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Evolution separates complex modern enzymes from their hypothetical simpler early ancestors, which raises the question of how unevolved sequences can develop new functions. Here a library of non-natural protein sequences was subjected to ultrahigh-throughput screens in microfluidic droplets, leading to the isolation of a phosphodiesterase enzyme capable of hydrolysing the biological second messenger, cyclic AMP.
Two-dimensional covalent organic frameworks (2D COFs) enable the construction of bespoke functional materials, but designing dynamic 2D COFs is challenging. Now it has been shown that perylene-diimide-based COFs can open and close their pores upon uptake or removal of guests, while fully retaining their crystalline long-range order. Moreover, the variable COF geometry enables stimuli-responsive optoelectronic properties.
A robust organometallic platform is developed for stoichiometric cross-couplings of common aryl and alkyl electrophiles under a single set of conditions. Inexpensive and persistent organonickel complexes are prepared by electrolysis and implemented in the diversification of drug-like molecules with high reliability from a diverse set of alkyl precursors.
Overcrowded alkene-derived molecular motors convert light and heat into chirality-directed unidirectional rotary motion, but the efficiency of their photochemical isomerization remains limited. Now formylation of the motor core has been shown to boost all aspects of motor photochemistry by improving photochemical efficiency, diminishing competing processes and redshifting absorption.
The construction of analogues of natural gap junctions would provide a bottom–up strategy for building intercellular communication pathways for synthetic cells. Now artificial intercellular gap junctions have been prepared from unimolecular tubular channels by mimicking the hydrophobic–hydrophilic–hydrophobic triblock structure of natural junction channels.
Advances in the development of cytoskeletal-like materials with modular structures and mechanics are pivotal for the engineering of synthetic cells. Now actin-mimetic supramolecular peptide networks have been designed using programmable peptide–DNA crosslinkers, giving rise to tunable tactoid-shaped bundles and mechanical properties that control spatial localization, the diffusion of payloads and shape changes within artificial cells.
Knots reduce the tensile strength of macroscopic threads and fibres. Now it has been shown that the presence of a well-defined overhand knot in a polymer chain can substantially increase the rate of scission of the polymer under tension, as deformation of the polymer backbone induced by the tightening knot activates otherwise unreactive covalent bonds.
The selective synthesis of ultrahigh-molar-mass (UHMM) cyclic polymers from direct polymerization is elusive. Using a chemically recyclable polythioester as a model, it has now been shown that a common superbase mediates living linear-chain growth, followed by proton-triggered linear-to-cyclic topological transformation, producing UHMM cyclic polymers with a narrow dispersity.
Although metal-free catalysts, featuring defined active sites, represent alternatives to scarce or problematic metals, metal-free compounds rarely show activities as promising as metal-based materials. Now deprotonated 2-thiolimidazole is shown to serve as a metal-free electrocatalyst for selective acetylene hydrogenation and achieves competitive performances with metal-based catalysts.
Phenols and their derivatives are ubiquitous in nature and important within the chemical industry. Their properties are linked to their substitution patterns, but meta-isomers are underrepresented due to the difficulty of their synthesis. Now we address this challenge by describing a 1,2-transposition of phenols that enables a formal para- to meta-isomerization.
Enantioconvergent reactions convert both enantiomers of a racemic starting material into a single enantioenriched product. All currently known enantioconvergent processes necessitate the loss or partial loss of the racemic substrate’s stereochemical information. Now, an alternative approach has been developed that proceeds with full retention of the racemic substrate’s configuration.
Despite their intriguing photochemical activities, natural photoenzymes have not yet been repurposed for new-to-nature activities. Now, by leveraging the strongly oxidizing excited-state flavoquinone cofactor, fatty acid photodecarboxylases were engineered to catalyse unnatural decarboxylative radical cyclization with excellent chemo-, enantio- and diastereoselectivities.
Radical polymerizations yield polymers that cannot easily be degraded. The co-polymerization of cyclobutene-based monomers with conventional vinyl monomers has now been shown to result in co-polymers with cyclobutane mechanophores in their backbone, which facilitate on-demand degradation through a combination of mechanical activation and hydrolysis. This approach offers a promising avenue for the degradation of all-carbon-bond-backbone polymers.
RNA localization is key to regulating cellular function but is challenging to measure in an unbiased manner. Now a combination of enol-masked acylating probes with a bioorthogonal esterase to locally unmask them provides a non-radical RNA proximity labelling platform—termed BAP-seq—that enables the generation of high-resolution spatial maps of RNA.
The development of new methodologies to convert plastics into fuels without relying on noble metal-based catalysts is desirable. Now it is shown that a layered self-pillared zeolite enables the conversion of polyethylene to gasoline with a selectivity of 99% and yields of >80% without the need to use external hydrogen.
Chiral 1,2-benzazaborines are promising isosteres of naphthalene, but rarely explored due to the lack of efficient synthetic methods. Now, the copper-catalysed enantioselective hydroboration of alkenes with 1,2-benzazaborines has been developed, providing a general platform for the atom-economic and efficient construction of diverse chiral 1,2-benzazaborine compounds bearing a 2-carbon-stereogenic centre or allene skeleton.
Carbon capture, utilization and storage is key for climate change mitigation and developing more environmentally friendly technologies. Now it has been shown that CO2 capture in single-component water-lean solvents is accompanied by the self-assembly of reverse-micelle-like tetrameric clusters in solution that enable the formation of various CO2-containing compounds.
Despite the widespread utility of ruthenium catalysts, many protocols for their use require high temperatures or light irradiation. Now, the synthesis of an air- and moisture-stable ruthenium precatalyst has been reported. This versatile catalyst drives an array of transformations and enables rapid screening and optimization of reactions, revealing previously unknown in situ generated ruthenium complexes.
Lithium metal batteries are an attractive energy storage technology, but their development relies on the complex interplay between the components’ chemical, physical and mechanical properties. Now, selective methylation of dimethoxyethane ether electrolytes is shown to improve electrolyte, electrode and solid–electrolyte interphase stabilities to enable high-performance 4.3 V lithium metal batteries.
α-Amino acids possessing β-stereocentres are difficult to synthesize. Now, an iridium-catalysed protocol allows the direct upconversion of simple alkenes and glycine derivatives to give β-substituted α-amino acids with exceptional levels of regio- and stereocontrol. The reaction design is based on exploiting the native directing ability of a glycine-derived N–H unit to facilitate enolization of the adjacent carbonyl.