Poly(pentahydropyrimidine)-Based Hybrid Hydrogel with Synergistic Antibacterial and Pro-Angiogenic Ability for the Therapy of Diabetic Foot Ulcers

Bacterial infection and impaired angiogenesis make the treatment of diabetic foot ulcers (DFU) extremely challenging. Cationic polymers are expected to treat infected wounds due to their excellent antibacterial properties, but still, it is difficult to meet the therapeutic needs of pro-angiogenesis and anti-infections due to their simple construction units and outmoded synthesis methods. Herein, a cationic poly(pentahydropyrimidine) (PPHP) library with strong modifiability is synthesized to construct a hybrid hydrogel with synergistic therapeutic effects for the treatment of infected DFUs. It is found that the as-synthesized hybrid hydrogel can up-regulate angiogenesis-related gene (HIF-1, VEGF, and bFGFR/bFGF) expression and targeted disruption of bacterial cell membranes, which finally promotes the healing of infected DFU (wound healing rate: 92%) within 10 days. This hydrogel, thus, holds great promise in developing new strategies to significantly enhance the treatment of DFU and other bacterial-infected pathological diagnoses.     

Bioinspired Intervertebral Disc with Multidirectional Stiffness Prepared via Multimaterial Additive Manufacturing

Degenerative disc disease (DDD) has become a significant public health issue worldwide. This can result in loss of spinal function affecting patient health and quality of life. Artificial total disc replacement (A-TDR) is an effective approach for treating symptomatic DDD that compensates for lost functionality and helps patients perform daily activities. However, because current A-TDR devices lack the unique structure and material characteristics of natural intervertebral discs (IVDs), they fail to replicate the multidirectional stiffness needed to match physiological motions and characterize anisotropic behavior. It is still unclear how the multidirectional stiffness of the disc is affected by structural parameters and material characteristics. Herein, a bioinspired intervertebral disc (BIVD-L) based on a representative human lumbar segment is developed. The proposed BIVD-L reproduces the multidirectional stiffness needed for the most common physiological kinematic behaviors. The results demonstrate that the multidirectional stiffness of the BIVD-L can be regulated by structural and material parameters. The results of this research deepen knowledge of the biomechanical behavior of the human lumbar disc and may provide new inspirations for the design and fabrication of A-TDR devices for both engineering and functional applications.     

Fast Ion Transport in Li-Rich Alloy Anode for High-Energy-Density All Solid-State Lithium Metal Batteries

All-solid-state Li batteries (ASSLBs) with solid-polymer electrolytes are considered promising battery systems to achieve improved safety and high energy density. However, Li dendrite formation at the Li anode under high charging current density/capacity has limited their development. To tackle the issue, Li-metal alloying has been proposed as an alternative strategy to suppress Li dendrite growth in ASSLBs. One drawback of alloying is the relatively lower operating cell voltages, which will inevitably lower energy density compared to cells with pure Li anode. Herein, a Li-rich Li₁₃In₃ alloy electrode (LiRLIA) is proposed, where the Li₁₃In₃ alloy scaffold guides Li nucleation and hinders Li dendrite formation. Meanwhile, the free Li can recover Li's potential and facilitate fast charge transfer kinetics to realize high-energy-density ASSLBs. Benefitting from the stronger adsorption energy and lower diffusion energy barrier of Li on a Li₁₃In₃ substrate, Li prefers to deposit in the 3D Li₁₃In₃ scaffold selectively. Therefore, the Li–Li symmetric cell constructed with LiRLIA can operate at a high current density/capacity of 5 mA cm⁻²/5 mAh cm⁻² for almost 1000 h.     

Grafted MXenes Based Electrolytes for 5V-Class Solid-State Batteries

Polymer blends based solid polymer electrolytes (SPEs), combining the advantages of multiple polymers, are promising for the utilization of 5 V-class cathodes (e.g., LiCoMnO₄ (LCMO)) with enhanced safety. However, severe macro-phase separation with defects and voids in polymer blends restrict the electrochemical stability and ionic migration of SPEs. Herein, inorganic compatibilizer polyacrylonitrile grafted MXene (MXene-g-PAN) is exploited to improve the miscibility of the poly(vinylidene fluoride-co-hexafluoropropylene) (PVHF)/PAN blends and suppress the consolidation of phase particles. The resulting SPE exhibits a high anodic stability with an ionic conductivity of 2.17 × 10⁻⁴ S cm⁻¹, enabling a stable and reversible Li platting/stripping (over 2500 h). The fabricated solid Li‖LCMO cell delivers a 5.1 V discharge voltage with a decent capacity (131 mAh g⁻¹) and cycling performance. Subsequently, the solid all-in-one graphite‖LCMO battery is also constructed to extend the application of MXene based SPEs in flexible batteries. Benefiting from the interface-less design, outstanding mechanical flexibility and stability is achieved in the battery, which can endure various deformations with a low-capacity loss (< ≈10%). This study signifies a significant development on solid flexible lithium ion batteries with enhanced performance, stability, and reliability by investigating the miscibility of polymer blends, benefiting for the design of high-performance SPEs.     

Tuning the Intermolecular Electrostatic Interaction toward High-Efficiency and Low-Cost Organic Solar Cells

Organic solar cells (OSCs) have achieved much progress with rapidly increasing power conversion efficiencies (PCEs). It should be noted that the top-performance OSCs are generally consisted of active materials with complex chemical structures, resulting in high costs. Here, combining the material design and morphology control, high-efficiency OSCs are fabricated by a low-cost donor: acceptor blend. A completely non-fused electron acceptor named Tz is designed and synthesized via introducing thiazole units on both sides of a bithiophene core, which shows an outstanding PCE of 13.3% with a typical polythiophene donor. More importantly, optimization guidelines are presented to get excellent morphology for low-cost donor:acceptor systems. Three polythiophenes are selected, poly(3-hexylthiophene) and its two derivatives with electron-withdrawing substitutions (PDCBT and PDCBT-2F), as donors to fabricate the cell devices. The computational and experimental data reveal that decreasing the electrostatic interaction between polythiophene and Tz is the key to getting a suppressed miscibility and thus a high phase purity. This study provides insight into the molecular design and donor:acceptor matching requirements for high-efficiency and low-cost OSCs.     

Macrophage Membrane-Coated Nanoparticles Sensitize Glioblastoma to Radiation by Suppressing Proneural–Mesenchymal Transformation in Glioma Stem Cells

Radiotherapy is identified as a crucial treatment for patients with glioblastoma, but recurrence is inevitable. The efficacy of radiotherapy is severely hampered partially due to the tumor evolution. Growing evidence suggests that proneural glioma stem cells can acquire mesenchymal features coupled with increased radioresistance. Thus, a better understanding of mechanisms underlying tumor subclonal evolution may develop new strategies. Herein, data highlighting a positive correlation between the accumulation of macrophage in the glioblastoma microenvironment after irradiation and mesenchymal transdifferentiation in glioblastoma are presented. Mechanistically, elevated production of inflammatory cytokines released by macrophages promotes mesenchymal transition in an NF-κB-dependent manner. Hence, rationally designed macrophage membrane-coated porous mesoporous silica nanoparticles (MMNs) in which therapeutic anti-NF-κB peptides are loaded for enhancing radiotherapy of glioblastoma are constructed. The combination of MMNs and fractionated irradiation results in the blockage of tumor evolution and therapy resistance in glioblastoma-bearing mice. Intriguingly, the macrophage invasion across the blood-brain barrier is inhibited competitively by MMNs, suggesting that these nanoparticles can fundamentally halt the evolution of radioresistant clones. Taken together, the biomimetic MMNs represent a promising strategy that prevents mesenchymal transition and improves therapeutic response to irradiation as well as overall survival in patients with glioblastoma.     

Direct Growth of Uniform Bimetallic Core-Shell or Intermetallic Nanoparticles on Carbon via a Surface-Confinement Strategy for Electrochemical Hydrogen Evolution Reaction

Due to the surface inhomogeneity of the solid supports, direct growth of uniform bimetallic nanoparticles (NPs) with controllable structure and size thereon is particularly challenging. Herein, a surface-confinement strategy is reported to directly prepare ultrafine bimetallic Pt M NPs (MFe, Cu, and Co) with structure of core-shell or intermetallic compounds on an N functionalized carbon support (NC). It is found that the N species of NC support can atomically disperse metal cations of precursors, which largely renders uniform nucleation and growth of bimetallic NPs and fine structure modulation of them. In another regard, metal transfer is confined to a narrow region on NC via N-mediation, hence greatly favoring localized particle growth and formation of ultrafine bimetallic NPs. Remarkably, the ultrafine 3.1 ± 0.7 nm intermetallic Pt₃Fe NPs on NC displayed excellent catalytic activity and durability toward electrochemical hydrogen evolution reaction.     

Glycyrrhetinic Acid Liposomes Encapsulated Microcapsules from Microfluidic Electrospray for Inflammatory Wound Healing

In diabetic wound healing, M1 macrophage accumulation and elevated inflammation are prevalent issues. Intelligent delivery systems that can sustainably release antioxidizing and anti-inflammatory ingredients are expected for effective wound healing. Herein, a novel glycyrrhetinic acid (GA) liposomes encapsulated microcapsules delivery system that has desired features for inflammatory wound repair is presented. As the bacteria could break down the alginate shells, the GA liposomes could be controllably released from the microcapsules, which promotes M2 macrophage polarization and regulate their responses in the inflammatory wound microenvironment. Based on these, it is demonstrated that the GA liposomes encapsulated microcapsules delivery system exhibits an anti-inflammatory and immunomodulatory effect for diabetic wound healing in a full-thickness defect model in diabetic rats. These results indicate that the immunomodulatory capabilities of the microcapsules can be unitized for efficient wound repair, and such a delivery system is valuable for clinical wound healing applications.     

Modulating Backbone Conjugation of Polymeric Thermally Activated Delayed Fluorescence Emitters for High-Efficiency Blue OLEDs

Blue conjugated polymers-based OLEDs with both high efficiency and low efficiency roll-off are under big challenge. Herein, a strategy of local conjugation is proposed to construct high-efficiency blue-emitting conjugated polymers, in which the conjugation degree of polymeric backbones is adjusted by inserting different spacers. In this way, the energy level of triplet state and the energy transfer direction of the polymeric main-chains can be effectively regulated. Benefiting from such fine regulation, the prepared alternative copolymers Alt-PB36 with local conjugated main-chains can better suppress the accumulation of long-lived triplet excitons comparing with the complete conjugated polymers. The higher PLQY of Alt-PB36 also verifies the effective energy transfer from the polymeric main-chains to the TADF units. Accordingly, Alt-PB36 based solution-processed OLEDs achieve an EQE_max of 11.6% and a very low efficiency roll-off of 2.8% at 100 cd m⁻² and 15.2% at 500 cd m⁻². This result represents the best efficiency among blue light-emitting conjugated polymer-based OLEDs so far under high luminance.     

A Sensing and Stretchable Polymer-Dispersed Liquid Crystal Device Based on Spiderweb-Inspired Silver Nanowires-Micromesh Transparent Electrode

Polymer-dispersed liquid crystal (PDLC) devices are truly promising optical modulators for information display, smart window as well as intelligent photoelectronic applications due to their fast switching, large optical modulation as well as cost-effectiveness. However, realizing highly soft PDLC devices with sensing function remains a grand challenge because of the intrinsic brittleness of traditional transparent conductive electrodes. Here, inspired by spiderweb configuration, a novel type of silver nanowires (AgNWs) micromesh-based stretchable transparent conductive electrodes (STCEs) is developed to support the realization of soft PDLC device. Benefiting from the embedding design of AgNWs micromesh in polydimethylsiloxane (PDMS), the STCEs can maintain excellent electrical conductivity and transparency even in various extreme conditions such as bending, folding, twisting, stretching as well as multiple chemical corrosion. Further, STCEs with the embedded AgNWs micromesh endow the assembled PDLC device with excellent photoelectrical properties including rapid switching speed (<1 s), large optical modulation (69% at 600 nm), as well as robust mechanical stability (bending over 1000 cycles and stretching to 40%). Moreover, the device displays the pressure sensing function with high sensitivity in response to pressure stimulus. It is conceivable that AgNWs micromesh transparent electrodes will shape the next generation of related soft smart electronics.