Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain
the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in
Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles
and JavaScript.
The use of main-group elements in radical cross-coupling reactions has been little explored. Now, a low-valency bismuth complex has been shown to emulate the behaviour of first-row transition metals and undergo single-electron-transfer oxidative addition to redox-active electrophiles, leading to the development of a bismuth-catalysed C–N coupling reaction between amines and carboxylic acids.
Trihydrogen cations are abundant in interstellar space and play a vital role in both star and organic molecule formation. Now it has been shown that D3+ cations can be directly produced through photoionization of molecular D2–D2 dimers.
Supramolecular structures are typically formed by the one-step self-assembly of building blocks. Now, a greater level of control has been achieved using stepwise non-covalent reactions under kinetic control. Two-dimensional block supramolecular polymers with tailored compositions and sequences were synthesized, and a site selectivity that is reminiscent of regioselectivity in covalent synthesis was observed.
Ribosomal incorporation of non-α-amino acid monomers into proteins is largely restricted to in vitro translation. Now, pyrrolysyl-transfer RNA synthetase variants have been shown to acylate tRNAs with α-thio acids, malonic acids, and N-formyl amino acids. This work represents a key step towards the programmed ribosomal synthesis of sequence-defined non-protein polymers in cellulo.
Ultra-high-capacity Li–air batteries have low Coulombic efficiency and degrade during re-charging, resulting in a poor cycle life. Redox mediators enable improvements but only at undesirably high potentials. The origin of this high potential and the impact of purported reactive intermediates has now been elucidated by resolving the charging mechanism using Marcus theory.
Bioresponsive hyperpolarized probes contain magnetic resonance signals that can be many orders of magnitude larger than those of common, thermally polarized probes. This Perspective discusses how bioresponsive hyperpolarized probes can be directly linked to biological events to give functional information, enabling the mapping of physiological processes and diseases in real time using magnetic resonance.
H3+ and D3+ serve as initiators of many chemical reactions in interstellar clouds. Now the ultrafast formation dynamics of D3+ from a light-driven bimolecular reaction starting from D2–D2 dimers have been measured. It has also been shown that the emission direction of D3+ can be controlled by driving the reaction with a more complex two-colour laser pulse.
Complexity is a hallmark of biological systems, but scientific experiments are typically conducted in simplified conditions. Now, diverse polymers that mimic the local environments of complex biological mixtures have been shown to improve protein folding, stability and function.
Constructing aptamers with desired target-binding affinities may lead to new applications but is challenging. Now, a new method using a high-dimensional microfluidic approach enables quantitative isolation of aptamers with programable binding affinities.
From humans designing machines, to machines designing biology, deep learning is turning the tables for assisted exploration of biologically active and diverse protein designs. Now, a deep-learning-based strategy has been used to design artificial enzymes that catalyse a light-emitting reaction.
The biosynthesis of the methylated sesquiterpene sodorifen, which features a cryptic methylation pattern, has now been studied through extensive labelling experiments and computational chemistry. The methyl group formation is now understood to come from methylene carbons of the substrate farnesyl diphosphate and the absolute configuration of the biosynthetic intermediate presodorifen diphosphate has been revised.
Colloidal clathrate crystals self-assembled from hard polyhedral shapes in computer simulations are stabilized by entropy compartmentalization, whereby hosts and guests contribute unequally to the entropy. This creative solution to satisfying the laws of thermodynamics suggests new ways to make colloidal crystals with open cages and hierarchical host–guest structures.
Protein solutions can undergo liquid–liquid phase separation, by condensing into a dense phase that often resembles liquid droplets, which coexist with a dilute phase. Now it is shown that hydrophobic interactions, specifically at interfaces, can trigger a liquid–solid phase separation of a protein solution.
Clathrates—open crystals with a hierarchy of polyhedral cages—are mostly found in atomic and molecular systems. Now, it has been shown through Monte Carlo simulations that the formation of colloidal host–guest clathrates can be driven by entropy alone, through entropy compartmentalization.
A trivalent 4f cationic complex bearing two bis-silylamide ligands has been prepared that displays slow magnetic relaxation. The bulky ligands and weakly coordinating anion stabilize the pseudotrigonal geometry necessary to elicit strong ground-state magnetic anisotropy in this axially coordinated Yb(III) complex with well-localized charges.
Dipolar cycloadditions are excellent processes for generating heterocyclic systems from simple starting materials, but arenes as dipolarophiles have not been extensively explored. Now, the intramolecular dipolar cycloaddition of aromatic rings has been achieved using in situ generated diazoalkenes to produce bicyclic or tricyclic heterocycles.
1,3-Dipolar cycloadditions are well-known transformations in organic synthesis. However, the reactivity of benzene rings in these processes is underexplored. In situ-generated diazoalkenes have now been shown to undergo intramolecular 1,3-dipolar cycloadditions with aromatic rings. The transformation results in an unaromatized benzene ring that enables the synthesis of functionalized heterocycles.
Cellular membranes contain numerous lipids, and efforts to understand the biological functions of individual lipids demand approaches for controlled modulation of membrane composition in situ. Now, click chemistry-based directed evolution of a microbial phospholipase within mammalian cells affords an editor for optogenetic, targeted modification of phospholipids in cell membranes.
In vitro screening of a ribosomally synthesized macrocyclic peptide library containing cyclic γ2,4-amino acids (cγAA) afforded the discovery of potent inhibitors of the SARS-CoV-2 main protease (Mpro). A co-crystal structure revealed the contribution of this cγAA to Mpro binding and the proteolytic stability of these macrocycles.
Electronic spin influences chemistry profoundly, but its role in surface chemistry is poorly established. Now the spin-dependent reaction probabilities of oxygen atoms with a graphite surface have been studied. Molecular dynamics simulations help elucidate the mechanism for spin-flipping, which is observed to occur with low probability in surface scattering experiments.
