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Multi-mode emissive materials with stimuli-responsive producing invisible signals are very attractive for advanced security applications, but development of such materials remains highly challenging. In this work, oxygen-doped carbon nitrides (O-CNs) are prepared via microwave-assisted heating of urea, which exhibit ultraviolet (UV) solid-state fluorescence (SSFL), visible room temperature phosphorescence (RTP) and thermal-stimuli production of invisible UV delayed fluorescence (DF) properties. Further studies confirmed that the SSFL and RTP could be attributed to the introduction of oxygen functional group (e.g., C=O) in the skeleton of O-CNs, thus minimizing the aggregation caused quenching effect, facilitating intersystem crossing, and stabilizing the excited triplet states. The specific thermal-stimuli production of UV DF is deemed to be the relatively large energy gap between ground and excited singlet states as well as an effective triplet-triplet annihilation. Notably, the emission maximum of UV DF locates at ~310 nm with an ultra-narrow full width at half maximum (FWHM) down to 19 nm, so it is completely invisible to the naked eyes, but detectable by a UV camera. To employ the unique characteristics of O-CNs, security protection strategies with superior concealment by virtue of the thermal-stimuli quenching visible RTP and meanwhile producing invisible UV DF are demonstrated., (© 2024 Wiley‐VCH GmbH.)

Ulcerative colitis is an inflammation of the colon characterized by immune dysregulation and intestinal inflammation. Developing safe oral nanomedicines that suppress intestinal inflammation, while modulating colonic inflammatory microenvironment by scavenging reactive oxygen species (ROS) and hydrogen sulfide (H 2 S) is crucial for the effective treatment of colitis. Here, the tofacitinib citrate and copper coordination-based nanoparticle (TF-Cu nanoparticle, T-C) to dual-scavenge ROS and H 2 S by coordination competition is synthesized. Moreover, the coordination of T-C using computer simulation is explored. To enhance the acid stability and inflammatory targeting of T-C, it is encapsulated with hyaluronic acid-modified chitosan, along with a calcium pectinate coating (T-C@HP). Owing to the dual pH/pectinase-responsive characteristics of T-C@HP, the nanoplatform can target inflamed colonic lesions, inhibiting phosphorylated Janus kinase 1. Furthermore, T-C@HP scavenges ROS and H 2 S, as well as increases NADPH levels, which is investigated by combining biosensor (HyPer7 and iNap1/c) and chemical probes. T-C@HP also alleviates colitis by regulating the colonic inflammatory microenvironment through multiple processes, including the modulation of apoptosis, macrophage polarization, tight junction, mucus layer, and intestinal flora. Complemented by satisfactory anti-inflammatory and biosafety results, this nanoplatform represents a promising, effective, and safe treatment option for colitis patients., (© 2024 Wiley‐VCH GmbH.)

Regenerating bone defects in diabetic rats presents a significant challenge due to the detrimental effects of reactive oxygen species and impaired autophagy on bone healing. To address these issues, a metformin-modified biomimetic silicified collagen scaffold is developed utilizing the principles of biomimetic silicification. In vitro and in vivo experiments demonstrated that the scaffold enhanced bone tissue regeneration within the diabetic microenvironment through the release of dual bio-factors. Further analysis reveals a potential therapeutic mechanism whereby these dual bio-factors synergistically promoted osteogenesis in areas of diabetic bone defects by improving mitochondrial autophagy and maintaining redox balance. The present study provides critical insights into the advancement of tissue engineering strategies aimed at bone regeneration in diabetic patients. The study also sheds light on the underlying biological mechanisms., (© 2024 Wiley‐VCH GmbH.)

2D conjugated covalent organic frameworks (c-COFs) provide an attractive foundation as organic electrodes in energy storage devices, but their storage capability is long hindered by limited ion accessibility within densely π-π stacked interlayers. Herein, two kinds of 2D c-COFs based on dioxin and dithiine linkages are reported, which exhibit distinct in-plane configurations-fully planar and undulated layers. X-ray diffraction analysis reveals wavy square-planar networks in dithiine-bridged COF (COF-S), attributed to curved C─S─C bonds in the dithiine linkage, whereas dioxin-bridged COF (COF-O) features densely packed fully planar layers. Theoretical and experimental results elucidate that the undulated stacking within COF-S possesses an expanded layer distance of 3.8 Å and facilitates effective and rapid Li + storage, yielding a superior specific capacity of 1305 mAh g -1 at 0.5 A g -1 , surpassing that of COF-O (1180 mAh g -1 at 0.5 A g -1 ). COF-S also demonstrates an admirable cycle life with 80.4% capacity retention after 5000 cycles. As determined, self-expanded wavy-stacking geometry, S-enriched dithiine in COF-S enhances the accessibility and redox activity of Li storage, allowing each phthalocyanine core to store 12 Li + compared to 8 Li + in COF-O. These findings underscore the elements and stacking modes of 2D c-COFs, enabling tunable layer distance and modulation of accessible ions., (© 2024 Wiley‐VCH GmbH.)

Solid-state batteries (SSBs) are under development as high-priority technologies for safe and energy-dense next-generation electrochemical energy storage systems operating over a wide temperature range. Solid-state electrolytes (SSEs) exhibit high thermal stability and, in some cases, the ability to prevent dendrite growth through a physical barrier, and compatibility with the "holy grail" metallic lithium. These unique advantages of SSEs have spurred significant research interests during the last decade. Garnet-type SSEs, that is, Li 7 La 3 Zr 2 O 12 (LLZO), are intensively investigated due to their high Li-ion conductivity and exceptional chemical and electrochemical stability against lithium metal anodes. However, poor interfacial contact with cathode materials, undesirable lithium plating along grain boundaries, and moisture-induced chemical degradation greatly hinder the practical implementation of LLZO-based SSEs for SSBs. In this review, the recent advances in synthesis methods, modification strategies, corresponding mechanisms, and applications of garnet-based SSEs in SSBs are critically summarized. Furthermore, a comprehensive evaluation of the challenges and development trends of LLZO-based electrolytes in practical applications is presented to accelerate their development for high-performance SSBs., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

The unique optical and electrical properties of graphene-based heterojunctions make them significant for artificial synaptic devices, promoting the advancement of biomimetic vision systems. However, mass production and integration of device arrays are necessary for visual imaging, which is still challenging due to the difficulty in direct growth of wafer-scale graphene patterns. Here, a novel strategy is proposed using photosensitive polymer as a solid carbon source for in situ growth of patterned graphene on diverse substrates. The growth mechanism during high-temperature annealing is elucidated, leading to wafer-scale graphene patterns with exceptional uniformity, ideal crystalline quality, and precise control over layer number by eliminating the release of volatile from oxygen-containing resin. The growth strategy enables the fabrication of two-inch optoelectronic artificial synaptic device array based on graphene/n-AlGaN heterojunction, which emulates key functionalities of biological synapses, including short-term plasticity, long-term plasticity, and spike-rate-dependent plasticity. Moreover, the mimicry of visual learning in the human brain is attributed to the regulation of excitatory and inhibitory post-synapse currents, following a learning rule that prioritizes initial recognition before memory formation. The duration of long-term memory reaches 10 min. The in situ growth strategy for patterned graphene represents the novelty for fabricating fundamental hardware of an artificial neuromorphic system., (© 2024 Wiley‐VCH GmbH.)

Tissue-specific delivery of oligonucleotide therapeutics beyond the liver remains a key challenge in nucleic acid drug development. To address this issue, exploiting exosomes as a novel carrier has emerged as a promising approach for efficient nucleic acid drug delivery. However, current exosome-based delivery systems still face multiple hurdles in their clinical applications. Herein, this work presents a strategy for constructing a hybrid exosome vehicle (HEV) through a DNA zipper-mediated membrane fusion approach for tissue-specific siRNA delivery. As a proof-of-concept, this work successfully fuses a liposome encapsulating anti-NFKBIZ siRNAs with corneal epithelium cell (CEC)-derived exosomes to form a HEV construct for the treatment of dry eye disease (DED). With homing characteristics inherited from exosomes, the siRNA-bearing HEV can target its parent cells and efficiently deliver the siRNA payloads to the cornea. Subsequently, the NFKBIZ gene silencing significantly reduces pro-inflammatory cytokine secretions from the ocular surface, reshapes its inflammatory microenvironment, and ultimately achieves an excellent therapeutic outcome in a DED mouse model. As a versatile platform, this hybrid exosome with targeting capability and designed therapeutic siRNAs may hold great potential in various disease treatments., (© 2024 Wiley‐VCH GmbH.)

Fusarium wilt (FW) is widespread in global cotton production, but the mechanism underlying FW resistance in superior-fiber-quality Sea Island cotton is unclear. This study reveals that FW resistance has been the target of genetic improvement of Sea Island cotton in China since the 2010s. The key nonsynonymous single nucleotide polymorphism (SNP, T/C) of gene Gbar_D03G001670 encoding protein phosphatase 2C 80 (PP2C80) results in an amino acid shift (L/S), which is significantly associated with FW resistance of Sea Island cotton. Silencing GbPP2C80 increases FW resistance in Sea Island cotton, whereas overexpressing GbPP2C80 reduces FW resistance in Arabidopsis. GbPP2C80 and GbWAKL14 exist synergistically in Sea Island cotton accessions with haplotype forms "susceptible-susceptible" (TA) and "resistant-resistant" (CC), and interact with each other. CRISPR/Cas9-mediated knockout of GbWAKL14 enhances FW and Verticillium wilt (VW) resistance in upland cotton and overexpression of GbWAKL14 and GbPP2C80 weakens FW and VW resistance in Arabidopsis. GbPP2C80 and GbWAKL14 respond to FW and VW by modulating reactive oxygen species (ROS) content via affecting MPK3 expression. In summary, two tandem genes on chromosome D03, GbPP2C80, and GbWAKL14, functions as cooperative negative regulators in cotton wilt disease defense, providing novel genetic resources and molecular markers for the development of resistant cotton cultivars., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Constructing a flexible and chemically stable multifunctional layer for the lithium (Li) metal anodes is a highly effective approach to improve the uneven deposition of Li + and suppress the dendrite growth. Herein, an organic protecting layer of polythiophene is in situ polymerized on the Li metal via plasma polymerization. Compared with the chemically polymerized thiophene (C-PTh), the plasma polymerized thiophene layer (P-PTh), with a higher Young's modulus of 8.1 GPa, shows strong structural stability due to the chemical binding of the polythiophene and Li. Moreover, the nucleophilic C─S bond of polythiophene facilitates the decomposition of Li salts in the electrolytes, promoting the formation of LiF-rich solid electrolyte interface (SEI) layers. The synergetic effect of the rigid LiF as well as the flexible PTh-Li can effectively regulate the uniform Li deposition and suppress the growth of Li dendrites during the repeated stripping-plating, enabling the Li anodes with long-cycling lifespan over 8000 h (1 mA cm -2 , 1 mAh cm -2) and 2500 h (10 mA cm -2 , 10 mAh cm -2 ). Since the plasma polymerization is facile (5-20 min) and environmentally friendly (solvent-free), this work offers a novel and promising strategy for the construction of the forthcoming generation of high-energy-density batteries., (© 2024 Wiley‐VCH GmbH.)

Smart stimuli-responsive persistent luminescence materials, combining the various advantages and frontier applications prospects, have gained booming progress in recent years. The trap-controlled property and energy storage capability to respond to external multi-stimulations through diverse luminescence pathways make them attractive in emerging multi-responsive smart platforms. This review aims at the recent advances in trap-controlled luminescence materials for advanced multi-stimuli-responsive smart platforms. The design principles, luminescence mechanisms, and representative stimulations, i.e., thermo-, photo-, mechano-, and X-rays responsiveness, are comprehensively summarized. Various emerging multi-responsive hybrid systems containing trap-controlled luminescence materials are highlighted. Specifically, temperature dependent trapping and de-trapping performance is discussed, from extreme-low temperature to ultra-high temperature conditions. Emerging applications and future perspectives are briefly presented. It is hoped that this review would provide new insights and guidelines for the rational design and performance manipulation of multi-responsive materials for advanced smart platforms., (© 2024 Wiley‐VCH GmbH.)

Transition metal disulfide compounds (TMDCs) emerges as the promising candidate for new-generation flexible (opto-)electronic device fabrication. However, the harsh growth condition of TMDCs results in the necessity of using hard dielectric substrates, and thus the additional transfer process is essential but still challenging. Here, an efficient strategy for preparation and easy separation-transfer of high-uniform and quality-enhanced MoS 2 via the precursor pre-annealing on the designed graphene inserting layer is demonstrated. Based on the novel strategy, it achieves the intact separation and transfer of a 2-inch MoS 2 array onto the flexible resin. It reveals that the graphene inserting layer not only enhances MoS 2 quality but also decreases interfacial adhesion for easy separation-transfer, which achieves a high yield of ≈99.83%. The theoretical calculations show that the chemical bonding formation at the growth interface has been eliminated by graphene. The separable graphene serves as a photocarrier transportation channel, making a largely enhanced responsivity up to 6.86 mA W -1 , and the photodetector array also qualifies for imaging featured with high contrast. The flexible device exhibits high bending stability, which preserves almost 100% of initial performance after 5000 cycles. The proposed novel TMDCs growth and separation-transfer strategy lightens their significance for advances in curved and wearable (opto-)electronic applications., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Engineering F-rich solid electrolyte interphase (SEI) layers is regarded as an effective strategy to enable the long-term cycling stability of potassium-ion batteries (KIBs). However, in the conventional KPF 6 carbonate electrolytes, it is challenging to form F-containing SEI layers due to the inability of KPF 6 to decompose into K x F. Herein, AlCl 3 is employed as a novel additive to change the chemical environment of the KPF 6 carbonate electrolyte. First, due to the large charge-to-radius ratio of Al 3+ , the Al-containing groups in the electrolyte can easily capture F from PF 6 and accelerate the formation of K - and accelerate the formation of K x F in SEI layer. In addition, AlCl 3 also reacts with trace H 2 O or solvents in the electrolytes to form Al 2 O 3 , which can further act as a HF scavenger. Upon incorporating AlCl 3 into conventional KPF 6 carbonate electrolyte, the hard carbon (HC) anode exhibits an ultra-long lifespan of 10000 cycles with a high coulombic efficiency of ≈100%. When coupled with perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), the full cell exhibits a high capacity retention of 81% after 360 cycles-significantly outperforming cells using conventional electrolytes. This research paves new avenues for advancing electrolyte engineering towards developing durable batteries tailored for large-scale energy storage applications., (© 2024 Wiley‐VCH GmbH.)

Structural engineering is an appealing means to modulate osteogenesis without the intervention of exogenous cells or therapeutic agents. In this work, a novel 3D scaffold with anisotropic micropores and nanotopographical patterns is developed. Scaffolds with oriented pores are fabricated via the selective extraction of water-soluble polyethylene oxide from its poly(ε-caprolactone) co-continuous mixture and uniaxial stretching. The plate apatite-like lamellae are subsequently hatched on the pore walls through surface-induced epitaxial crystallization. Such a unique geometric architecture yields a synergistic effect on the osteogenic capability. The prepared scaffold leads to a 19.2% and 128.0% increase in the alkaline phosphatase activity of rat bone mesenchymal stem cells compared to that of the scaffolds with only oriented pores and only nanotopographical patterns, respectively. It also induces the greatest upregulation of osteogenic-related gene expression in vitro. The cranial defect repair results demonstrate that the prepared scaffold effectively promotes new bone regeneration, as indicated by a 350% increase in collagen I expression in vivo compared to the isotropic porous scaffold without surface nanotopology after implantation for 14 weeks. Overall, this work provides geometric motifs for the transduction of biophysical cues in 3D porous scaffolds, which is a promising option for tissue engineering applications., (© 2024 Wiley‐VCH GmbH.)

Wearable soft contact lens sensors for continuous and nondestructive intraocular pressure (IOP) monitoring are highly desired as glaucoma and postoperative myopia patients grow, especially as the eyestrain crowd increases. Herein, a smart closed-loop system is presented that combines a Ti 3 C 2 T x MXene-based soft contact lens (MX-CLS) sensor, wireless data transmission units, display, and warning components to realize continuous and nondestructive IOP monitoring/real-time display. The fabricated MX-CLS device exhibits an extremely high sensitivity of 7.483 mV mmHg -1 , good linearity on silicone eyeballs, excellent stability under long-term pressure-release measurement, sufficient transparency with 67.8% transmittance under visible illumination, and superior biocompatibility with no discomfort when putting the MX-CLS sensor onto the Rabbit eyes. After integrating with the wireless module, users can realize real-time monitoring and warning of IOP via smartphones, the demonstrated MX-CLS device together with the IOP monitoring/display system opens up promising platforms for Ti 3 C 2 T x materials as the base for multifunctional contact lens-based sensors and continuous and nondestructive IOP measurement system., (© 2024 Wiley‐VCH GmbH.)

Alkaline anion-exchange-membrane water electrolyzers (AEMWEs) using earth-abundant catalysts is a promising approach for the generation of green H 2 . However, the AEMWEs with alkaline electrolytes suffer from poor performance at high current density compared to proton exchange membrane electrolyzers. Here, atomically dispersed Pt-Ru dual sites co-embedded in nanoporous nickel selenides (np/Pt 1 Ru 1 -Ni 0.85 Se) are developed by a rapid melt-quenching approach to achieve highly-efficient alkaline hydrogen evolution reaction. The np/Pt 1 Ru 1 -Ni 0.85 Se catalyst shows ampere-level current density with a low overpotential (46 mV at 10 mA cm -2 and 225 mV at 1000 mA cm -2 ), low Tafel slope (32.4 mV dec -1 ), and excellent long-term durability, significantly outperforming the benchmark Pt/C catalyst and other advanced large-current catalysts. The remarkable HER performance of nanoporous Pt 1 Ru 1 -Ni 0.85 Se is attributed to the strong intracrystal electronic metal-support interaction (IEMSI) between Pt-Se-Ru sites and Ni 0.85 Se support which can greatly enlarge the charge redistribution density, reduce the energy barrier of water dissociation, and optimize the potential determining step. Furthermore, the assembled alkaline AEMWE with an ultralow Pt and Ru loading realizes an industrial-level current density of 1 A cm -2 at 1.84 volts with high durability., (© 2024 Wiley‐VCH GmbH.)

Tissue engineering at single-cell resolution has enhanced therapeutic efficacy. Droplet microfluidics offers a powerful platform that allows deterministic single-cell encapsulation into aqueous droplets, yet the direct encapsulation of cells into microgels remains challenging. Here, the design of a microfluidic device that is capable of single-cell encapsulation within polyethylene glycol norbornene (PEGNB) hydrogels on-chip is reported. Cells are first ordered in media within a straight microchannel via inertial focusing, followed by the introduction of PEGNB solution from two separate, converging channels. Droplets are thoroughly mixed by passage through a serpentine channel, and microgels are formed by photo-photopolymerization. This platform uniquely enables both single-cell encapsulation and excellent cell viability post-photo-polymerization. More than 90% of singly encapsulated mesenchymal stromal cells (MSCs) remain alive for 7 days. Notably, singly encapsulated MSCs have elevated expression levels in genes that code anti-inflammatory cytokines, for example, IL-10 and TGF-β, thus enhancing the secretion of proteins of interest. Following injection into a mouse model with induced inflammation, singly encapsulated MSCs show a strong retention rate in vivo, reduce overall inflammation, and mitigate liver damage. These translational results indicate that deterministic single-cell encapsulation could find use in a broad spectrum of tissue engineering applications., (© 2024 Wiley‐VCH GmbH.)

Noble metals have been widely used in catalysis, however, the scarcity and high cost of noble metal motivate researchers to balance the atomic efficiency and atomic density, which is formidably challenging. This article proposes a robust strategy for fabricating 3D amorphous noble metal-based oxides with simultaneous enhancement on atomic efficiency and density with the assistance of atomic channels, where the atomic utilization increases from 18.2% to 59.4%. The unique properties of amorphous bimetallic oxides and formation of atomic channels have been evidenced by detailed experimental characterizations and theoretical simulations. Moreover, the universality of the current strategy is validated by other binary oxides. When Cu 2 IrO x with atomic channels (Cu 2 IrO x -AE) is used as catalyst for oxygen evolution reaction (OER), the mass activity and turnover frequency value of Cu 2 IrO x -AE are 1-2 orders of magnitude higher than CuO/IrO 2 and Cu 2 IrO x without atomic channels, largely outperforming the reported OER catalysts. Theoretical calculations reveal that the formation of atomic channels leads to various Ir sites, on which the proton of adsorbed * OH can transfer to adjacent O atoms of [IrO 6 ]. This work may attract immediate interest of researchers in material science, chemistry, catalysis, and beyond., (© 2024 Wiley‐VCH GmbH.)

As a potential material to solve rampant dendrites and hydrogen evolution reaction (HER) problem of aqueous zinc metal batteries (AZMB), hydrogel electrolytes usually require additional additives or multi-molecular network strategies to solve existing problems of ionic conductivity, mechanical properties and interface stability. However, the intrinsic zincophilic properties of the gel itself are widely neglected leading to the addition of additional molecules and the complexity of the preparation process. In this work, we innovatively utilize the characteristics of acrylamide's high zincophilic group density, activating the intrinsic zincophilic properties of PAM gel through a simple concentration control strategy which reconstructs a novel zinc-electrolyte interface different from conventional PAM electrolyte. The activated novel gel electrolyte with intrinsic zincophilic properties has high ionic conductivity and effectively suppresses water activity, thereby inhibiting HER corrosion. Meanwhile, it induces uniform deposition of (002) crystal planes, leading to excellent deposition kinetics and long cycle life, thereby ensuring high interfacial stability. Compared with conventional PAM gel electrolytes, the activated zincophilic group-rich hydrogel maintained excellent cycling stability (1 mA/cm 2 , 1 mAh/cm 2 ) over 2250 hours; The Zn//MnO₂ coin cell using novel zincophilic group -rich hydrogel still retains a high specific capacity of more than 170 mAh/g at 0.5 A/g after 1000 cycles., (© 2024 Wiley-VCH GmbH.)

Noble metal single-atom-catalysts (SACs) have demonstrated significant potential to improve atom utilization efficiency and catalytic activity for hydrogen evolution reaction (HER). However, challenges still remain in rationally modulating active sites and catalytic activities of SACs, which often results in sluggish kinetics and poor stability, especially in neutral/alkaline media. Herein, precise construction of Pt single atoms anchored on edge of 2D layered Ni(OH) 2 (Pt-Ni(OH) 2 -E) is achieved utilizing in situ electrodeposition. Compared to the single-atom Pt catalysts anchored on the basal plane of Ni(OH) 2 (Pt-Ni(OH) 2 -BP), the Pt-Ni(OH) 2 -E possesses superior electron affinity and high intrinsic catalytic activity, which favors the strong adsorption and rapid dissociation toward water molecules. As a result, the Pt-Ni(OH) 2 -E catalyst requires low overpotentials of 21 and 34 mV at 10 mA cm -2 in alkaline and neutral conditions, respectively. Specifically, it shows the high mass activity of 23.6 A mg -1 for Pt at the overpotential of 100 mV, outperforming the reported catalysts and commercial Pt/C. This work provides new insights into the rational design of active sites for preparing high-performance SACs., (© 2023 Wiley‐VCH GmbH.)

The aggravation of energy problems and the scarcity of lithium resources have forced us to look for new energy storage systems. Aluminum ion batteries, as a promising energy storage system, have the advantages of environmental friendliness and abundant aluminum resources, and have the potential for application in large-scale energy storage and personal portable electronic devices. To solve the stability problem of aluminum ion batteries during cycling for large-scale energy storage needs, we report a polythiophene-based conductive polymer, poly(3,4-dimethylthiophene) (PDMT), as a high performance cathode material for aluminum ion batteries. By introducing two methyl groups on the thiophene ring, we successfully adjust the local charge density of the heterocyclic thiophene, thus changing the electron delocalization characteristics, and improving the electrochemical reaction activity of the polythiophene (PTH) material as a redox electrode material. This also maintains the symmetry and regularity of the polymer structure, giving the material better cycling stability. The discharge specific capacity reaches 110 mAh g -1 at a current density of 200 mA g -1 , far exceeding conventional PTH cathodes (~70 mAh g -1 ), and the capacity retention rate is 92.7 % after 1000 cycles. It also shows excellent rate performance due to the flexible structure of the conductive polymer., (© 2024 Wiley‐VCH GmbH.)

Traditional palladium-catalyzed dearomatization of (hetero)arenes takes place via an ionic pathway and usually requires elevated temperatures to overcome the energy barrier of the dearomative insertion step. Herein, a combination of the radical and two-electron pathways is disclosed, which enables room temperature dearomative 3D transformations of nonactivated phenyl rings with Pd(0) as the catalyst. Experimental results together with density functional theory (DFT) calculations indicate a versatile π-allyl Pd(II) species, cyclohexadienyl Pd(II), possibly is involved in the dearomatization. This species is generated by combining the cyclohexadienyl radical and Pd(I). The cyclohexadienyl Pd(II) provides chemoselective (carboamination and trieneylation), regioselective (1,2-carboamination), and diastereoselective (carbonyl-group directed face selectivity) conversions., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Intestinal commensal microbiota dysbiosis and immune dysfunction are significant exacerbating factors in inflammatory bowel disease (IBD). To address these problems, Pluronic F-127-coated tungsten diselenide (WSe 2 @F127) nanozymes are developed by simple liquid-phase exfoliation. The abundant valence transitions of elemental selenium (Se 2- /Se 4+ ) and tungsten (W 4+ /W 6+ ) enable the obtained WSe 2 @F127 nanozymes to eliminate reactive oxygen/nitrogen species. In addition, the released tungsten ions are capable of inhibiting the proliferation of Escherichia coli. In a model of dextran sodium sulfate-induced colitis, WSe 2 @F127 nanozymes modulate the gut microbiota by increasing the abundance of bacteria S24-7 and significantly reducing the abundance of Enterobacteriaceae. Moreover, WSe 2 @F127 nanozymes inhibit T-cell differentiation and improve intestinal immune barrier function in a model of Crohn's disease. The WSe 2 @F127 nanozymes effectively alleviate IBD by reducing oxidative stress damage, modulating intestinal microbial populations, and remodeling the immune barrier., (© 2023 Wiley-VCH GmbH.)

Along with the demand for further miniaturization of high and pulsed power devices, it becomes more and more important to realize ultrahigh recoverable energy storage density (W rec ) with high energy storage efficiency (η) and ultrahigh discharge energy storage density (W d ) accompanied by high power density (P d ) in dielectrics. To date, it remains, however, a big challenge to achieve high W rec or W d in glass ceramics compared to other dielectric energy storage materials. Herein, a strategy of defect formation modulation is applied to form "amorphous-disordered-ordered" microstructure in BaTiO 3 -based glass ceramics so as to achieve a high W rec of 12.04 J cm -3 with a high η of 81.1% and an ultrahigh W d of 11.98 J cm -3 with a superb P d of 973 MW cm -3 . This work demonstrates a feasible route to obtain glass ceramics with an outstanding energy storage performance and proves the enormous potential of glass ceramics in high and pulsed power applications., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Lattice strain engineering optimizes the interaction between the catalytic surface and adsorbed molecules. This is done by adjusting the electron and geometric structure of the metal site to achieve high electrochemical performance, but, to date, it has been rarely reported on anti-poisoned oxygen reduction reaction (ORR). Herein, lattice-strained Pd@PdBiCo quasi core-shell metallic aerogels (MAs) were designed by "one-pot and two-step" method for anti-poisoned ORR. Pd@PdBiCo MAs/C maintain their original activity (1.034 A mg Pd -1 ) in electrolytes with CH 3 OH and CO at 0.85 V vs. reversible hydrogen electrode (RHE), outperforming the commercial Pd/C (0.156 A mg Pd -1 ), Pd MAs/C (0.351 A mg Pd -1 ), and PdBiCo MAs/C (0.227 A mg Pd -1 ). Moreover, Pd@PdBiCo MAs/C also show high stability and anti-poisoning with negligible activity decay after 8000 cycles in 0.1 m KOH+0.3 m CH 3 OH. These results of X-ray photoelectron spectroscopy, CO stripping, and diffuses reflectance FTIR spectroscopy reveal that the tensile strain and strong interaction between different elements of Pd@PdBiCo MAs/C effectively optimize the electronic structure to promote O 2 adsorption and activation, while suppressing CH 3 OH oxidation and CO adsorption, leading to high ORR activity and anti-poisoning property. This work inspires the rational design of MAs in fuel cells and beyond., (© 2023 Wiley-VCH GmbH.)

Multimodal cancer therapies show great promise in synergistically enhancing anticancer efficacy through different mechanisms. However, most current multimodal therapies either rely on complex assemblies of multiple functional nanomaterials and drug molecules or involve the use of nanomedicines with poor in vivo degradability/metabolizability, thus restricting their clinical translatability. Herein, a nanoflower-medicine using iron ions, thioguanine (TG), and tetracarboxylic porphyrin (TCPP) are synthesized as building blocks through a one-step hydrothermal method for combined chemo/chemodynamic/photodynamic cancer therapy. The resulting nanoflowers, consisting of low-density Fe 2 O 3 core and iron complex (Fe-TG and Fe-TCPP compounds) shell, exhibit high accumulation at the tumor site, desirable degradability in the tumor microenvironment (TME), robust suppression of tumor growth and metastasis, as well as effective reinvigoration of host antitumor immunity. Triggered by the low pH in tumor microenvironment, the nanoflowers gradually degrade after internalization, contributing to the effective drug release and initiation of high-efficiency catalytic reactions precisely in tumor sites. Moreover, iron ions can be eliminated from the body through renal clearance after fulfilling their mission. Strikingly, it is also found that the multimodal synergistic therapy effectively elicits the host antitumor immunity without inducing additional toxicity. This easy-manufactured and degradable multimodal therapeutic nanomedicine is promising for clinical precision oncology., (© 2023 Wiley-VCH GmbH.)

Liver metastasis is a common cause of death in progressive colorectal cancer patients, but the molecular mechanisms remain unclear. Here, it is reported that a conserved and oxidative pentose phosphate pathway-associated circular RNA, circNOLC1, plays a crucial role in colorectal cancer liver metastasis. It is found that circNOLC1 silencing reduces the oxidative pentose phosphate pathway-related intermediate metabolites and elevates NADP + /NADPH ratio and intracellular ROS levels, thereby attenuating colorectal cancer cell proliferation, migration, and liver metastasis. circNOLC1 interacting with AZGP1 to activate mTOR/SREBP1 signaling, or sponging miR-212-5p to upregulate c-Met expression, both of which can further induce G6PD to activate oxidative pentose phosphate pathway in colorectal cancer liver metastasis. Moreover, circNOLC1 is regulated by the transcription factor YY1 and specifically stabilized HuR induces its parental gene mRNA expression. The associations between circNOLC1 and these signaling molecules are validated in primary CRC and corresponding liver metastasis tissues. These findings reveal that circNOLC1 interacting with AZGP1 and circNOLC1/miR-212-5p/c-Met axis plays a key role in oxidative pentose phosphate pathway-mediated colorectal cancer liver metastasis, which may provide a novel target for precision medicine of colorectal cancer., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Colon leakage is one of the most severe complications in abdominal trauma or surgery cases. It can lead to severe abdominal infection and abdominal adhesions, resulting in prolonged hospital stays and increased mortality. In this study, a photosensitive hydrogel is proposed, which can swiftly form a strong adhesion coating on the damaged colon after UV irradiation, to realize quick cure and suture-free repair of colon leakage. The newly developed biological gel consists of hyaluronic acid methacryloyl (HAMA) and hyaluronic acid o-nitroso benzaldehyde (HANB) in the optimal ratio of 3: 1, which exerts both the rapid photocuring properties of HAMA and the strong tissue adhesion properties of HANB. HAMA/HANB shows excellent adhesion stability on wet surfaces, presenting controllable mechanical properties, ductility, adhesion stability, and chemical stability; it also evades foreign body response, which relieves the degree of abdominal adhesion. The underlying mechanism for HAMA/HANB promoting wound healing in colon leakage involves the reconstruction of the colon barrier, as well as the regulation of the immune reaction and neovascularization. In all, HAMA/HANB is a promising alternative suture-free approach for repairing colon leakage; it has a reliable healing effect and is expected to be extended to clinical application for other organ injuries., (© 2023 Wiley-VCH GmbH.)

While hydrovoltaic electrical energy generation developments in very recent years have provided an alternative strategy to generate electricity from the direct interaction of materials with water, the two main issues still need to be addressed: achieving satisfactory output power density and understanding the reliable mechanism. In the present work, the integration of capacitors and water evaporation devices is proposed to provide a stable power supply. The feasible device structure consuming only water and air is green and environmentally sustainable, achieving a recorded power density of 142.72 µW cm -2 . The output power of the series of devices is sufficient to drive portable electronic products with different voltage and current requirements, enabling self-driving systems for portable appliances. It has been shown that the working behavior originates from evaporating potential other than streaming potential. The present work provides both theoretical support and an experimental design for realizing practical application of hydrovoltaic electrical energy generation devices., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Developing well-defined structures and desired properties for porous organic polymer (POP) supported catalysts by controlling their composition, size, and morphology is of great significance. Herein, we report a preparation of polyaniline (PANI) supported Pd nanoparticles (NPs) with controllable structure and morphology. The protocol involves the introduction of MnO 2 with different crystal structures (α, β, γ, δ, ϵ) serving as both the reaction template and the oxidant. The different forms of MnO 2 each convert aniline to a PANI that contains a unique regular distribution of benzene and quinone. This leads to the Pd/PANI catalysts with different charge transfer properties between Pd and PANI, as well as different dispersions of the metal NPs. In this case, the Pd/ϵ-PANI catalyst greatly improves the turnover frequency (TOF; to 88.3 h -1 ), in the reductive coupling of furfural derivatives to potential bio-based plasticizers. Systematic characterizations reveal the unique oxidation state of the support in the Pd/ϵ-PANI catalyst and coordination mode of Pd that drives the formation of highly dispersed Pd nanoclusters. Density functional theory (DFT) calculations show the more electron rich Pd/PANI catalyst has the lower energy barrier in the oxidative addition step, which favors the C-C coupling reaction., (© 2023 Wiley-VCH GmbH.)

Although single metal atoms on porous carbons (PCs) are widely used in electrochemical CO 2 reduction reaction, these systems have long relied on flat graphene-based models, which are far beyond reality because of abundant curved structures in PCs; the effect of curved surfaces has long been ignored. In addition, the selectivity generally decreases under high current density, which severely limits practical application. Herein, theoretical calculations reveal that a single-Ni-atom on a curved surface can simultaneously enhance the total density of states around Fermi level and decrease the energy barrier for *COOH formation, thereby enhancing catalytic activity. This work reports a rational molten salt approach for preparing PCs with ultra-high specific surface area of up to 2635 m 2 g -1 . As determined by cutting-edge techniques, a single Ni atom on a curved carbon surface is obtained and used as a catalyst for electrochemical CO 2 reduction. The CO selectivity reaches up to 99.8% under industrial-level current density of 400 mA cm -2 , outperforming state-of-the-art PC-based catalysts. This work not only offers a new method for the rational synthesis of single atom catalysts with strained geometry to host rich active sites, but also provides in-depth insights for the origin of catalytic activity of curved structure-enriched PC-based catalysts., (© 2023 Wiley-VCH GmbH.)

Cancer cells in secondary tumors are found to form metastases more efficiently as compared to their primary tumor counterparts. This is partially due to the unfavorable microenvironments encountered by metastasizing cancer cells that result in the survival of a more metastatic phenotype from the original population. However, the role of deleterious mechanical stresses in this change of metastatic potential is unclear. Here, by forcing cancer cells to flow through small capillary-sized constrictions, it is demonstrated that mechanical deformation can select a tumor cell subpopulation that exhibits resilience to mechanical squeezing-induced cell death. Transcriptomic profiling reveals up-regulated proliferation and DNA damage response pathways in this subpopulation, which are further translated into a more proliferative and chemotherapy-resistant phenotype. These results highlight a potential link between the microenvironmental physical stresses and the enhanced malignancy of metastasizing cancer cells which may be utilized as a therapeutic strategy in preventing the metastatic spread of cancer cells., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Liposomes have received tremendous attention as a class of versatile pharmaceutical vehicles of great potential over the past several decades. However, the application of liposomes encounters major challenges due to the knowledge gaps in their in vivo delivery process. Immunoglobulin M (IgM) displays both pervasiveness and complexity in regulating the biological functions as well as eliciting adverse effects of liposomes. Understanding, mitigating, and exploiting the duality of IgM are prerequisites for achieving various biomedical applications of liposomes. In this review, the intricate relationship between liposomes and their biological environments has been summarized, with an emphasis on the regulatory effects of IgM on in vivo performance of liposomes. Corresponding solutions have also been discussed to evade IgM-mediated opsonization for safe and efficient drug delivery., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Heterogeneous catalysts are highly advantageous for industrial applications owing to their distinctive merits including easy separation and effective recovery. However, utilizing heterogeneous photocatalysts to harness longer wavelength light remains a critical area of research. This contribution explores the use of edge-functionalized metal-free polyphthalocyanine networks (PPc-x) to promote efficient polymer synthesis under near infrared (NIR) light irradiation. Our screening process revealed that both phenyl-edged PPc-x (PPc-p) and naphthyl-edged PPc-x (PPc-n) offer promising performance for photopolymerization. With the assistance of ppm-level PPc-n catalyst, well-defined polymers were synthesized within a few hours under the regulation of three NIR lights, regardless of shielded by synthetic and biological barriers. An excellent control over the molecular weight and molecular weight distribution was achieved. Furthermore, PPc-x can be easily recovered and reused for multiple cycles, with negligible leaching and maintenance of the catalytic performance. This study expands a new avenue in developing versatile photocatalysts for the modern synthetic toolkits and offer benefits in diverse applications., (© 2023 Wiley-VCH GmbH.)

The structural disruption of mechanical barrier and dysfunction of immune barrier in intestinal, are important factors, that aggravate inflammatory bowel disease (IBD). To tackle this challenge, a multifunctional nanozyme capable of scavenging reactive oxygen species (ROS) and inhibiting ferroptosis or T cells differentiation for IBD therapy is here reported. In this work, zero-valence selenium-enriched Prussian blue nanozymes (Se-HMPB nanozymes) are prepared via the hard template method. PB nanozymes with multi-enzyme activities can effectively scavenge various ROS in inflammatory tissues. Meanwhile, the presence of selenium element endows the glutathione peroxidase activity of Se-HMPB nanozymes, which can inhibit ferroptosis and reverse the lipid peroxidation of intestinal epithelial cells to protect the intestinal mechanical barrier in ulcerative colitis (UC) model. In addition, selenium supplementation can realize efficient inhibition on the differentiation of T cells in Crohn's disease (CD) model, regulating the intestinal immune barrier. Thus, the Se-HMPB nanozymes reconstructed intestinal barrier via inhibiting ferroptosis and T cells differentiation in UC and CD models, depicting great potential to alleviate IBD., (© 2023 Wiley-VCH GmbH.)

Ammonia is a key chemical feedstock worldwide. Compared with the well-known Haber-Bosch method, electrocatalytic nitrogen reduction reaction (ENRR) can eventually consume less energy and have less CO 2 emission. In this study, a plasma-enhanced chemical vapor deposition method is used to anchor transition metal element onto 2D conductive material. Among all attempts, Ru single-atom and Ru-cluster-embedded perovskite oxide are discovered with promising electrocatalysis performance for ENRR (NH 3 yield rate of up to 137.5 ± 5.8 µg h -1  mg cat -1 and Faradaic efficiency of unexpected 56.9 ± 4.1%), reaching the top record of Ru-based catalysts reported so far. In situ experiments and density functional theory calculations confirm that the existence of Ru clusters can regulate the electronic structure of Ru single atoms and decrease the energy barrier of the first hydrogenation step (*NN to *NNH). Anchoring Ru onto various 2D perovskite oxides (LaMO-Ru, MCr, Mn, Co, or Ni) also show boosted ENRR performance. Not only this study provides an unique strategy toward transition-metal-anchored new 2D conductive materials, but also paves the way for fundamental understanding the correlation between cluster-involved single-atom sites and catalytic performance., (© 2023 Wiley-VCH GmbH.)

When mono-radical ipso-cyclization of aryl sulfonamides tend to undergo Smiles-type rearrangement through aromatization-driven C-S bond cleavage, diradical-mediated cyclization must perform in a distinct reaction pathway. It is interesting meanwhile challenging to tune the rate of C-S bond cleavage to achieve a chemically divergent reaction of (hetero) aryl sulfonamides in a visible-light induced energy transfer (EnT) reaction pathway involving diradical species. Herein a chemically divergent reaction based on the designed indole-tethered (hetero)arylsulfonamides is reported which involves a diradical-mediated ipso-cyclization and a controllable cleavage of an inherent C-S bond. The combined experimental and computational results have revealed that the cleavage of the C-S bond in these substrates can be controlled by tuning the heteroaryl moieties: a) If the (hetero)aryl is thienyl, furyl, phenanthryl, etc., the radical coupling of double dearomative diradicals (DDDR) precedes over C-S bond cleavage to afford cyclobutene fused indolines by double dearomative [2+2]-cycloaddition; b) if the (hetero)aryl is phenyl, naphthyl, pyridyl, indolyl etc., the cleavage of C-S bond in DDDR is favored over radical coupling to afford biaryl products., (© 2022 Wiley-VCH GmbH.)

Single-atom catalysts have attracted extensive attention due to their unique atomic structures and extraordinary activities in catalyzing chemical reactions. However, the lack of general and efficient approaches for producing high-density single atoms on suitably tailored supporting matrixes hinders their industrial applications. Here, a rapid melt-quenching strategy with high throughput to synthesize single atoms with high metal-atom loadings of up to 9.7 wt% or 2.6 at% on nanoporous metal compounds is reported, representing several-fold improvements compared to benchmarks in the literature. Mechanism characterizations reveal that the high-temperature melting provides the essential liquid environment and activation energy to achieve the atomization of metals, while the following rapid-quenching pins the isolated metal atoms and stabilizes the coordination environment. In comparison with carbon-supported single-atom catalysts, various collaboration combinations of single atoms and nanoporous metal compounds can be synthesized using the strategy, thus achieving efficient hydrazine oxidation-assisted H 2 production. This synthesis protocol is highly compatible with automatic operation, which provides a feasible and general route to design and manufacture specific single-atom catalysts with tunable atomic metal components and supporting matrixes, thus promoting the deployment of single-atom catalysts for various energy technology applications., (© 2022 Wiley-VCH GmbH.)

The design for non-Cu-based catalysts with the function of producing C 2+ products requires systematic knowledge of the intrinsic connection between the surface state as well as the catalytic activity and selectivity. In this work, photochemical in situ spectral surface characterization techniques combined with the first principle calculations (DFT) were applied to investigate the relationships between the composition of surface states, coordinated motifs, and catalytic selectivity of a titanium oxynitride catalyst. When the catalyst mediates CO 2 photoreduction, C 2 product selectivity is positively correlated with the surface Ti 2+ /Ti 3+ ratio and the surface oxidation state is regulated and controlled by coordinated motifs of N-Ti-O/V[O], which can reduce the potential dimerization energy barriers of *CO-CO* and promote spontaneous formation of the subsequent *CO-CH 2 * intermediate. This phenomenon provides a new perspective for the design of heterogeneous catalysts for photoreduction of CO 2 into useful products., (© 2022 Wiley-VCH GmbH.)

Designing metal-organic framework (MOF)-based catalysts with superior oxygen evolution reaction (OER) activity and robust durability simultaneously is highly required yet very challenging due to the limited intrinsic activity and their elusive evolution under harsh OER conditions. Herein, a steady self-reconstructed MOF heterojunction is constructed via redox electrochemistry and topology-guided strategy. Thanks to the inhibiting effect from hydrogen bonds of Ni-BDC-1 (BDC=1,4-benzenedicarboxylic acid), the obatained MOF heterojunction shows greatly improved OER activity with low overpotential of 225 mV at 10 mA cm -2 , relative to the totally reconstructed Ni-BDC-3 (332 mV). Density function theory calculations reveal that the formed built-in electric field in the MOF heterojunction remarkably optimizes the ad/desorption free energy of active Ni sites. Moreover, such MOF heterojunction shows superior durability attributed to the shielding effect of the surface-evolved NiOOH coating., (© 2022 Wiley-VCH GmbH.)

Covalent triazine frameworks (CTFs) are among the most valuable frameworks owing to many fantastic properties. However, molten salt-involved preparation of CTFs at 400-600 °C causes debate on whether CTFs represent organic frameworks or carbon. Herein, new CTFs based on the 1,3-dicyanoazulene monomer (CTF-Azs) are synthesized using molten ZnCl 2 at 400-600 °C. Chemical structure analysis reveals that the CTF-Az prepared at low temperature (400 °C) exhibits polymeric features, whereas those prepared at high temperatures (600 °C) exhibit typical carbon features. Even after being treated at even higher temperatures, the CTF-Azs retain their rich porosity, but the polymeric features vanish. Although structural de-conformation is a widely accepted outcome in polymer-to-carbon rearrangement processes, the study evaluates such processes in the context of CTF systems. A proof-of-concept study is performed, observing that the as-synthesized CTF-Azs exhibit promising performance as cathodes for Li- and K-ion batteries. Moreover, the as-prepared NPCs exhibit excellent catalytic oxygen reduction reaction (ORR) performance; hence, they can be used as air cathodes in Zn-air batteries. This study not only provides new building blocks for novel CTFs with controllable polymer/carbon features but also offers insights into the formation and structure transformation history of CTFs during thermal treatment., (© 2022 Wiley-VCH GmbH.)

Perovskite solar cells (PSCs) suffer from significant nonradiative recombination at perovskite/charge transport layer heterojunction, seriously limiting their power conversion efficiencies. Herein, solution-processed chromium multioxide (CrO x ) is judiciously selected to construct a MAPbI 3 /CrO x /Spiro-OMeTAD hole-selective heterojunction. It is demonstrated that the inserted CrO x not only effectively reduces defect sites via redox shuttle at perovskite contact, but also decreases valence band maximum (VBM)-HOMO offset between perovskite and Spiro-OMeTAD. This will diminish thermionic losses for collecting holes and thus promote charge transport across the heterojunction, suppressing both defect-assisted recombination and interface carrier recombination. As a result, a remarkable improvement of 21.21% efficiency with excellent device stability is achieved compared to 18.46% of the control device, which is among the highest efficiencies for polycrystalline MAPbI 3 based n-i-p planar PSCs reported to date. These findings of this work provide new insights into novel charge-selective heterojunctions for further enhancing efficiency and stability of PSCs., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Structural design is an intriguing strategy to improve the physical and electrochemical performance of polymer electrolytes (PEs) for lithium-ion batteries. However, the complex synthetic process and introduction of nonelectrolyte composition severely limit the development and practical application of PEs. Here, a facile method is reported for the fabrication of a double network polymer electrolyte (DN-PE) through combining the lithium salt-accelerated thiol-Michael addition and lithium salt-catalyzed radical polymerization. By adjusting the reaction temperature, the double network with the cross-linking structure can be in situ formed step by step at room temperature and 80 °C. Notably, using lithium salt as the accelerator and catalyst avoids the addition of extra species and the related side reactions in the electrolyte system. Compared with single network polymer electrolyte (SN-PE), DN-PE has a distinctly improved mechanical strength and a better interfacial compatibility with the electrode, which leads to a stable cycling of the symmetric Li|DN-PE|Li cell over 1000 h at a current density of 0.05 mA cm -2 . In addition, the Li|DN-PE|LiFePO 4 cell shows a high discharge specific capacity of 150.3 mAh g -1 at 0.1 C and coulomb efficiency of 99%., (© 2022 Wiley-VCH GmbH.)

It is challenging to establish single metal atoms with a uniform coordination environment at targeted sites of a zeolite. In this study, single platinum atoms were selectively encaged in the six-membered rings of sodalite (SOD) cages within Y zeolite using a template-guiding strategy. During the in situ synthesis process, template molecules were designed to occupy supercages and thereby force coordinated platinum species into SOD cages. Subsequent control of the post-treatment conditions yielded the Y zeolite with selectively encaged single platinum atoms, denoted Pt@Y-SOD. The Pt@Y-SOD catalyst had good stability and excellent catalytic selectivity in the semihydrogenation reaction, and it exhibited interesting thiophene and carbon monoxide resistance in this transformation because interactions with these poisons are weakened by the configuration of the encaged single platinum atoms., (© 2022 Wiley-VCH GmbH.)

5-Hydroxymethylfurfural (HMF) can be oxidized to 2,5-furandicarboxylic acid (FDCA) for the production of biorenewable plastics to replace fossil resourced polyethylene terephthalate (PET). Development of a highly efficient electrocatalyst using renewable electricity as energy input is highly desired. In this work, Ru cluster-embedded Ni(OH) 2 nanosheets [Ru/Ni(OH) 2 ] were synthesized and exploited as electrochemical catalysts for the conversion of HMF to FDCA. Ru/Ni(OH) 2 exhibited significantly improved current density (40 mA cm -2 at 1.41 V vs. reversible hydrogen electrode) of over 7.7 times in comparison with Ni(OH) 2 , and nearly 100 % conversion degree for HMF and 98.5 % selectivity towards FDCA were obtained. Operando Raman experiments revealed the catalysis was facilitated by the interconversion between Ni 3+ and Ni 2+ . Density functional theory calculations further revealed the effect of Ru clusters of Ni(OH) 2 , thereby promoting HMF adsorption capacity on Ni sites to boost HMF oxidation activity. This work provides a novel strategy using Ru clusters to modify earth abundant Ni based catalyst for HMF oxidation to obtain high-value biomass-derived products., (© 2022 Wiley-VCH GmbH.)

A record power conversion efficiency (PCE) of over 19% is realized in planar-mixed heterojunction (PMHJ) organic solar cells (OSCs) by adopting the asymmetric selenium substitution strategy in making a pseudosymmetric electron acceptor, BS3TSe-4F. The combined molecular asymmetry with more polarizable selenium substitution increases the dielectric constant of the D18/BS3TSe-4F blend, helping lower the exciton binding energy. On the other hand, dimer packing in BS3TSe-4F is facilitated to enable free charge generation, helping more efficient exciton dissociation and lowering the radiative recombination loss (ΔE 2 ) of OSCs. As a result, PMHJ OSCs based on D18/BS3TSe-4F achieve a PCE of 18.48%. By incorporating another mid-bandgap acceptor Y6-O into D18/BS3TSe-4F to form a ternary PMHJ, a higher open-circuit voltage (V OC ) can be achieved to realize an impressive PCE of 19.03%. The findings of using pseudosymmetric electron acceptors in enhancing device efficiency provides an effective way to develop highly efficient acceptor materials for OSCs., (© 2022 Wiley-VCH GmbH.)

A major challenge hindering the further development of all-polymer solar cells (all-PSCs) employing polymerized small-molecule acceptors is the relatively low fill factor (FF) due to the difficulty in controlling the active-layer morphology. The issues typically arise from oversized phase separation resulting from the thermodynamically unfavorable mixing between two macromolecular species, and disordered molecular orientation/packing of highly anisotropic polymer chains. Herein, a facile top-down controlling strategy to engineer the morphology of all-polymer blends is developed by leveraging the layer-by-layer (LBL) deposition. Optimal intermixing of polymer components can be achieved in the two-step process by tuning the bottom-layer polymer swelling during top-layer deposition. Consequently, both the molecular orientation/packing of the bottom layer and the molecular ordering of the top layer can be optimized with a suitable top-layer processing solvent. A favorable morphology with gradient vertical composition distribution for efficient charge transport and extraction is therefore realized, affording a high all-PSC efficiency of 17.0% with a FF of 76.1%. The derived devices also possess excellent long-term thermal stability and can retain >90% of their initial efficiencies after being annealed at 65 °C for 1300 h. These results validate the distinct advantages of employing an LBL processing protocol to fabricate high-performance all-PSCs., (© 2022 Wiley-VCH GmbH.)

Lithium metal anodes have long been considered as "holy grail" in the field of energy storage batteries, but dendrite growth and large volume changes hinder their practical applications. Herein, a facile and eco-friendly CF 4 plasma treatment is employed for the surface modification of Li anodes, and an artificial layer consisting of LiF and Li 2 C 2 is fabricated for the first time. Experimental results and theoretical calculations reveal that the high adsorption energy of LiF and low Li + diffusion barriers in Li 2 C 2 induce uniform nucleation and planar growth of Li, guaranteeing a stable and dendrite-free Li structure during the repeated plating/stripping process of cycling. Symmetric cells using CF 4 plasma-treated Li operate stably for more than 6500 h (at 2 mA cm -2 and 1 mAh cm -2 ) or 950 h (at 1 mA cm -2 and 10 mAh cm -2 ). When paired with a LiFePO 4 cathode, full batteries deliver a high reversible capacity of 136 mAh g -1 (at 1 C) with considerable cycling stability (97.2% capacity retention over 200 cycles) and rate performance (116 mAh g -1 up to 5 C). This powerful application of plasma technology toward novel LiF-Li 2 C 2 artificial layers provide new routes for constructing environment-friendly and high-performance energy storage devices., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

β-Ketoacyl-ACP synthase III (KAS III) is a class of important C-C bond-forming enzymes that mostly catalyze the initiation of polyketide and fatty acid biosynthesis. In this study, we elucidated an unusual polyketide synthase (PKS) system that involves two unique KAS IIIs (AsuC3 and C4) in the biosynthesis of the upper triene chain of asukamycin. Significantly, AsuC3 and C4 have both initiation and iterative elongation activity, while being functionally biased toward the elongation and initiation steps, respectively. Mutational analysis revealed that their catalytic activities rely on the catalytic triad Cys-His-Asn. Unlike other KAS IIIs, AsuC3 and C4 are very promiscuous and can accept various lengths of acyl-CoAs with either cyclic, branched or linear acyl moieties. By cooperation with the permissive ketoreductase (AsuC7) and dehydratase (AsuC8/C9), a large variety of polyenes can be efficiently synthesized. This study significantly broadens the understanding of KAS IIIs and polyketide biosynthesis., (© 2022 Wiley-VCH GmbH.)

Companion diagnostics (CDx) provides critical information for precision medicine. However, current CDx is mostly limited to in vitro tests, which cannot accurately evaluate the disease progression and treatment response in real time. To overcome this challenge, herein a glucose oxidase (GOx)-engineered conjugated polymer (polyaniline, PANI) nanoplatform (denoted as PANITG) is reported for activatable imaging-based CDx and multistage augmented photothermal/starvation synergistic therapy. PANITG comprises a pH-activatable conjugated polymer as a photothermal convertor and photoacoustic (PA) emitter, a GOx as a cancer starvation inducer as well as a H 2 O 2 and acid producer, and a H 2 O 2 -cleavable linker as a "switch" for GOx activity. The in vivo PA imaging and photothermal therapy abilities are activated by acidic tumor microenvironment and self-augmented by the reaction between GOx and glucose. Meanwhile, the photothermal effect will enhance the GOx activity in turn. Such multistage augmentation of the therapeutic effects will facilitate effective cancer management. In addition, the in vivo PA imaging with PANITG reveals the tumor pH level which is correlated to the efficiency of the photothermal therapy and to the catalytic activity of GOx at each stage, enabling real-time activatable CDx., (© 2022 Wiley-VCH GmbH.)