The direct four‐electron oxygen reduction reaction (4e− ORR) critically governs efficiency and lifespan in metal‐air batteries and fuel cells, yet selectively suppressing competitive 2e− and stepwise 2e− pathways that generate corrosive hydrogen peroxide remains a major challenge. Herein, we demonstrate the strategic incorporation of secondary coordinated sulfur atoms into transition metal‐N‐C electrocatalysts

Visible light photoredox catalysis has become a rapidly emerging area owing to its potential of using sunlight to tame previously hard‐to‐harness radicals for organic synthesis. At present, such blueprint faces a significant challenge, namely how to accomplish thermodynamically demanding reactions with sunlight encompassing a wide range of low energy photons. Here, we report a new reaction framework

A metal‐controlled enantiodivergent rearrangement of α‐diazo‐β‐keto oxime ethers has been developed. Switching the metal catalyst from Co(II) to Fe(II) with an identical ligand completely reverses the asymmetric induction. Both enantiomers of chiral 2H‐azirines and its derivatives are accessible under thermal or photolytic conditions. The cobalt‐based reaction is highly efficient even at 0.05 mol%

Targeted protein degradation (TPD) technology holds significant potential for modulating protein homeostasis and treating diseases. However, current methods for degrading membrane protein highly depend on the lysosome‐targeting ligands or membrane receptors. In this study, we present a set of multivalent targeting chimeras (multi‐TACs) for tumor‐specific degradation of programmed death ligand 1 (PD‐L1)

The undesired phase distribution and intrinsic residual lattice strain remain the bottleneck for high‐performance and stable two‐dimensional (2D) or Q‐2D perovskite solar cells (PSCs), especially for the Dion‐Jacobson (DJ) type Q‐2D PSCs. Here, we showcase employing halogen bonds to stabilize the halide anions and fine‐tuning the residual lattice strain by introducing perfluorodecyl iodide (PFI). It

Aliphatic polyesters, such as poly(adipate)esters, are attracting substantial attention as sustainable materials due to their degradability, recyclability, and versatility in various applications. However, the conventional production of poly(adipate)esters relies on energy‐intensive processes and petroleum‐derived adipic acid (AA), whose synthesis poses environmental concerns, including nitrous oxide

As a unique class of framework electronic materials, two‐dimensional conjugated metal‐organic frameworks (2D c‐MOFs) exhibit intrinsic porosity, superior electrical conductivity, and abundant active sites. These properties endow them with great potential in electrochemical lithium‐ion storage. However, the development of 2D c‐MOF‐based capacitors has encountered a bottleneck in enhancing Li‐ion storage

Polyhydroxyalkanoate (PHA) is a biodegradable polyester that can serve as a promising alternative to petrochemical plastics which present a serious source of pollution. PHA synthase (PhaC) is a key enzyme responsible for producing a wide variety of PHAs in microorganisms. Here we present crystal structures of full‐length PhaC from Aeromonas caviae, a high‐performance PhaC employed for industrial use

The catalytic enantioselective synthesis of aza‐sulfur(VI) compounds holds significant potential in pharmaceuticals owing to their broad spectrum of biological properties. Herein, we report the first N‐heterocyclic carbene (NHC)‐organocatalyzed enantioselective synthesis of cyclic sulfonimidamides (SIAs). The free N‐H containing SIAs often exhibit configurational lability through tautomerization. We

Cooperative intermolecular interactions, usually observed in solid state, can confer useful properties to stimuli‐responsive spin transition materials. Here we evidence for the first time intramolecular cooperativity between the two Fe‐Co subunits of a molecular cyanido‐bridged square Fe2Co2 Prussian blue analog (PBA) in solution, which upon single photon excitation sequentially undergo electron transfer

The controlled generation and utilization of singlet oxygen (1O2) are crucial for its diverse applications but remain challenging due to its high reactivity and short‐lived nature. Here, we report a box‐shaped metallacage prepared via multicomponent coordination‐driven self‐assembly using tetrapyridyl perylene diimide (PDI) and tetracarboxylate anthracene as building blocks. Upon photo‐irradiation

Photocatalytic CO2 conversion with H2O to carbonaceous fuels is a desirable strategy for CO2 management and solar utilization, yet its efficiency remains suboptimal. Herein, efficient and durable CO2 photoreduction is realized over a RuNPs/Ru‐PHI catalyst assembled by anchoring Ru single atoms (SAs) and nanoparticles (NPs) onto poly(heptazine imide) (PHI) via the in‐plane Ru‐N4 coordination and interfacial

Photocatalysis is a pivotal area in synthetic chemistry. Despite extensive application potential in nuclear industry, uranium‐based photocatalysts are historically limited to uranyl(VI/V) redox cycle. Here, we report the discovery of the first tetravalent uranium [U(IV)] photocatalyst that enables efficient C(sp3)–C(sp3) bond cleavage and formation under ideal visible light. The U(IV) alkoxy species

Although several diazotases have been recently reported, the details of the reaction mechanism are not yet understood. In this study, we investigated the mechanism of CmaA6, an ATP‐dependent diazotase that catalyzes the diazotization of 3‐aminocoumaric acid using nitrous acid. X‐ray crystallography and cryogenic electron microscopy‐single particle analysis revealed CmaA6 structures in the substrate‐free

Nickel‐based perovskite oxides are identified as promising candidates for oxygen evolution reaction (OER) catalysts in view of their low cost, highly tunable structure, and potential high activity. However, the performance and catalyst design are hindered by their sluggish surface reconstruction kinetics. We introduce a ferric ion pre‐etching strategy to enhance the surface reconstruction of typical

Mammalian secreted venoms mainly consist of peptides and proteases used for defense or predation. Blarina paralytic peptides (BPPs), mealworm‐targeting neurotoxins from shrew, are very similar to human synenkephalin. This peptide is released from proenkephalin in the brain along with opioid peptides that mediate analgesic and antidepressant effects, though its physiological function is unclear. Here

As a 4d–transition metal, the spin state of Pd is extremely difficult to directly regulate for the optimized d orbital states owing to the strong spin–orbit coupling effect and further extended d orbital. Herein, we devise "spin–selective electron donation" strategy to tune specific d orbital electrons of Pd inspired by Dewar−Chatt−Duncanson model theory. Co−S−Pd bridges with different spin–states

The light polarization modulation involves the capacity to respond selectively to light‐mater interaction and is dependent on the optical anisotropy of crystalline materials. The π‐conjugated component is almost typically utilized to produce such materials in the short‐wave ultraviolet region, however, the conflicting link between high optical anisotropy and strong layered habit is difficult to reconcile

closo‐Carboranes are icosahedral carbon‐boron clusters with unique properties and broad applicability. They particularly stand out in the context of drug development as privileged structural motifs for boron neutron capture therapy (BNCT) and as highly hydrophobic bioisosteres for the rotational volume of phenyl rings. Herein, we unveil the synthesis of N‐protected carboranyl analogs of β‐arylethylamines

This study presents a phosgene‐ and isocyanate‐free route for the synthesis of polyurethanes using (R)‐limonene as a bio‐based starting material. The synthesis of the cyclic limonene‐based carbamate monomer LU is achieved in high yields using dimethyl carbonate as a sustainable, less hazardous phosgene surrogate and is verified by NMR, SC‐XRD, ESI‐MS, GC‐MS, and elemental analysis. Polymerizations

J. Zhang, H. Zheng, F. Chen, Z. Wang, H. Li, F. Sun, D. Zhao, V. Valtchev, S. Qiu, Q. Fang, Angew. Chem. Int. Ed. 2025, 64, e202500161. https://doi.org/10.1002/anie.202500161 In the original publication, the description of [8+6]-c connectivity in the pdp network did not fully align with established topological nomenclature standards (Accounts of Chemical Research 2008, 41, 1782; Crystal Growth & Design

DNA methylation modulates gene expression without altering the DNA sequence. Aberrant DNA methylation patterns characterise a wide range of diseases, from cancer to neurological disorders, and serve as validated therapeutic targets and diagnostic tools. Among the proteins involved in DNA methylation regulation, the human reader Methyl‐CpG Binding Domain 2 protein (MBD2) exhibits a strong preference

This study presents the development and evaluation of five dyes with varying conjugated energy levels and donor‐π‐acceptor (D‐π‐A) structures as photoinitiators for free radical polymerization. Their photoinitiation efficiencies are systematically assessed under both visible‐light LED and sunlight. Notably, the conversions reach up to 81% within just 30 s under sunlight, demonstrating the ultra‐fast

CD59 is an immunomodulatory cell surface receptor associated with human disease. Despite its importance in complement regulation and bacterial pathogenesis, CD59 remains a challenging therapeutic target. Research to date has focused on antibody or protein‐based strategies. Here we present a new approach to target CD59 using macrocyclic peptides with low nanomolar affinity for CD59. Through X‐ray crystallographic

Constructing cluster‐based nodes and using them as catalytic sites can bring new structure and function for metal‐organic cages (MOCs). However, successful examples are very limited. Herein, we found that a 2‐mercapto‐5‐methyl‐1,3,4‐thiadiazole (Hmmt) based {Ni6} subunit is robust in building such MOCs. The {Ni6} node is based on the central Ni4 cubane and two wing Ni(II) ions with virtually three

Achieving ultrafast dissociation of photogenerated excitons and efficient charge transport within the photocatalyst is a fundamental issue. Additionally, enhancing the interaction between semiconductors and water is crucial for efficient photocatalytic water splitting. Herein, we synthesized a carboxylate‐based hydrophilic polymer, hPTB7‐Th. Exposed carboxylates enhance semiconductor‐water interfacial

Cold‐adapted bidomain enzymes have the potential to foster industrial sustainability by reducing energy consumption and greenhouse gas emissions. Despite their allure, these benefits are unattainable as the molecular basis of cold adaptation remains elusive and there are no strategies to guide the acquisition of this behavior. To uncover principles of cold adaptation, we selected the cold‐adapted Saccharophagus

Ammonia synthesis is a cornerstone in the chemical industry. Given the traditional Haber‐Bosch (H‐B) process requires very high temperature and pressure, it is imperative to develop catalysts capable of facilitating ammonia synthesis under mild conditions. In this work, a post‐metal replacement strategy is developed to improve the Fe loading in single‐atom Fe‐implanted N‐doped carbon catalysts. Starting

A one‐pot synthesis for previously unknown heavy homologues of group 9 metal carbynes [(Me3P)3CoºGeAr*] (1), [(Me3P)3RhºGeAr*] (2), [(Me3P)3IrºGeAr*] (3), [(Me3P)3IrºSnAr*] (5), and [(Et3P)3IrºPbAr*] (7) is presented [Ar* = C6H3‐2,6‐(Trip)2, Trip = 2,4,6‐C6H2iPr3]. During these preparations the tetrylidynes [(Me3P)3RhºSnAr*] (4), and [(Me3P)3RhºPbAr*] (6), were also prepared in a one‐pot procedure

The transamination reaction, which involves the conversion of one amine to another, traditionally relies on biological enzyme catalysts. Although chemists have recently developed a few transition metal‐catalyzed methods, mimicking these enzymes to interconvert amine groups in acyclic substrates via transamination metathesis of a single C(sp2)–N bond, transamination of cyclic tertiary amines has remained

Covalent drugs have experienced a revival in recent decades due to their advantageous pharmacodynamic profiles and targeting of “undruggable” proteins. However, balancing selectivity, reactivity, and potency is essential for the safe and effective drugs. Here we employ a cell‐selective bioorthogonal prodrug design to enhance the selectivity for covalent inhibitors without compromising the reactivity

The valorisation of glycerol using renewable electricity is recognised as an effective and attractive approach for producing high‐value compounds from biomass by‐products. Two‐dimensional conjugated metal‐organic frameworks (2D c‐MOFs) have emerged as promising electrocatalysts due to their tunable structures, high electronic conductivity, and efficient utilisation of well‐defined active centers. In

Precise engineering single‐atom catalysts (SACs) with optimal hierarchical structures and favorable local chemical environment remains a significant challenge to cater for multiphase heterogeneous processes. Here, we develop a universal strategy for synthesizing channel‐digging microspherical SACs that markedly enhance gas–liquid–solid mass transfer and fine‐tune the thermodynamics of catalytic ozonation

Developing artificial enzymes is challenging because it requires precise design of active sites with well‐arranged amino acid residues. Histidine‐rich oligopeptides have been recently shown to exhibit peroxidase‐mimetic activities, but their catalytic function relies on maintaining unique supramolecular structures. This work demonstrates the design of a specific array of histidine residues on the internal

Over the past two decades, main group elements have gained attention as promising substitutes for precious metals in catalytic processes. Additionally, mechanochemistry is emerging as a field with the potential to promote catalytic reactions under mild conditions. Herein, we report a scalable, main‐group mechanocatalytic synthesis of cyclic carbonates from both solid and liquid epoxides, using CO₂

Phosphodiester groups occur ubiquitously in nature, e.g. in nucleic acids or in cyclic (di‐)nucleotides important for signal transduction. Proteins often use polar or positively charged amino acids to interact with the negatively charged phosphodiester groups via hydrogen bonds and salt bridges. In contrast, the acidic amino acids aspartate and glutamate are generally not considered as important determinants

Engineering polymersome shape is a keen area of interest because minimal variations in polymersome properties can greatly affect the performance of nanoreactors, drug delivery vehicles, and more. Although methods to transform polymersome shapes have been evolving rapidly, limitations remain in the scope of applicable polymersome compositions and adaptability to engineer a desired shape. In this work

The integration of metal‐organic frameworks (MOFs) with polymers for efficient C4 hydrocarbon separation membranes remains challenging, primarily due to inherent phase incompatibility. This work presents an in‐situ synthesis strategy for polymer‐zeolitic‐imidazolate frameworks (polyZIF), utilizing polymer‐metal‐ligand coordination bonds combined with structural directing agents to produce crystalline

We present a versatile platform for fabricating two‐photon excitable carbon dot‐based nanocomposite thin films by harnessing the structural versatility of polymer brushes in combination with electron‐beam lithography (EBL). This approach enables the precise spatial organization of carbon dots (CDs) at the nanoscale, facilitating dynamic modulation of their photoluminescent properties in response to

The exploitation of noncovalent bonding in the solid state is attractive to generate one‐dimensional (1D) wire‐like assemblies of metals and uncover dynamic and physical properties of such intriguing structures. Herein, we describe a metal‐organic crystal based on Ag(I) ions that assemble to be organized into 1D wire‐like assemblies maintained by argentophilic interactions. UV‐light irradiation of

The output power densities for osmotic energy harvesting are often limited by the insufficient membranes permselectivity and inherent ion concentration polarization (ICP) phenomenon. In this work, a bio‐inspired plasmonic ion diode membrane (PIDM) was designed and fabricated for enhanced ion transport and osmotic energy harvesting by integrating covalent organic frameworks (COFs) and three‐dimensional

The activation of the cyclic GMP‐AMP synthase‐stimulator of interferon genes (cGAS‐STING) pathway has shown promise in enhancing antitumor immunity. However, the pathway involved de novo transcription and translation processes, which delays immune responses. Besides, the rapid clearance of the secondary messenger cyclic GMP‐AMP (cGAMP) by extracellular hydrolase limits its availability, attenuating

Hyperpolarized (HP) MRI using [1‐13C]pyruvate is emerging as a promising molecular imaging approach. Among hyperpolarization methods, Signal Amplification By Reversible Exchange (SABRE) is attractive because SABRE polarizes the substrates directly in room‐temperature solutions avoiding complex hardware. Most SABRE experiments have historically been performed in methanol, a relatively toxic and difficult

Tracing lipid metabolism in mammalian cells presents a significant technological challenge due to the vast structural diversity of lipids involved in multiple metabolic routes. Biorthogonal approaches based on click chemistry have revolutionized analytical performance in lipid tracing. When adapted for mass spectrometry (MS), it enables highly specific and sensitive analyses of lipid transformations

Spontaneous redox shuttling at silicon is very rare, primarily reflecting the thermodynamic challenges associated with reduction processes for lighter p‐block elements. Here we show that the reactions of boryl‐substituted silylene {PhC(tBuN)2}Si{B(NDippCH)2} with an organo‐azide proceed through a Si(IV)‐Si(II)‐Si(IV) series of redox processes involving both oxidative and reductive ligand migration

The prebiotic synthesis and symmetry breaking of ribose are crucial processes in the origin of life. However, the prebiotic emergence of enantiomerically enriched ribose on primitive Earth remains an unresolved challenge. Herein, we propose that the prebiotic enantioselective synthesis of ribose from glycolaldehyde and glyceraldehyde can be catalyzed by minerals naturally endowed with chiral structure

Endowing the electrochemiluminescence (ECL) imaging technique with three‐dimensional (3D) resolution to investigate specimens at varying axial depths poses a challenging yet significant objective. Herein, a “confocal” 3D ECL imaging method was developed using luminol as the ECL probe, in which the excited luminophore was formed in the vicinity of electrode surface through homogeneous chemical reactions

A cationic Ir(I)‐complex modified with the chiral diphosphine DM‐SEGPHOS mediates the hydroalkylation of diverse α‐methyl styrenes with N‐aryl glycine derivatives. The processes occur with complete branched selectivity and high enantioselectivity. Styrenes possessing higher α‐alkyl substituents also participate to provide the targets with moderate to excellent levels of diastereoselectivity. The products

Layered oxide cathode materials with primary‐secondary architecture face challenges of inhomogeneous Li+ diffusion and chemomechanical degradation due to misorientations between equiaxed primary particles. While a radial architecture, featuring elongated grains, is widely believed to enhance diffusion, it does not address the root cause of chemomechanical failure—crystallographic misorientation. The

Recent years have witnessed an increasing application of machine learning (ML) in reaction development. These ML methods, in general, require huge training set examples. The published literature has large amounts of data, but there are modelling challenges due to the sparse nature of these datasets. Here we report a meta‐learning workflow that can utilize the literature‐mined data and return accurate

Traditional design of conductive hydrogels involves embedding conductive components within a hydrated polymeric network to establish interconnected electron pathways. While the hydration shell of the polymeric network is typically considered insulating, we demonstrate that it can, in fact, enhance electron transport. Using a PEDOT:PSS hydrogel, we propose a hierarchical network with an inhomogeneous