The interactions between building units govern both the structural integrity and processability of porous materials. This study introduces a new class of porous framework materials constructed through precisely modulated ion–dipole interactions, which overcome the challenges posed by the strong solvation effects and non-directionality of alkali metal ions. We employ an assembly strategy employing anionic silicate R[SiO4]− clusters as structural units, where their high charge density and optimal Lewis basicity enable efficient cation binding, even in competitive solvent environments. Single crystal X-ray diffraction (SCXRD) reveals well-defined silicate cage-based framework architectures, while comprehensive characterization demonstrates the simultaneous retention of molecular-scale host-guest recognition in solution and framework-level gas adsorption properties in the solid state. One of the silicate cage-based framework, MeSi-K, exhibits exceptional separation potential for C2H2/C2H4 with an IAST selectivity reaching as high as 7.2, benefiting from electrostatic interactions and π-complexation between C2H2 and the alkali metal ions. The crystallinity porous solid, exhibiting selective gas separation performance, can be easily regenerated through solvent removal. This work establishes a new paradigm for utilizing ion–dipole interactions to construct porous materials, opening exciting possibilities for developing multifunctional materials with tailored properties.
Photodynamic therapy (PDT) holds great promise for treating periodontitis, yet its clinical efficacy is limited by the lack of specificity of conventional photosensitizers toward pathogenic bacteria. Herein, we developed a targeted photosensitizer system using a host–guest supramolecular strategy to address this challenge. The design features a selenoviologen cyclophane (SeVB) host molecule that encapsulates a Porphyromonas gingivalis (P. gingivalis)-specific binding peptide (PQGPPQF, abbreviated PQ), forming the supramolecular complex SeVB⊃PQ. Leveraging the high affinity of PQ for P. gingivalis fimbriae, SeVB⊃PQ demonstrates exceptional bacterial targeting capability, achieving a colocalization coefficient of 0.669. Upon light activation, SeVB⊃PQ generates elevated intracellular reactive oxygen species while disrupting adenosine triphosphate synthesis in P. gingivalis, resulting in a 33.12% enhancement in antimicrobial activity compared to SeVB alone at 0.1 µM. Beyond its direct bactericidal effects, SeVB⊃PQ-mediated PDT effectively restores subgingival microbiome homeostasis and attenuates microbial pathogenicity through metabolic modulation. In comparative studies with both SeVB and clinical-grade methylene blue (MB), SeVB⊃PQ demonstrated superior performance in mitigating inflammatory tissue damage and promoting periodontal regeneration. This targeted supramolecular platform not only advances PDT for periodontitis treatment but also provides a novel paradigm for the rational design of pathogen-selective photosensitizers.
Carbon dots (CDs) have emerged as a promising platform for constructing optoelectronic devices. However, the synthesis of multicolor CDs with high quantum yield (QY) and the elucidation of their luminescence mechanisms remain challenges. Here, we successfully synthesize RGB-CDs by precisely controlling the ratio of o-phenylenediamine and phytic acid. The QYs of the RGB-CDs are up to 60.3%, 68.7%, and 19.0%, respectively. Experimental data and DFT calculations reveal that the fluorescence emission of the RGB-CDs originates from molecule state (5,14-dihydroquinoxalino[2,3-b] phenazine), carbon core state, and clusteroluminescence state induced by the through-space interactions of heteroatom groups, respectively. Moreover, leveraging the outstanding fluorescence properties of the RGB-CDs, we fabricate both a white light-emitting diode (WLED) with an ultra-high color rendering index of 98 and a luminescent solar concentrator achieving a high power conversion efficiency of 1.6%. Finally, we integrate a self-powered lighting system combining the WLED and LSC, which provides approximately 6 h of continuous illumination to a 0.1 W WLED after a single day's charging. Our results demonstrate a facile method for preparing multicolor CDs with high QYs, enabling their use as phosphor sources for various optoelectronic device applications.
Chiral nanomaterials have recently stimulated significant interest in both fundamental research and practical applications (e.g., nanoprobes for biomolecular recognition). However, achieving chiral nanoclusters is still a major challenge. Herein, we report an effective strategy that affords achiral diphosphine ligand-protected, chiral Au11 nanoclusters. Synchrotron radiation X-ray diffraction solves the chiral structure of Au11(dppp)5Cl3 (dppp = 1,3-bis(diphenylphosphino)propane) and further reveals that the critical feature of bidentate binding of diphosphine induces the unique ansa-metallamacrocycle pattern (i.e., the “Au─P─CH2CH2CH2─P─Au” staple). All the possible ansa-metallamacrocycle patterns are transferred to the most robust pattern by “ligand confinement,” giving rise to the chiral enantiomers. Using Density Functional Theory (DFT), we show that the chirality can emerge due to the low energy barriers facilitating the transformation of the symmetric Au11 core into the corresponding asymmetric chiral cluster, driven by a favorable fit of ligand bridges. This new type of chiral nanomaterial holds promise in chiral sensing/recognition and enantioselective applications.
Achieving multicolor, precisely tunable cluster-induced emission in nonconjugated polymers remains a considerable challenge. Herein, we present a generalizable and scalable methodology for fabricating monodisperse, color-tunable clusteroluminescence (CL) microspheres, enabling multimodal color tuning across the spectrum from blue to orange-red through precise control of monomer type and ratio, sulfonation time, and pH conditions. Density functional theory (DFT) simulations demonstrate that conformational rigidity, resulting from the synergistic combination of prevalent hydrogen-bonding interactions, short interatomic contacts, and oxygen cluster formation, significantly enhances emission efficiency, leading to dual broadband visible emissions across the 400–700 nm wavelength range. The optimized sulfonated poly(divinylbenzene-styrene-methyl methacrylate) microspheres with 30% methyl methacrylate (MMA) content (SPSMMAs-30) exhibit excellent monodispersity and strong fluorescence across 13 standard channels of flow cytometry, with fluorescence coefficient of variation (CV) values consistently below 3%, fulfilling requirements for routine flow cytometer calibration. Compared with commercial calibration microspheres, SPSMMAs-30 show significantly higher photobleaching resistance and long-term environmental stability. Significantly, this protocol enables the first kilogram-scale synthesis of CL microspheres with highly reproducible optical properties. Furthermore, SPSMMAs-30 demonstrate sensitive tetracycline detection and promising performance in multicolor anticounterfeiting applications, substantially broadening the scope of nonconjugated CL materials for biomedicine, diagnostics, and materials science.
Mercury ions present severe threats to both human health and the environment, making their detection of paramount importance. Here, we innovatively designed and synthesized coumarin derivative–based probe TXDS. By virtue of the robust interaction between the thiocarbonyl moiety of TXDS and Hg2+, which effectively regulated intramolecular conformational locking, a superior aggregation-induced emission (AIE) characteristic was successfully constructed. Probe TXDS, coupled with 100 nm Stokes shift, enabled highly sensitive and selective detection of Hg2+ within the concentration range of 0.1–10 µM. In addition, probe TXDS demonstrated excellent solid–liquid dual-mode detection capability for Hg2+. Colorimetric sensing extended the detection range of Hg2+ by 10-fold, realizing the complementary advantages of the wide dynamic range of colorimetry and the high sensitivity of fluorimetry. Mechanochemical treatment, involving grinding TXDS with soil samples, achieved visual analysis of Hg2+ within 20 s, highlighting the green, efficient, and cost-effective nature of this approach. Moreover, the dye TXDO exhibited tunable piezochromic behavior, offering potential applications in forensic identification and information encryption.
Natural antimicrobial peptides (AMPs) encounter significant challenges in transitioning to clinical application, primarily due to low bioactivity, high toxicity, and poor stability. This study proposes a strategy to enhance the stability of AMPs through molecular assembly while exploring the advantages of the newly designed self-assembled peptides compared to unimer peptides. We conducted a comprehensive investigation of antimicrobial activity, biocompatibility, in vitro stability, and particularly protease stability, aiming to develop highly efficient and stable designer peptides as alternatives to traditional antibiotics. A series of designer peptides with self-assembling capabilities was constructed by attaching various hydrophobic scaffolds to an enzyme-resistant short peptide sequence. The self-assembled designer peptide Pba* with 1-pyrenebutyric acid (Pba) as the hydrophobic scaffold exhibited the highest antibacterial activity (GMMIC = 2.88) and the greatest clinical potential (GMSI = 44.44), while maintaining excellent biocompatibility and physiological stability. Mechanistic studies revealed that Pba* self-assembled into spherical micelles and nanofibers, trapping bacteria and disrupting cell membranes, interfering with respiration and energy metabolism. Notably, Pba* displayed negligible toxicity and alleviated bacterial infections in mice. This study paves the way for the development of highly effective antimicrobial materials.
Immunotherapy has emerged as one of the most promising strategies for achieving complete tumor eradication. However, its effectiveness against solid tumors remains limited due to the presence of an immunosuppressive tumor microenvironment. In addition, severe side effects such as cytokine storms further constrain its clinical application. Therefore, there is an urgent need to develop efficient and controllable immunotherapeutic approaches. Herein, we report the development of a novel mitochondrial DNA-releasing photosensitizer, MQ-PPy, which exhibits outstanding mitochondrial localization and robust reactive oxygen species generation. Upon light irradiation, MQ-PPy induces pronounced mitochondrial oxidative damage in tumor cells, triggering the release of immunogenic damage-associated molecular patterns and mitochondrial DNA, which activates the cGAS-STING signaling pathway. Meanwhile, MQ-PPy effectively induces immunogenic cell death, thereby remodeling the tumor immune microenvironment and enhancing antitumor immune responses. In vivo studies confirmed that MQ-PPy-mediated photodynamic therapy significantly inhibits tumor growth and notably increases the infiltration of cytotoxic T cells within the tumor. Moreover, we demonstrated that tumor cells treated with MQ-PPy-mediated PDT can function as a whole-cell vaccine, effectively establishing systemic immune memory and significantly suppressing tumor growth upon rechallenge. This study presents a promising and controllable strategy for advancing tumor immunotherapy through mitochondria-targeted photoactivation.
Mitochondria-targeted aggregation-induced emission (AIE) materials have emerged as promising candidates for precision medicine by enabling the controllable induction of oxidative stress within mitochondria. Yet, a comprehensive overview of the antitumor and other biological effects resulting from such oxidative stress remains lacking. This review summarizes the roles of both excessive and moderate oxidative stress triggered by mitochondria-targeted AIE materials across diverse applications, including: (1) direct induction of various forms of cancer cell death and degradation of cancer-associated proteins; (2) synergistic enhancement of chemo-, radio-, immune-, and other therapies; and (3) treatments beyond cancer. In addition, the challenges and key issues limiting their broader application are discussed. This review highlights the therapeutic potential of controllably induced oxidative stress by mitochondria-targeted AIE materials, aiming to accelerate their development for precise disease intervention and biological regulation.
Atomically precise metal nanoclusters have emerged as versatile photocatalysts for photo-induced organic reactions owing to their unique photophysical properties, such as broad absorption cross-section, long excited-state lifetime, and tunable excited-state energy and redox ability. Exploiting metal nanoclusters in photocatalytic synthetic organic chemistry has not only provided fresh opportunities to expand the potential applications of these emergent nanomaterials but also offered a compelling alternative catalyst system for fine chemicals synthesis. This review outlines the recent advancements in synthetically useful photocatalytic organic transformations enabled by metal nanoclusters. We begin our discussion with a brief introduction of metal nanoclusters and the fundamental principles of photocatalysis. Then, we discuss the progress in metal nanocluster-mediated photocatalytic organic transformations involving energy transfer and electron transfer, sequentially, with a highlight on the underlying reaction mechanism. At the end, an outlook on the potential future direction in this field is provided.
Stacking angles played a decisive role in the coupling strength of the excited state, the overlap of electronic orbitals, and behavior of excitons, which further have ultimately affected the luminescent properties. However, developing effective strategies to precisely tailor molecular stacking anglets of chromophores still remains challenges. In this work, we constructed a series of figure-eight supramolecules S1–S3 through the coordination-driven self-assembly of anthracene-based 180° di-platinum(II) acceptor L and ditopic pyridyl ligands L1–L3, respectively. Variation in ligand length enabled regulation of intramolecular anthracene stacking angles in the assembled structures and photoluminescent properties. Photophysical studies revealed that larger stacking angles significantly enhance fluorescent intensities and photoluminescence quantum yields in both solution and solid states. Femtosecond transient absorption spectroscopy further demonstrated that the excited-state lifetimes of S1–S3 were extended due to suppressed non-radiative decay pathways. Moreover, density functional theory calculations showed that the increasing stacking angles weakened intramolecular anthracene interactions, leading to enhanced radiative transition rates. This study elucidated the relationship of molecular packing and luminescent properties, which will pave the way for construction of materials with excellent luminescent performance.
The precise control of supramolecular assembly to achieve multifunctional integration remains a significant challenge in materials science. In this study, we synthesized a novel, previously unreported AIE-active molecule (BA) through an exceptionally simple procedure. Subsequently, we constructed two cucurbituril-mediated assemblies (Q[8]-BA and Q[10]-BA) using BA as the building block. These assemblies were systematically investigated for their differences in ion recognition, cellular imaging, and cytotoxicity. The Q[8]-BA assembly exhibited enhanced fluorescence intensity, pH sensitivity, and high specificity for Co2+ detection (LOD = 4.8 × 10−7 M), making it a promising candidate for environmental sensing and cell imaging. In contrast, the Q[10]-BA assembly demonstrated selective cytotoxicity toward melanoma cells while protecting normal cells, highlighting its potential in cancer theranostics. These findings reveal the critical role of cavity size and assembly mode in regulating material properties, providing new insights for designing multifunctional supramolecular systems with tailored functionalities for environmental monitoring and biomedical applications.
Room-temperature phosphorescence (RTP) materials are a significant research field for anti-counterfeiting, bioimaging, and optoelectronic devices, but anti-Kasha RTP still lacks clear molecular design strategies, and conventional rigid polymer matrices fail to break Kasha's rule. To address these issues, this work proposes an acceptor dendronization strategy to synthesize the dendrimer emitter dTC-BPSAF. Carbazole dendrons regulate triplet hybridization, enabling dTC-BPSAF to form near-degenerate lowest triplet (T1) and high-lying triplet (T2) states with hybrid local-charge transfer (HLCT) character and large spin-orbit coupling. Integrating dTC-BPSAF into rigid polymers further stabilizes T2 by suppressing non-radiative decay. Temperature-dependent time-resolved phosphorescence spectra and transient absorption spectra confirm that rigid matrix-based films exhibit thermally activated endothermic T1→T2 up-conversion and dual-band anti-Kasha RTP. In contrast, a moderately rigid polymer matrix shows weak T2 emission, while a soft polymer matrix only produces T1 emission. This study establishes a dendrimer-matrix synergy strategy combining molecular-level triplet engineering, providing a generalizable approach for efficient anti-Kasha RTP materials and new avenues for advanced photonics.
Supramolecular assembly is a versatile bottom-up strategy for creating advanced functional materials. Metallic platinum–platinum (Pt···Pt) interactions provide a distinctive driving force for supramolecular assembly due to their strong, directional, and long-range nature. Despite their importance, the microscopic dynamics underlying the self-assembly of Pt(II) complexes remain challenging to probe experimentally. Molecular dynamics (MD) simulations can capture these processes at atomic resolution, but extracting kinetic pathways is complicated by the indistinguishability and permutation of identical monomers within self-assembled structures. In this study, we employ GraphVAMPnet, a deep learning framework based on graph neural networks (GNN), on extensive MD simulations of amphiphilic PtB complexes during the early stage of self-assembly. GraphVAMPnet inherently accounts for permutational, rotational, and translational invariance, making it well-suited for analyzing self-assembly dynamics. Our analysis reveals three slow collective variables (CVs) that govern PtB self-assembly. The slowest mode (CV1) separates two distinct kinetic growth routes: an incremental growth mechanism, in which single monomers join existing aggregates with predominantly antiparallel packing between two adjacent PtB complexes (CV3), and a hopping growth mechanism, in which clusters of smaller size merge via heterogeneous collisions, yielding a mix of antiparallel and parallel packing arrangements (CV2). Further energetic analysis indicates that incremental growth is favored, potentially leading to the well-ordered nanosheet morphologies observed experimentally. Our findings provide molecular-level insight into PtB self-assembly pathways and showcase the capability of GraphVAMPnet in dissecting the complex dynamics of supramolecular assembly.
The management of iodine species, notorious for their environmental persistence and health risks, requires innovative materials capable of efficient capture and conversion. Herein, we report the self-assembly and characterization of a Zr-based metal–organic tetrahedron (1) functionalized with redox-active triazatriangulenium (TATA+) panels. The cage exhibits a high binding affinity for triiodide (I3−) (ca. 106 M−1) in methanol. The strong host–guest complexation significantly facilitates the disproportionation hydrolysis of I2 to generate I3− and HOI. It also enables photocatalytic aerobic oxidation of I− into I3− within its cavity. Mechanistic investigations revealed the key steps involving guest-to-host photoinduced electron transfer (ET) to generate radicals I• and 1• and ET from 1• to dioxygen to generate superoxide. Solid-state adsorption experiments showed the rapid removal of I2 and I3− from water by 1-NTf2 because of the high affinity for polyiodides. Importantly, although solid-state 1-NTf2 has no ability to directly adsorb I− from water, we have for the first time developed a light-driven strategy that enables removal of I− through coupled photooxidation and sequestration. This work highlights the significant potential of integrating photoredox-active moieties within stable metal–organic cages for controlling iodine binding and speciation and opens new avenues to address environmental and energy-related sequestration challenges.
Organic photothermal materials based on conjugated structures hold great potential for solar harvesting but are often constrained by narrow absorption and limited solar–thermal conversion efficiency. A general molecular design strategy that can simultaneously broaden absorption and enhance nonradiative decay remains elusive. Here, we pioneer a quinoid–donor–acceptor (Q–D–A) architecture specifically tailored for photothermal applications. Incorporating quinoidal unit into a D–A polymer backbone yields the novel polymer PAQM-TBz, which exhibits a reinforced backbone planarity, intensified π–π interactions, and enhanced diradical character compared with its D–A analogue, P2T-TBz. These synergistic features enable broadband absorption (400–1500 nm) and rapid nonradiative relaxation, yielding an outstanding photothermal conversion efficiency of 80.6% under 808 nm laser irradiation—nearly twice that of P2T-TBz. Under 1.0 kW m‒2 simulated sunlight, PAQM-TBz achieves a record-high solar-to-vapor efficiency of 97.3% with an evaporation rate of 1.41 kg m‒2 h‒1. It also generates a peak thermoelectric voltage of 126.1 mV, and in integrated water–electricity cogeneration, attains an evaporation rate of 1.28 kg m‒2 h‒1 and a voltage 95.8 mV, ranking among the highest for organic materials. This work establishes the Q–D–A strategy as a transformative platform for advanced solar–thermal energy conversion and multifunctional solar-harvesting applications.
Biomolecular condensates play crucial roles in cellular physiology and are implicated in neurodegenerative diseases and cancer. However, the mechanisms governing their formation and spatial organization remain poorly understood, largely due to technical challenges. Here, using FUS as a paradigmatic system, we reveal how single-protein sequences determine condensate architecture that is intrinsically linked to biological function. We demonstrate a domain-specific preferential distribution organization: the low-complexity domain (LCD), which drives condensate formation, localizes to the inner layer, while the RNA recognition motif (RRM) preferentially occupies the interfacial layer. This spatial arrangement enhances RNA-binding accessibility, suggesting a direct structure–function relationship. We further propose a sequence–structure–function paradigm for biomolecular condensates: through the cooperation emerging from multiple “stickers,” individual domains function as integrated units in shaping the structure and functionality of biomolecular condensates, which may represent a broader mode of protein–protein interaction (PPI) within condensates. Our findings elucidate the evolutionary logic of protein sequences in driving liquid–liquid phase separation (LLPS) and provide a foundation for designing therapeutics targeting aberrant condensates in disease.
The synthesis of chiral unsubstituted poly(para-phenylene) (PPP) chains has remained elusive for decades, with the production of high-molecular-weight PPP still inaccessible to date. Drawing inspiration from the intrinsic structural chirality of cellulose nanocrystals (CNCs), which plays a crucial role in their self-assembly, we propose a novel strategy to address this synthetic obstacle by effectively immobilizing PPP on individual CNCs. This approach leverages intermolecular forces between CNC and PPP, including the CH–π interaction between the CH group of the pyranose ring and the aromatic ring of the PPP building block, as well as hydrogen bonds formed between the boronic acid groups of the PPP oligomers and the hydroxyl groups of the glucose units within the CNC structure, thereby facilitating the chirality transfer from CNCs to PPP chains. PPP immobilized on the CNC surface exhibits right-handed intrachain helical self-assembly and interchain helical π-stacking, with the degree of polymerization reaching up to 80.2. This helical organization of PPP further laterally demonstrates the right-handedness of individual CNCs in their undried state. Furthermore, suspensions, powders, and films composed of chiral CNC–PPP clusters exhibit pronounced fluorescence, structural coloration, chirality, and circularly polarized luminescence. This work opens novel insights and strategies for inducing chirality into polymer chains via transferring chirality from the nanoobject surface to prepare various chiral assemblies of nanoparticles or conjugated polymers.
Apoptotic vesicles (ApoVs) are membrane structures formed during cell apoptosis and play crucial roles in homeostasis maintenance, signal transduction, and immune regulation. Importantly, ApoVs inherit the properties and contents of parental cells that show great potential in the diagnosis and treatment of diseases. Monitoring the formation process of ApoVs (such as quantity, morphological changes, release rules, etc.) can reveal the regulatory mechanism of apoptosis, and is also helpful for optimizing the preparation and application of ApoVs. However, due to the limitations of existing technologies, the formation processes of ApoVs have been challenging to precisely and entirely capture. Herein, we subtly constructed a versatile AIEgen (ADTP) that could induce ApoVs production and in situ monitor the formation process, and it was successfully applied to explore the formation mechanism of ApoVs. ADTP specifically targeted the plasma membrane, and it could effectively induce apoptosis under laser irradiation, so it was able to dynamically monitor the entire formation process of ApoVs and had validated ApoVs formation from membrane protrusions (including filopodia, tunneling nanotubes, and retraction fibers). Further investigation revealed that ApoVs derived from membrane protrusions with different components exhibited significant heterogeneity. Additionally, the near-infrared emission characteristic of ADTP was compatible with the stimulated emission depletion (STED) microscopy equipped with a 775 nm depletion laser, enabling high-resolution visualization of detailed dynamic changes in membrane protrusions during ApoVs formation. This work provided powerful tools for tracking the entire ApoVs formation process and also offered crucial scientific evidence for revealing the ApoVs formation mechanism.
Electron transfer is considered to play a critical role in the Type-I photodynamic therapy process, which offers superior performance under hypoxic conditions. However, developing efficient Type-I photosensitizers remains challenging because of the competition between energy and electron transfer processes. Therefore, we designed cyanine dyes (Cy-R) with tunable intersystem crossing (ISC) efficiencies, with the ISC rate reaching 9.29 × 106 s−1. Unlike conventional dimers with short-lived charge-separated states, Cy-R aggregates having sufficiently high ISC efficiency undergo symmetry-breaking charge separation (SBCS) in the triplet state, generating long-lived triplet charge-separated species (Cy-R•+−Cy-R•−). This mechanism significantly enhances the production of Type-I reactive oxygen species. Furthermore, Cy-Ac self-aggregation facilitated passive tumor targeting and lysosomal accumulation. Upon photoactivation, Cy-Ac induces lysosomal membrane permeabilization, disrupts autophagy, and triggers lysosome-mediated cell death. This study provides a promising strategy for the development of hypoxia-tolerant Type-I photosensitizers via triplet-state SBCS.
Copper hydride clusters have become especially fascinating in the field of functional cluster-based materials due to the various compositions and architectures as well as intriguing properties especially hydride-related applications. A comprehensive understanding of the synthesis, structure determination, the relationship between structure and properties of copper hydride clusters hold great significance for development of the functional characteristics. In this review, advances in the methodology for the preparation and understanding of atomically precise copper hydride clusters are comprehensively summarized. The functional properties of copper hydride clusters including luminescence behaviors, especially for the tailoring emission features, chirality and catalysis were mainly highlighted. Furthermore, the importance of balancing the stability of copper hydride clusters and the effective development of their functional properties is emphasized. The review discusses the potential of hydride atoms in modulating functionality of copper hydride clusters, which is expected to bring about significant advancements in catalysis and chiral applications. Finally, we provide insights into the prospects for future development on the copper hydride clusters.
The rise in pancreatic diseases, resulting from improved living quality and lifestyle habits changes, has imposed a serious social burden. To better understand the pancreatic functions during disease progression, constructing a bionic pancreas is vital yet challenging in tissue engineering. Herein, inspired by the physiological anatomy of the pancreas, we introduce core-shell microfibers with pancreatic stellate cells (PSCs) in the shell and pancreatic β-cells in the core. Compared to traditional plate culture, the β-cells encapsulated in the microfiber exhibit enhanced glucose-stimulated insulin secretion. Such microfibers also serve as a platform to study the progression of diabetes of the exocrine pancreas, where the PSCs are activated under conditions of pancreatic exocrine diseases such as chronic pancreatitis. The activated PSCs impede insulin synthesis and increase apoptosis in β-cells, resulting in elevated blood glucose. This high-glucose microenvironment further exacerbates the activation of PSCs, causing a vicious cycle of diabetes. Additionally, the bio-inspired pancreas also demonstrates its potential in drug screening, as evidenced by testing the glucagon-like peptide 1 receptor agonist, Exendin-4. Building upon such features, it is convincing that these multi-component microfibers hold promise for exploring the pancreatic exocrine and endocrine interactions, and showing potential in disease modeling, drug screening, and regenerative medicine.
Current phototherapeutic agents based on heptamethine cyanine dyes often rely on symmetric structures, limiting their photodynamic therapy (PDT) efficiency. Herein, we report a novel asymmetric heptamethine cyanine dye (Cyp-TPE) that features a twisted tetraphenylethylene moiety. This design facilitates the formation of stable aggregate nanoparticles (NPs) with a cross-arranged structure, as revealed by molecular dynamics simulations. This specific aggregation mode promotes exciton delocalization and dramatically enhances spin-orbit coupling, leading to an unprecedented ROS quantum yield of 154.54%. Under 808 nm laser irradiation, the Cyp-TPE NPs demonstrate potent synergistic photodynamic and photothermal activity, concurrently triggering ferroptosis and lysosomal dysfunction, thereby achieving multimodal death of cancer cells. Furthermore, the excellent NIR absorption and photothermal conversion of these aggregates enable precise photothermal imaging (PTI) and photoacoustic imaging (PAI). This work highlights the potential of asymmetric molecular design to overcome the limitations of conventional photosensitizers, offering a robust nanoplatform for imaging-guided cancer therapy.
Carbon dots (CDs), as an emerging class of zero-dimensional carbon-based nanomaterials, have attracted widespread attention owing to their remarkable optical properties, solution processability, and environmental friendliness, showing broad application prospects in optoelectronic devices. Nevertheless, although significant research progress has been achieved in recent years, a comprehensive theoretical framework is still absent for clarifying the correlations among the structure, optical properties, and performance of CDs in practical device applications. In this regard, the present review highlights recent developments in utilizing the distinctive optical features of CDs for various optoelectronic systems, including key examples such as photodetectors, optical memristors, lasers, electroluminescent diodes, and photovoltaic cells. Moreover, the current limitations and future research directions for CDs-based optoelectronic technologies are analyzed. The insights provided herein are expected to stimulate further research on enhancing the optical properties of CDs and promoting the rational design of high-performance devices from a new perspective.
The interactions that occur in the interface of proteins and ligand-stabilised metal nanoclusters are crucial to understand the adsorption process of biomolecules on the surface of these nanomaterials. Despite the relevance of the adsorption phenomena for biological applications, such as bioimaging, biosensing and targeted drug delivery, efforts to model the interactions observed in the interface of those systems are still scarce in the literature. In this work, a model of the interactions observed in the peptide–Au38(p-MBA)24 interface was developed, employing clustering analysis, an unsupervised machine learning technique. The accuracy of this model was evaluated by simulating the peptide–Au38(p-MBA)24 interaction using molecular dynamics simulations and density functional theory calculations. The insights derived from this model can also be applied to the context of protein–AuNC interactions, given that the model was developed to provide a generalisable approach. The developed model was able to predict the amino acids that could interact well or poorly with the gold nanoclusters (AuNC), defining the specific chemical groups responsible for the effect. The results obtained in this study can lead efforts to accelerate discoveries in the fields that rely on the understanding of the interaction observed in the protein–AuNC interface.
Methicillin-resistant Staphylococcus aureus (MRSA), often residing within biofilms and host cells, exhibits heightened resistance to conventional antibiotics and immune clearance, resulting in persistent and recurrent infections. Given the central role of DNA in bacterial proliferation and virulence, it represents an ideal target for the development of next-generation antibacterial agents. In this study, we report the development of a DNA-targeting photosensitizer (PS), TPE-CN, designed for the effective treatment of MRSA-associated infections. TPE-CN demonstrates high specificity for bacterial DNA, along with excellent membrane permeability, enabling disruption of both bacterial DNA and membrane structures. This allows for the efficient eradication of planktonic MRSA. Moreover, TPE-CN can also selectively colocalize with the lysosome of macrophages, facilitating effective eradication of intracellular bacteria while preserving host cell integrity. Furthermore, in vivo studies further validate the potent antimicrobial effects of TPE-CN, resulting in accelerated wound healing in severe MRSA infection models. Collectively, this work presents a novel molecular design strategy for precise bacterial DNA targeting, offering a promising therapeutic avenue for combating drug-resistant pathogens and advancing the development of next-generation antimicrobial therapies.
The visualization of phase separation in immiscible polymer blends holds significant industrial and academic relevance, as the resultant phase architecture governs the macroscopic properties and ultimate performance of blended materials. To address this challenge, a dual-fluorophore labeling strategy is introduced, enabling high-contrast differentiation of polymeric phases. By covalently tethering two spectrally orthogonal fluorophores to their respective polymer components, unambiguous spatial resolution of blend morphologies is achieved through laser scanning confocal microscopy (LSCM). When compatibilizers are incorporated, LSCM imaging reveals fundamentally reconfigured phase architectures compared to uncompatibilized systems. This fluorescence-based approach permits direct assessment of blend compatibility through quantitative evaluation of interfacial domain coherence and phase dispersion homogeneity. The methodology demonstrates exceptional versatility, successfully resolving phase boundaries in both chemically dissimilar systems (e.g., polylactic acid [PLA]/poly (butylene adipate-co-terephthalate) [PBAT] blends with pronounced polarity disparities) and structurally congruent polymers (e.g., polyethylene [PE]/polypropylene [PP] variants). The universal applicability stems from the substantial spectral distinction between fluorophore-labeled polymers, independent of variations in polymer polarity or structural configurations.
The near-infrared (NIR) afterglow visualization in photodeformation materials offers real-time, light-off tracking of dynamic photoresponsive processes in deep tissues and optomechanical systems. However, it remains a fundamental challenge to simultaneously achieve photodeformation and NIR afterglow, due to the competing requirements of molecular design: molecular flexibility for photodeformation versus structural rigidity for afterglow emission, in addition to the intrinsic difficulty in realizing NIR afterglow. To resolve this dichotomy, we developed a rigidity–flexibility compartmentalized molecular structure. A rigid conjugated framework with strong charge transfer (CT) character is responsible for the persistent NIR afterglow via radiative recombination of charge-separated states (CSS), while flexible tautomerism units featuring an excited-state intramolecular proton transfer (ESIPT) process enable photodeformation. Once these dyes are doped into polyethylene terephthalate (PET) films, the visible-light-driven photocontraction (with a contraction rate up to 48%) and persistent NIR afterglow can be realized. Furthermore, it has been successfully utilized for in vivo precision control in bioimaging with high signal-to-background ratio (SBR), and applied in the dynamic modulation of vascular stents with afterglow visualization.
The structural tautomerism of nanoclusters plays an indispensable role in establishing dynamic structure–activity relationship models and designing nanocluster-based intelligent functional materials, yet precise control of this dynamic process remains challenging. This study proposes a steric-hindrance-driven conformational switching strategy, achieving spatial torsion of a Au1(SR)2 motif on Au24(SR)16 nanoclusters. The conformational transition alters spatial proximity and electron cloud density of Au24(SR)16, thereby modulating reaction kinetics to trigger or inhibit its global structural tautomerism. Crystallographic analysis and density functional theory (DFT) calculations confirm that ligand steric effects and metal–ligand interactions govern the tautomeric pathway. The equilibrium dynamics of this tautomeric system demonstrates pronounced temperature dependence, wherein a mathematical relationship between the absorbance and temperature is established, thus endows it with the function of a nano-thermometer, showing a temperature measurement error of ≤0.3°C. In addition, this conformational switching strategy is demonstrated to be extensible to other gold nanocluster systems, thereby establishing its broad applicability. This work offers a paradigm for designing functional nanomaterials through dynamic conformational reconstruction.
Combining high mobility and high-efficiency luminescence in one material is challenging because of their contradictory design principles. Here, under the three-state exciton model, a molecular descriptor O = (|th + te| - |th - te|)/2J is proposed to quantitatively design materials with balanced luminescence and mobility in aggregated states, where a large O would promise high crystalline photoluminescence quantum yield (PLQY) with small J (excitonic coupling) and significant th and te (hole and electron transfer integrals) would indicate high mobility. Through theoretical calculation and experimental validation, it is found that the asymmetric anthracene derivatives are quite effective in simultaneously achieving high mobility and high PLQY. Following the asymmetric guideline, the newly developed compounds, 2-phenyl vinyl anthracene (2-PhVA) and 6-(2-(anthracene-2-yl)vinyl)benzo[b]thiophene (6-BTVA) demonstrate high O values alongside excellent performance: 2-PhVA exhibits a PLQY of 81.5% and a maximum hole mobility of 10.0 cm2 V-1 s-1, and 6-BTVA shows a PLQY of 30.9% with a maximum mobility of 9.3 cm2 V-1 s-1. The above results demonstrate the validation of the descriptor and the asymmetric strategy in further developing high-mobility light-emitting aggregated materials.
Third-order nonlinear optical (NLO) materials are critical for applications such as optical limiting, all-optical switching, and ultrafast photonic devices, yet their performance remains constrained by the intricate balance between electronic delocalization and dimensional synergy. This study demonstrates a multidimensional assembly strategy to engineer aromatic synergy in osmium–organic π-clusters, achieving unprecedented enhancement of third-order NLO response. Guided by the concept of metal–organic π-cluster, we design a prototypical Os3-plane unit as a foundational building block. Through horizontal covalent extension (C─C bonding) and vertical metallophilic stacking (Os─Os interactions), four hierarchical architectures (Os6-prism, Os6-plane, Os9-prism, and Os9-plane) are constructed, each exhibiting amplified NLO properties. Systematic analysis reveals that horizontal assembly enhances in-plane π-conjugation through quasi-two-dimensional π-delocalization, while vertical stacking facilitates interlayer π-orbital overlap. The novel structure, constructed via a multidimensional assembly strategy, exhibits a narrow HOMO–LUMO gap. The expanded π-delocalization reduces exciton binding energy, promotes electron delocalization, and consequently yields a stronger third-order NLO response. The Os9-plane exhibits excellent third-order NLO response coefficient (γ = 2.93 × 107 a.u.), which is two orders of magnitude higher than that of the Os3-plane. This work establishes a paradigm of synergistic integration between multidimensional assembly and aromatic π-conjugation for enhanced NLO performance, opening new avenues for optoelectronic material design.
Atomically precise coinage metal nanoclusters represent an emerging class of photocatalysts with exceptional structural uniformity and tunable optoelectronic properties. This review comprehensively summarizes recent advances in the application of coinage metal nanoclusters in visible-light-driven organic synthesis, highlighting their catalytic versatility across a diverse array of bond-forming reactions. Key transformations discussed include singlet oxygen-mediated aerobic oxidations, [2+2] cycloadditions, hydroborylations, cross-couplings, multi-component reactions, click reactions, and others. These processes often proceed under mild conditions with high selectivity and efficiency, attributable to the unique quantum size effects, tailored surface ligands, and well-defined core structures of coinage metal nanoclusters. Mechanistic insights derived from state-of-the-art studies reveal the involvement of energy transfer and single-electron transfer pathways, underscoring the role of coinage metal nanoclusters as tunable photoredox platforms. This review not only showcases the catalytic prowess of coinage metal nanoclusters in complex organic conversions but also outlines future directions for designing next-generation cluster-based photocatalysts with enhanced performance and broader applicability.
Zwitterionic hydrogels have attracted considerable attention as advanced biomaterials. However, the fabrication of traditional zwitterionic hydrogels typically relies on harsh polymerization conditions, and their backbone structures are non-biodegradable. In this study, we develop a self-aggregation-induced polymerization (SAIP) mechanism that enables the spontaneous formation of multifunctional zwitterionic hydrogels under mild aqueous conditions, utilizing a rationally designed lipoic acid-carboxybetaine monomer with lipoic acid-modified hyaluronic acid (LAHA) crosslinker. This SAIP mechanism is driven by the synergistic interaction between the strongly hydrophilic zwitterionic moieties and hydrophobic 1,2-dithiolanes, promoting monomer self-aggregation into high-concentration reactive microenvironments, thus facilitating efficient ring-opening polymerization without external catalysts or stimuli. The incorporation of LAHA as a crosslinker results in the formation of a stable zwitterionic hydrogel, distinguished by its mild preparation conditions, rapid spontaneous gelation (116 s), and controlled depolymerization through dynamic disulfide bonds. Furthermore, the resulting hydrogel demonstrates high water content (>76%), robust mechanical properties (compressive stress up to 3.86 MPa), exceptional antioxidant activity (>90% DPPH scavenging), high biocompatibility, and superior living cell encapsulation and protection. This study provides a fundamental understanding of hydrogel formation through the SAIP mechanism and advances the development of zwitterionic hydrogels, making the resulting hydrogel an attractive candidate for biomedical applications.
Stereochemistry is a potent way to direct the molecular packing in condensed phases. Here, we synthesized the enantiopure, racemic, and achiral isomers of p-type small molecule, that is, indacenodithieno[3,2-b]thiophene, to understand the impact of stereochemistry on molecular packing and solid-state properties. In the solution state, the optical properties remain nearly identical among the isomers; however, a significant difference was observed in the condensed phase. X-ray diffraction pattern revealed enantiopure isomers were more tightly packed and exhibited strong π-stacking relative to their racemic and achiral counterparts. Two-dimensional arrangement of the stacked enantiopure isomers gives more dense-packed crystalline phases than an achiral analog, which is unusual anti-Wallach type condensed phases. The enantiopure one exhibited two times higher photoconductivity than its achiral or racemic analogues, as well as showing high electron spin polarizability (∼75%) with electrical current throughput (100 nA). The result highlights the role of stereochemistry as a key strategy to direct the condensed phase packing and properties in conjugated crystals.
Cooperative self-assembly based on multiple non-covalent interactions is ubiquitous in nature, yet the rational design of artificial cooperative systems remains challenging. Here we synthesize two carbazole derivatives, CbzE (with an ester group) and CbzA (with amide groups), to investigate how hydrogen bonding (HB) and halogen bonding (XB) jointly guide self-assembly into nanotubular supramolecular polymers. Using 1,4-diiodotetrafluorobenzene (DITFB) as XB donor or diplatinum(II) as linker, two types of [4 + 4] macrocycles are constructed and characterized by high-resolution mass spectrometry, ultraviolet-visible, infrared, and atomic force microscopy. CbzA, benefiting from strong HB, cooperatively assembles with DITFB into nanofibers and nanotubes, whereas CbzE, lacking amide groups, forms only disordered aggregates. Pt(II) coordination disrupts HB networks and redirects CbzA toward lateral aggregation, underscoring the sensitivity of assembly pathways to the balance of interactions. Remarkably, nanotubular CbzA + DITFB structures disassemble rapidly under trifluoroacetic acid vapor but are restored by triethylamine, demonstrating a reversible gel–sol–gel transition. This orthogonal acid/base responsiveness highlights the tunable and dynamic features of cooperative HB/XB systems. Overall, these results reveal the critical role of HB and XB cooperativity in directing ordered architectures and provide new design principles for intelligent supramolecular polymers with stimuli-responsive functions.
Cyanine dyes, despite their strong near-infrared (NIR) absorption, often undergo symmetry-breaking Peierls’ transitions in water known as the “cyanine limit,” resulting in suboptimal optical properties. In this work, we present a strategy to overcome this limitation by entrapping cyanine dye (Cy746) within the micellar nanoparticle (Np@M1-Cy746) of a bichromophoric [1+1] macrocycle M1 comprising of perylene diimide (PDI) and aza-BODIPY (Aza) that exhibits Förster resonance energy transfer (FRET), formed from an amphiphilic polymer 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)]. This approach not only stabilizes the cyanine dye but also enables two-step FRET from PDI to Aza of the macrocycle to Cy746, resulting in panchromatic absorption, enhanced NIR emission, and achieved near-white light emission. The micellar FRET assembly Np@M1-Cy746 also serves as a ratiometric temperature sensor with a sensitivity of 0.0379%°C−1 and was utilized as a supramolecular photocatalyst in aqueous-phase photocatalytic Knoevenagel condensation of benzaldehyde and malononitrile. The two-step FRET process in Np@M1-Cy746 enabled its superior photocatalytic performance compared to the micelle of only M1 (Np@M1), which shows one-step FRET. This study offers a distinct approach for constructing multichromophoric macrocycle nanoparticles in aqueous media, leveraging upon its sequential energy transfer to achieve efficient and scalable photocatalytic transformation.
With the rapid advancement of wearable electronics and bioelectronics, the construction of flexible energy-supplying systems that simultaneously integrate high-efficiency energy conversion, excellent body-conformability, and mechanical durability has emerged as a critical challenge urgently requiring breakthroughs in the thermoelectric field. Recently, Lei et al. have developed a robust thermoelectric elastomer that simultaneously exhibits a high thermoelectric figure of merit (ZT value), excellent tensile resilience, and low modulus. This innovation overcomes the long-standing challenge of balancing the “mechanical-electrical-thermal” performance of thermoelectric materials, thereby opening up new avenues for the continuous self-powering and solid-state cooling of wearable devices.
Temperature-responsive luminescent materials hold great potential for applications in various advanced photoelectronic fields. However, realizing dual-mode, temperature-activated luminescence within a single molecular system remains a significant challenge. Here, two neutral Mn(II) complexes with dual-mode temperature-activated luminescent properties have been successfully synthesized by an alkoxy chain engineering strategy. At room temperature, these complexes are strongly emission-quenched. Reducing or increasing temperature triggers pronounced luminescence enhancement, due to the prohibition of thermal population to the upper lying quenching state or the removal of trace water molecules. Notably, this study provides the first definitive evidence of the dual-mode temperature-activated photoluminescent behavior in quartet excited states. Furthermore, simple digit-display patterns and anti-counterfeiting applications are demonstrated in this work.