http://onlinelibrary.wiley.com/rss/journal/10.1002/(ISSN)1521-4095

The actuation of stomata—referring to their opening and closing—is crucial for photosynthesis because it regulates gas exchange and water balance. Here, it is investigated if this life-like property could enhance the photocatalytic properties of soft materials. A hybrid supramolecular and covalent polymer hydrogel is developed to integrate photocatalytic chromophores and stimuli-responsive properties for controlling or improving light-driven superoxide or hydrogen peroxide generation.

Mechanical expansion and contraction of pores within photosynthetic organisms regulate a series of processes that are necessary to manage light absorption, control gas exchange, and regulate water loss. These pores, known as stoma, allow the plant to maximize photosynthetic output depending on environmental conditions such as light intensity, humidity, and temperature by actively changing the size of the stomal opening. Despite advances in artificial photosynthetic systems, little is known about the effect of such mechanical actuation in synthetic materials where chemical reactions occur. It is reported here on a hybrid hydrogel that combines light-activated supramolecular polymers for superoxide production with thermal mechanical actuation of a covalent polymer. Superoxide production is important in organic synthesis and environmental remediation, and is a potential precursor to hydrogen peroxide liquid fuel. It is shown that the closing of pores in the hybrid hydrogel results in a substantial decrease in photocatalysis, but cycles of swollen and contracted states enhance photocatalysis. The observations motivate the development of biomimetic photosynthetic materials that integrate large scale motion and chemical reactions.

A novel multifunctional fiber energy storage device consisting of LMO-LTP-AC is developed by the coating-extrusion method. Due to the continuous preparation process, devices exhibited an ultra-high production rate of 6000 km year−1. This innovative approach significantly enhanced the device performance, achieving a specific capacity of 89.4 mAh g−1 for fiber batteries and rate performance of 20 C for fiber hybrid supercapacitors.

The rise of wearable electronics demands flexible energy storage solutions like flexible fiber energy storage devices (FESDs), known for their flexibility and portability. However, it remains difficult for existing fabrication methods (typically, finite-coating, thermal-drawing, and solution-extrusion) to simultaneously achieve desirable electrochemical performances and fast production of FESDs. Here, a new scalable coating-extrusion method is developed, utilizing a novel extruded spinneret with tapered apertures to create dual pressure zones. These attributes reduced porosity, enhanced electrode materials loading, and stabilized the interface between the fiber electrode and gel electrolyte of FESDs, enabling the integration of three functional electrodes for the fabrication of both fiber LMO-LTP batteries and fiber LMO/LTP-AC hybrid supercapacitor within a single energy storage device. The resultant multifunctional device achieved a high specific capacity of 89.4 mAh g−1 in battery mode and demonstrated excellent rate performance of 20 C with nearly 50% capacity retention in supercapacitor mode, with a production rate of 6000 km year−1.

A negative enthalpy doping strategy can significantly increase its in-plane stability of the transition metal layer, which considerably suppresses destructive P2 to O2 phase transition and reduces lattice distortion, stabilizing the cycling performance of P2-type Na0.67Ni0.33Mn0.67O2 cathode for sodium-ion batteries.

P2-type Na0.67Ni0.33Mn0.67O2 (NNMO) as cathode material for sodium-ion batteries (SIBs) largely suffers from continuous accumulation of local stress caused by destructive structural evolution and irreversible oxygen loss upon cycling, leading to rapid capacity degradation. Herein, a strategy of negative enthalpy doping (NED), wherein transition metal (TM) sites are substituted with 0.01 mol each Sn, Sb, Cu, Ti, Mg, and Zn to increase the stability of the TM layers, is proposed. The robust structure of NED-NNMO significantly suppresses the P2 to O2 phase transition and improves the Na+ kinetics upon long-term cycling. Consequently, the NED-NNMO exhibits much smoothened voltage platforms and improved oxygen redox reversibility, thus considerably extended lifetime as compared with the pristine NNMO sample. The NED-NNMO delivers a high capacity of 138.9 mAh g−1 with an operation voltage of 3.51 V under 0.1 C and prominent capacity retention of 94.6% after 100 cycles under 1 C, and 90.0% over 3000 cycles under ultra-high rate of 30 C, which is among the best over previous reports. Moreover, an ampere-hour scale pouch cell based on the NED-NNMO demonstrates an energy density of 139 Wh kg−1. This work sheds light on a route of negative enthalpy doping to design high-performance sodium-ion batteries.

An unprecedented flexible porous polymer HCP-DPP, constructed by the flexible building unit with the rigid external crosslinker, achieves a desirable trade-off between porosity and density while displaying an unusual gate-opening effect; which set a record-high volumetric methane storage capacity among reported adsorbents, revealing a great promise for flexible hyper-cross-linked polymers in methane storage applications.

Adsorbed natural gas (ANG) storage is emerging as a promising alternative to traditional compressed and liquefied storage methods. However, its onboard application is restricted by low volumetric methane storage capacity. Flexible porous adsorbents offer a potential solution, as their dense structures and unique gate-opening effects are well-suited to enhance volumetric capacity under high pressures. This study developes a series of hyper-cross-linked polymers (HCPs) with tunable flexibility by modifying the aliphatic chain length in double-benzene-ring building blocks, employing a cost-effective external crosslinking approach. The resulting flexible polymer, HCP-DPP, exhibits pore expansion under specific methane pressures, producing a high-pressure adsorption isotherm with gate-opening behavior. Combined with its intrinsic dense skeleton, this feature leads to superior volumetric methane storage performance over rigid counterparts. Notably, HCP-DPP achieves a record-high volumetric total uptake of 333 cm3 STP cm−3 and a working capacity of 291 cm3 STP cm−3 at 273 K and 100 bar, exceeding the U.S. Department of Energy (DOE) target of 263 cm3 STP cm−3. These findings lay a foundation for developing advanced flexible porous adsorbents for practical ANG applications.

This work presents an effective strategy to address a longstanding challenge in the practical application of soft bioelectrodes: integrating excellent electrical performance, high compactness, and environmental durability. By leveraging the synergy between holey graphene and conductive polymer, this approach realizes reliable electron-ion transduction through the construction of robust ionic and electronic transfer pathways at the molecular level.

Bioelectrodes function as a critical interface for signal transduction between living organisms and electronics. Conducting polymers (CPs), particularly poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), are among the most promising materials for bioelectrodes, due to their electrical performance, high compactness, and ease of processing, but often suffer from degradation or de-doping even in some common environments (e.g., electrical stimulation, chemicals, and high temperatures). This instability therefore severely undermines their reliability in practical application. To resolve this critical issue, a novel strategy of separating electron transfer from electron-ion transduction is proposed. Specifically, chemically derived holey graphene (HG), serving as an ultra-stable mixed ion-electron conductor, is introduced into the CP matrix. The HG can restore the CP's destructed conductive pathways, whilst its porosity and its intercalation by the CP synergically preserve fast ionic and molecular diffusion. The resulting bioelectrode therefore exhibits excellent low impedance, high charge injection capacity, electrochemical activity, and outstanding resilience to various harsh conditions, outperforming HG, reduced graphene oxide, CP, or graphene-coated CP electrodes. Furthermore, this strategy also exhibits broad compatibility with various processing techniques and proves adaptable to other electrode systems, such as stretchable electrodes, paving the way for practical applications in electrophysical capture, neuron modulation, and biochemical analysis.

The c-B-Mo2C catalyst, constructed through a phase and orbital engineering strategy, significantly enhances its catalytic activity by restructuring the basal surface for the conversion of lithium–sulfur batteries. Consequently, c-B-Mo2C-based batteries exhibit elevated capacity, excellent rate capability, and stable cycling life.

The delicate construction of electrocatalysts with high catalytic activity is a strategic method to enhance the kinetics of lithium–sulfur batteries (LSBs). Adjusting the local structure of the catalyst is always crucial for understanding the structure–activity relationship between atomic structure and catalyst performance. Here, in situ induction of electron-deficient B enables phase engineering Mo2C, realizing the transition from hexagonal (h-Mo2C) to cubic phase (c-B-Mo2C). Meanwhile, the empty sp3 orbital of B favors the effective bonding with electron-rich sulfur, creates a more valid orbital engineering available. Relying on the binary engineering via B doping, the adsorption and conversion of polysulfides are promoted. Hence, the c-B-Mo2C based cell achieves a low-capacity degradation of 0.04% with the coulombic efficiency exceeding 99.8% in 1000 cycles. Uniform Li+ transport is consistently achieved at 2 mA cm−2 for over 600 h. A 6.67Ah-c-B-Mo2C based pouch cell has a high energy density of up to 502.1 Wh kg−1 (E/S ratio of 2.4 µL mg S −1), while the pouch cell of 2 Ah exhibits an energy density of 372 Wh kg−1 more than 100 cycles. This study takes advantage of the combined engineering method to provide a guiding approach for elevating the activity of the electrocatalysts rationally.

Base editing using nanoneedles efficiently corrects pathogenic variants in the type VII collagen gene of primary fibroblasts from patients with recessive dystrophic epidermolysis bullosa. Nanoneedle editing induces minimal and reversible transcriptional perturbations while restoring the production and secretion of functional type VII collagen. The study highlights the value of nanoneedles as a tool for base editing in cell therapies for genetic disorders.

Base editing, a CRISPR-based genome editing technology, enables precise correction of single-nucleotide variants, promising resolutive treatment for monogenic genetic disorders like recessive dystrophic epidermolysis bullosa (RDEB). However, the application of base editors in cell manufacturing is hindered by inconsistent efficiency and high costs, contributed by suboptimal delivery methods. Nanoneedles have emerged as an effective delivery approach, enabling highly efficient, non-perturbing gene therapies both in vitro and in vivo. Here we demonstrate that nanoneedle delivery of an adenine base editor corrects a heterozygous single-nucleotide pathogenic variant in COL7A1 in primary RDEB fibroblasts in vitro with 96.5% efficiency, without inducing off-target variants. The nanoneedle delivery maintains cell viability and displays modest phenotypical alterations unlike conventional cationic lipid transfection. The nanoneedle-mediated editing significantly increases the production and secretion of full-length type VII collagen protein, contributing to restore functional fibroblasts phenotype by improving cell adhesion. These findings underscore the suitability and safety of nanoneedles for gene editing in a clinically relevant context of cell manufacturing, establishing a foundation for their use in cell therapies.

This work proposes an in-situ self-welding strategy that uses dynamic hydrogen bonds to integrate multilayer conductive elastomers into robust wearable electronics with superior structural stability and excellent pressure-sensing performance. The data reflecting resistance training are collected by the welded electronics and further analysed and classified by machine learning models, which enables home-based active rehabilitation.

Patients with hand dysfunction require joint rehabilitation for functional restoration, and wearable electronics can provide physical signals to assess and guide the process. However, most wearable electronics are susceptible to failure under large deformations owing to instability in the layered structure, thereby weakening signal reliability. Herein, an in-situ self-welding strategy that uses dynamic hydrogen bonds at interfaces to integrate conductive elastomer layers into highly robust electronics is proposed. This strategy enables the interlocking of functional layers with different microstructures, achieving high interfacial toughness (e.g., ≈700 J m−2 for micropyramid layer with the smallest welding areas) and preventing structural failure. The welded electronics exhibit excellent pressure-sensing performance, including high sensitivity, a wide sensing range, and excellent long-term stability, surpassing those of the unwelded electronics. This enables a reliable collection of comprehensive pressure signals during joint rehabilitation, which is beneficial for assessing the rehabilitation levels of a patient. Furthermore, a machine learning-assisted system using t-distributed stochastic neighbor embedding and artificial neural network models to facilitate home-based active rehabilitation is established, which reduces the need for frequent hospital visits. This system analyzes and quantifies rehabilitation levels in a timely manner, allowing patients to adjust training programs autonomously, thereby accelerating the rehabilitation process.

In this work, the architecture of a plant fiber cell wall is simplified to design novel concepts of 4D printed tubular moisture-driven structural actuators, using the hygromorphic properties of continuous flax fiber (cFF) reinforced materials named meta biocomposites. The potential applications are illustrated through a proof of concept for a meteosensitive rotative structure that transmits motion to an external device.

Biological structures provide inspiration for developing advanced materials from sustainable resources, enabling passive structural morphing. Despite an increasing interest for parsimony-oriented innovation, sustainable shape-changing materials based on renewable resources remain underexplored. In this work, the architecture of a single plant fiber cell wall (S2, for instance) is simplified to design novel concepts of 4D printed tubular moisture-driven structural actuators, using the hygromorphic properties of continuous flax fiber (cFF) reinforced materials. This new class of bioinspired active materials is referred to as metabiocomposites. Before bioinspired design, the materials are produced with a customized rotary 3D printer, qualified, and tested for sorption behavior. A parametric experimental, analytical, and FEA analysis highlights the programmability of the material through the effects of mesostructural parameters (printing inclination α) and geometric factors (operational length L, inner diameter D, and thickness h) on the actuation authority. The overall performance is a trade-off between rotation and torque, with energy density comparable to that of the source of inspiration: natural fibers cell wall. The potential applications are illustrated through a proof of concept for a meteosensitive rotative structure that transmits motion to an external device, such as a solar tracker.

The development of hydrogel-impregnated robust interlocking nano connector (HiRINC) aims to address stent migration by improving tissue adhesion and reducing mechanical mismatch in self-expandable metallic stents (SEMSs). The network-like porous layer of HiRINC enhances adhesion and energy dissipation, demonstrates through ex vivo and in vivo tests, effectively preventing migration in esophageal models.

Migration of implanted self-expandable metallic stent (SEMS) in the malignant or benign esophageal stricture is a common complication but not yet resolved. Herein, this research develops a hydrogel-impregnated robust interlocking nano connector (HiRINC) to ensure adhesion and reduce the mechanical mismatch between SEMSs and esophageal tissues. Featuring a network-like porous layer, HiRINC significantly enhances adhesion and energy dissipation during esophageal peristalsis by utilizing mechanical interlocking and increasing hydrogen bonding sites, thereby securing SEMS to tissues. The anti-swelling property of HiRINC prevents excessive hydrogel expansion, avoiding esophageal blockage. Ex vivo and in vivo adhesion tests confirm that the HiRINC outperforms flat surfaces without RINC structures and effectively prevents stent migration. HiRINC-coated SEMS maintains its position and luminal patency, minimizing stent-induced tissue hyperplasia and inflammatory responses in rat and porcine esophageal models during the 4-week follow-up. This novel HiRINC-SEMS can ensure anti-migration and prolonged stent patency in the rat and porcine esophagus and seems to be expanded to other nonvascular luminal organs and various implantable metallic devices.

A controllable electrodeposition combined phosphorization method is reported to synthesize a high-entropy phosphide/carbon (FeCoNiCuYP/C) composite. The Fe and Co/Ni sites in FeCoNiCuYP preferentially stabilize HO* and HOO* intermediates during the oxygen evolution reaction (OER), disrupting the traditional scaling relation of Gibbs free energy for these intermediates. The FeCoNiCuYP/C demonstrates excellent OER performance, requiring low overpotentials of 316 mV@100 mA cm−2.

The alkaline oxygen evolution reaction (OER) mainly encompasses four elementary reactions, involving intermediates such as HO*, O*, and HOO*. Balancing the Gibbs free energies of these intermediates at a single active site is a challenging task. In this work, a high-entropy metal-organic framework incorporating Fe, Ni, Co, Cu, and Y metal elements is synthesized using an electrodeposition method, which then serves as a template for preparing a high-entropy phosphide/carbon (FeCoNiCuYP/C) composite. Notably, the obtained composite exhibits an amorphous structure with multiple catalytically active sites. Combined theoretical calculations and experimental measurements reveal the critical roles of Co/Ni and Fe atoms in tuning the electronic structure of FeCoNiCuYP and optimizing the binding strength of intermediates. Furthermore, Fe and Ni/Co sites prefer to stabilize the HO* and HOO* intermediates respectively, conducive to breaking their scaling relation of Gibbs free energy during OER. Owing to its fine-tuned composition and the synergistic effect of multiple active sites, the FeCoNiCuYP/C electrocatalyst demonstrates superior OER performance in alkaline solutions, requiring a mere 316 mV overpotential to yield 100 mA cm−2 current density with excellent stability. This work provides an innovative route to design efficient high-entropy electrocatalysts, holding significant promise for cutting-edge electrocatalytic applications.

Cancer Vaccine

In article number 2412654, Qianqian Ni, Xiaoyuan Chen, Longjiang Zhang, and their team present a novel STING-activating polymer (PD) to enhance mRNA vaccine immunogenicity. By incorporating PD polymer into lipid nanoparticle, the resulted vehicle (PD LNP) improved lymphatic delivery and immune activation of mRNA cancer vaccine, demonstrating the promising potential of PD LNPs for cancer immunotherapy.

Ligand Inter-Relation Modeling

In article number 2414356, Heemin Kang, Sung-Gyu Park, Woo Young Jang, and co-workers show that RGD nano-ligand inter-relation inversely proportional to the shortest path distance in graph theory modeling activates integrin-bearing filopodia penetration and adhesion-mediated pro-regenerative polarization of host macrophages.

Catalyzing Sulfur Conversion Reactions

The sluggish sulfur conversion reaction is a bottleneck for the improvement of lithium-sulfur battery performance. In article number 2413653, Feng Li, Zhenhua Sun, Tong Yu, and co-workers reveal that long-range interactions in high-entropy single-atom catalysts regulate the electron states, facilitating sulfur conversion. The cover illustrates that different metal atoms accelerate electron transport, thereby boosting high-rate performance.

Mn-Based 2D Magnetoplumbites

In article number 2417906, Xin Gui and co-workers report the first Mn-based M-type hexaferrites, also known as magnetoplumbites. Mn3+ cations construct frustrated triangular, Kagome, and puckered honeycomb sublattices. Magnetic and heat capacity do not exhibit long-range magnetic order. Two-dimensional magnetic correlations and frustration within the Mn3+ Kagome layers are confirmed via the reverse Monte Carlo refinements on neutron powder diffraction patterns.

E?cient Lanthanide Recovery

In article number 2412607, Ariel Furst and co-workers report microbes decorated with the protein lanmodulin (LanM) as a displayed protein material for high-efficiency rare earth element recovery. This material serves as a low-cost, robust approach to enable environmentally-friendly recycling and retrieval of critical elements.

Proton Storage Chemistry

The cover image highlights the recent advances on the proton storage chemistry in aqueous zinc-inorganic batteries with moderate electrolytes from the perspective of the competition Taiji diagram of H+ and Zn2+ storage to better realize the peak-load shifting of solar and wind energy supply. More details can be found in article number 2414019 by Wenbin Li, QianQian Song, Yan Yu, Xifei Li, and co-workers.

High-Entropy Catalyst for Oxygen Evolution

In article number 2410295, Soumyabrata Roy, Bijun Tang, Hongyan Wang, Keyong Tang, and co-workers present a high-entropy phosphide catalyst that significantly enhances the oxygen evolution reaction. In FeCoNiCuYP, Fe and Ni sites respectively stabilize the HO* and HOO* intermediates, effectively breaking their scaling relation of Gibbs free energy and boosting catalytic performance.

LNP is modified by a novel STING-activating polymer (PD) to enhance immune effect of mRNA vaccines by boosting cellular uptake and triggering robust immune activation. Optimizing the polymerization of PD significantly amplifies mRNA translation efficiency and STING-mediated immune responses, offering a powerful approach to advance mRNA-based immunotherapy.

The unprecedented success of mRNA vaccines against COVID-19 has inspired scientists to develop mRNA vaccines for cancer immunotherapy. However, using nucleoside modified mRNA as vaccine, though evading innate immune toxicity, diminishes its therapeutic efficacy for cancers. Here, we report a polyvalent stimulator of interferon genes (STING) activating polymer (termed as PD) to bolster the immunogenicity of mRNA vaccine. PD is made of tertiary amine units and conjugated with a biodegradable alkyl chain. Co-formulation of PDs bearing different number of tertiary amines with lipid materials and mRNA resulted in the lipid-like nanoparticles (PD LNPs) which effectively promoted lymphatic delivery and elicited robust immune activation via the STING signaling pathway. Notably, PD with eighteen tertiary amines (PD18) is predominant in balancing immune activity and tolerability. Subcutaneous administration of PD18 LNPs containing ovalbumin (OVA) mRNA enhanced the frequency of antigen specific CD8+ T cell with immune memory, leading to potent anticancer efficacy that surpassed 2′3’-cGAMP in both prophylactic and therapeutic cancer models. Additionally, PD18 LNP-based mRNA vaccine showed conferred resistance to cancer challenge for up to 60 days. Overall, this study offers a new perspective of using STING- activating polymer for imparting synergistic activity in mRNA vaccine-based cancer immunotherapy.