Electrochemical CO2 reduction is typically constrained by proton-coupled electron transfer, which intrinsically intertwines CO2 conversion with the competing H2 evolution reaction. Here we introduce a Janus palladium membrane electrode that circumvents proton-coupled electron transfer by enabling selective CO2 reduction through heterogeneous hydride transfer. The membrane spatially separates hydrogen generation from CO2 reduction and independently polarizes the CO2-facing interface, converting permeated hydrogen atoms into Pd–H species with tunable hydricity. This design sustains directional hydride flux from water to CO2, enabling highly selective formate production under mild cathodic polarization. We achieve excellent Faradaic efficiencies and turnover frequencies in aqueous electrolytes, while isotope labelling experiments confirm hydride transfer as the dominant reaction pathway. Continuous hydrogen delivery stabilizes a hydrogen-rich surface of the electrode, suppressing CO formation and enabling stable operation. This electrode’s success for CO2 reduction in both aqueous and fully aprotic electrolytes offers a general route to access heterogeneous hydride reactivity beyond proton-mediated electrocatalysis. Electrochemical CO2 reduction is typically constrained by proton-coupled electron transfer, which couples CO2 conversion with competing H2 evolution. Now it has been shown that a Janus palladium membrane electrode enables selective formate production through heterogeneous hydride transfer, providing access to electrochemical hydride-based reactivity beyond proton-mediated electrocatalysis.
Chemical recycling back to monomer represents an attractive methodology to tackle plastic waste. However, current reports focus on either thermally unstable 'designer' polymers or highly diluted solution depolymerizations. Here we report a simple, yet efficient, bulk main-chain scission pathway, whereby the presence of N-hydroxyphthalimides triggers a hydrogen-atom-transfer reaction on the polymer backbone, followed by the rapid and near-quantitative depolymerization of polymethacrylates. Notably, this strategy can be directly applied to crude commercial polymers, does not rely on preinstalled end-groups or sacrificial co-monomers, operates at relatively low temperatures in the absence of light irradiation and precludes the use of a solvent, therefore enabling direct isolation of pristine monomers in high yields (∼90%). The methodology is compatible with polymethacrylates synthesized by either anionic, free radical or controlled radical polymerization and can also be applied to ultrahigh-molecular-weight materials (>106 Da).
The programmable synthesis of complex alkene skeletons, including regioisomers, stereoisomers and conjugated homologues in a single operation, is a long-standing goal in synthetic chemistry, given the profound influence of these structural features on molecular function. Traditional methods typically rely on predesigned substrates or rigid reaction pathways, which often restrict structural diversity. Here we report a nickel-catalysed sequential coupling of alkynes, organohalides and a diboron reagent. This method not only simultaneously achieves regioselective and unique stereoselective modulation in alkyne difunctionalization, affording uncommon 1,2-trans and 2,1-cis alkenes, but also accomplishes the construction of conjugated homologues via the controlled incorporation of two alkynes, thereby achieving the rare divergent synthesis of two conjugated diene products. Mechanistic studies reveal that the electronic properties of the ligands regulate the generation of organometallic species versus radicals, while the intrinsic metal-binding ability of the various radicals further modulates their reactivity, collectively governing product selectivity.
Conferences are built by community members who plan the scientific programme, professional development activities, and social events. Shira Joudan describes how helping to organize a meeting can be a rewarding activity that can shape your scientific community — and how to get involved.
Connor Delaney traces the chemical legacy of thalidomide, from the regulatory disaster of the 1960s to the first FDA approval of a PROTAC in 2026.
Bioorthogonal reactions enable the study and modulation of biological systems, but achieving precise control over when and where the reactions occur remains challenging. Here we show that cyclopropanol (CPol) can serve as a compact, energy-loaded chemical handle that is stable under physiological conditions, yet can be selectively activated using mild electrochemical stimuli. This strategy generates reactive β-haloketone moieties in situ, enabling efficient protein labelling for cellular imaging and proteomic analysis. Unexpectedly, CPol preferentially modifies acidic amino acids, such as glutamate and aspartate, within hydrophobic regions of proteins, rather than more commonly targeted residues. The electrochemical reaction is compatible with living cells, allowing real-time visualization using fluorogenic probes. We further demonstrate its utility by developing a choline-derived CPol probe that integrates into membrane lipid metabolism to label membrane-associated and cytoplasmic proteins. By combining bioorthogonality with electrochemical control, this approach offers a general and controllable platform for protein conjugation, with broader applications in chemical biology and live-cell studies.
Understanding and suppressing gas evolution is critical to enabling high-energy-density lithium metal batteries (LMBs). Yet, comprehensive investigations in ether-based systems remain limited. Here we quantify gas generation in ether-based LMBs and elucidate the underlying mechanisms. We link CO and CO2 production to the cathode, and CH4 evolution to the anode. Notably, CO and CO2 are consumed at the Li anode to form Li-containing species such as Li2CO3. Although CH4 ultimately dominates the gaseous products, its evolution during cycling is delayed until a distinct onset point. We show that in a high-concentration ether electrolyte, anode activation improves Li deposition morphology and suppresses interfacial reactions, extending the number of cycles to gas onset and cell failure by an order of magnitude. Achieving these gains without altering the electrolyte enables the reconsideration of seemingly impractical electrolytes, highlighting a practical strategy to enhance the safety and performance of commercial LMBs.
High-voltage batteries are limited by electrolyte oxidation. Now, a pathway-selective strategy limits electrolyte oxidation by replacing the susceptible α-hydrogens, moving beyond frontier orbital-based design and enabling stable operation at high voltage without fluorination.
The construction of protocell networks with self-regulated spatial dynamics and functions is an important challenge in the emerging field of colloidal systems chemistry. Existing strategies predominantly produce protocell networks with fixed or randomly distributed spatial organization, relying on direct surface interactions or externally imposed conditions, while largely overlooking dynamic interactions with the surrounding environment, thereby limiting the emergence of reconfigurable network behaviours. Here we demonstrate chemical strategies for implementing the spontaneous segregation and selective translocation of binary/ternary populations of enzyme-containing proteinosomes in dextran droplet/polyethylene glycol aqueous phase-separated media. The segregated proteinosomes exhibit tunable membrane wettability, engage in cross-community chemical signalling and undergo signal-induced reversals in phase compatibility to produce reconfigurable networks capable of protocell-mediated recruitment and dispatchment. We exploit the protocell phase dynamics to spatiotemporally modulate DNase I activity in a subpopulation of translocating proteinosomes. Our methodology provides a platform for developing protocell communities with self-regulated spatiotemporal order and offers opportunities in cytomimetic modelling and colloidal systems chemistry.
The α-arylation of carbonyl compounds is a cornerstone transformation in the synthesis of pharmaceuticals and natural products. Despite decades of efforts using transition metal, main-group and photoredox strategies, a general and practical α-arylation method with broad substrate scope has remained elusive. Here we show that 9-bismatriptycene (BisTrip), a rigid, shackled form of triphenylbismuth, functions as a universal aryl group transporter, enabling controlled and regiospecific α-arylation of diverse ketones, allowing the formation of sterically demanding quaternary centres and incorporation of iodoaryl units. BisTrip is readily loaded with aryl groups by a one-pot procedure using arylboronic acids to give Aryl-BisTrip and, after transferring the aryl to the enolate, is recovered quantitatively. Arylation of lithium enolates proceeds within seconds even at -78 °C and shows high fidelity in a memory-of-chirality experiment. Computations support a low barrier for C-C bond formation and account for the observed axial selectivity, establishing BisTrip as a practical platform for α-arylation.
Synthetic biology has enabled the production of natural and unnatural products from inexpensive sustainable feedstocks. Yet, the scope of available products has been limited largely to compounds accessible from nature's chemical reactions. Evolved enzymes can catalyse reactions of unnatural substrates or reactions not found in nature but often require the addition of synthetic reagents to purified enzymes or to resting cells containing those enzymes. Here we show that chemical reactions of metabolic intermediates produced intracellularly in living cells can include intermolecular nitrene transfers. The biosynthesis of N-acetoxyanilines, in combination with the generation and transfer of N-aryl nitrene intermediates from them catalysed by a cytochrome P450, generates amino alcohols, diamines, diarylamines and aminoalkyl arenes from simple carbon feedstocks. These products-common substructures of pharmaceuticals and agrochemicals-are challenging to synthesize by standard organic chemistry and were produced from inexpensive, renewable feedstocks. Evolution of the enzymes in this pathway showed that titres can be increased by engineering and that the products can be synthesized with high enantioselectivity.
While energy transfer photocatalysis has recently been used in the synthesis of multisubstituted polycyclic alkanes as benzene bioisosteres, the use of highly reactive noble-metal and organo-photocatalysts often leads to rapid generation of diradical intermediates, triggering polymerization side reactions and limiting functional-group tolerance. Here we show that heteroleptic copper(I)-BINAP complexes containing bidentate (pyrazolyl)pyridine ligands act as effective triplet photosensitizers for cycloadditions between bicyclo[1.1.0]butanes and alkenes. These copper catalysts, with their extended excited-state lifetimes, enable endergonic photosensitization for substrate activation, thereby moderating radical generation, suppressing alkene polymerization and broadening the substrate scope to include electron-deficient alkenes, enynes, dienes and even aliphatic alkenes. Bicyclo[2.1.1]hexanes with an aryl substituent at either the 3- or 2-position can be synthesized by activating either styrenes or bicyclo[1.1.0]butanes. These findings suggest that copper photocatalysis holds promise for enhancing the synthetic versatility of visible-light-driven energy transfer processes.
Constructing artificial assemblies that combine proteins and synthetic ligands has been hampered by the lack of protein-ligand interfaces that are sufficiently large and organized to enable precise structural control. Here ribosome display selection is used to identify a protein that binds a helical aromatic foldamer both tightly and selectively through a sizeable surface area. We used this complex as a supramolecular synthon to create well-defined hybrid foldamer-protein architectures. Examples include foldamers that bind two proteins and hold them at a precise distance, proteins that bind two foldamers and crystals in which proteins and foldamers are connected in cyclic or infinite arrays. The modularity of aromatic foldamers brings a further dimension to protein-based assemblies.
Conductive van der Waals metal–organic frameworks (vdW–MOFs) are an emerging class of electronic materials whose properties are highly sensitive to layer stacking. Now, a strategy enables precise control over the stacking structures of vdW–MOFs by using solvents to direct the formation of metastable supramolecular ligand aggregates prior to framework assembly.
Patricia O’Hara discusses how the molecular structure of oleic acid shapes olive oil’s physical properties, culinary behaviour and health benefits, linking ancient symbolism to modern chemistry.
Is there a subterranean communication network between trees and fungus or has discussion in popular culture outpaced the evidence? Bruce Gibb discusses the chemistry of plant–fungus interactions, revealing a complex world that is far from well understood.
High-capacity anodes are desirable for high-energy lithium-ion batteries but suffer from limited cycle life due to large volume changes during cycling. The LiF-based solid-electrolyte interphase (SEI) has led to prolonged cycling stability. However, current LiF-forming electrolyte designs require anions to enter the Li+ solvation sheath, which inherently reduces the electrolyte's ionic conductivity, limiting both fast-charging and low-temperature performance. Here we develop solvent-bridged electrolytes composed of LiPF6 dissolved in a cosolvent system comprising a bridging cyclic ether that solvates both PF6- and Li+ to form a LiF-rich SEI, and a structural linear ether that governs the electrolyte liquid range. By mitigating direct Li+-anion interactions, the electrolytes maintain high ionic conductivity, enabling stable cycling of micrometre-sized silicon anodes under extreme conditions involving high rates (>4 C), low temperatures (down to -55 °C) and Li plating. Solvent-bridged electrolytes address the intrinsic trade-offs between LiF-rich SEI formation and electrolyte ionic conductivity, offering a promising approach for high-capacity anodes operating under demanding conditions.
The nature of the aqueous proton has been traditionally interpreted through two limiting structural motifs: the Zundel and Eigen cations. However, experimental infrared (IR) spectra of the solvated proton reveal a far more dynamic character, as evidenced by distinct intensity modulations within the characteristic continuum absorption band. In fact, recent ultrafast two-dimensional IR spectroscopy suggests that solvation-induced structural distortions around H2O⋯H+⋯OH2 motifs critically shape the IR response. Here we investigate the role of such asymmetry through full-dimensional quantum dynamics simulations of the extended Zundel complex H+(H2O)6, which structurally encompasses both Zundel and Eigen motifs. Systematic removal of one water molecule from the second solvation shell gradually introduces deviations from the perfectly symmetric Zundel-like complex towards Eigen-like spectral features. These results provide a direct map between the asymmetric solvation environment and the structural response of the first and second solvation shells of the aqueous proton, offering a structural and dynamical basis for understanding how this asymmetry governs proton mobility in aqueous environments.
