The development of antibacterial hydrogel with stretchable and self-healing properties is an urgent problem in the field of biomedical engineering. Herein, a series of hydrogels with antibacterial activity was successfully fabricated using polyvinyl alcohol (PVA), borax, 4-formylphenyl-β-D-allopyranoside (HLC), 3,3'-dithiobis (propionohydrazide) (DPH) and ionic liquid, 1-aminopropyl-3-methylimidazolium bromide (C3MimNBr). The hydrogels were formed via in situ crosslinking through multiple dynamic covalent bonds, primarily including borate ester bonds, imine bonds and acylhydrazone bonds. A Field Emission Scanning Electron Microscope (FE-SEM) revealed that the formed hydrogels possessed a typical three-dimensional network structure. Notably, the interpenetrating network structure endowed the hydrogels with excellent stretchability and self-healing capability, as demonstrated by their ability to be molded into various shapes and stretched up to five times their original length. Furthermore, the mechanical properties of the hydrogel were affected by the amount of the ionic liquid added. Antibacterial evaluation using the colony counting method showed that the hydrogels exhibited outstanding antibacterial activity against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli). In summary, the multifunctional hydrogels, with favorable stretchability and antibacterial activity, represent promising alternative materials for biomedical engineering applications.

Neuronal function requires precise long-distance axonal transport mediated by molecular motors and RNA-binding proteins like SFPQ, though regulatory mechanisms remain poorly defined. We identify long non-coding RNA NORAD as a master regulator of this process through liquid-liquid phase separation (LLPS). While SFPQ and kinesin-1 mediate cargo delivery, the specific RNA coordinating their interaction was unknown. We demonstrate NORAD directly binds kinesin light chain 1 (KLC1) and promotes SFPQ condensation into dynamic LLPS droplets, enabling efficient transport. CRISPR-assisted mapping and functional assays show NORAD depletion disrupts granule dynamics, impairs neuroprotective mRNA localization, and induces axonal degeneration. In vitro reconstitution confirms NORAD-KLC1 synergy enhances SFPQ phase separation, and neuron-specific knockout mice exhibit motor deficits with reduced neuronal density. These findings establish the first evidence of lncRNA NORAD-mediated LLPS in axonal transport, revealing a new paradigm for RNA-guided neuronal maintenance.

Cuprophilic interactions are increasingly recognized as key determinants in the design of functional assemblies, particularly for enhancing luminescence. However, achieving precise control of cuprophilic interactions in self-assembled, atomically precise copper nanoclusters remains challenging. Here, we present a straightforward strategy to systematically modulate cuprophilic interactions through the supramolecular self-assembly of an atomically precise Cu(I) nanocluster, [Cu6(MBID)6] (Cu6, HMBID = 2-mercaptobenzimidazole). The aggregation behavior of Cu6 is finely regulated by solvation engineering, with controlled self-assembly into well-defined hexagonal nanoplates occurring exclusively within a solvent fraction range (f w = 50-60%). This process strengthens cuprophilic interactions, thereby leading to pronounced improvements in photoelectrical properties, including luminescence and photocurrent generation. Ab initio molecular dynamics (AIMD) simulations reveal that in a 50:50 water/DMSO medium, Cu & centerdot;& centerdot;& centerdot;Cu distances within Cu6 are significantly shortened, providing computational evidence for strengthened metallophilic interactions during aggregation. Complementarily, Raman spectroscopy directly tracks the evolution of Cu & centerdot;& centerdot;& centerdot;Cu distances across distinct aggregation states, offering experimental confirmation of aggregation-induced reinforcement of cuprophilic interactions. Collectively, this work establishes Cu6 as a robust model for supramolecular cluster self-assembly and underscores the pivotal role of metallophilic interactions in constructing cluster-based aggregates with tunable optical properties.

A small organic molecule caffeic acid (CA) was used to manipulate the self-assembly of diphenylalanine (FF) molecules. Bidirectional hierarchical morphology of typical bowknot-like assemblies was constructed through supramolecular co-assembly of FF and CA. By controlling the preparation condition, versatile bowknot-like structures could be exclusively obtained. The FTIR, XRD, UV and XPS results indicated the co-existence of the FF and CA components in the assembly. Intermolecular interaction of hydrogen bonding and it-it interaction between the FF and CA might be the primary driving force. This work provides novel bowknot-like structure of peptide which is rarely observed in biological molecules through a convenient co-assembly way. We believe that such manipulation may not only provide us with a deeper understanding of the principles of the dipeptide coassembly process but also may enable us to construct more unprecedented peptide-based materials for comprehensive applications.

Developing thermally activated delayed fluorescence (TADF)-active silver clusters with near-unity quantum efficiency is of practical importance in cutting-edge optoelectronic devices, but remains a tremendous challenge due to the difficulty of de novo synthesis and uncertainty of properties. Herein, we demonstrate a lattice modulation on parent TADF- active silver cluster, achieving TADF-driven photoluminescence quantum yield (PLQY) from 12 % to near-unity. Systematic experimental and calculated results reveal that the lattice modulation effectively lowers the singlet-triplet splitting (ΔEST) from 718 to 549 cm-1, thereby facilitating thermally activated reverse intersystem crossing: T5→S5, leading to extremely efficient TADF by surpassing both phosphorescence and non-radiative decay, thus boosting the near-unity PLQY. Such high PLQY is extremely rare in the TADF-active silver clusters and even in the whole noble-metal clusters. This research showcases an unparalleled example of lattice modulation to realize near unity PLQY of TADF-active silver clusters.

The past decades have witnessed great strides in phototherapy as an experimental option or regulation-approved treatment in numerous cancer indications. Of particular interest is nanoscale photosensitizer-based phototherapy, which has been established as a prominent candidate for advanced tumor treatment by virtue of its high efficacy and safety. Despite considerable research progress on materials, methods and devices in nanoscale photosensitizing agent-based phototherapy, their mechanisms of action are not always clear, which impedes their practical application in cancer treatment. Hence, from a new perspective, this review elaborates the working mechanisms, involving impairment and moderation effects, of diverse phototherapies on cells, organelles, organs, and tissues. Furthermore, the most current available phototherapy modalities are categorized as photodynamic, photothermal, photo-immune, photo-gas, and radio therapies in this review. A comprehensive understanding of the inferiority and superiority of various phototherapies will facilitate the advent of a new era of cancer phototherapy.

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Autism spectrum disorder (ASD) is a complex neurodevelopmental disorder for which current treatments are limited and drug development costs are prohibitive. Identifying drug targets for ASD is crucial for the development of targeted therapies. Summary-level data of expression quantitative trait loci obtained from GTEx, protein quantitative trait loci data from the ROSMAP project, and two ASD genome-wide association studies datasets were utilized for discovery and replication. We conducted a combined analysis using Mendelian randomization (MR), transcriptome-wide association studies, Bayesian colocalization, and summary-data-based MR to identify potential therapeutic targets associated with ASD and examine whether there are shared causal variants among them. Furthermore, pathway and drug enrichment analyses were performed to further explore the underlying mechanisms and summarize the current status of pharmacological targets for developing drugs to treat ASD. The protein-protein interaction (PPI) network and mouse knockout models were performed to estimate the effect of therapeutic targets. A total of 17 genes revealed causal associations with ASD and were identified as potential targets for ASD patients. Cathepsin B (CTSB) [odd ratio (OR) = 2.66 95, confidence interval (CI): 1.28-5.52, P = 8.84 × 10-3], gamma-aminobutyric acid type B receptor subunit 1 (GABBR1) (OR = 1.99, 95CI: 1.06-3.75, P = 3.24 × 10-2), and formin like 1 (FMNL1) (OR = 0.15, 95CI: 0.04-0.58, P = 5.59 × 10-3) were replicated in the proteome-wide MR analyses. In Drugbank, two potential therapeutic drugs, Acamprosate (GABBR1 inhibitor) and Bryostatin 1 (CASP8 inhibitor), were inferred as potential influencers of autism. Knockout mouse models suggested the involvement of the CASP8, GABBR1, and PLEKHM1 genes in neurological processes. Our findings suggest 17 candidate therapeutic targets for ASD and provide novel drug targets for therapy development and critical drug repurposing opportunities.

We propose an effective highest occupied d-orbital modulation strategy engendered by breaking the coordination symmetry of sites in the atomically precise Cu nanocluster (NC) to switch the product of CO2 electroreduction from HCOOH/CO to higher-valued hydrocarbons. An atomically well-defined Cu-6 NC with symmetry-broken Cu-S2N1 active sites (named Cu-6(MBD)(6), MBD=2-mercaptobenzimidazole) was designed and synthesized by a judicious choice of ligand containing both S and N coordination atoms. Different from the previously reported high HCOOH selectivity of Cu NCs with Cu-S-3 sites, the Cu-6(MBD)(6) with Cu-S2N1 coordination structure shows a high Faradaic efficiency toward hydrocarbons of 65.5 % at -1.4 V versus the reversible hydrogen electrode (including 42.5 % CH4 and 23 % C2H4), with the hydrocarbons partial current density of -183.4 mA cm(-2). Theoretical calculations reveal that the symmetry-broken Cu-S2N1 sites can rearrange the Cu 3d orbitals with dx2-y2 ${d_{x<^>2 - y<^>2 } }$ as the highest occupied d-orbital, thus favoring the generation of key intermediate *COOH instead of *OCHO to favor *CO formation, followed by hydrogenation and/or C-C coupling to produce hydrocarbons. This is the first attempt to regulate the coordination mode of Cu atom in Cu NCs for hydrocarbons generation, and provides new inspiration for designing atomically precise NCs for efficient CO2RR towards highly-valued products.

This chapter introduces cluster and cluster-assembled materials. It discusses the prospects and the classifications of the nanocluster assembling processes. The chapter also discusses all the plausible future possibilities for creating new cluster-assembled materials and outlines the direction in which the upcoming research will continue to flourish. Encouraged by the concept of atom-precision, the research in nanotechnology is set to explore the opportunities in every new possible direction to counteract the inherent disadvantages of conventional metal nanoparticles. The chapter summarizes the advancement of the newly generated techniques of assembling metal nanoclusters and finds their potential applications with tailored structure–property correlation. It attempts to produce a logical guide to the different methodologies embraced in yesteryears in the design of atom-precise cluster-assembled materials, which features the crucial logical necessities and points of interest of utilizing such materials.

Conceptually mimicking biomolecules' ability to construct multiple-helical aggregates with emergent properties and functions remains a long-standing challenge. Here we report an atom-precise 18-copper nanocluster (NC), Cu18 H(PET)14 (TPP)6 (NCS)3 (Cu18 H) which contains a pseudo D3 -symmetrical triple-helical Cu15 core. Structurally, Cu18 H may be also viewed as sandwich type of sulfur-bridged chiral copper cluster units [Cu6 -Cu6 -Cu6 ], endowing three-layered 3D chirality. More importantly, the chiral NCs are aggregated into an infinite double-stranded helix supported by intra-strand homonuclear C-H⋅⋅⋅H-C dihydrogen contacts and inter-strand C-H/π and C-H/S interactions. The unique multi-layered 3D chirality and the double-helical assembly of Cu18 H are evocative of DNA. Moreover, the collective behaviours of the aggregated NCs not only exhibit crystallization-induced emission enhancement (CIEE) and aggregation-induced emission enhancement (AIEE) effects in the deep-red region, but also efficiently catalyze electron transfer (ET) reaction. This study thus presents that hierarchical assemblies of atomically defined copper NCs could be intricate as observed for important biomolecules like DNA with emergent properties arising from aggregated behaviours.

Metal nanoclusters (NCs) with atomic precision are growing into a fascinating class of building blocks for supramolecular chemistry. What makes it more interesting is the enhanced optical properties of the ordered structures, including aggregation-induced emission (AIE). However, algorithm dictating the self-assembly of metal NCs in multicomponent environment remains largely unknown, and effective means to manipulate the self-assembly is still lacking, especially under kinetic control. Herein, nanofibers which contain sub-1 nm nanowires and exhibit circularly polarized phosphorescence (CPP) are obtained from crystallization-induced self-assembly (CISA) of water-soluble, negatively charged silver NCs (Ag9 -NCs) in the presence of glutamic acid (Glu). By the introduction of a positively-charged additive (choline chloride, CC), the structure of the nanowires is modulated and the lateral interaction between adjacent nanofibers is adjusted, leading to simultaneous improvement of the phosphorescence and chirality which finally enhances CPP. Importantly, changing the time at which CC is introduced altered the kinetic pathway of the CISA, which enables to effectively manipulate both the final structures of the self-assembled Ag9 -NCs and the output of the optical signals.

金属纳米团簇由几个至几百个金属原子组成,通常尺寸在1～10 nm.其中,银纳米簇(Silver Nanoclusters,Ag NCs)具有合成方法简单、荧光发射波长可调等优点,已成为纳米簇领域里发展前景最好的材料之一.Ag NCs的聚集诱导发光(AIE)现象可以通过超分子策略将Ag NCs与不同类型的小分子材料相结合来实现.通过吡啶二羧酸(2,6-DPA)诱导原子精确的银(9)纳米团簇(Ag9-NCs)自组装,在多重非共价键作用下,构筑了具有AIE特性的水凝胶,其荧光寿命提高了～574倍,荧光寿命达到1.88μs.透射电子显微镜(TEM)和扫描电子显微镜(SEM)的表征结果证明水凝胶由形状特殊的棱形纳米棒组成.红外光谱(FT-IR)和X射线衍射(XRD)的结果证明水凝胶形成的主要驱动力是氢键和π-π堆积作用.这项工作的开展扩展了原子精确纳米团簇自组装行为的研究,为新型纳米团簇AIE凝胶体系的构筑提供了新的研究思路.

Fluorescent imaging based on near-infrared(NIR)fluorophores has revolutionized the techniques employed for detecting biological events in depth owing to their advantages referring to diminished photon scattering,high signal-to-noise ratio and better light transparence through tissue.As for con-ventional luminogens,the nanofabrication of those innately hydrophobic π-conjugated architectures into water-dispersible nanoparticles(NPs)may result in attenuated fluorescent intensity deriving from the detrimental distribution of π-π interactions in the confined space.Oppositely,chromophores pos-sessing aggregation-induced emission(AIE)characteristics emit boosted brightness at aggregate level according to the mechanism of restriction of intramolecular motion(RIM).In this review,we summarize the recent progresses of NIR emissive AIE NPs for multifarious biomedical applications from the view-point of different fabricated manners,mainly covering self-assembly and matrices assisted approaches.Furthermore,the current challenges and future research directions of NIR AIE NPs are briefly discussed.

Construction of versatile nanotemplate bearing inherent distinctive functions and prominent drug-carrying capability is an appealing yet significantly challenging task. Here, inspired by the guiding role of surfactant in preparing nanoparticles, an amphiphilic aggregation-induced emission (AIE) photosensitizer, namely MeOTTVP, is synthesized with attractive near-infrared (NIR) emission and high-performance reactive oxygen species production, and followed by dual-templating-assisted one-pot method involving MeOTTVP as the skeleton to fabricate organosilica nanoparticles (AIE-ONs). The presented AIE-ONs perfectly inherit the functions of MeOTTVP, and are also capable of loading antibiotics and anticancer drugs. Doxorubicin can be assembled on AIE-ONs and then capped with hyaluronic acid, endowing the resulting hybrid with NIR fluorescence imaging-guided synergetic photodynamic/chemotherapy performance, thereby offering boosted anticancer efficacy and reduced side effects. Furthermore, by loading antibiotic rifampicin, the newly obtained AIE-ONs integrating chemo-photodynamic antibacterial functions provide broad-spectrum antibacterial activity and fluorescence monitoring behavior. This study thus not only offers a promising strategy to fabricate NIR nanoparticles on a large scale, but also provides useful insights into designing an advanced theranostic protocol for treating both cancer and bacterial infections.

Phototheranostics, as an emerging treatment integrating the functions of light-driven diagnostic imaging and therapy, has aroused extensive attention for both fundamental research and clinical application in recent years because of its advantages of high temporal and spatial selectivity, low side effects, small trauma and high controllability. The conjugated polymers have distinct advantages including excellent optical properties, easy chemical structure regulation, good biocompatibility and solution processability, showing great potential application in the field of phototheranostics. However, traditional fluorescent molecules including the conjugated polymers suffer from the phenomenon of aggregation-caused quenching (ACQ) in aggregate state resulted from their rigid planar structures, thus hindering their biological applications. Luminogens with aggregation-induced emission (AIE) characteristics have attracted much attention because of their high fluorescence quantum efficiency in aggregate. This review is aimed to summarize the state-of-the-art advancements of AIE polymers in phototheranostics, especially the D-A type conjugated polymers, involving the construction strategies of AIE polymers and their applications in three aspects of biological imaging, tumor diagnosis and therapy, and bacterial eradication. According to the practical applications, the different requirements of construction strategies for AIE polymers, as well as the comparisons of the structure and properties advantages between the small molecules and polymers are also discussed. For biological imaging, the review is mainly focused on the development of AIE polymers with NIR-II fluorescence emission and high brightness to achieve high-resolution fluorescence imaging in deep tissues. In the aspect of tumor diagnosis and treatment, the review illustrates the AIE polymers with great advantages compared with small molecules in photon absorption and photosensitization performance, and their applications in photodynamic therapy, photothermal therapy and combined therapy. Also, the applications of AIE polymers for photodynamic therapy of bacterial infections are illustrated. Although the development of AIE polymers have lagged behind that of small molecules mainly due to their complex molecular structures and more difficult AIE mechanism studies, it is necessary to pay more attention to pushing forward the studies on ME polymers and having in-depth understanding about structure-properties relationship. Additionally, the future development in the field of AIE polymers is prospected at the end of this review. [GRAPHICS] .

Recently, advanced optical materials with circularly polarized phosphorescence (CPP) have attracted much attention. However, such materials are limited due to the difficulty of preparation and the scarcity of precursors. Herein, CPP materials are constructed for the first time using water‐soluble, pseudo‐chiral silver nanoclusters with atomic precision ((NH 4 ) 9 [Ag 9 (mba) 9 ], H 2 mba = 2‐mercaptobenzoic acid, abbreviated to Ag 9 ‐NCs hereafter). Induced by the complexation of l ‐ or d ‐tartaric acid (TrA) through hydrogen bonding, Ag 9 ‐NCs crystallize from aqueous solutions, during which the chirality of the hybrid is amplified and the phosphorescence of Ag 9 ‐NCs is enhanced. It is speculated that the chiral transfer from TrA to Ag 9 ‐NCs is the main source of the well‐defined circular dichroism signals with good repeatability. The Ag 9 ‐NCs/TrA cocrystals exhibit good CPP performance with dissymmetric factors up to 1.05 × 10 −2 , which is the highest value for metal NCs‐based CPP materials. This work is expected to be an inspiration for preparing metal NCs‐based CPP materials by supramolecular strategy. The so‐obtained organic–inorganic CPP materials can find a variety of applications in optoelectronic devices.

Developing effective intelligent nanotheranostics is highly desirable for cancer treatment but remains challenging. In this study, an acidic tumor microenvironment-activated organosilica nanosystem, namely AD-Cu-DOX-HA, is straightforwardly constructed, which is composed of aggregation-induced emission (AIE)-active photosensitizer, copper ion-engineered aminosilica, direct coordination polymer of doxorubicin (DOX), and targeting component hyaluronic acid (HA). AD-Cu-DOX-HA is able to accurately distinguish cancer cells over normal cells; meanwhile, it simultaneously exhibits selective accumulation and copper ion-mediated rapid disassembly and turn-on fluorescence in tumor tissue, consequently achieving efficient tumor diagnosis and tumor-growth inhibition through fluorescence imaging-navigated synergetic photodynamic therapy, copper ion-mediated chemodynamic therapy, and DOX-enabled chemotherapy. This work thus brings fresh insight into the exploration of versatile theranostics and presents a momentous advance for potential clinical cancer treatment.