Volume 16 Issue 10, October 2024

Although all-solid-state Li batteries offer a safe, energy-dense alternative to commercial Li-ion batteries, their development is impeded by the sluggish Li-ion transport within solid electrolytes. Now, anion configuration regulation has been shown to promote Li-ion migration, offering a new approach for designing highly Li-ion-conductive solid electrolytes.

Determining the ligandability of the human proteome can provide key insights to characterize biological processes and promote drug discovery. Now, multi-tiered activity-based protein profiling provides comprehensive proteomic maps of chiral small-molecule interactions. Over 300 distinctive proteins were identified to ligand tryptoline acrylamides, including stereoselective and site-specific events.

The enzymatic conversion of NH₄⁺ and NO₂^– to N₂ catalysed by bacteria is critical to maintain nitrogen balance in the environment and for wastewater treatment. Now, a simple abiotic catalyst, the naturally occurring mineral, covellite, shows a remarkable mimicry for the entire reaction pathway.

The translocation of alkenes and remote functional groups is an ingenious strategy to reorganize complex structures, yet it is rarely investigated, owing to the challenges in controlling multiple selectivities. Now, an efficient photo/cobalt dual-catalytic method has been developed to accomplish alkene difunctionalization.

Liposomal systems frequently face challenges, such as low encapsulation efficiency and inadequate controlled release capabilities. Innovatively designed multi-compartment liposomes now overcome these limitations by facilitating precise control over cargo loading and release kinetics, and by serving as microreactors for biochemical synthesis.

Photocatalytic overall water splitting (OWS) is highly desirable for hydrogen production but challenging owing to rapid charge recombination. We demonstrate a dynamic metal–organic framework (MOF) photocatalyst that achieves OWS via one-step photoexcitation. Upon excitation by light, the MOF undergoes a structural twist that suppresses charge recombination and achieves OWS.

Living anionic polymerization is generally carried out using a metal-based initiator under stringent, and ideally water-free, conditions. Now, proton transfer anionic polymerization is developed using an organic compound with an acidic C–H bond as the initiator in the presence of a base catalyst. This method offers easy access to well-defined polymers under moderate conditions.

While solid-state lithium-ion batteries offer promising energy densities for safe energy storage, typical solid electrolytes show poor room-temperature ionic conduction. Now the origin of the superionic transition observed in Li₃YCl₆-type Li-ion conductors is revealed by in-depth crystal structure characterizations and improved ionic conductivities achieved by lowering the transition temperature.

The ligandability of the human proteome can be expanded using covalent chemistry. A multi-tiered chemical proteomic strategy now provides in-depth maps of tryptoline acrylamide–protein interactions in cancer cells. This platform afforded the discovery of stereoselective covalent ligands for hundreds of human proteins, including compounds that disrupt protein–protein interactions regulating the cell cycle.

The discovery of anaerobic ammonium oxidation, termed anammox, has changed views on ammonium activation in biology, but no synthetic models of this reaction have been identified. Now biological anammox, catalysed by three metalloenzymes, is shown to be replicable by a single copper sulfide mineral.

Most lipid nanoparticles are structurally simplistic, existing as single-compartment assemblies. Now, a microfluidic technology to create liposomes-in-liposomes—with full control over particle features, such as the composition of each membrane, the intermembrane distance and payload of each compartment—has been developed. These particles are exploited for multi-stage release and in situ enzymatic synthesis within the particle’s attolitre volume.

Simultaneous functionalization of reactive and inert remote sites presents a powerful approach to access complex molecules, yet it is hindered by precise remote C(sp³)–H activation. Now, the accurate translocation of functional groups and remote C–H desaturation has been achieved in parallel through combining functional group migration and cobalt-promoted hydrogen atom transfer.

Living anionic polymerization generally requires stringent conditions and one metal initiator per polymer chain. Now it has been shown that a weakly acidic compound serves as the initiator or chain-transfer agent in the presence of a potassium base catalyst to produce a polymer chain through a proton transfer anionic polymerization mechanism.

Solar water splitting holds great promise for hydrogen production but is significantly hindered by rapid recombination of photogenerated charges. Now a metal–organic framework photocatalyst has been shown to undergo, upon photoexcitation, a dynamic excited-state structural twist that greatly suppresses charge recombination to enable efficient photocatalytic overall water splitting.

Unlike homo-dihalogenation, selective hetero-dihalogenation reactions are underdeveloped. Now an oxidative alkene hetero-dihalogenation reaction adds chloride and fluoride ions over unactivated alkenes with high regio-, chemo- and diastereoselectivity. A switch in the mechanism triggers a reversal of the diastereoselectivity to promote either anti- or syn-addition.

Although natural terpenoid cyclases generate polycyclic structures through cationic intermediates, alternative radical cyclization pathways are underexplored. Now an artificial radical cyclase has been prepared by anchoring a biotinylated cobalt Schiff-base complex within a chimeric streptavidin scaffold. Chemogenetic optimization of the catalytic performance affords enantioenriched terpenoids via a metal-catalysed H-atom transfer mechanism.

Expanded use of earth-abundant chromophores for excited-state chemistry requires the ability to increase the energy content of excited states while simultaneously lengthening their lifetimes. It has now been shown that this goal can be achieved in Co(III)-based chromophores by virtue of their photophysical dynamics occurring in the Marcus inverted region.

Due to their challenging isolation, stannynes are underexplored and poorly understood. Now, a stannyne has been synthesized and isolated at room temperature using a bulky cyclic phosphino ligand, and it has been shown to exhibit the reactivity characteristics of carbenes, stannylenes and carbon–tin multiply bonded compounds.

The mechanistic details of entangled triplet pair formation in organic materials have been debated over the past decade. Now, the concept of coherent triplet pair formation is revived using a library of pentacene derivatives, invoking charge resonance mixing as a material design principle for harnessing the effect.

A class of cationic—amidine-based degradable—lipids can now be readily synthesized through a tandem multi-component amine–thiol–acrylate conjugation reaction. Mechanistic studies provided key insights, from which the observed lead lipid enabled mRNA delivery to multiple organs, highlighting the potential for developing mRNA vaccines and therapeutics to treat various diseases.

The mechanism of collagen heterotrimer folding is difficult to recapitulate synthetically. Now an ABC collagen mimetic heterotrimer has been designed that employs pairwise amino acid interactions, validated by X-ray crystallography, to promote composition- and register-specific assembly. The high specificity of its assembly leads to an increased rate of folding compared with similar collagen heterotrimers.

De novo syntheses of 1,2-arylheteroaryl ethanes, key scaffolds in drug discovery, are challenging, typically relying on pre-functionalized synthons, harsh conditions and multi-step processes. Now a modular assembly of arenes, ethylene and heteroarenes yields diverse drug-like 1,2-arylheteroaryl ethanes, highlighting the importance of radical polarity matching in selective multi-component couplings.

Standard DNA is limited by low information density and functional diversity. Now it has been shown that an expanded genetic alphabet—incorporating a synthetic nucleotide, dZ—allows for the creation of stable three-dimensional DNA structures under mild alkaline conditions. Such stable structures enrich our understanding of DNA’s structural diversity and its potential in synthetic biology applications.

Nitrogen-rich Ruddlesden–Popper nitrides are notoriously difficult to stabilize. Now a high-pressure high-temperature synthesis method has enabled the preparation of Pr₂ReN₄, Nd₂ReN₄ and Ce₂TaN₄. Neutron diffraction analysis reveals fully nitrided materials and intricate magnetic structures.

Adam Noble discusses the diverse uses of eosin Y over its 150-year history, from its origin as a dye and pigment used by post-impressionist masters to its versatile reactivity as a catalyst in visible light photochemistry.