The idea of preparation a water-soluble Pt-containing AIEgen successfully realized by direct RAFT copolymerization of a Pt(II) complex ( LPtPV) containing a vinyl group and polyvinylpyrrolidone ( p(VP)). The resulting block-copolymer p(VP-b-LPtPV) containing 5-8 Pt(II) chromophores exhibits intriguing photophysical properties - strong solvent and concentration dependence of absorption and emission characteristics. Various physicochemical and analytical methods (NMR spectroscopy, XRD analysis, ESI-MS, AUC, DLS, ICP-OES, GPC, viscometry, TEM) were used to characterize the initial complex, its binuclear analogues, p(VP) and p(VP-b-LPtPV). The obtained data indicate that the photophysical properties of the latter are dictated by the type of aggregation process rather than solvatochromic effects. It is shown that at low concentration in organic solvents the platinum chromophores aggregation is either absent (DMF) or occurs predominantly at intramolecular level (MeCN), whereas in aqueous media p(VP-b-LPtPV) readily aggregates into micellar-type nanoparticles with a hydrophilic p(VP) corona and a hydrophobic Pt-containing core, in which strong intra- and intermolecular Pt···Pt and/or π···π interactions result in a significant redshift of absorption and emission down to 600 nm and 816 nm, respectively. Despite of emission shift into NIR area where it is commonly quenched by nonradiative vibrational relaxation increase in emission quantum yield occurs in complete agreement with typical features of AIE emitters. Quantum mechanics/molecular mechanics simulations of aggregation processes also confirm the trends in the relationship between aggregation mode and photophysical behavior, particularly, in the variations of energy gaps between the ground state of the AIEgens and their excited singlet and triplet states.

Coinage bonds, a type of non-covalent 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 multi-switchable 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.

Developing single fluorescent probe for simultaneously visualizing mitophagy flux and oxidative stress with super-resolution is highly demanded yet quite challenging. Herein, we design and synthesize a ratiometric HClO probe AHOH, which is capable of simultaneously staining lysosomes and mitochondria with red and green color, respectively. AHOH could be selectivity oxidized by HClO, leading to a large emission blue shift (90 nm) and an over 1300-fold enhancement of the emission ratio of Fl547 nm/Fl637 nm. We apply AHOH in super-resolution microscopy and clearly visualize the dynamics of mitochondria-lysosomes interactions and the oxidative stress states upon different stimuli. Mitochondria dysfunction triggered by different drugs and genetic defect lead to elevated oxidative stress and higher levels of mitophagy. Moreover, AHOH could serve as a reliable tool for evaluating the efficacy of drugs regulating mitochondria dysfunction. This work provides a powerful dual-color super-resolution imaging agent for real time monitoring the dynamics of organelle interactions and oxidative stress.

Antibacterial lysozyme hydrogels show attractive advantages in wound dressings due to their intrinsic antibacterial activity, excellent biochemical and mechanical properties. Unfortunately, the development of such hydrogels is still greatly limited due to the lack of universal gelation strategies. Herein, a universal gelation strategy between lysozyme-nanofiber (LZF) and inorganic salts is proposed for the first time to construct functional nanofibrous lysozyme-based hydrogels. Specially, divalent anions are found to universally drive LZF for the aggregation and transformation into three-dimensional nanofibrous network hydrogels via electrostatic interaction, and the key role of divalent anions in the gelation is further proved by molecular dynamics simulation. In addition, near infrared light-mediated photothermal characteristics are endowed for LZF to enhance its inhibitory activity of multi-drug-resistant bacteria by the skeleton modification with genipin to produce genipin-conjuagted LZF (GLZF). As a distinct application paradigm, the brilliant immunomemory MnSO 4-crosslinked GLZF hydrogel is constructed to sensitize cGAS-STING pathway and skillfully establish an antibacterial immune microenvironment. It can excellently realize the infected anti-recurrence of diabetic wound via photo-enhanced bacterial killing and cGAS-STING pathway. Thereby, it paves the way to employ the universal divalent anion-mediated gelation strategy for future developing functional inorganic salt-hybrided lysozyme hydrogels.

The regulation of emission color, emission efficiency and asymmetry factor is of great significance for the real applications of circularly polarized luminescent (CPL) materials. Herein, we develop a modular synthetic strategy toward full-color-tunable CPL materials based on chiral macrocyclic aggregation-induced emission (AIE) luminogens via delicate molecular engineering. Modular synthesis of chiral AIEgens with different acceptor moieties has afforded series of bright solid emitters with tunable emission colors. These chiral cyclic AIEgens have retained high solid state emission quantum yield and displayed CPL emission from blue to red as nano-aggregates, in liquid crystal matrix and polymer film. The strong acceptor units in the red-emitting chiral AIEgens RBTPE-2CN and SBTPE-2CN have rendered them twisted intramolecular charge transfer property and solvatochromic luminescence. And polymer matrix with different polarity further facilitates the tuning of CPL emission color from green to red emission. These results have paved a reliable approach toward constructing full-spectra solid-state CPL material.

The poor prognosis of triple-negative breast cancer (TNBC) resulting from its high metastasis, whereas inflammation accompanied by excessive reactive oxygen species (ROS) is prone to aggravate tumor metastasis. Although photothermal therapy (PTT) has extremely high therapeutic efficiency, the crafty tumor cells allow increase the expression of heat shock proteins to limit its effect, and PTT induced inflammation is also thought to be a potential trigger for tumor metastasis. Herein, myricetin, iron ions and polyvinylpyrrolidone were utilized to develop nanomedicines by self-assembly strategy for the treatment of metastatic TNBC. The nanomedicines with marvellous water solubility and dispersion can inhibit glucose transporter 1 and interfer with mitochondrial function to block the energy supply of tumor cells, achieving starvation therapy on TNBC cells. Nanomedicines with excellent photothermal conversion properties allow down-regulate the expression of HSPs to enhance the effect of PTT. Interestingly, the broad spectrum of ROS scavenging ability of nanomedicines successfully attenuat PTT induced inflammation as well as regulate metastasis-related proteins through glycometabolism inhibition to reduce tumor cell metastasis. Moreover, the nanomedicines have negligible side effects and good clinical application prospect, which provides a valuable paradigm for the treatment of metastatic TNBC through glycometabolism interference, anti-inflammation, starvation and photothermal synergistic therapy.

Highly sensitive stimuli-responsive multifunctional luminescent materials are crucial for applications in optical sensing, high-level security, and anticounterfeiting. Here, we report two zero-dimensional (0D) hybrid copper(I) halides, (TEP) 2Cu 2Br 4 and (TEP) 2Cu 4Br 6, which are comprised of isolated [Cu 2Br 4] 2- and [Cu 4Br 6] 2- inorganic cluster units, respectively, separated by TEP + (TEP = tetraethylphosphonium) cations. (TEP) 2Cu 2Br 4 and (TEP) 2Cu 4Br 6 demonstrate ultrabright greenish-white and orange-red emissions, respectively, with near unity photoluminescence quantum yields. Optical spectroscopy measurements and density-functional theory (DFT) calculations reveal that photoemissions of these compounds originate from the formation of self-trapped excitons (STEs) due to the excited-state distortions in the copper(I) halide units. Single crystals of both compounds are radioluminescence (RL) active at room temperature under both X- and γ-rays exposure. The excellent energy resolution values and light yields up to 15,800 ph/MeV under 662 keV γ-rays of 137Cs suggest their potential for scintillation applications. Remarkably, (TEP) 2Cu 2Br 4 and (TEP) 2Cu 4Br 6 are interconvertible through external chemical stimuli or reverse crystallization. In addition, both compounds demonstrate luminescence on-off switching upon thermal stimuli. The sensitivity of (TEP) 2Cu 2Br 4 and (TEP) 2Cu 4Br 6 to the chemical and thermal stimuli coupled with their ultrabright emission allows their consideration for practical applications such as solid-state lighting, sensing, information storage, and anticounterfeiting.

Adsorbents with high adsorption efficiency and excellent biosafety for biomedical applications are highly required. MXene is a promising candidate owning these advantages, yet pristine MXene faces dilemmas including insufficient utility of surface site as well as limited processibility. Here, we develop MXene-encapsulated porous microcapsules via microfluidics. The microcapsules have a biomass hydrogel shell that provides a robust support for MXene in the core, by which the microcapsules are endowed with high MXene dosage and remarkable biosafety. Additionally, the MXene nanoflakes assemble into a three-dimension (3D) network via metal ion-induced gelation, thereby avoiding restacking and significantly improving surface utilization. Moreover, a freeze-pretreatment of the microcapsules during preparation results in the formation of a macroporous structure in the shell, which can facilitate the diffusion of the target molecules. These features, combined with additional magneto-responsiveness rendered by the incorporation of magnetic nanoparticles, contribute to prominent performances of the microcapsules in cleaning uremia toxins including creatinine, urea, and uric acid. Thus, it is anticipated that the MXene-encapsulated microcapsules will be promising adsorbents in dialysis-related applications, and the combination of microfluidic encapsulation with metal ion gelation will provide a novel approach for construction of hybrid MXene materials with desired functions.

Interview with Professor Guoqing Zhang

The side-chain has a significant effect on the optical properties and aggregation behaviors of the organic small molecule acceptors, which becomes an important strategy to optimize the photovoltaic performance of organic solar cells (OSCs). In this work, we designed and synthesized three novel nonfused ring electron acceptors (NFREAs) OC4-4Cl-Ph, OC4-4Cl-Th and OC4-4Cl-C8 with hexylbenzene, hexylthiophene and octyl side chains on the π-bridge units. Compared with OC4-4Cl-Ph and OC4-4Cl-Th, OC4-4Cl-C8 with linear alkyl side chain has more red-shift absorption, which is conducive to obtaining higher short-circuit current density. Additionally, the OC4-4Cl-C8 film exhibits a longer exciton diffusion distance and the D18:OC4-4Cl-C8 blend film displays faster hole transfer, weaker bimolecular recombination, and more efficient exciton transport. Furthermore, the D18:OC4-4Cl-C8 blend films can form good nano fibril-like interpenetrating networks, which can facilitate exciton dissociation and charge transport. Finally, OC4-4Cl-C8 based devices can generate an excellent PCE of 16.56%, which is much higher than OC4-4Cl-Ph (12.29%) and OC4-4Cl-Th based (11.00%) ones, being the highest PCE among the NFREA based binary devices. All in all, we have demonstrated that side-chain engineering is an efficient way to achieve high-performance NFREAs.

Amyloid-β peptide (Aβ) oligomers, characteristic symptom of Alzheimer’s disease (AD), have been identified as the most neurotoxic species and significant contributors to neurodegeneration in AD. However, due to their transient and heterogeneous nature, the high-resolution structures and exact pathogenic processes of Aβ oligomers are currently unknown. Using light-controlled molecular tweezers (LMTs), we describe a method for precisely capturing specific Aβ oligomers produced from synthetic Aβ and AD animal models. Light irradiation can activate LMTs, which are composed of two Aβ-targeting pentapeptides (KLVFF) motifs and a rigid azobenzene (azo) derivative, to form a tweezer-like cis configuration that preferentially binds to specifc oligomers matching the space of the tweezers via multivalent interactions of KLVFF motifs with the oligomers. Surprisingly, cis-LMTs can immobilize the captured oligomers in transgenic Caenorhabditis elegans (C. elegans) in vivo under light irradiation. The LMTs may serve as spatiotemporally controllable molecular tools to extract specific native oligomers for the structure and function studies via their reversible photoisomerization, which would improve the understanding of the toxic mechanisms of Aβ oligomers and development of oligomer-targeted diagnosis and therapy.

Fluorescent-magneto nanoemitters have gained considerable attention for their applications in mechanical controlling-assisted optical signaling. However, the incompatibility between magnetic and fluorescent components often leads to functional limitations in traditional magneto@fluorescence nanostructure. Herein, we introduce a new compact-discrete spatial arrangement on a “fluorescence@magneto” core–shell nanostructure consisting of a close-packed aggregation-induced emission luminogen (AIEgen) core and a discrete magnetic shell. This structural design effectively eliminates the optical and magnetic interferences between the dual components by facilitating AIEgens loading in core region and reducing the magnetic feeding amount through effective exposure of the magnetic units. Thereby, the resulting magneto-AIEgen nanoparticle (MANP) demonstrates “win-win” performances: (i) high fluorescent intensity contributed by AIEgens stacking-enhanced photoluminescence and reduced photons loss from the meager magnetic shell; (ii) marked magnetic activity due to magneto extraposition-minimized magnetic shielding. Accordingly, the dual functions-retained MANP provides a proof of concept for construction of an immunochromatographic sensing platform, where it enables bright fluorescent labeling after magnetically enriching and separating procalcitonin and lipoarabinomannan in clinical human serum and urine, respectively, for the clinical diagnosis of bacterial infections-caused inflammation and tuberculosis. This study not only inspires the rational design of magnetic-fluorescent nanoemitter, but also highlights promising potential in magneto-assisted point-of-care test and biomedicine applications.

Photoresponsive supramolecular materials have been fabricated by controlling the density of reversible cross-links or the distribution of movable cross-links. This study prepared photoresponsive polyurethane (CD-Azo-PU) based on controlling the crystallization of the hard segments in polyurethane (PU) by complexation between azobenzene (Azo) and cyclodextrins (CDs). CD-Azo-PU incorporated polyurethane as the main chain and a 1:2 inclusion complex between Azo and γCD as a movable crosslink point. Upon ultraviolet light (UV, λ = 365 nm) irradiation, the photoresponsiveness of CD-Azo-PU bent toward the light source (defined as positive), while that of the linear Azo polyurethane (Azo-LPU) without TAcγCD-diOH as a movable crosslinker bent in the direction opposite the light source. The bending rates were determined to be 0.058°/s for CD-Azo-PU and 0.027°/s for Azo-LPU, indicating that the bending rate for CD-Azo-PU was faster than that for Azo-LPU. By incorporating movable cross-links into CD-Azo-PU, we successfully achieved specific photoresponsive actuation with an enhanced rate.

The efficacy of nanoparticle (NP)-based drug delivery technology is hampered by aberrant tumor stromal microenvironments (TSMs) that hinder NP transportation. Therefore, the promotion of NP permeation into deep tumor sites via the regulation of tumor microenvironments is of critical importance. Herein, we propose a potential solution using a dihydrazidine (HDZ)-loaded nanoparticle drug delivery system containing a pH-responsive, cyclic RGD peptide-modified prodrug based on doxorubicin (cRGD-Dex-DOX). With a combined experimental and theoretical approach, we find that the designed NP system can recognize the acid tumor environments and precisely release the encapsulated HDZ into tumor tissues. HDZ can notably downregulate the expression levels of hypoxia-inducible factor 1α (HIF1α), α-smooth muscle actin, and fibronectin through the dilation of tumor blood vessels. These changes in the TSMs enhance the enrichment and penetration of NPs and also unexpectedly promote the infiltration of activated T cells into tumors, suggesting that such a system may offer an effective “multifunctional therapy” through both improving the chemotherapeutic effect and enhancing the immune response to tumors. In vivo experiments on 4T1 breast cancer bearing mice indeed validate that this therapy has the most outstanding antitumor effects over all the other tested control regimens, with the lowest side effects as well.

Centrifugal and shear forces are produced when solids or liquids rotate. Rotary systems and devices that use these forces, such as dynamic thin-film flow technology, are evolving continuously, improving material structure-property relationships at the nanoscale, representing a rapidly thriving and expanding field of research high with green chemistry metrics, consolidated at the inception of science. The vortex fluidic device (VFD) provides many advantages, with fluidic waves causing high shear and producing large surface areas for micro-mixing as well as rapid mass and heat transfer, enabling reactions beyond diffusion control in the processing. Combining these abilities allows for a green and innovative approach to altering materials for various research and industry applications by controlling small-scale flows and regulating molecular and macromolecular chemical reactivity, self-organization phenomena, and the synthesis of novel materials. This review highlights the aptitude of the VFD as clean technology, with an increase in efficiency for a diversity of top-down, bottom-up, and novel material transformations, benefiting from effective vortex-based processing for the transformation of material structure-property relationships.

Macroscopic chiral spherulites prepared by hierarchical self-assembly have attracted considerable attention due to their excellent property as chiroptical materials. However, preparing controllable handedness spherulites in bulk film remains a challenge due to the absent knowledge of the evolution mechanism from the molecule to macroscopic crystal during chiral assembly. In this contribution, we constructed chiral controllable macroscopic spherulites with circularly polarized luminescence (CPL) using enantiomeric tartaric acid and Rhodamine B co-assembled with liquid crystal block copolymers, poly (ethylene oxide)-b-poly (methyl methacrylate) bearing azobenzene group side chains. It was found that the chiral liquid crystal field induced by exogenous chiral molecules was closely related to the formation of macroscopic chiral spherulites. Moreover, the transformation of azobenzene cis-trans isomerization under photo-thermal endows films with adjustable CPL. This facile strategy provides a platform to design large-scale chiral structures for chiroptical switching, encryption, and memory storage materials.

Crosslinking thermosets with hyperbranched polymers confers them superior comprehensive performance. However, it still remains a further understanding of polymer crosslinking from the molecular chains to the role of aggregates. In this study, three hyperbranched polysiloxane structures (HBPSi-R) are synthesized as model macromolecules, each featuring distinct terminal groups (R denotes amino, epoxy, and vinyl groups) while similar molecular backbone (Si-O-C). These structures were subsequently copolymerized with epoxy monomers to construct interpenetrating HBPSi-R/epoxy/anhydride co-polymer systems. The spatial molecular configuration and flexible Si-O-C branches of HBPSi-R endow them with remarkable reinforcement and toughening effects. Notably, an optimum impact strength of 28.9 kJ mol-1 is achieved with a mere 3% loading of HBPSi-V, nearly three times that of the native epoxy (12.9 kJ mol-1). By contrasting the terminal effects, the aggregation states and crosslinking modes were proposed, thus clarifying the supramolecular-dominant aggregation mechanism and covalent-dominant dispersion mechanism, which influences the resulting material properties. This work underscores the significance of aggregate science in comprehending polymer crosslinking and provides theoretical insights for tailoring material properties at a refined molecular level in the field of polymer science.

Antibiotic resistance is a major challenge in the clinical treatment of bacterial infectious diseases. Herein, we constructed a multifunctional DNA nanoplatform as a versatile carrier for bacteria-specific delivery of clinical antibiotic ciprofloxacin (CIP) and classic nanoantibiotic silver nanoparticles (AgNP). In our rational design, CIP was efficiently loaded in the self-assembly double-bundle DNA tetrahedron through intercalation with DNA duplex, and single-strand DNA-modified AgNP was embedded in the cavity of the DNA tetrahedron through hybridization. With the site-specific assembly of targeting aptamer in the well-defined DNA tetrahedron, the bacteria-specific dual-antibiotic delivery system exhibited excellent combined bactericidal properties. With enhanced antibiotic accumulation through breaking the out membrane of bacteria, the antibiotic delivery system effectively inhibited biofilm formation and promoted the healing of infected wounds in vivo. This DNA-based antibiotic delivery system provides a promising strategy for the treatment of antibiotic-resistant infections.