Angew. Chem. Int. Ed. Engl. [JOURNAL]
Sun
200 papers
High-Throughput Virtual Screening of Small Molecule Quenchers for Near-Infrared Fluorophores.
Wang C, Yang T, Qiao Q … +7 more , An K, Martinez AG, Li X, Luo Z, Li X, Xu Z, Liu X
Angew Chem Int Ed Engl · 2026 Jun · PMID 42333861 · Publisher ↗
Energy transfer (EnT)-based near-infrared (NIR) fluorescent probes are preferred for biosensing due to their low phototoxicity, deep photon penetration, and high signal-to-noise ratios in vivo. A significant challenge in...
Energy transfer (EnT)-based near-infrared (NIR) fluorescent probes are preferred for biosensing due to their low phototoxicity, deep photon penetration, and high signal-to-noise ratios in vivo. A significant challenge in this domain is the scarcity of small-molecule quenchers (SMQs) that can effectively modulate NIR fluorescence. This study presents the first large-scale screening of SMQs, performing high-throughput virtual screening (HTVS) of 26,695 compact candidate structures (≤ 6 non-hydrogen atoms). We identified several promising molecular moieties, such as ─N═O, ─C═S, and ─B─N═ fragments, and experimentally validated the ─N═O motif as a representative proof-of-concept by constructing three red-to-NIR probes (P2-P4) that operate from ∼590 to 820 nm and successfully image nitric oxide in cells and in vivo. The resulting SMQ library includes candidates predicted to be compatible with NIR fluorophores emitting beyond 800 nm and provides a design blueprint that may accelerate the development of next-generation EnT-based NIR fluorescent probes.
High-Performance, Activation-Free Magnesium-Ion Batteries Enabled by Ionic Liquid Electrolyte Additive.
Li R, Du Y, Lei Y … +5 more , Song L, Sun J, Man Y, Wang G, Zhou X
Angew Chem Int Ed Engl · 2026 Jun · PMID 42333804 · Publisher ↗
Magnesium-ion batteries (MIBs), as a highly promising next-generation energy storage technology, benefit from the high theoretical volumetric capacity (3833 mAh L) of magnesium metal and its intrinsic safety. However, it...
Magnesium-ion batteries (MIBs), as a highly promising next-generation energy storage technology, benefit from the high theoretical volumetric capacity (3833 mAh L) of magnesium metal and its intrinsic safety. However, its commercialization is still hindered by sluggish de-solvation kinetics during cycling, which prolongs the activation periods to reach maximum capacity and impairs rate performance. To overcome this bottleneck, we add 4-ethyl-4-methylmorpholinium cation (EMM) as an additive into the conventional all-phenyl-complex (APC) electrolyte. Density functional theory computations confirm that EMM shows a strong affinity for chloride ions (-0.513 eV), which weakens the Mg-Cl coordination and, thus promotes Mg de-solvation. In CuS-based MIBs, the modified APC-EMM electrolyte eliminates the activation cycles that are required with pure APC, and achieves a high specific capacity of 405.1 mAh g at 100 mA g, while maintaining excellent rate performance (220.1 mAh g at 1 A g). Notably, this electrolyte also shows significant improvements in capacity, activation kinetics, and cycling stability when applied to other cathode materials, including CuSe, CuTe, MoS, and perylene-3,4,9,10-tetracarboxylic dianhydride. This study establishes a de-solvation-accelerated electrolyte design concept as a universal paradigm for the development of high-performance MIBs.
Iterative Synthesis of Pyrene-Coronene Molecular Graphene Nanoribbons.
Medel MA, Wen G, Morón-Blanco A … +4 more , Bonn M, Wang HI, Melle-Franco M, Mateo-Alonso A
Angew Chem Int Ed Engl · 2026 Jun · PMID 42333801 · Publisher ↗
The synthesis of molecular, or monodisperse, graphene nanoribbons with full atomic precision is essential for establishing fundamental structure-property relationships, validating theoretical predictions, and meeting the...
The synthesis of molecular, or monodisperse, graphene nanoribbons with full atomic precision is essential for establishing fundamental structure-property relationships, validating theoretical predictions, and meeting the property requirements for the diverse potential applications of graphene nanoribbons. The synthesis of undoped molecular graphene nanoribbons remains challenging, as many edge topologies have yet to be realized and the reported structures still exhibit limited lengths. This is mostly because iterative synthetic methods for undoped molecular GNRs remain practically undeveloped, with current approaches relying predominantly on noniterative strategies. The iterative synthesis of a new family of undoped molecular GNRs, featuring both a novel edge topology and an unprecedented length, is reported. These nanoribbons are accessed through a borylation/Suzuki/cyclodehydrogenation reaction sequence, in which the Suzuki and cyclodehydrogenation are merged into one transformation, giving rise to an effective two-step iteration sequence. The resulting pyrene-coronene graphene nanoribbons exhibit strong absorption and high fluorescence efficiency, with molar absorptivity and fluorescence brightness values on the order of 10 M cm, and an intrinsic charger carrier mobility of 475 ± 32 cm V s.
Enhancing Enzyme Activity With Mutation Combinations Guided by Few-Shot Learning and Causal Inference.
Guo L, Yan X, Lu Y … +13 more , Nie S, Ge M, Li Y, Li W, Zhang X, Liang D, Zhao Y, Tan H, Chen X, Fan S, Tang Y, Qiao J, Tian B
Angew Chem Int Ed Engl · 2026 Jun · PMID 42329188 · Publisher ↗
Designing enzyme sequences to enhance product yield represents a fundamental challenge in metabolic engineering. Here, we established a workflow that integrates computational predictions with efficient experimental itera...
Designing enzyme sequences to enhance product yield represents a fundamental challenge in metabolic engineering. Here, we established a workflow that integrates computational predictions with efficient experimental iteration to obtain outsized gains in product yield. Based on causal inference and examination of published datasets, we realized and ultimately experimentally confirmed that in vivo unit yield (yield/expression) can serve as an attractive surrogate for aqueous k/K when optimizing for activity. In our workflow, we initially predict activity-enhancing single mutants by calculating the binding affinities of reactive intermediates, followed by experimental investigations of unit yield. Subsequently, we predict activity-enhancing mutation combinations using a few-shot learning model we developed called Physics-Inspired Feature Selection of Protein Language Models (PIFS-PLM), which requires only 60-100 experimentally examined mutation combinations as input. In a case study of a bicyclogermacrene (BCG) synthase, we achieve a 73-fold increase in BCG yield or a 15% increase in BCG selectivity based on combinations of 12 individual mutations, and provide extensive crystallographic and biochemical evidence for impacts from specific mutations. Thus, optimizing for unit yield is highly efficient as an alternative to optimizing for thermostability, and our study provides a powerful workflow for the efficient engineering of high-yield enzyme variants.
Non-Superacid-Catalyzed Preparation of Anion Exchange Membranes for High-Performance Water Electrolyzers.
Shi J, Chen Z, Zhang H … +7 more , Zhou C, Shi X, Wang X, Yin T, Wang X, Sun Z, Yan F
Angew Chem Int Ed Engl · 2026 Jun · PMID 42329184 · Publisher ↗
Recent advances in anion exchange membrane water electrolyzers (AEMWEs) have been primarily driven by anion exchange membranes (AEMs) prepared via superacid-catalyzed polymerization. However, the reliance on highly corro...
Recent advances in anion exchange membrane water electrolyzers (AEMWEs) have been primarily driven by anion exchange membranes (AEMs) prepared via superacid-catalyzed polymerization. However, the reliance on highly corrosive trifluoromethanesulfonic acid (TFSA; pKa = -14.7) employed both as catalyst and solvent poses significant safety, handling, and scalability challenges for industrial AEM manufacturing. Herein, we report a nonsuperacid polymerization strategy for AEMs, utilizing methanesulfonic acid (MSA; pKa = -1.9) to catalyze the Friedel-Crafts alkylation between electrophilic aminobenzaldehyde and electron-rich dibenzo-18-crown-6. Crown ether incorporation expands interchain spacing, thereby facilitating the formation of continuous hydrophilic ion-conducting channels. Furthermore, complexation of potassium ions with crown ether moieties weakens the electrostatic interaction between K and OH, thereby lowering the dissociation energy of the KOH electrolyte. As a result, the optimized QPCA-70 membrane exhibits a high alkaline conductivity of 628.93 mS cm at 80 °C and delivers a current density of 8.8 A cm at 2.0 V using a NiFeCo anode. Critically, MSA serves as a safer, more practical, and cost-effective alternative to TFSA: it eliminates the extreme hazards associated with superacid handling, thereby enabling scalable, industrially viable, and low-risk AEM production.
Water-Splitting-Suppressed High-Capacity Bipolar Electrodes Enabled by Topochemical Electron Buffering for Symmetric Aqueous Batteries.
Huang T, Zhang Y, Liao M … +5 more , Jiao M, Wang Y, Duan M, Xu K, Liu H
Angew Chem Int Ed Engl · 2026 Jun · PMID 42329182 · Publisher ↗
Symmetric aqueous batteries (SABs) that employ bipolar materials as electrodes have attracted tremendous attention due to their intrinsic safety and satisfactory capacity, while they still suffer from water-splitting and...
Symmetric aqueous batteries (SABs) that employ bipolar materials as electrodes have attracted tremendous attention due to their intrinsic safety and satisfactory capacity, while they still suffer from water-splitting and thus a narrow voltage window. In this work, we propose a novel topochemical design of introducing an electron buffer (EB) to control the electron stream when working, which efficiently attenuates the electron flow toward the water-splitting reactions at the voltage ends. Careful measurements confirm the sharp reduction of current density applied for water-splitting due to the EB effect. Theoretical calculations for voltage end verify the lower surface electron density of EB-involved electrode than that of EB-excluded electrode, demonstrating the superiority of this EB design in suppressing charge shock for water splitting. Consequently, the charging/discharging plateau of the assembled SABs based on EB increases ∼0.16 V, as well as a high capacity of 80.7 mA h g achieved, which is superior to reported state-of-the-art aqueous bipolar materials. Moreover, the electrolyte loss of EB-involved SABs reduces to only 24% of that of EB-excluded SABs, validating suppressed water splitting by confining the electron pathway. This work provides a new thought to guide electron stream through introducing a rational buffer layer, aiming at hindering water splitting while maintaining energy storage performance.
Breathing Bimetallic MOF Confined Polyoxometalates for Hydration Layer Loosening and Electronic Redistribution Toward Efficient Nitrate Electroreduction and Zn-Nitrate Batteries.
Jiang Q, Wang X, Wang C … +6 more , Tian S, Zhao N, Pang H, Lv C, Yu Z, Zang HY
Angew Chem Int Ed Engl · 2026 Jun · PMID 42329178 · Publisher ↗
The traditional Haber-Bosch method suffers from harsh conditions and high energy consumption, while electrocatalytic nitrate reduction to ammonia (ENRA) is a green route for ammonia synthesis and can serve as a cathode r...
The traditional Haber-Bosch method suffers from harsh conditions and high energy consumption, while electrocatalytic nitrate reduction to ammonia (ENRA) is a green route for ammonia synthesis and can serve as a cathode reaction for Zn-nitrate batteries. Its development is limited by sluggish intermediate hydrogenation and severe hydrogen evolution reaction (HER). Herein, we develop topology-engineered isomeric polyoxometalate (POM)-confined bimetallic metal-organic framework (MOF) electrocatalysts (NH-MIL-53, -88, -101). Flexible NH-MIL-88(FeNi) enables tight encapsulation of [PWO] (PW) clusters via the "breathing effect", yielding PW@NH-MIL-88(FeNi) with synergistically modulated electronic distribution and proton transfer. Combined experimental and theoretical studies reveal that confined PW induces electronic redistribution over Fe/Ni centers, concurrently strengthening NO adsorption on Fe and accelerating *NO hydrogenation on Ni. Beyond electronic effects, PW loosens the rigid hydration layer and forms conjugated acid-base pairs with MOF amino groups, promoting proton diffusion, boosting *NO hydrogenation, and suppressing HER. Thus, PW@NH-MIL-88(FeNi) achieves an NH yield rate of 20.1 mg h mg with a Faradaic efficiency of 98.6% under neutral electrolytes. When used as a cathode in rechargeable Zn-nitrate batteries, it delivers a peak power density of 13.2 mW cm. This study establishes a generalizable paradigm for engineering interfacial proton transport and electronic properties via POM confinement in MOFs.
Enhancing Built-in Electric Fields in Covalent Organic Frameworks With High Surface Area and High Stability for Boosted Photocatalytic Activity.
Xu M, Liu P, Duong TD … +5 more , Huang W, Zhou Z, Yang S, Cheng P, Shi W
Angew Chem Int Ed Engl · 2026 Jun · PMID 42329171 · Publisher ↗
The built-in electric field (BIEF) is a fundamental driving force governing the separation, transfer, and lifetime of photogenerated charge carriers, thereby dictating the activity of photocatalysts. Herein, a local p-π...
The built-in electric field (BIEF) is a fundamental driving force governing the separation, transfer, and lifetime of photogenerated charge carriers, thereby dictating the activity of photocatalysts. Herein, a local p-π conjugation regulation strategy was developed to tailor the BIEF in covalent organic frameworks (COFs) as advanced photocatalysts. Three COFs of NKU-191, NKU-191-OH, and NKU-191-OMe, featuring robust acid-base resistance, high stability, and high specific surface area, were synthesized via Schiff base reactions under mild conditions. Without altering their intrinsic backbone structure, the photocatalytic hydrogen evolution activity was enhanced from 4.8 mmol g h (NKU-191) to 35.6 mmol g h (NKU-191-OMe). Comprehensive characterizations and systematic analysis revealed that the introduction of electron-donating groups effectively strengthens the local p-π conjugation within the COF skeletons, which in turn reinforces the BIEF intensity. This enhanced BIEF accelerates the separation and migration kinetics of photogenerated charge carriers, thereby enabling remarkable photocatalytic activity. This work not only establishes a facile synthetic protocol for synthesizing COFs with high specific surface areas and high stability but also clarifies the regulatory role of local p-π conjugation in regulating the BIEF intensity of COF-based photocatalysts, providing valuable insights for promoting the rational design and development of high-performance COF-based photocatalysts.
Hydrogen-Tolerant CuO/TiO Catalysts Enabled by Oxygen Anchoring for Nitrile Hydrogenation.
Fan T, Zhao H, Zhang X … +7 more , Li J, Li T, Shen H, Gao S, Li J, Long Y, Ma J
Angew Chem Int Ed Engl · 2026 Jun · PMID 42329170 · Publisher ↗
Designing reducible metal oxide catalysts that remain stable under hydrogenation conditions represents a longstanding challenge in heterogeneous catalysis, as most oxides are readily reduced and structurally degraded in...
Designing reducible metal oxide catalysts that remain stable under hydrogenation conditions represents a longstanding challenge in heterogeneous catalysis, as most oxides are readily reduced and structurally degraded in H-rich environments. Here, we report an oxygen-anchoring strategy that enables hydrogen-tolerant metal oxide catalysts. Using this approach, a CuO/TiO catalyst stabilized by an oxygen-rich C─O framework (HT-CuO/TiO) was constructed for the selective hydrogenation-coupling of nitriles to secondary amines. The oxygen functionalities within the C─O framework act as anchoring sites that stabilize CuO nanoclusters and suppress their reduction under hydrogen. The stabilized CuO nanoclusters function both as hydrogen activation centers and Lewis acid sites for nitrile adsorption. Meanwhile, the introduction of TiO leads to the formation of intimate CuO─TiO interfacial structures, accompanied by the presence of Ti species and enhanced hydrogen activation behavior. Notably, this hydrogen-tolerant behavior extends to a range of reducible metal oxides, including CuO, CuO, CoO, and NiO, demonstrating the generality of the oxygen-anchoring stabilization principle. This work establishes a general strategy for stabilizing reducible metal oxides under hydrogen and unlocks their catalytic potential for hydrogenation chemistry.
Breaking the Fixed Output: Harnessing Photonic Reabsorption and Photothermal Effects for Tunable NIR Waveguiding in a Flexible Organic Crystal.
Li Z, Yang X, Zhou Y … +1 more , Zhang H
Angew Chem Int Ed Engl · 2026 Jun · PMID 42329164 · Publisher ↗
Flexible organic crystals have emerged as promising materials for integrated photonic devices and optical communication systems. However, the output wavelength and intensity of optical signals are typically fixed by the...
Flexible organic crystals have emerged as promising materials for integrated photonic devices and optical communication systems. However, the output wavelength and intensity of optical signals are typically fixed by the intrinsic molecular structures and crystal packing modes, rendering continuous and reversible modulation of a sole crystal highly challenging. Herein, we design and synthesize a near-infrared flexible organic crystal, in which dual-mode waveguide output modulation of wavelength and intensity is achieved by synergistically exploiting photonic re-absorption and photothermal-driven fluorescence deactivation. Owing to the pronounced overlap between the absorption and emission spectra, the waveguide output wavelength of the crystal can be continuously tuned from 730 to 824 nm based on the light propagation distance. Meanwhile, the crystal exhibits rapid, stable, and highly reversible photothermal conversion under 660 nm laser irradiation. Coupled with temperature-dependent fluorescence deactivation, this photothermal effect enables remote modulation of waveguide output intensity by simply adjusting the irradiation power of the input laser. This work establishes a non-contact, structure-preserving strategy for overall modulation of optical waveguides, providing new opportunities for the development of flexible near-infrared photonic devices and reconfigurable optical systems.
Selective Two-Electron Phenol Oxidation Polymerization for Water Purification.
Chen T, Wang R, He B … +6 more , Li M, Li X, Yang X, Lin J, Long M, Zhang L
Angew Chem Int Ed Engl · 2026 Jun · PMID 42329157 · Publisher ↗
Highly reactive phenoxonium ion (PhO), generated via two-electron oxidation, exhibits remarkable efficacy in polymerizing and removing phenolic contaminants. However, the sequential two-electron abstraction from phenol t...
Highly reactive phenoxonium ion (PhO), generated via two-electron oxidation, exhibits remarkable efficacy in polymerizing and removing phenolic contaminants. However, the sequential two-electron abstraction from phenol to form PhO remains a significant kinetic and thermodynamic challenge. Herein, we report an N-bridged double-iron site (≡Fe─N─Fe ≡) catalyst that enables PhO generation through peroxymonosulfate (PMS) activation. In situ spectroscopy and theoretical calculations reveal that PMS adsorbs onto the ≡Fe─N─Fe ≡ site via both peroxide oxygen atoms (─O─O─), forming a ≡Fe-(μO─O)─Fe≡ intermediate. This unique structure provides dual low-lying Fe─O σ*( -p) orbitals, and minimizes the energy gap between the Fe orbital and the O─O σ* orbital, thereby catalyzing two-step single-electron transfer from phenol to the ─O─O─ and enabling the PhO formation. This PhO-induced C─O coupling polymerization achieves an 81.8% polymerization transfer ratio, significantly higher than that obtained via the phenoxy radical (PhO•)-mediated process (35.0%). This system enables the rapid phenol removal (98.1% in 3 min) and the effective treatment of coking wastewater, maintaining > 97% phenol removal over 10 d in a continuous-flow reactor. Our work provides an atomic-level design principle for steering oxidation pathways, opening a sustainable route for water purification that simultaneously eliminates pollutants and recovers carbon resources.
Peroxide-Assisted Solvate Engineering Enables Record-High Birefringence in a Solar-Blind Transparent Crystal.
Li Y, Jin C, Ok KM
Angew Chem Int Ed Engl · 2026 Jun · PMID 42329153 · Publisher ↗
Developing birefringent materials that simultaneously exhibit short ultraviolet (UV) cutoff edges and large birefringence is highly desirable but remains challenging. Here, we report a peroxide-containing solvate crystal...
Developing birefringent materials that simultaneously exhibit short ultraviolet (UV) cutoff edges and large birefringence is highly desirable but remains challenging. Here, we report a peroxide-containing solvate crystal, 4HP·HO (4HPO2, 4HP = 4-hydroxypyridine), obtained by incorporating HO into the 4HP lattice through a mild aqueous-solution method. 4HPO2 exhibits a solar-blind UV cutoff edge at 278 nm together with a giant experimental birefringence of 0.609@546 nm, representing an approximately 14-fold enhancement compared with pristine 4HP. Structural analysis reveals that HO induces a pronounced reorganization of the 4HP packing, converting a nearly orthogonal arrangement into an ordered, nearly parallel alignment through strengthened hydrogen-bonding interactions. Combined experimental and theoretical analyses indicate that the aligned 4HP sublattice serves as the dominant source of optical anisotropy, whereas HO mainly acts as a hydrogen-bond-directed structural modulator with a secondary direct optical contribution. The reordered packing also creates an anisotropic local-field environment that further amplifies the molecular polarizability anisotropy (Δα). These findings highlight peroxide-assisted solvate engineering as an effective strategy for tuning packing and optical anisotropy and provide a promising design principle for developing ultraviolet birefringent materials.
Molecular Engineering of Vibronic Coupling Enables High-Temperature Solar-Thermal Conversion in an Organic Material.
Xu H, Liu Y, Jiang X … +8 more , Han P, Wang W, Zhou W, Song B, Zhai Y, Hu B, Qin A, Tang BZ
Angew Chem Int Ed Engl · 2026 Jun · PMID 42329152 · Publisher ↗
Solar-thermal conversion offers a direct route for harvesting solar energy, yet most organic materials reported are limited to moderate temperatures and low-temperature applications. Here, we report BTDyA, an organic mat...
Solar-thermal conversion offers a direct route for harvesting solar energy, yet most organic materials reported are limited to moderate temperatures and low-temperature applications. Here, we report BTDyA, an organic material designed for high-temperature solar-thermal conversion, achieved by bridging triphenylamine donors with [1,2,5]thiadiazolo[3,4-f]benzotriazole acceptor via ethynyl linkages. BTDyA demonstrates a high molar absorption coefficient and broadband solid-state absorption, enabled it to reach a temperature as high as 330 °C under concentrated outdoor sunlight, the highest reported value for organic solar-thermal materials. Moreover, under 1064 nm laser irradiation, the temperature could be further elevated to 377 °C. The transient absorption and photoinduced Raman spectroscopies reveal that BTDyA undergoes ultrafast nonradiative decay in the excited-state, coupled with significant vibronic activation. These promote efficient conversion of photon energy into molecular vibronic energy and heat, while suppressing radiative losses and enhancing photothermal performance. The high-temperature capability of BTDyA positions it as a promising candidate for solar energy harvesting and thermal storage. These findings offer critical insights into the design principles and photothermal mechanisms of organic materials for high-temperature solar-thermal applications, paving the way for their future use in renewable energy technologies.
Microdroplets Boosted Photocatalytic HO Production Over Covalent Organic Frameworks via Tri-Phase Interface Catalysis.
Xu Y, Xie W, Sun N … +7 more , Ci X, Lang Y, Yang C, Liu T, Yang L, Deng WQ, Li Z
Angew Chem Int Ed Engl · 2026 Jun · PMID 42329151 · Publisher ↗
Photocatalytic HO production from HO/O is a green solar energy conversion strategy, but the conventional bulk liquid systems suffer from poor mass transfer and limited active site accessibility. Here, by introducing sess...
Photocatalytic HO production from HO/O is a green solar energy conversion strategy, but the conventional bulk liquid systems suffer from poor mass transfer and limited active site accessibility. Here, by introducing sessile water microdroplets into the system using a covalent organic framework (DS-OH-COF) as a photocatalyst, the HO production rate was significantly enhanced. The yield strongly depends on droplet size. At 1 µL under air atmosphere, HO yield reached 11.11 mmol g h, representing a 12.3-fold increase over bulk water systems. Under O, the yield increases to 14.79 mmol g h, outperforming most reported photocatalysts. The large specific surface area of microdroplets enhances O mass transfer into the liquid phase, promoting interaction with catalyst active sites. Most importantly, the gas-liquid-solid tri-phase interface plays a vital role in the catalytic process. Density functional theory calculations confirm that the O adsorption behavior is modulated by the substrate, which regulates O reduction at the tri-phase interface. The microdroplet system also enabled efficient methyl orange degradation, demonstrating its practical potential. This microdroplet-based catalytic path effectively overcomes the inherent limitations of insufficient oxygen mass transfer and low efficiency in bulk reactions, providing new insights for catalytic HO generation.
Liquid Crystal Elastomers for Adaptive Intelligent Systems: From Molecular Design to Multifunctional Applications.
Zheng X, Lv M, Li T … +4 more , Chen Y, Lv P, Yu H, Feng W
Angew Chem Int Ed Engl · 2026 Jun · PMID 42329150 · Publisher ↗
Liquid crystal elastomers (LCEs), particularly nematic and cholesteric variants, have emerged as pivotal adaptive intelligent materials due to their unique capacity to reversibly translate microscopic molecular reorienta...
Liquid crystal elastomers (LCEs), particularly nematic and cholesteric variants, have emerged as pivotal adaptive intelligent materials due to their unique capacity to reversibly translate microscopic molecular reorientation into macroscopic deformation and optical responses. This review provides a comprehensive overview of recent breakthroughs in LCE-based adaptive systems, systematically examining their fundamental stimulus-response mechanisms, network architecture engineering, advanced fabrication techniques, and cutting-edge applications. Special emphasis is placed on strategies for lowering actuation thresholds to near-ambient or body temperatures through chemical composition modulation, dynamic covalent adaptable networks, and innovative processing methods such as hybrid cooling 3D printing. We further highlight the integration of LCEs into multifunctional platforms for dynamic thermal management, multispectral camouflage, high-density information encryption, deformable energy storage, and closed-loop soft actuators with intrinsic sensing capabilities. Despite significant progress, challenges regarding large-scale manufacturing, long-term cyclic stability, and precise spatiotemporal control remain. By synthesizing current design principles and identifying critical technological bottlenecks, this review aims to guide the rational development of next-generation programmable, multifunctional, and environmentally resilient LCE systems, ultimately accelerating their transition from laboratory prototypes to real-world adaptive intelligent applications.
Ligand-Enabled Stereoselective Coupling of Methylene C(sp)─H Bonds With Alkenyl Bromide via Pd/Pd/Pd Catalysis.
Zhang ZY, Zhang T, Ouyang Y … +2 more , Sheng T, Yu JQ
Angew Chem Int Ed Engl · 2026 Jun · PMID 42329149 · Publisher ↗
Utilizing C(sp)─H bonds as coupling partners for the formation of C(sp)─C(sp) bonds remains a significant challenge despite the progress in the past two decades. Notably, the previously reported coupling reactions of C(s...
Utilizing C(sp)─H bonds as coupling partners for the formation of C(sp)─C(sp) bonds remains a significant challenge despite the progress in the past two decades. Notably, the previously reported coupling reactions of C(sp)─H bonds with vinyl halides employing Pd/Pd catalysis are highly limited in two ways: activated alkenyl halides and strong external directing groups were typically required. Here, we report stereoselective C(sp)─C(sp) cross-coupling of methylene C(sp)─H bonds from aliphatic acids with alkenyl bromides via Pd/Pd/Pd catalysis. A diverse array of readily available cyclic and acyclic aliphatic acids and various alkenyl bromides were coupled smoothly, affording a versatile method for forging C(sp)─C(sp) bonds. Complex acids and the alkenyl bromide coupling partners derived from natural products and pharmaceuticals are compatible, rendering this method amenable to late-stage modification. The stereoselectivity of this C(sp)─C(sp) coupling reaction with respect to both the sp carbon center and the double bond configuration is a valuable feature.
New Water Oxidation Mechanism in Photosystem II Resolves Major Experimental Controversies.
Pushkar Y
Angew Chem Int Ed Engl · 2026 Jun · PMID 42329146 · Publisher ↗
Light-driven oxygen formation in photosystem II protein is a fundamental process that sustains our biosphere. The research by advanced physical techniques has delivered new insights on the structure and function of the M...
Light-driven oxygen formation in photosystem II protein is a fundamental process that sustains our biosphere. The research by advanced physical techniques has delivered new insights on the structure and function of the MnCaO cluster. However, discrepancies in experimental observations and computational models persist, impeding the understanding of O-O bond formation and the role of the protein environment in the process. Here, we show that i) assignment of the OEC unique oxygen O3 ligated by histidine (His337) via dynamic H-bond as a slow exchanging substrate and ii) its coupling with O6 oxygen generated at Mn1 in the S to S transition-giving an O─O bond formation mechanism most consistent with all currently available experimental data. We propose a mechanism by which the protein environment can steer the O─O bond formation by charge control via H-bonding and open coordination of Mn1. Obtained O3-O6 peroxide is at lower energy than peroxides in the most studied O5─O6 bond formation pathway. His337 appears to be similar to distal His in globins used for management of the O and HO intermediates. This new mechanism breaks the prior impasse and will undoubtedly invigorate future detailed studies uncovering further details.
An Enantioselective Alkene Aminoarylation to Form Chiral Indolines via Electrostatically-Directed Palladium Catalysis.
Kadarauch M, Jirsch PT, Diepers HE … +2 more , Sharif H, Phipps RJ
Angew Chem Int Ed Engl · 2026 Jun · PMID 42329142 · Publisher ↗
Most design strategies in asymmetric transition metal catalysis invoke repulsive interactions between ligand and substrate. Yet those that incorporate attractive interactions can offer advantages, such as rate accelerati...
Most design strategies in asymmetric transition metal catalysis invoke repulsive interactions between ligand and substrate. Yet those that incorporate attractive interactions can offer advantages, such as rate acceleration and greater generality, due to the fundamentally different mode of operation. Here we deploy electrostatically-directed Pd catalysis using the chiral sulfonated ligand sSPhos to realize an asymmetric aminoarylation of ortho-allyl anilines under mild conditions. A wide variety of substituted aryl bromides and anilines provide access to 2-benzylindolines with high enantioselectivity. Our study uncovers trends relating the electronics of both coupling partners to ee. These trends allowed tuning of the sulfonamide protecting group to enable good results across a broader range of substrates.
Electron-Isolating Band Solidified Fe─O Bond in Ni/NiFe Layered Double Hydroxide Composite for Stable Ampere-Level Simulated Seawater Oxidation.
Guo Z, Zhu Q, Wang S … +14 more , Ge Y, Fan X, Zhang W, Hou X, He Y, Zhang Y, Zhang M, Liang N, Wang Y, Huang H, Shao Z, Wu X, Huang K, Feng S
Angew Chem Int Ed Engl · 2026 Jun · PMID 42329140 · Publisher ↗
The dissolution of iron ions triggers irreversible structural collapse and resultant catastrophic deactivation in NiFe-layered double hydroxides (NiFe LDHs), representing a formidable challenge to their implementation in...
The dissolution of iron ions triggers irreversible structural collapse and resultant catastrophic deactivation in NiFe-layered double hydroxides (NiFe LDHs), representing a formidable challenge to their implementation in sustainable hydrogen production. Herein, by adjusting the Ni nanoparticle content in Ni/NiFe LDH composites synthesized via reduction-coprecipitation method, Fe t orbital occupancy is regulated to protect the Fe─O bond from cleavage. Specifically, with considerable electron transfer from Ni to Fe t orbital, the low-energy antibonding of Fe t* band separates from the (Fe─O) bonding band, lying near and crossing the Fermi level, as evidenced by x-ray absorption spectra (XAS) and the calculated density of states. This band serves as an electron-isolating band to avoid electron removal from the (Fe─O) bonding band, which significantly solidifies the Fe─O bond confirmed by operando XAS. Additionally, the modulation lowers the adsorption energy of Cl, suppressing the chloride-induced electrocatalyst corrosion in seawater electrolysis. Consequently, the optimal sample operates stably at 1 A cm for over 10 000 h in the three-electrode system and beyond 450 h in an anion-exchange membrane water electrolyzer under simulated seawater oxidation, ranking among the state-of-the-art powder-type NiFe LDH-based catalysts. This work highlights the manipulation of antibonding orbital state for fundamentally enhancing electrocatalyst stability.
Synergistic Pore Microenvironment Engineering in Zinc Metal-Organic Frameworks for High SF/N Selectivity and Humidity-Resistant Trace SF Capture.
Xu L, Zhang LP, Li YT … +1 more , Yang QY
Angew Chem Int Ed Engl · 2026 Jun · PMID 42329133 · Publisher ↗
Sulfur hexafluoride (SF) is a potent greenhouse gas widely used in electrical insulation. Although the size difference between SF and N enables separation in principle, achieving high SF selectivity at trace concentratio...
Sulfur hexafluoride (SF) is a potent greenhouse gas widely used in electrical insulation. Although the size difference between SF and N enables separation in principle, achieving high SF selectivity at trace concentrations, large adsorption capacity, and long-term stability remains a formidable challenge. Herein, we report a family of new zinc-based metal-organic frameworks (Zn-tcpb, Zn-tcpb-bim, Zn-tppb-bim) with systematically tunable pore sizes and electrostatic microenvironments. By integrating a mixed-ligand strategy (tetracarboxylic acids plus 2,2'-biimidazole) with pore functionalization, we achieve synergistic control over adsorption and separation properties. Among them, Zn-tppb-bim-featuring electron-withdrawing pyrazine rings-exhibits a remarkable low-pressure SF uptake of 3.06 mmol/g at 0.1 bar, and an excellent SF/N IAST selectivity of 606 (1:9, 1 bar), achieving a balance between uptake and selectivity. Theoretical calculations reveal that the N-heterocyclic units in Zn-tppb-bim generate a stronger positive framework charge, enhancing C─H···F interactions with SF. Dynamic breakthrough experiments confirm complete separation of SF/N mixtures. Remarkably, the materials retain full separation performance even at 80% relative humidity. This work demonstrates a viable and generalizable design strategy that synergistically optimizes adsorption capacity, selectivity, and humidity resistance, providing a rare example of metal-organic framework that are both highly efficient and stable under practical conditions.
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