Barham and co-workers report a sustainable, transition-metal-free platform for radical cross-couplings photocatalyzed by covalently linked, rotating organic dyads. Through weak non-covalent interactions with electronically complementary target substrates, this approach successfully generates, stabilizes, and selectively cross-couples otherwise highly reactive radical intermediates in close proximity. Facile tuning of the catalyst’s donor moiety switches mechanisms between assembly-assisted consecutive photoinduced electron transfer and ternary charge-separated EDA complexation. Non-covalent templating prevents destructive side reactions, enabling efficient, selective C–C bond formation with excellent atom economy, including late-stage pharmaceutical modifications.

Allylamines are important motifs in pharmaceuticals, agrochemicals, and materials, but their direct preparation often depends on costly oxidants and complex catalyst systems. We report a practical palladium-catalyzed oxidative amination of alkenes that uses air as the oxidant and does not require specialized ligands. The method converts diverse amines and alkenes into allylamines with high selectivity and can be performed on a gram scale, offering a greener route to valuable allylamine products.

Coupled cation and oxygen vacancies in NiOOH create a distinct dual-site oxygen evolution pathway that bypasses conventional adsorbate scaling and avoids sustained bulk lattice-oxygen turnover. Direct O–O coupling through a bridged oxygen intermediate enhances intrinsic activity while preserving structural integrity, thus enabling durable operation for more than 1,600 h under industrially relevant alkaline electrolysis conditions. The work shows how defect coupling can redirect reaction mechanisms to reconcile activity and stability.

A novel class of light-charged air filtration systems (LCFSs) is designed by integrating a photothermal-ferroelectric coating layer (PCL) with a polypropylene melt-blown membrane. The LCFS offers energy-efficient, light-activated surface charge generation and facilitates continuous capture of hazardous airborne particles with FE exceeding 99%, enabling sustainable air purification and anti-clogging performance. The LCFS is demonstrated as a proof of concept for indoor air purification, epidemic disease prevention, and personal hygiene protection.

Biosynthesis and biocatalysis are increasingly integrated to reshape the landscape of sustainable chemistry. The translation of natural biosynthetic enzymes into viable practical biocatalysts remains constrained by bottlenecks in structural stability, substrate tolerance, and catalytic efficiency. This perspective highlights the synergistic potential unlocked by the merge of biosynthesis and biocatalysis.

Pérez-Sánchez, Zou, et al. present El Agente Quntur, a domain-specific multi-agent system that translates open-ended chemistry questions into literature-informed computational workflows. Benchmarks against a general-purpose coding agent and research-level case studies show that specialized reasoning improves workflow reliability, method selection, error recovery, and result interpretation while revealing persistent limitations in geometric reasoning and post-analysis.

The annulenes typically coordinate with transition metals to form out-of-plane metallo-annulene. Expanding the ring cavity shifts the metal into the ring core via metal–carbon σ bonds, establishing a unique structural paradigm. Herein, we systematically explore planar metallo-[n]annulenes (12 ≤ n ≤17), mapping out their spatial boundaries. By establishing a “periodic table” for in-plane metallo-annulenes, this work offers key conceptual insights to guide the rational design of novel organometallic architectures.

Sustainable methanol production via CO2 hydrogenation is critical for a circular carbon economy. Yet, progress remains bottlenecked because catalyst innovation and process engineering advance in isolation. Here, we present a process-level paradigm shift that unifies catalyst design with process design and thermodynamic realities. This multiscale integration prevents industrial performance losses and provides a blueprint to scale up CO2 utilization technologies for a net-zero chemical industry.

Lipid nanoparticles have transformed RNA therapeutics, with ionizable lipids serving as primary drivers of delivery, safety, and targeting. This review bridges ionizable-lipid chemistry and structural design to functional performance and clinical translation, while highlighting key strategies to overcome current limitations.

Integrating synthetic light-harvesting materials with enzymes offers a powerful strategy for solar CO2 conversion, yet molecular design principles governing semiconductor-enzyme interfaces remain underdeveloped. Here, we establish a molecular design framework based on metal-free conjugated polyelectrolyte photocatalyst sheets that spontaneously bind CO2-reducing enzymes. Systematic engineering of polymer side chains and backbones co-optimizes charge separation and biointerfacial chemistry, enhancing CO2 reduction activity by >100-fold. These structure-property-function relationships provide actionable principles for designing high-performance biohybrid platforms for solar chemical production.

A catalytic atroposelective macrocyclization strategy is developed to construct structurally tunable triazole-based dominant rotors in macrocyclic peptides. Different rotor configurations direct distinct macrocycle organizations and intramolecular interactions, leading to well-defined conformational states. This strategy enables atroposelective control in peptide macrocyclization and highlights the potential of axially chiral rotors as versatile structural elements for shaping macrocyclic architectures.

Optical excitation of antiferromagnetically coupled chromium(III) containing heterometallic systems leads to enhanced spin polarization and microwave emissions with chemically tunable g values. The optically generated states show long lifetimes that could be of interest in the context of quantum information processing.

Olefins are valuable intermediates for the construction of C(sp3)-rich frameworks. 1,1-Disubstituted olefins are especially privileged precursors because their unique geminal substitution pattern enables diverse, regioselective transformations. Despite this utility, 1,1-disubstituted olefins are less readily available than other olefin substitution classes, and many established syntheses require harsh conditions or specialized starting materials. The reported mild metallaphotoredox hydroalkylation couples abundant alcohols with bench-stable alkynes to access 1,1-di- and trisubstituted olefins.

Au(III)-mediated cysteine S-arylation enables site-selective covalent modification of metalloenzymes while preserving the integrity of their active metal sites. This organometallic bioconjugation strategy establishes a blueprint for predictable metalloprotein functionalization and broader applications in chemical biology, protein engineering, and biotechnology.

Yi et al. show that incorporating a low loading of Ru nanoparticles into Fe–N–C simultaneously tunes Fe–N4 active sites and the interfacial microenvironment. This concerted modulation improves oxygen-reduction kinetics and local oxygen transport, demonstrating that active-site chemistry and the interfacial water structure can be engineered together to enhance the practical performance of proton-exchange membrane fuel-cell catalysts.

Kumar et al. investigate the earliest light-driven steps of photosynthesis directly in living cyanobacterial cells. By resolving ultrafast energy and charge transfer in the native cellular environment, this work opens new opportunities for understanding how photosynthesis functions in vivo under physiologically relevant conditions.

Translating organic electrosynthesis from laboratory discovery to practical manufacturing remains challenging. This study introduces steady-state engineering to maintain stable reaction environments, enabling productive and cost-effective electrosynthesis of hypervalent iodine reagents and facilitating scale-up from batch reactions to kilogram-scale continuous-flow processing and industrial demonstration.

A crown ether-incorporated metal−organic framework with preorganized K+ ions in the 18-crown-6 cavities enables specific recognition of [AuCl4]− through cation-assisted host−guest interactions. This design affords sensitive gold detection as well as rapid and highly selective gold adsorption, while maintaining excellent performance at ultra-trace concentrations. Moreover, the material displays excellent gold adsorption performance across a wide range of complex real-world aqueous systems, including e-wastewater, freshwater, seawater, and gold mine wastewater.

Copper-catalyzed azide-alkyne cycloaddition is one of the most robust platforms to connect two molecules—utilized by scientists working across fields ranging from chemical biology to polymer topology—but its operational simplicity should not be mistaken for a naive and universal mechanism. This perspective analyzes the different catalyst identities in this click reaction and outlines a dynamic catalytic network of interconverting copper species, thereby providing a framework for more translatable and predictive copper-catalyzed click reactions.

Alkene geometry strongly influences molecular structure and function, yet methods that provide stereodivergent access to both E- and Z-configured chiral building blocks remain rare. In an upcoming issue of Chem Catalysis, You and co-workers combine contra-thermodynamic alkene isomerization with iridium-catalyzed asymmetric allylic substitution to access either E- or Z-allylated 3-isochromanones with high regio- and enantioselectivity.

We report the first well-defined binuclear copper catalyst for asymmetric radical difunctionalization of alkenes, enabled by a crescent-shaped ligand that preorganizes a rigid cavity. Unlike spontaneous self-assembly, this architecture ensures uniform azide coordination and exceptional stereocontrol, thereby providing a general platform for the synthesis of chiral α-quaternary trifluoromethylated amino acids and peptides.

Organic molecular additives are transforming how sulfide solid electrolytes interact with electrodes and their environment. As interfacial stability increasingly limits battery performance, this review examines how molecules, polymers, and supramolecular assemblies tune interfacial behavior, revealing emerging structure-function relationships that can guide the design of safer, higher-performance all-solid-state batteries.

Chirality in mechanically interlocked molecules arises from threading topology, yet their enantioselective construction remains challenging. We report a cobalt-catalyzed C–H annulation that affords rotaxanes with both macrocyclic and mechanical planar chirality in excellent enantiopurity. Absolute configuration is unambiguously assigned via the second-generation crystalline sponge method, using crystallographic characterization of three-layered rotaxane-in-cage complexes.

Structurally minimal nickel-thiolate complexes function as both light absorbers and reactive centers for photochemical carbon–sulfur bond formation. Ground- and excited-state characterization identifies mononuclear nickel-thiolate motifs as compact photoreactive cofactors whose reactivity can be tuned through nuclearity, substrate structure, and solvent environment. Guided by these structural and reactivity requirements, nickel-thiolate motifs were incorporated into proteins while retaining photochemical activity, providing a foundation for the design of artificial photoreactive metalloproteins.

A triangle association strategy (TAS) uses shared chemical reactants to systematically predict new reactions and overcome the limitations of traditional serendipity. Guided by a condition-correlation metric, this approach discovered six unprecedented catalytic reactions and enables efficient synthesis of structurally complex rings and macrocycles for drug discovery.

Efficient proton exchange membrane water electrolysis requires more than highly active catalysts. It also depends on effective transport within the anode catalyst layer. This review highlights how catalyst architecture, ionomer engineering, hierarchical pore design, and interface engineering collectively regulate water delivery, oxygen removal, proton conduction, and electron transport, providing design principles for transport-efficient, ultralow-Ir oxygen evolution catalyst layers in acidic water electrolysis for sustainable hydrogen production.

This review establishes a process-oriented framework linking single-atom catalyst structure to oxidant adsorption, electron-transfer behavior, intermediate evolution, and reactive-species selectivity. It further summarizes design strategies for selectively generating radicals in advanced oxidation systems.

In this perspective, we introduce a concept of photothermal evaporation-coupled catalysis (PECC) for simultaneous sunlight-driven water purification and chemical upgrading and propose the cost-effectiveness, life-cycle sustainability, emerging system integration, AI-assisted design, and near-zero compatibility (CLEAN) paradigm to leverage the microscale principles of PECC and macroscale technoeconomic feasibility toward scalable, sustainable solar water-chemical factories.

Spectroscopic measurements on individual catalysts during active operation remain difficult and typically necessitate specialized reaction conditions. This work presents a single-catalyst operando study of lead halide perovskite quantum dots, an emerging photocatalyst platform with exceptional electronic and chemical tunability. Traditional reactant concentration limits are overcome by immobilizing and directly interrogating individual QDs via single-particle photoluminescence spectroscopy. Thus, charging/discharging dynamics, particle-to-particle heterogeneities, activity fluctuations, and catalyst degradation can be characterized under authentic reaction conditions.

Plastic-degrading enzymes represent a promising strategy to address the global plastic waste problem, but their catalytic efficiency still falls short of industrial needs. Rather than relying on a single static structure, the authors use a probability-based simulation framework to capture the full ensemble of reactive pathways in PETase and LCCICCG, two promising candidates for biotechnological plastic recycling. These insights are translated into a rationally engineered PETase variant with improved activity, showcasing probability-guided design as a general strategy for enzyme engineering.

Helium is increasingly valuable, but separating it efficiently remains difficult. This work shows that metal coordination can reorganize polymer chains to create highly selective molecular pathways, thereby providing a simple strategy to improve membrane performance beyond conventional trade-offs.

Achieving the scalable and controlled formation of self-assembled monolayers during blade coating remains challenging. Here, we introduce a multidentate thiol-anchoring co-adsorbate that suppresses SAM aggregation and constructs a hydrogen-bonded, hydrophilic buried interface. By coupling molecular dispersion, interfacial wettability, and stress relaxation, this strategy offers a general design principle for blade-coated, efficient, and durable perovskite photovoltaics.

A synthetic molecular cage reproduces the key features of the Bohr/Haldane effect in hemoglobin. Protonation and deprotonation unfold and fold the cage framework, promoting anionic cargo uptake and release, respectively; meanwhile, anion loading and unloading reciprocally decrease and increase the acidity of the cage by several pKa units. This feature enables pH-gradient-driven directional anion transport across an organic liquid membrane.

MOFs are promising porous materials for energy, environmental, and industrial applications but only if they are stable under relevant conditions. Smoljan et al. present a tutorial-style perspective outlining rigorous, multi-technique characterization protocols for four major stability classes: thermal, chemical, mechanical, and radiation. Demonstrated across seven well-known MOFs, these protocols provide a practical roadmap toward standardized, comparable stability reporting.

Mechanically interlocked proteins represent an emerging frontier in chemical topology and protein engineering. Here, we demonstrate the direct synthesis of protein olympiadanes—higher-order catenanes inspired by the Olympic rings—within living cells using a modular assembly strategy. The platform enables the construction of multiple constitutional isomers and produces exceptionally stable architectures. By providing a modular route to increasingly complex protein topologies, this work establishes a foundation for the programmable construction of mechanically interlocked proteins.

Agentic artificial intelligence (AI) promises self-driving laboratories (SDLs) capable of autonomous reasoning, yet general-purpose synthetic chemistry remains overwhelmingly manual. Automation still stumbles on ordinary tasks, remains costly and inaccessible, and offers too little relief to justify adoption. Moreover, poor FAIR (findable, accessible, interoperable, reusable) data practices leave AI models ill trained for chemistry. The authors call for democratized, modular hardware; rigorous FAIR data collection; and a Slurm-like workload manager distributing experiments across mature SDLs—freeing chemists to conceive questions rather than run columns.

Self-driving laboratories can accelerate electrochemical discovery, but optimization alone is not enough. We argue that agentic artificial intelligence should recognize when objectives, models, or measurements are inadequate; explain anomalous results; propose competing hypotheses; and design discriminating experiments. But even with these capabilities, human scientists remain essential in identifying meaningful questions, evaluating explanations, setting research priorities, and ensuring accountability.

Why is the Mo nitrogenase more adept at N2 reduction than its alternative nitrogenase counterparts (V and Fe-only)? To investigate this question, we undertook a comparative structural and spectroscopic analysis of synthetic [MoFe3S4] and [Fe4S4] clusters. We found differences in how the clusters distribute electron density, with the iron centers in the [MoFe3S4] clusters being better at backbonding to weakly π-acidic ligands. Such differences may account for the greater efficiency of the Mo nitrogenase.

Of the three nitrogenase isozymes (Mo, V, and Fe-only), the Mo nitrogenase shows the highest selectivity for N2 vs. H+ reduction. Here, we study the reduction chemistry of a series of synthetic [MFe3S4] clusters and find that only those that contain large auxiliary metals bind N2 at Fe. These results support an electronic role for “heterometals” featuring diffuse orbitals in facilitating N2 binding at neighboring Fe sites.

Self-driving laboratories (SDLs) are evolving from automated experimental engines into reasoning scientific partners. In agentic SDLs, artificial intelligence (AI) agents coordinate perception, planning, experimentation, analysis, and reflection across the research cycle. By making metadecisions, including what to measure, which models to trust, when to ask humans, and how to revise hypotheses, agentic SDLs move beyond closed-loop optimization toward adaptive, context-aware scientific discovery. This Catalysis article discusses how reasoning agents can expand autonomy, accelerate learning, and reshape scientific practice.

The convergence of agentic artificial intelligence (AI) and self-driving laboratories promises to move autonomous science beyond closed-loop optimization toward deliberate scientific reasoning. But this transition will not be a single leap. We argue that it runs through semi-autonomous laboratories, where AI agents and human scientists share cognitive and physical workloads. The more consequential question is not when full autonomy arrives but what we optimize for along the way and whether we build systems that narrow science or expand its scope.

Agentic self-driving laboratories are transforming artificial intelligence (AI) from a mere experimental optimizer into a collaborator that hypothesizes, reasons, and adapts. To avoid becoming an “eloquent layer over brittle automation,” we must advocate for explainable reasoning, digital safety twins to counter the “curse of rarity,” safety-critic agents, verifiable agent-to-agent identity, and institutional governance. As autonomy expands, scientists shift from experimenters to stewards, a role sustained only by robust technical safeguards and a shared culture of safety.

We report that interfacial proton accumulation is the key limitation on the Faradaic efficiency (FE) of direct ethylene oxidation to ethylene glycol at industrially relevant current densities. Thus, a phytic acid-modified AgPd (AgPd-PA) electrocatalyst is designed to facilitate the diffusion of interfacial protons and accelerate the formation of ∗OH. This strategy achieves a record FE of 40.8% and a yield rate of 758.6 μmol h−1 at 100 mA cm−2 for ethylene glycol synthesis.

Self-driving laboratories are moving from automated execution to scientific reasoning. This reaction argues that the next step requires experimentally grounded models of the chemical world. Such models connect laboratory actions, latent chemical states, observations, uncertainty, and updates. They allow agents to choose experiments that test beliefs and improve metrics. Building them will require machine-executable protocols, multimodal measurements, provenance, transferable representations, and human judgment so that autonomous laboratories can accumulate chemical understanding across instruments, campaigns, and sites over time more reliably.

Organopotassium compounds are highly reactive organometallic species whose poor solubility and stability have long limited their synthetic applications. This study reports the potassium-mediated anti-selective difunctionalization of alkynes via reductive borylpotassiation. Reduction of alkyne with a potassium reductant in the presence of reduction-resistant trialkoxyborane results in anti-diboration. Performing the reductive borylpotassiation in flow microreactors enables the unsymmetrical borylfunctionalization of alkynes in an anti-fashion. These distinctive anti-selective difunctionalization reactions afford synthetically valuable multi-substituted alkenes, such as tamoxifen, with excellent regio- and stereoselectivity.

Multi-principal single-atom materials (MPSAMs) are inspired by the compositional complexity of high-entropy materials and the site-specific control of single-atom catalysis. This perspective conceptualizes key terminology, examines how high-entropy principles shape atomically dispersed designs, and critically assesses strategies to control atomic arrangements. The discussion explores how MPSAMs support cooperative functions across multiple metal sites within a confined space, enabling reactivity and selectivity unattainable with conventional SAMs. Challenges and future outlooks for entropy-informed catalyst design are further outlined.

Nitrenes are well-known reactive intermediates used to form a variety of nitrogen-containing molecules, but their reduced radical anions have remained inaccessible under ambient temperature. Here, a persistent nitrene can be converted into an isolable radical anion that features a non-Aufbau electronic configuration. This species acts as a nucleophilic nitrogen radical that forms new N–Se, N–Si, and N–C bonds under mild conditions.

Obtaining clean water requires removing both salt and harmful volatiles—a dual challenge where conventional membranes fall short. This study engineers a synthetic membrane with tailored nanoscale channels that overcome this limitation. It achieves high rejection of salt and volatiles while permitting fast water flow. This is enabled by a unique phenomenon where water molecules line up in a single file to move rapidly through the sub-nanometer pores.