Modifications to the alkyl side chains of Y6-type nonfullerene acceptors (NFAs) continuously break through the organic solar cells (OSCs) efficiency by enhancing electron mobility. However, the role of side chains in molecular aggregation and charge transport across different aggregates remains unclear. By employing a multiscale approach in combination with density functional theory (DFT), molecular dynamics (MD) simulations, and kinetic Monte Carlo (KMC), we addressed the issue of how side chains impact molecular aggregation, energy disorder, and the formation of near-macroscopic (∼0.3 µm) conductive network, which are critical for boosting electron mobility. Specifically, the side-chain structure greatly influences the un-conjugated enveloping effect on backbones within aggregates. The effect diminishes with longer linear side chains and is further minimized by using branched side chains. Though static energy disorder increased, the improved connectivity of the conductive network led to a notable increase in electron mobility (from 2.4 × 10–4 to 3.9 × 10–4 cm2·V–1·s–1). The findings offer insight into controlling molecular aggregation via alkyl side chains, which helps to further unlock the potential of Y6-type NFAs.
Lipid droplets (LDs) are dynamic intracellular organelles that participate in a wide range of physiological and pathological processes. Consequently, the development of high-selectivity and high-resolution tools for LD detection and tracking is of paramount importance. In this study, we describe the straightforward synthesis of a series of novel BODIPY analogs, BOQHYs 3a–3e, through the condensation of 2,3-dihydrazinylquinoline with acetone or benzophenone, followed by complexation with BF3·OEt2. Spectroscopic properties indicate that these dyes exhibited significantly larger Stokes shifts (>100 nm) than the commercial LD-Tracker BODIPY 493/503 (≈10 nm). Additionally, the incorporation of phenyl “rotors” endows BOQHYs 3b–3e with heightened aggregation-induced emission activity, viscosity responsiveness, and exceptional lipophilicity, enabling their selective staining of LDs in a rapid and wash-free manner, with outstanding signal-to-noise ratios. Time-resolved confocal fluorescence imaging of 3d further validates these dyes’ capability to effectively capture LD fusion and fission events, highlighting their potential applications in LD-related cell biology and disease diagnostics.
Frequent nocturia-induced nighttime visits aggravate falls in seniors, requiring synthetic antidiuretic drugs that risk the dangerous syndrome of inappropriate antidiuretic hormone secretion (SIADH), thus the detection of sodium ion and uric acid alterations during treatment is obligatory for drug-safe management. Herein, we design a convolutional neural network (CNN)-enhanced smart wearable microneedle array-based colorimetric (WMNC) sensor to independently detect in vivo interstitial fluid (ISF) sodium ions and uric acid alterations. The WMNC sensor is composed of a vacuum tube-driven microneedle array patch and a built-in colorimetric sensing paper, enabling an efficient ISF extraction and rapid colorimetric assay. Furthermore, leveraging self-designed CNNs, the WMNC sensor efficiently eliminates the influence of ambient light on colorimetric outcomes, facilitating a rapid and accurate colorimetric result classification. This study provides an ISF-based rapid, intuitionistic, user-friendly, wearable point-of-care technique for the elderly suffering from nocturia in monitoring their health status for early warnings of SIADH.
The surface coverage of two-dimensional (2D) materials has been a challenge, requiring facile growth of conformal 2D materials as well as considerations for transparency, energy level, and interface contact. Self-assembly holds promise for addressing this challenge by constructing precisely structured 2D assemblies using intentionally designed building blocks, guided by diverse noncovalent interactions. In this study, we utilize a self-assembled 2D supramolecular organic framework (SOF) to cloak inorganic semiconductors and form composite materials for infrared photodetection. The charged SOF backbone regulates the energy levels, facilitating the migration of electrons at the organic-inorganic interface. Additionally, the oxygen (O) of the ethylene glycol chains forms coordination bonds with the Pb(II) in the inorganic semiconductor, establishing ohmic contacts. The composite device shows excellent detectivity under 500 K blackbody and 1550 nm infrared illumination, achieving D*bb(500 K) of 6.3 × 109 Jones under 500 K blackbody radiation. Moreover, the device exhibits low noise due to the SOF potential barrier impeding the photogenerated and/or thermally excited holes, and high stability as a result of bonding and passivation of vacancy defects. This study showcases the versatile functionality of 2D SOF materials in the field of optoelectronics, opening doors to innovative advancements in composite devices through a self-assembled organic–inorganic approach.
Nerve guidance conduits have demonstrated great promise for the restoration of injured peripheral nerves in recent decades. Associated research has focused on improving the structure and function of these conduits as well as simplifying the manufacturing processes. Herein, a novel decellularized umbilical cord (DUC) wrapped with conductive hydrogel is presented for peripheral nerve regeneration, which is prepared by integrating the DUC matrix into a methacrylate gelatin (GelMA)/Ti3C2Tx MXene (MXene) composite hollow conduit (named DUC–MXene–GelMA conduit). The obtained DUC–MXene–GelMA conduit displays superior mechanical properties, electrical conductivity, and biocompatibility. Particularly, ascribed to the introduction of DUC and MXene, the DUC–MXene– GelMA conduit exhibits satisfactory biological effects in promoting neuron growth and Schwann cell proliferation and migration. Through in vivo experiments using a rat sciatic nerve injury model, the beneficial effects of the DUC–MXene–GelMA conduit on axonal regeneration and motor function recovery are demonstrated. These findings indicate that the DUC–MXene–GelMA conduit may be a promising candidate for peripheral nerve injury repair.
Atomically precise alloyed nanoclusters (NCs) have attracted widespread attention due to synergistic effect but their controllable synthesis remains a challenge. Among them, Ag–Cu alloyed NCs are particularly limited due to significant difference in redox potential, and it is highly desirable to develop controllable and mild synthesis methods. This work proves the feasibility of photochemical synthesis method for Ag12Cu7(4-tBuPhC≡C)14(Dpppe)3Cl3(SbF6)2 (Ag12Cu7) alloyed NC that exhibits remarkable ligand-supported cuprophilic interaction. Experimental and time-dependent UV–Vis spectroscopy first reveals that the formation of Ag12Cu7 is a step-by-step process, in which light induces the reduction of Ag+ to Ag19 cluster containing two electrons, then CuCl incorporates into Ag NC to yield the target NC, providing an alternative pathway toward alloyed NCs. Remarkably, Cu···Cu interaction endows Ag12Cu7 with a strong long-lived red phosphorescence of 30 µs at room temperature, which is superior to the majority of Ag–Cu-alloyed NCs. Theoretical calculations indicate that the phosphorescence originates from cluster-centered triplet–excited state modified by cuprophilic interactions, mixed with ligand-to-metal charge transfer.
Photodynamic therapy (PDT) is a promising noninvasive method for targeted cancer cell destruction. Still, its effectiveness is often hindered by the aggregation-caused quenching effect of organic photosensitizer (PS) in aqueous environments. Here, we have employed a combination of covalent and noncovalent restricted-intramolecularrotation strategies to develop supramolecular PSs with aggregation-induced emission (AIE) characteristics. Firstly, a water-soluble octacationic molecular cage (1) with a bilayer tetraphenylethene (TPE) structure has been designed and synthesized, which minimizes intramolecular rotation of TPE moieties and achieves the single-molecule-level aggregation by the covalent restriction of intramolecular rotation (RIR) via molecular engineering synthesis. Compared with its single-layer TPE analog, 1 exhibits superior efficiency in generating reactive oxygen species (ROS) including superoxide radical (O2–•) and singlet oxygen (1O2) upon whitelight irradiation. Subsequently, by forming a 1:4 host–guest complex (1@CB[8]4) between 1 and cucurbit[8]uril (CB[8]), O2–• generation can be further enhanced by the noncovalent RIR via the host–guest assembly. Additionally, 1@CB[8]4 as a photocatalyst promotes rapid oxidation of nicotinamide adenine dinucleotide (NADH) in water. Given its Type-I ROS generation and catalytic activity for NADH oxidation, 1@CB[8]4 acts as a supramolecular AIE-type PS to exhibit strong photo-induced cytotoxicity upon white-light irradiation under hypoxic conditions, showcasing its potential for synergistic PDT.
Hierarchical plasmonic biomaterials constructed from small nanoparticles (NPs) that combine into larger micron-sized structures exhibit unique properties that can be harnessed for various applications. Using diffusion-limited aggregation (DLA) and defined peptide sequences, we developed fractal silver biomaterials with a Brownian tree structure. This method avoids complex redox chemistry and allows precise control of interparticle distance and material morphology through peptide design and concentration. Our systematic investigation revealed how peptide charge, length, and sequence impact biomaterial morphology, confirming that peptides act as bridging motifs between particles and induce coalescence. Characterization through spectroscopy and microscopy demonstrated that arginine-based peptides are optimal for fractal assembly based on both quantitative and qualitative measurements. Additionally, our study of diffusion behavior confirmed the effect of particle size, temperature, and medium viscosity on nanoparticle mobility. This work also provides insights into the facet distribution in silver NPs and their assembly mechanisms, offering potential advancements in the design of materials for medical, environmental, and electronic applications.
Multiple metal ions are traditionally detected using inductively coupled plasma mass spectrometry (ICP-MS) and atomic fluorescence spectrometry. Although thesemethods are sensitive and accurate, they depend on complex instruments and require highly trained operators, making low costly rapid detection challenging. It is urgent to develop a convenient, rapid and sensitive method to detect multiple metal ions. Herein, we designed a bispyrene derivative (BP) with aggregation-induced enhanced emission (AIEE) property to construct a high fluorescent sensor array to realize the effective identification of four metal ions (Fe3+, Cu2+, Co2+ and Cd2+). The differential coordination capability between metal ions and BP with the aid of acetate ions resulted the possibility of array-based sensing. The four heavy metal ions could be immediately classified in the concentration of 100 nM. The limit of detection (LOD) of Fe3+, Cu2+, Co2+, and Cd2+ were as low as 16.2, 21.8, 51.4, and 25.9 nM, respectively. Furthermore, the sensor array was applied for identification multiple heavy metal ions in environmental samples and iron ion in rat serums with identified of 100%. The sample consumption as low as 2 µL for each detection and the results could be extracted by smartphones under ultraviolet lamps. It provided a rapid, sensitive, low-cost, and on-site multiple metal ions detection method.
Copper nanoclusters with stable compositions and precise structures have long been sought after, as they possess properties that are absent in gold and silver counterparts. However, the creation of copper nanoclusters with novel compositions, structures, and functionalities remains largely unexplored in the literature. In this study, we demonstrate that selenide doping is an effective method for fabricating stable copper nanostructures through controlled synthesis and structure determination of a copper– selenide nanocluster. The nanocluster of [Cu32Se7(BnSe)18(PPh3)6]+ (denoted as Cu32Se7, Bn is benzyl) has been prepared by reducing copper salts in the presence of organic diselenides. The atomic structure of the Cu32Se7 cluster, accurately determined through single-crystal X-ray diffraction, reveals a core–shell arrangement of Cu20Se7@Cu12(BnSe)18(PPh3)6, where Se2– anions are well dispersed in the Cu20 framework. Notably, this cluster represents a rare example of copper–selenide semiconductor nanoclusters. Experimental and theoretical analysis shows strong interactions between Se ligands and metal atoms, resulting in high stability of the Cu32Se7 cluster. Furthermore, the cluster exhibits excellent catalytic performance in the hydroboration reaction of alkynes, producing a range of vinylboron compounds with adjustable structures and functions. Importantly, the cluster undergoes no structural or nuclearity changes during the reaction, as confirmed by extended X-ray absorption fine structure and X-ray photoelectron spectroscopy studies. This study not only presents a molecular cluster model highlighting the effectiveness of selenide dopants in fabricating new copper nanostructures but also paves the way for utilizing stable copper nanoclusters in diverse and exciting areas beyond catalysis.
Organic agents possessing NIR-II and photoacoustic duplex imaging capabilities, coupled with high-efficiency photothermal conversion, offer significant potential for noninvasive and precise phototheranostics of glioblastoma, which is further augmented when these agents can concurrently exhibit tumor targeting and blood–brain barrier (BBB) permeability. This study reports a series of finely tunable NIRII molecular luminophores based on the aza-BODIPY scaffold, featuring unique twisted and rotatable structures. They are further constructed to folate-decorated polymeric nanoparticles, exhibiting remarkable NIR-II/photoacoustic imaging performance and superior photothermal conversion efficiency (49.7%). Folate modification enables tumor targeting and BBB permeability through receptor-mediated transcytosis, allowing for precise and efficient phototherapy in 4T1-/glioblastomabearing mice after a single intravenous injection and irradiation. This study presents a rational molecular engineering approach and a versatile structural scaffold for designing NIR-II emitters with tailored photophysical properties and desirable phototherapeutic efficacy, thereby offering novel perspectives on the development of advanced depth imaging probes and brain tumor therapeutics.
Bacterial biofilm infections (BBI) on wound surfaces and implants pose a significant clinical challenge due to the impermeable nature of biofilms and obstacles in tissue repair. Traditional photothermal therapy (PTT) or chemodynamic therapy (CDT), whether used alone or in combination, often causes damage to surrounding normal tissues from high operating temperatures or elevated levels of reactive oxygen species, leading to unsatisfactory anti-biofilm effects. This study introduces a novel copper ions loaded zinc porphyrin polymer vesicle (Cu-PPS) that employs a triple synergistic approach involving PTT, CDT, and bacterial cuproptosis-like death (BCD). Cu-PPS exhibits exceptional photothermal efficiency of 51.06%, promoting the release of copper ions under photothermal stimulation, enhancing CDT and BCD effectiveness, and facilitating mature biofilm clearance and tissue repair. This approach achieves a bactericidal rate exceeding 99% and an anti-biofilm rate of 93.32% in vitro and also excellent efficacy in treating BBI in vivo. This study presents an innovative therapeutic strategy for combating biofilm infections, addressing the challenges encountered in the clinical management of BBI.
Coinage bonds, a type of noncovalent interaction, occur between group 11 elements (Au, Ag, and Cu) with electron donor groups. Despite theoretical validation, empirical evidence remains limited. In this study, an aggregation-induced emission (AIE)-active Au(I) complex, ITCPAu, which exhibits Au···I coinage bonds, was revealed based on the single-crystal X-ray diffraction and theoretical calculations. Further examination of the luminescence properties of the ITCPAu revealed multiswitchable behavior, including mechanochromism and thermochromism. Nearly pure white-light emission was achieved with Commission Internationale de L’Eclairage (CIE) 1931 chromaticity coordinates of (0.30, 0.31) by grinding the green-emissive ITCPAu monomer crystals. Moreover, visualization and manipulation of solid-state molecular motion (SSMM) in the yellow-emissive ITCPAu dimer crystals, driven by the robust Au···I coinage bonds, were revealed through a combination of crystal engineering and luminescent properties. Furthermore, to support the robust Au···I coinage bonds, a versatile carrier for small solvent molecules in crystal lattices was developed for uptake and release. Our findings provide experimental and theoretical evidence for Au···I coinage bonds, highlighting their ability to boost photoluminescence quantum yield (PLQY) and trigger SSMM, emphasizing their potential in developing smart materials with stimuli-responsive properties.
Covalent triazine frameworks (CTFs), known as highly conjugated layered solids, have garnered significant interest due to their distinctive structural and property characteristics. However, the exfoliation of CTF solids towards nanoCTFs in high yields is currently inadequate and inefficient, limiting their utility. This study presents the design and synthesis of CTFs containing non-crystalline regions and their random stacks using a methyl-containing nitrile monomer. Incorporating in-plane methyl groups enhances the polarity of CTFs and disrupts layered interactions, facilitating smooth exfoliation under competing solvent-layer interactions and producing nanocolloids in dilute dispersions. Furthermore, CTFs can rapidly disperse in DMF at a high concentration, enabling the formation of CTF organogel for the first time. Additionally, the designed CTF nanocolloids allow for the first simple physical modification of carbon nanotubes. The assembly, associated with conjugated features, enables the fabrication of CTF/carbon nanotube organogel.
Diabetes significantly impairs the body’s wound-healing capabilities, leading to chronic, infection-prone wounds. These wounds are characterized by hyperglycemia, inflammation, hypoxia, variable pH levels, increased matrix metalloproteinase activity, oxidative stress, and bacterial colonization. These complex conditions complicate effective wound management, prompting the development of advanced diabetic wound care strategies that exploit specific wound characteristics such as acidic pH, high glucose levels, and oxidative stress to trigger controlled drug release, thereby enhancing the therapeutic effects of the dressings. Among the solutions, hydrogels emerge as promising due to their stimuli-responsive nature, making them highly effective for managing these wounds. The latest advancements in mono/multi-stimuli-responsive smart hydrogels showcase their superiority and potential as healthcare materials, as highlighted by relevant case studies. However, traditional wound dressings fall short of meeting the nuanced needs of these wounds, such as adjustable adhesion, easy removal, real-time wound status monitoring, and dynamic drug release adjustment according to the wound’s specific conditions. Responsive hydrogels represent a significant leap forward as advanced dressings proficient in sensing and responding to the wound environment, offering a more targeted approach to diabetic wound treatment. This review highlights recent advancements in smart hydrogels for wound dressing, monitoring, and drug delivery, emphasizing their role in improving diabetic wound healing. It addresses ongoing challenges and future directions, aiming to guide their clinical adoption.
Spherulites are generally fabricated from cooling polymer melts, while their fabrication under mild conditions or from small molecule materials has been barely reported. Besides, organic luminescent molecules typically suffer from low quantum yields in a solid state. Moreover, preparing material with interconnected and simultaneous changes in structural and fluorescent colors is challenging. Here, we present the first solution-derived spherulites with unique interconnected structural and fluorescent colors, self-assembled from stearoylated monosaccharides at room temperature. D-galactose stearoyl ester self-assembled into banded spherulites, containing twisted nanoplates and interconnected simultaneously changing structural and fluorescent colors. In comparison, D-mannose stearoyl ester can only form nonbanded spherulites, which contain oriented nanoplates and uniform structural and fluorescent colors. Such materials revealed a novel negative correlation between fluorescence and birefringence, termed alignment-promoted quenching propensity. Remarkably, the solid-state fluorescence quantum yields of galactose and mannosederived spherulites are as high as 49 ± 2% and 51 ± 2% respectively, approximately ten times higher than those of unmodified monosaccharides. These quantum yield values are among the highest of reported organic nonconventional fluorophores and even comparable to those of conventional aromatic chromophores. Moreover, these spherulites manifested an unexpected excitation-dependent multicolor photoluminescence with a broad-spectrum emission (410–620 nm). They show multiple peaks in the photoluminescent emission spectra and broad fluorescence lifetime distributions, which should be attributed to the clustering of a variety of oxygen-containing functional groups as emissive moieties.
Ionically bonded organic metal halide perovskite-like luminescent materials, which incorporate organic cations and metal halides, have emerged as a versatile multicomponent material system. However, these materials still face challenges in terms of low phosphorescence quantum yields and limited long persistent luminescence (LPL) colors. Herein, we present the design and synthesis of an intraligand chargetransfer organic-based metal halide perovskite-like material, in which organic cations form a compact supramolecular hydrogen-bonded organic framework (HOF) structure, exhibiting crystallization-induced phosphorescence emission of ligand, while metal halides form a unique two-dimensional (2D) structure that displays intrinsic self-trapped excitons (STE) emission under the radiation of UV light. Notably, the metal halide hybrid is found to exhibit enhanced phosphorescent photoluminescence efficiency of up to 81.05% and tunable LPL from cyan to orange compared to the pristine organic phosphor, due to the structural distortion and scaffolding effects of 2D metal halides as well as a well-packed HOF structure. Optical characterizations and theoretical calculations reveal that charge transfer from organic cations and halogen to ligand as well as STE from inorganic layers are responsible for the tunable LPL. Meanwhile, the high-efficiency phosphorescent quantum yield is attributed to stronger hydrogen bond stacking as well as structural distortion of metal halogen bands. Thus, the obtained LPL provides potentials in anti-counterfeiting, security systems, and so on.
To meet the high requirements of biomedical applications in antimicrobial agents, it is crucial to explore efficient nanoantimicrobial agents with no resistance and good biocompatibility for treating infected wounds. In this study, composite nano-antibiotic TPA-Py@AuNCs⊂BSA nanoparticles (TAB NPs) are prepared using hollow mesoporous Au nanocages (AuNCs) loaded with a photosensitizer (namely TPA-Py) with D-π-A structure showing aggregation-induced emission properties. When TPA-Py is encapsulated in the cavity of AuNCs, its fluorescence is suppressed. In the presence of photothermal induction, TPA-Py can be released from the AuNCs, allowing for the restoration of fluorescence illumination and the specific imaging of Grampositive bacteria. TAB NPs demonstrate outstanding antimicrobial activity against a variety of bacteria, and this multimodal antimicrobial property does not lead to the development of bacterial resistance. In vitro experiments show that TAB NPs could eliminate bacteria and ablate bacterial biofilm. In vivo experiments show that the synergistic antimicrobial effect of TAB NPs has a significant positive impact on the treatment of infectedwounds, including rapid antibacterial action, promotion of M2 macrophage polarization, and enhancement of chronic wound healing. This study provides an effective strategy for developing wide-spectrum nano-antibiotics for the ablation of bacterial biofilms and the treatment of infected wounds.
Messenger RNA (mRNA) has demonstrated immense potential in disease therapeutic applications. The current direction is focused on imparting mRNA with competitive synthetic functions and delicate carrier systems. Here, inspired by the collaborative regulation of growth factors by the cellular microenvironment, we present novel transitionmetal carbide/nitride (MXene) hydrogel microneedles loaded with a biomimetic triplet mRNA formulation (TM) for diabetic wound treatment. Such microneedles were composed of TM, MXene, and hyaluronic acid hydrogel. The presence of MXene imparted the microneedles with great photothermal responsiveness properties, thus realizing controlled active release by the shrinkage/swelling of hydrogel. With the effective release of TM, the microneedles were proven to enhance endothelial cell migration, growth, and angiogenesis. Through in vivo animal experiments, we have confirmed that TM-microneedles (TM-MNs) can promote tissue regeneration and collagen deposition more effectively than intravenous and intradermal administration. Thus, we believe that the proposed TM-MNplatform with precise delivery and controllable release of TMwill show great potential for promoting the healing of clinic diabetic wounds.
While nanomedicine research shows a great progress in the treatment of cancer, it still faces challenges of tumor recurrence and metastasis. Numerous studies have demonstrated intricate crosstalk between platelets and tumor cells. The re-education of platelets by tumor cells enables these platelets to provide critical assistance for tumor proliferation, recurrence, and metastasis. Engineered platelets have shown promising potential in the treatment of tumors, postoperative tumor recurrence, and tumor metastasis. Different engineering technologies such as surface modification, gene editing, membrane coating, and loading into hydrogels can producemultifunctional and customized engineered platelets. These engineered platelets inherit the key properties of platelets, including long blood circulation, tumor targeting, and thrombus targeting, and can be stimulated to generate derivatized particles. In this review, we elucidate the critical role of platelets in the complex processes of tumorigenesis and tumor progression and summarize the emerging paradigm of engineered platelets in tumor therapy. The purpose of this review is to comprehensively explore the potential value of engineered platelets toward the clinical treatment of cancer, providing a valuable reference for the further development of engineered platelets and their broader applications in the field of cancer therapy.