Xiaozhong Qu

Bioadhesives for internal organ repair suffer from weak underwater adhesion, poor mechanical compatibility and indiscriminate tissue adhesion. Herein, we report the synthesis of poly(lipoic acid‐co‐caffeic acid) (poly(LA‐CA)) exhibiting tunable adhesive and mechanical properties according to the polymer configuration. By copolymerization of caffeic acid, thermal polymerization of lipoic acid yields branched copolymer of poly(LA‐CA), which is viscous and highly adhesive in wet conditions, while radical polymerization initiated by ammonium persulphate produces elastic and non‐adhesive linear poly(LA‐CA). Robust asymmetrically adhesive Janus patch is then fabricated by coating a branched poly(LA‐CA) layer on a linear copolymer substrate. The patch demonstrates combined performances, particularly showing universal, tough, and sustained adhesion in various environments, together with antioxidant, anti‐inflammatory and antibacterial properties. Using the Janus poly(LA‐CA) patch, gastric perforations of as large as 1 cm in diameter are cured in Bama miniature pigs without suturing. The sutureless treatment simultaneously prevents postoperative adhesion and gastric fluid leakage, resulting in 100% survival of the animals, superior to conventional suture repair method. The poly(LA‐CA) material is promising for soft tissue injury repair with high clinical translation potential.

Periodontitis, the sixth most prevalent global disease, causes tooth loss and systemic disorders, imposing a significant global burden. Functional regeneration of the periodontium remains a major challenge due to the hierarchical soft‐hard tissue interface and complex spatiotemporal functional demands. In this study, a synchronously in situ co‐injectable, interlayer‐bonding, and wet‐adhesive bilayer hydrogel (Bio‐Fun bilayer) consisting of PCAC and PCMC layers is developed. An anti‐delamination interface is engineered via polymer chain topological entanglement and dynamic boronate ester and ionic networks, while precise complex viscosity matching enables synchronized microscale laminar co‐extrusion. Concurrently, the hydrogel maintains wet adhesion, especially to moist root and bone surfaces. Spatiotemporal biofunctionalization is achieved by loading microRNA‐26a liposomes in the PCAC layer to activate Wnt/β‐catenin signaling for osteogenesis, and covalently tethering a PDGF‐BB mimetic peptide within the PCMC layer to trigger PI3K/Akt‐LOX signaling for fibroblast recruitment and functional collagen formation. In vivo, the Bio‐Fun bilayer hydrogel achieves integrated regeneration of alveolar bone and aligned periodontal ligament fibers, forming Sharpey's fiber‐like structures with firm bone‐ligament attachment. Meanwhile, the modular and injectable design might provide broad reference for the reconstruction of periodontal, osteochondral, and other soft‐hard tissue interfaces.

Dynamic visualization of strain and its distribution in materials are still challenging. Herein, dual-fluorophore three-dimensional covalent organic frameworks (3D-COFs) and the PEGylated 3D-COFs (PEG-3D-COFs) were synthesized for the construction of physically interacted assemblies to realize fluorescence imaging on not only strain distribution but also strain-related surface friction and flow velocity distributions in various media including polymer elastomers, organic or aqueous dispersions. The responsiveness arises from the controllability of the aggregation structure of 3D-COFs and PEG-3D-COFs, showing concentration-dependent morphology and photoluminescence, and meanwhile having a concentration-deformation equivalence on the structural evolution dynamics which drives the color change of the COF emission in the solids and liquids with high sensitivity and reversibility, whenever the superstructure of the COF assemblies is affected by the applied strain on the matrices. The report will inspire further efforts to construct responsive COFs for optical measurement aims.

Multielemental transition metal compounds represent a class of promising candidates for the biomedical field due to their unique structure and biomedical application potential. However, their synthesis process remains challenging, which was subject to the high-temperature treatment of the multimetallic elements integrated within one system. Herein, for the first time, we have fabricated the nanotripod, i.e., (FeCoNiCuZnAl)O_x (denoted as HEO) agent, via the structural topotactic transformation of layered double hydroxide (LDH) precursors with the tunable disorder degree, for highly efficient high-entropydynamic therapy associated with metabolism homeostasis. By virtue of this unique high-entropy structure, the outburst reactive oxygen species (ROS) generation can be regulated via turbulence. These unique high-entropy oxides not only presented outstanding ROS generation efficiency but also broke the intracellular metabolic balance cycle (NADH/NAD⁺) by NO_x-like activity, which can disturb the tumor energy metabolism homeostasis, leading to cell apoptosis. Furthermore, in vitro and in vivo experiments both indicate that this agent was a satisfying candidate for magnetic resonance imaging (MRI)-guided therapy. The findings offer a strategy for the development of high-entropydynamic therapy.

Non-contact measurement of surface pressure via an oxygen-quenching photoluminescence pathway may be interrupted by environmental temperature since most oxygen-sensitive probes are temperature sensitive. The inclusion of a proper temperature indicator for pressure correction is of importance for the application of the technique. In this work, we prepared aggregation-induced emission (AIE) luminogen (AIEgen)-incorporated polyacrylonitrile nanoparticles, which are highly sensitive to temperature change with preferable reversibility and possess desirable insensitivity to oxygen concentration and preferable stability against photobleaching. AIEgen-incorporated nanoparticles (AIE-NPs) are capable as a temperature-sensitive probe for constructing dual pressure- and temperature-sensitive coatings with a ruthenium complex as the oxygen-sensitive probe, and an oxygen-permeable room-temperature vulcanizing silicone rubber as the matrix. The coating enables the accurate mapping of oxygen or air pressure distribution on its surface, even under a condition of temperature variation, through simultaneous measurement of photoluminescence from the ruthenium complex and AIE-NPs. Such characteristics realized the utility of the coatings in the field of hydrodynamics and possibly in other applications.

Conventional embolists disreputably tend to recanalization arising from the low filling ratio due to their rigidity or instability. As a result, intelligent hydrogels with a tunable modulus may meaningfully improve the therapeutic efficacy. Herein, an injectable composite double-network (CDN) hydrogel with high shear responsibility was prepared as a liquid embolic agent by cross-linking poly(vinyl alcohol) (PVA) and carboxymethyl chitosan (CMC) via dynamic covalent bonding of borate ester and benzoic-imine. A two-dimensional nanosheet, i.e., layered double hydroxide (LDH), was incorporated into the network through physical interactions which led to serious reduction of yield stress for the injection of the hydrogel and the capacity for loading therapeutic agents like indocyanine green (ICG) and doxorubicin (DOX) for the functions of photothermal therapy (PTT) and chemotherapy. The CDN hydrogel could thus be transported through a thin catheter and further in situ strengthened under physiological conditions, like in blood, by secondarily cross-linking with phosphate ions for longer degradation duration and better mechanical property. These characteristics met the requirements of arterial interventional embolization, which was demonstrated by renal embolism operation on rabbits, and meanwhile favored the inhibition of subcutaneous tumor growth on an animal model. Therefore, this work makes a breakthrough in the case of largely reducing the embolism risks, thus affording a novel generation for interventional embolization.

The construction of variable structured multi‐protein nano‐assemblies is of great interest for the development of protein‐based therapeutic systems. This study showcases the synthesis of polymer‐protein assemblies with tunable structure like single‐ and multi‐layer polymer‐crosslinked protein vesicles, Janus protein vesicles and other hierarchical‐structured assemblies by utilizing a dynamic template‐assistant intermittent‐assembly approach. The generalization of the methodology helps the protein assemblies to gain notable functional complexity. And we demonstrate compelling evidence highlighting the substantial impact of the topological morphology of protein nanoaggregates on their cellular uptake capacity.