological advancements.
The single-locked photosensitizers (PSs) still suffer from off-target activation and skin phototoxicity in photodynamic therapy (PDT). Moreover, the efficacy of PDT is significantly limited by the antioxidant defense system of tumor cells, particularly reduced glutathione (GSH). To address these limitations, we have developed a programmed activatable PS, designated as LET-19, specifically designed for acidity/GSH dual-locked PDT of tumors. LET-19 is constructed upon an iodinated cyanine structure, incorporating an oxazinane moiety and a 3,5-bis(trifluoromethyl)benzenethiol group. One lock is the oxazinane moiety that is capable of responding to acidic tumor microenvironment (TME), another lock is the 3,5-bis(trifluoromethyl)benzenethiol group that reacts to GSH. Notably, the fluorescence (FL), photoacoustic (PA), and photodynamic properties of LET-19 are initially suppressed. The programmed activation of acidity/GSH dual-locked PS is achieved by following steps: i) Once LET-19 enters tumor tissues, it is activated by the acidic TME; ii) Subsequently, LET-19 is taken up by tumor cells and further activated by GSH. Only in the occurrence of H+ and GSH, whether in vitro or in vivo, both of the responsive units were sequentially recognized, thereby restoring FL/PA signals and the photodynamic capability of LET-19. This mechanism allows LET-19 to perform precise tumor identification by FL/PA dual-modality imaging, as well as improve the efficacy and safety of PDT. Meanwhile, in vitro and in vivo results demonstrate that LET-19 depletes GSH to inhibit the activity of glutathione peroxidase 4, disrupting redox homeostasis and thus amplifying the efficacy of PDT. This study provides a strategy to construct programmed activatable PSs for precision photodynamic theranostics of tumors.
The aggregation of superatoms, serving as stable building blocks, can be understood in terms of classical chemical bonding concepts, thereby enabling a rational design of molecular materials despite their different sizes, shapes, and compositions. From this perspective, the interaction between superatomic electronic shells from different building blocks is analogous to that between atomic orbitals, yielding cluster based supermolecular counterparts of prototypical molecules. The resulting intercluster bonding modes, including single, multiple, and hybrid bonds, are found in linear, cyclic, and three-dimensional aggregates. Moreover, the notion of concentric bonding in multilayered clusters is explored, highlighting electronic interactions across nested structural layers. These insights advance the understanding of electronic structure, bonding variability, and aggregation in ligand-protected coinage metal clusters, providing a robust foundation for the rational design of superatomic materials with tailored electronic, catalytic, and optical functionalities. This framework bridges classical chemical bonding and emerging nanoscale architectures, promoting the development of cluster-based functional materials with novel properties.
The resulting product of biocoupling is a bioconjugate, typically formed by linking molecules to proteins, oligosaccharides, nucleic acids, or synthetic polymers. By conjugating fluorescent probes with bioactive molecules via click chemistry or bioorthogonal reaction, functional materials with high specificity, sensitivity, and accuracy can be developed. A particularly promising strategy involves the use of aggregation-induced emission (AIE) fluorophores, which exhibit augmented luminescence intensity and excellent photostability when in the aggregated state, making them especially suitable for bioimaging and biosensing applications. The rapid expansion of AIE active bioconjugates now calls for a comprehensive review to summarize and systematize recent advances. In this review, we direct our focus toward the biosensing, bioimaging, and therapeutic applications of AIE active bioconjugates prepared via click chemistry or bioorthogonal reactions. We anticipate that this overview will promote the development of versatile AIE bioconjugates and inspire further innovations in bioorthogonal chemistry for biomedical applications.
Rotational dynamics in molecular crystals influence not only internal structures but also bulk properties such as photophysical behavior. In this work, we present novel crystalline chiral binuclear N-heterocyclic carbene (NHC) Au(I) complexes, 1-R and 1-S, which display a distinct axially chiral conformation with C2-symmetry, derived from non-equivalent orientations of phenyl groups on the NHC ligands. These phenyl moieties undergo two distinct types of rapid rotational motion, as revealed by variable-temperature solid-state 2H NMR studies. Such dynamic motions promote structural symmetrization within the crystal, shifting from C2-symmetry toward a more D2-like symmetry. This symmetry evolution significantly affects the chiroptical properties of the crystals. Both experimental measurements and TD-DFT calculations confirm that such motion modulates chiroptical properties, leading to temperature-dependent changes in emission intensity and the luminescence dissymmetry factor (glum). These results highlight dynamic molecular rotation as a powerful tool for tuning symmetry and chiroptical responses in crystalline materials, offering new design principles for solid-state chiral systems.
Circularly polarized luminescence (CPL) has attracted considerable attention owing to its wide range of potential applications. Cholesteric liquid crystals (CLCs) are promising candidates for CPL-active materials because of their ease of fabrication, stimulus responsiveness, and ability to achieve high dissymmetry factors (|glum|). In most studies on CPL-active CLCs, non-mesogenic luminophores are doped into commercially available liquid crystals (LCs). However, their low solubility in LCs (typically only a few wt%) and their tendency to disrupt LC alignment present challenges in achieving high |glum| values—particularly in thin cells—and in broadening the CPL spectra. Here, we report a new LC mixture comprising our previously designed mesogenic fluorophore and a commercially available LC. This strategy enables a markedly increased luminophore loading (up to ∼50 wt%) and enhances the birefringence of the LC matrix. As a result, we achieved a notably high |glum| value of 1.25 even in thin cells (2 µm), together with significantly broadened CPL spectra. Furthermore, the emission wavelength was successfully tuned via Förster resonance energy transfer. This work demonstrates a rational design strategy for LC mixtures that yield CPL materials with high |glum|, advances the fundamental understanding of CPL generation in photoluminescent CLCs, and highlights their potential for future photonic and optoelectronic applications.
The performance of organic solar cells (OSCs) is governed by how molecular packing evolves into interconnected networks that facilitate exciton dissociation and charge transport. Using an all-small-molecule blend DR3TSBDT:Y6 as a model system, we study how local molecular stacking evolves into performance-relevant morphology during solvent vapor annealing (SVA) and subsequent thermal annealing (TA). SVA promotes end-to-end stacking of amorphous acceptors to form interconnected fibrils, while TA compacts inter-fibril spacing without disrupting favorable local order. Such molecular-to-morphological refinements broaden light absorption, enhance charge transport, and markedly improve device efficiency. Extending this approach to additional blend systems (D18:Y6, D18:L8-BO, and DR3TSBDT:L8-BO) yields similar structural evolution and performance gains, with the D18:L8-BO system achieving up to 20.10% PCE. Our study establishes control over local stacking in amorphous acceptors into fibrillar networks as a general and effective route to realize high-performance OSCs.
Ischemic stroke inflicts severe neurological damage by disrupting the neurovascular unit. While promising, mesenchymal stem cell (MSC) therapies are hampered by poor posttransplantation survival and nonspecific secretomes. Here, we introduce a bioengineering strategy that employs cadherin-functionalized interfaces to generate cohesive multicellular MSC aggregates (Cad-MAs). Priming MSCs with recombinant N-cadherin and VE-cadherin stimulated endogenous cadherin expression and facilitated the self-assembly of stable spheroids with reinforced intercellular adherens junctions. Cad-MAs exhibited increased resistance to inflammatory stress and anoikis, and secreted a reparative profile enriched in neurotrophic and angiogenic factors, as well as exosomes carrying therapeutic miRNAs such as miR-21-5p and miR-126-3p. The in vitro analyses indicate that cadherin-empowered assembly yields MSC aggregates in which structural stability is coupled with a pro-survival, proregenerative phenotype. Furthermore, in a mouse stroke model, systemically delivered Cad-MAs significantly outperformed conventional dissociated MSCs, promoting functional recovery, reducing infarct volume, and improving cerebral perfusion alongside evidence of enhanced angiogenesis and preservation of blood-brain barrier integrity markers. This approach, termed functional aggregation-induced emergence (F-AIE), provides a versatile framework for engineering integrated cellular therapeutics with tailored functional outputs for regenerative applications.
Circularly polarized luminescence (CPL) materials, which exhibit their unique chiroptical properties, display great potential for applications in optoelectronics and bioimaging. However, it remains a significant challenge to synthesize CPL materials with high dissymmetry factors (glum) and photoluminescence quantum yields (PLQY) simultaneously. Herein, we report a deep-eutectic-solvent (DES)-assisted self-assembly protocol integrated with an active-learning (AL) framework that enables the targeted fabrication of G-quadruplex (G4) supramolecular gels with high glum and PLQY. AL pinpointed the optimal synthesis parameters in just four iterations, dramatically accelerating material development. The top-performing gel achieved a glum of 0.29, setting a new benchmark for nucleoside/nucleotide-based CPL materials. The maximum PLQY reached 10.64%, which represents a substantial level of performance. Furthermore, by integrating SHapley Additive exPlanations (SHAP), we elucidated the relationship between reaction parameters and target properties. Building on this result, we also demonstrated multicolor fluorescence resonance energy transfer (FRET) by incorporating dyes, successfully developing a series of multicolor CPL-active materials. This work not only provides new insights into the design of bio-based chiral CPL materials but also highlights the promising role of artificial intelligence in advancing material development.
Although metal nanoclusters (NCs) are ideal building units, significant challenges remain in manipulating their gathering and tuning the as-obtained aggregate properties. Herein, we introduce an electro-driven strategy and reveal the voltage-dependent assembly on interdigitated microelectrodes based on Au25 NCs: crystallizing at 0.5 V, NC-based filming at 1.3 V, and nanocrystal-based filming at 2.6 V. More interestingly, the film formed at 2.6 V can be varied from an insulator to a conductor, and even such a large conductivity tunability (from ∞ to ∼0.3 Ω) can be extended to the films formed from some other metal NCs such as Ag25, Pt23, and Pd8. The as-obtained films show novel, promising properties not found in molecular NCs, as illustrated by the electrothermy and current-limiting properties. Thus, this work not only provides a novel strategy for metal NCs’ gathering but also pioneers metal NC-based electro-manufacturing for novel findings and potential applications.
Maxillofacial wounds are often deep, irregularly shaped, and prone to scarring, which can cause significant psychological distress. Developing advanced wound dressings to address these issues is therefore very important. This study created a novel two-component zwitterionic hydrogel (PNPs@COL@Gel) by adding cationic polymer nanoparticles (PNPs) and type III collagen (COL), which demonstrates excellent mechanical strength and injectability, allowing it to conform smoothly to irregular maxillofacial wound shapes. In vitro tests showed that the PNPs had synergistic photothermal and photodynamic antimicrobial effects under near-infrared-II (NIR-II) laser irradiation, with killing rates of 96.9% and 97.5% against methicillin-resistant Staphylococcus aureus (MRSA) and Escherichia coli, respectively. The hydrogel also effectively breaks down biofilms and prevents their formation, while COL supports infected wound healing and helps prevent scarring. In vivo studies further demonstrated the therapeutic potential of this zwitterionic hydrogel. Mice with infected maxillofacial wounds healed faster, with the hydrogel penetrating deeply to treat subcutaneous pustular infections. Additionally, the hydrogel modulated the immune environment of wound tissues, encouraged epithelial cell growth, improved blood vessel formation, and greatly reduced scarring. These results offer a promising new approach for achieving scarless healing in maxillofacial wounds.
Therapy-resistant acute myeloid leukemia (AML) depends on mitochondrial oxidative phosphorylation (OXPHOS) to meet its energy demands, and succinate dehydrogenase assembly factor 1 (SDHAF1) is essential for the proper assembly of Complex II in OXPHOS. Targeted inhibition of SDHAF1, therefore, holds great potential for AML therapy, but potent and selective small-molecule inhibitors of SDHAF1 remain to be developed. Herein, we develop cationic tripyrrole oligomers that selectively accumulate in mitochondria, specifically bind to SDHAF1, and suppress Complex II activity, thereby eradicating AML cells and reducing leukemic burden without discernible systemic toxicity, concomitant with the normalization of white blood cells and restoration of neutrophil, erythrocyte, and platelet levels. Meanwhile, the twisted molecular geometry of tripyrrole oligomers endows them with aggregation-induced emission properties, enabling real-time visualization of the therapeutic process. Therefore, these tripyrrole oligomers provide a mitochondria-targeted SDHAF1-directed theranostic platform for eradicating OXPHOS-dependent cancers.
Overexposure to ultraviolet (UV) and high-energy blue-violet light (HEBV) can cause severe skin and eye damage. In this study, lignin-containing cellulose nanofibrils (LCNF) films are prepared from cellulose pulps with varying lignin contents obtained through hydrogen peroxide-acetic acid pretreatment of bagasse. The LCNF films possess excellent hydrophobicity and mechanical properties, as well as certain UV radiation resistance properties, by leveraging the inherent properties of lignin. To enhance the UV shielding performance of LCNF films, blue- and green-emitting carbon dots (BL-CQDs, GL-CQDs) derived from lignin are prepared and incorporated as UV absorbers alongside LCNF to construct sustainable, biodegradable composite films with high-efficiency UV shielding properties, in which lignin-based carbon quantum dot (L-CQDs) are uniformly embedded within the LCNF network via hydrogen bonding. Through the synergistic interaction between lignin and L-CQDs, the UV blocking rate of L-CQDs@LCNF films increased by 8.15%-36.40%, and the HEBV blocking rate increased by 2.95%-41.52% while maintaining excellent visible light transmittance and mechanical properties (with tensile strength reaching up to 82 MPa), compared to pure LCNF films. Simultaneously, by regulating the lignin content in LCNF and the properties of L-CQDs, the films exhibit tunable UV blocking and blue-violet light shielding capabilities. Additionally, the prepared BL-CQDs achieve a fluorescence quantum yield of 31.10%, representing a leading level among lignin-derived CQDs. This study will provide a strategy for preparing transparent and full-lignocellulose films with tunable UV-blocking and blue-violet light shielding properties through a design integrating function and structure.
Metal-organic cages (MOCs) are versatile supramolecular platforms, but their modest binding affinities in aqueous solution limit practical utility. Chiral MOCs with enhanced binding capabilities are highly desirable for diverse applications, yet their synthesis remains challenging. Here, we report an “Axial-Chiral Vertex Integration” (ACVI) strategy, which enables the construction of an enantiopure chiral cage (MOC-2) from a non-chiral Pd6L4 MOC (MOC-1) by substituting two axial Pd vertices with axially chiral BINOL units. This design strengthened the hydrophobic effect of the confined cavity, delivering ultrahigh aqueous binding affinity (up to 109 M−1) for MOCs. At the same time, the integration of a well-defined chiral microenvironment endows MOC-2 with notable enantioselectivity (up to 9.2) and the ability to transfer chirality to achiral guests, producing significant circularly polarized luminescence (|glum| up to 10−3). This strategy provides a powerful blueprint for designing high-affinity chiral MOCs, unlocking opportunities in molecular recognition and advanced chiral functional materials.
Optoelectronic technology plays a pivotal role in energy conversion, information processing, and bioanalysis, where efficient transduction between optical and electrical signals critically depends on materials with strong light absorption, rapid electronic response, and well-controlled optical properties. Chiral metal nanoclusters (NCs), distinguished by their molecular-level structural precision, high photostability, and hierarchical chirality reminiscent of biomolecular architectures, have emerged as promising candidates for optoelectronic applications, in which the multilevel origins of chirality—from the metal core to the metal-ligand (M-L) interface and surface ligands—provide effective means to tailor chiroptical properties and enable enantioselective luminescence and sensing platforms. This review provides a systematic overview of the structural origins, synthetic strategies, and optoelectronic applications of chiral metal NCs. The discussion outlines the multilevel origins of chirality in NCs architectures, followed by recent advances in enantioselective synthesis. Subsequent sections focus on their applications in chiral sensing, circularly polarized luminescence (CPL), and the emerging opportunities in chiral electrocatalysis inspired by the chiral-induced spin selectivity (CISS) effect. The insights summarized here aim to guide the rational design of chiral metal NCs and to advance their integration into optoelectronic systems with enhanced chiral functionality.
Polymer-based materials, from composites to hybrid ones, are part of our daily life, contribute to fundamental societal advancements, and showcase increasingly complex design, so that seizing their microscale properties poses new and unmet challenges. Monitoring polymer chain mobility is a fundamental task to understand materials properties, but despite promises, luminescence methods are currently applicable only within narrow experimental conditions. We describe an aggregation-induced emission (AIE)-based fluorescent rotor showing unique temperature-independent photophysics that stands out as universal probe for polymer relaxation time and viscosity, correlated to macromolecular chain mobility: Its fluorescence lifetime is independent on the polymer chemical nature and on temperature, while being highly sensitive to the low mobility regime typical of cooperative segmental motions of rubbery polymers, close to the glass transition. The calibration curve obtained with five different polymers allows even nonexperts to assess local mobility in polymers with a single measurement. Fluorescence lifetime imaging microscopy (FLIM) yields quantitative mobility maps of complex and dynamic materials with sub-micrometric resolution. This robust and versatile tool allows access to polymer dynamics even in complex and responsive materials, in a broad temperature range, in real space and time.
Electrochemiluminescence (ECL) populates the luminescent excited states through electrochemical reactions. It is challenging to mediate the ECL behaviors of molecular nanoaggregates because both the photophysical and electrochemical properties usually deteriorate in aggregate states. In this work, we demonstrate an unprecedented supramolecular strategy that simultaneously modulates both the photophysical and electrochemical factors governing ECL. The ECL performance of rubrene (RUB) nanoaggregates can be significantly enhanced through the incorporation of hole-transporting molecules as both redox and photophysical mediators. A balanced state, inhibiting the singlet fission (SF) and retaining the triplet-triplet annihilation (TTA), was achieved for RUB, which not only reduced the quenching of luminescent singlet state excitons but also well utilized the electrochemically generated triplet state excitons. The redox-mediating properties of hole-transporting molecules toward co-reactant not only promote the formation of excitons but also reduce the luminescent potential. The RUB nanoaggregates showed significantly enhanced photoluminescence quantum efficiency (2.3-fold) and ECL intensity (50-fold) in aqueous conditions and were demonstrated as promising ECL imaging probes. This work opens up a new avenue for the preparation of ECL nano-emitters with high-brightness in aqueous conditions.
Over 40 amyloidogenic proteins have been identified to cause amyloidosis diseases in clinics. Tissue deposition of amyloid proteins entangled with interacting partners is a characteristic pathological hallmark of amyloidosis diseases. However, the proteomic complexity of co-aggregated amyloid deposits poses a clinical challenge to diagnose the exact disease-causing pathogenic proteins in patients’ biopsied tissue. Herein, we present a photocatalytic proteomic method, named Amyloid-ID, as a promising approach to identify the composition of amyloid deposits for clinical proteotyping of amyloidosis diseases. Amyloid-ID is enabled by a photosensitized probe analogous to a pan-amyloid sensor, Thioflavin T. We show this probe photocatalyzes protein labeling via reactive oxygen species and demonstrate its applicability in both AD mouse models and human laryngeal samples. Next, we exemplify its utility by proteotyping the pathogenic protein underlying the rare laryngeal amyloidosis (LA). Using patients’ biopsied tissue sections, we label, enrich, and profile the amyloid deposits. Proteomics analysis top-ranks fibrinogen as a potential pathogenic protein. Biochemical and biophysical characterizations confirm that fibrinogen can aggregate into amyloid fibrils. Intriguingly, we observe that fibrinogen's fibrillation is sensitive to mechanical forces, particularly impacted by sonication. Such observation coincides with its primary larynx deposition, where frequent vocal cord friction occurs. Overall, given the photocatalytic properties, our Amyloid-ID serves as a promising clinical proteotyping method for amyloidosis diseases.
Gold nanocluster (NC)-induced ferroptosis has emerged as a promising method for malignant tumors. However, the immune clearance and suboptimal reactive oxygen species (ROS) generation efficiency have limited its clinical application. Here, we engineered macrophage-membrane-coated gold nanocluster@nanoflower (CM-NC@NF) nanocomposites to address these challenges. In vitro studies demonstrated that the combination of NC and NF significantly enhanced ROS generation (∼9 times than NC), GSH depletion, and photothermal therapy (PTT) under laser irradiation, therefore promoting apoptosis in both 4T1 and MCF-7 cells. Furthermore, experimental evidence demonstrates that macrophage membrane encapsulation enables CM-NC@NF to evade clearance by immune cells. In the murine breast cancer model, CM-NC@NF exhibited significant tumor accumulation 4 h post-intravenous administration. Subsequent laser irradiation induced robust ROS generation and PTT within the tumor, leading to a tumor inhibition rate 5.7 times higher than that achieved with CM-NC alone. This therapeutic efficacy was further validated in an intra-tumoral injection experiment, showing a tumor inhibition rate 5.4 times higher than that of CM-NC alone. This multimodal strategy synergizes ferroptosis-like therapy with PTT, holding significant therapeutic promise for precision breast cancer treatment.
The explosive growth of artificial intelligence has intensified demands for new computing paradigms beyond conventional von Neumann architectures. In response, brain-inspired computing-in-memory technologies are emerging as a promising path forward. Here, we designed a two-terminal optical synaptic device utilizing organic heterojunctions doped with gold nanorods (AuNRs), leveraging the electric field enhancement innate to the localized surface plasmon resonance (LSPR) effect. The device doped with 1 wt% AuNRs demonstrates a markedly enhanced light absorption capacity in the near-infrared (NIR) region of 808 nm. The generation rate of photogenerated excitons increases by 16.8%, while the probability of exciton dissociation rises by 8.4%. The paired-pulse facilitation (PPF) index reaches 114.6% (Δt = 1 s), indicating heightened sensitivity to optical pulse parameters. Additionally, Hall effect measurements were performed to characterize the electrical properties of the PEDOT:PSS:AuNRs films. The carrier mobility of the doped films increased 20-fold compared to pristine PEDOT:PSS due to electron injection from AuNRs. This enhanced mobility contributes to faster synaptic response and higher conductance tunability in the synapse device, further supporting its performance in neuromorphic computing tasks. Furthermore, we successfully simulated the dynamic “learning-forgetting-relearning” processes associated with human visual memory. By exploiting the tunable conductance of the optimized synaptic device, we implemented both convolutional neural networks (CNNs) and convolutional spiking neural networks (CSNNs) for weight updates. After 100 and 150 training epochs, the system achieved recognition accuracies up to 98.57% for handwritten digits and 92.01% for dynamic gestures. This work presents an effective plasmon-doping approach to enhancing the performance of organic memristors and can be extended to other material systems.
Engineering biomaterials that actively interface with and instruct their biological milieu have given rise to a new generation of platforms for tissue repair and companion diagnostics. Among them, aerogel scaffolds, with their ultra-porous architecture, ultralow density, tunable mechanics, and versatile chemistries, have emerged as transformative candidates capable of emulating and interpreting extracellular environments. This review highlights up-to-date advances shaping the landscape of aerogel-based scaffolds in tissue repair and diagnostic applications. We first summarize emerging fabrication and assembly strategies, including sol-gel processing, freeze-drying, electrospinning, and 3D printing, which unlock hierarchical morphologies and bioinspired features. The recent implementations of intelligent aerogels for tissue repair and neuroregeneration are then highlighted, together with related applications in bioactive functionalization, immune modulation, wound healing, sustained drug delivery, and moist repair dressings. Meanwhile, we outline aerogel-based disease diagnosis regarding genotypic physiological cues, focusing on faithfully detecting nucleic acids, tumor biopsy, virus antigen testing of infectious disease, and state-of-the-art demos with innovative signal transduction mechanisms. Data-driven strategies powered by machine learning are also reviewed, alongside integration into smart wearables for self-adapting, responsive platforms. Finally, persisting challenges and present perspective of aerogel scaffolds in medicine research and practice are also discussed.
Spatiotemporal profiling of nuclear-associated proteomes is crucial for elucidating disease mechanisms, identifying key therapeutic targets, and guiding the design of effective drugs. Currently, proximity labeling (PL) using genetically transfected enzymes or photocatalyst-based probes has emerged as a powerful tool for proteomic mapping. However, these approaches are limited by their incompatibility with hard-to-transfect cells and primary tissues, as well as by the lack of efficient nucleus-targeting strategies. In this study, we developed a photocatalytic PL strategy (Pc-PL) that enables efficient enrichment of nuclear-associated proteins by combining a nucleus-targeted photosensitizer (NCP) with photocatalysis-mediated reactive biotin labeling. Compared with traditional photocatalysts such as chlorin e6 and rose Bengal, NCP exhibited superior nuclear accumulation across various cell types. Cellular experiments confirmed that NCP-mediated photoactivation precisely localized biotin labeling within the nucleus, enabling selective enrichment of nuclear proteins via subsequent streptavidin-based magnetic capture. Coupling Pc-PL with quantitative mass spectrometry enabled highresolution mapping of nuclear proteomes and led to the discovery of previously unrecognized senescence-associated regulators, including TMPO. Collectively, these findings establish Pc-PL as an innovative and versatile tool for highresolution nuclear proteomics, offering broad potential for target discovery and drug development.
The thiolate (RS)-protected neutral gold cluster Au25(SR)180, which has an icosahedral Au13 core, is regarded as a superhalogen due to its comparably high electron affinity (EA) to those of halogen atoms. Here, the EAs of Au13 superhalogens protected by various thiophenolate derivatives were determined by using gas-phase photoelectron spectroscopy of the corresponding anions [Au25(SR)18]−. Correlation analysis revealed a linear relationship between the EA and the dipole moment of the RS ligands. The relationship can be explained by the concept of surface potential, which has been widely used to describe changes in the work function of bulk metals modified by self-assembled monolayers. Based on these results, we propose a unified design principle of ligand for tuning the EA of the Au13 superhalogen.
There is an urgent need to develop innovative therapeutic strategies for hepatocellular carcinoma (HCC) treatment with severe hypoxia. Covalent organic frameworks (COFs) hold promise for photodynamic therapy (PDT), yet their antitumor efficacy is limited by the hypoxia intolerance of type II PDT. Herein, we report a COF-based nanoplatform grafted with type I photosensitizer (Enbs-Ar-NH2) and co-loaded with lenvatinib (Len) and curcumin (Cur), enabling concurrent type I PDT and chemotherapy (CT). The platform is conjugated with galactose (GalNAc) and RGD peptides, denoted as LC@GR-COF-E, which achieves dual-targeting toward hepatocytes via ASGPR recognition and tumor-associated endothelia binding. In vitro results demonstrate that the combination of Len and Cur effectively suppresses tumor cell proliferation. Importantly, LC@GR-COF-E can be activated to eradicate hypoxic tumor cells via oxygen-independent type I PDT under NIR irradiation. LC@GR-COF-E/NIR exhibits potent anti-metastatic effects, particularly against HCC cancer stem cell-like cells (C5WN1), by downregulating MMP-2 and MMP-9 and modulating epithelial-mesenchymal transition (EMT)-related protein expression (N-cadherin). In a subcutaneous C5WN1 hypoxic tumor-bearing mouse model, the platform achieves a tumor inhibition rate of 95.5% ± 1.7%, offering a powerful strategy to overcome HCC hypoxia barriers. Our work pioneers a COF-based type I PDT platform for precise therapy against hypoxic HCC.
Manganese (Mn)-based halide perovskites have attracted tremendous attention due to their low-cost and environment-friendly characteristics. Nevertheless, their applications are hindered by limited photoluminescence (PL) efficiency and insufficient stability. Dimensional engineering offers a viable pathway to modulate their photophysical properties and enhance their robustness. Herein, we design 2D@3D perovskites based on the dimensional reduction of CsMnCl3·2H2O 3D perovskites via alternating cation interactions (ACIs) by employing chitosan as a polymeric spacer cation. ACI effectively stabilized the 2D@3D perovskite and passivated surface defects through enriched H-bonding. As such, the PL intensity can be boosted by 50 times with a PL quantum yield (PLQY) of 18.1%. Intriguingly, 2D@3D perovskites experienced valence transition (VT: Mn2+ → Mn4+) at high temperatures, resulting in NH4CsMnCl6 perovskite. Density functional theory calculations indicated that an interfacial orbital hybridization-driven reaction mechanism triggered VT, which was initiated by the synergistic effect of octahedral distortion and ACI within 2D@3D perovskite. Notably, the proposed VT perovskites exhibited narrowband emission of Mn4+ with remarkable air-, photo-, and thermally stability, achieving a PLQY up to 80.7%. This approach paves the way for exploring organic-inorganic interactions in designing highly luminescent Mn-based perovskites.
In-situ X-ray diffraction (XRD) of metal-organic framework (MOF) provides unique insights into the correlation between the dynamic structural transformation and the photophysical evolution under external stimuli. Herein, we present MOF TCPE-Tb from the butterfly-shaped ligand H4TCPE [1,1,2,2-tetra(4-carboxyphenyl)ethylene], which exhibited the exceptional stability (up to 500 K and 24.6 GPa). The fluorescence evolution of TCPE-Tb directly reflected the orientation of the tetraphenylene (TPE) core with the stimuli of temperature and pressure. In the temperature range of 80-460 K, TCPE-Tb underwent a symmetric transition from P21/n to P21/m and a non-monotonic fluorescence trend (intensity: decrease-increase-decrease, maximum emission wavelength: 502 nm to 486 nm). In contrast, externally applied pressure shortened the intermolecular distances of the TCPE ligand, resulting in π-π stacked excimers that triggered a 100 nm red shift (480-580 nm) with the colors blue, blue-green, green, yellow-green, and activated excimer-mediated decay pathways. For the first time, in-situ temperature-dependent single-crystal XRD and in-situ high-pressure spectroscopy revealed the underlying relationship of the detailed conformational dynamics of the TCPE ligand (dihedral angle evolution) with the photophysical behavior under the external stimuli. The responses of TPE core to the thermal- and mechanical-stimuli were completely distinct, the intramolecular torsion vs. the intermolecular packing. This work established a design paradigm for mechanically robust, stimuli-responsive MOFs, advancing the applications in multimodal sensing and adaptive optoelectronics.
N-oxides, characterized by a highly polar N+-O− bond, have recently demonstrated rapidly growing applications in biomedicine and material science due to their high solubility and redox activity. However, the chemical and physical properties of the N-oxide have not been fully studied, limiting its advanced applications. Herein, we report the unprecedented observation that N-oxide could undergo structure-dependent aggregation. This observation is initiated by the appearance of dimers and trimers of a model compound, (4-piperidinophenyl)methanol N-oxide, in mass spectrometry. More convincingly, when it is conjugated with tetraphenylethylene (TPE) derivatives via the benzyloxy group, 4-piperidinobenzyl N-oxide promotes the aggregation and fluorescence emission of the resulting conjugate, though it is highly polar. This observation of aggregation is further confirmed by the morphology study via scanning electron microscopy. Interestingly, no aggregation is observed when N-oxide is conjugated directly to TPE, indicating that N-oxide-induced aggregation is structure-dependent. Based on these fundamental observations and studies, we develop a novel heme-targeting probe that can specifically and sensitively detect the level of total heme in the plasma from hemolytic mice to distinguish hemolysis. Altogether, these findings will advance our understanding of structure-dependent aggregation of the N-oxide and help to bring new insights into its application in biomedicine and material science.