Research Highlights

Boroxines, resulting from the reversible dehydration of boronic acids, have been incorporated as structural units into functional materials and molecular assemblies, but their applicability is restricted to non-aqueous environments owing to their inherent water instability. Now, a boroxine structure spontaneously formed from the 2-hydroxyphenylboronic acid dimer enables water-compatible dynamic B–O covalent bonds, expanding their future applicability.

Covalent cysteine labeling is an important tool in protein modification, however, current methodologies suffer from limited reactivities and require the prior synthesis of individual derivative reagents. Now, a covalent cysteine labeling method that converts the cysteinyl thiol into episulfonium electrophiles in situ has been developed, enabling reactions with various nucleophiles in one step.

Pomalidomide is an E3 ligase recruiter exploited by PROTACs to degrade target proteins, but its application is hampered by the off-target degradation of other vital endogenous zinc finger (ZF) proteins. Now, the off-target ZF binding of pomalidomide-based PROTACs is evaluated by a high-throughput imaging screening platform, and minimization of off-target degradation as well as enhanced potency are achieved through selective functionalization at the C5 position of the phthalimide ring.

Conformational dynamics are integral to enzyme catalysis, yet they are barely explored when designing synthetic catalysts. Now, a catenane-based organocatalyst, which dynamically switches between two conformations, speeds up the catalysis of carbodiimide hydration through spontaneous conformational adaptation for different reaction steps.

Molecular skeletal editing has a wide range of applications in late-stage derivatization, but metal–carbon exchange is underexplored due to the challenges in selectively cleaving highly inert chemical bonds and forming stable intermediates. Here, skeletal metalation of lactams enables a carbonyl-to-nickel exchange via Ni(0) reagent-mediated selective C–N bond oxidative addition and decarbonylation, generating synthetically useful organonickel reagents for the deletion and exchange of single atoms in the lactam core.

Fluorochemicals have a wide range of applications in industry, but accessing these relies on the energy intensive conversion of acid-grade fluorspar (CaF₂) to toxic hydrogen fluoride (HF) gas, which is in turn used for the downstream production of fluorochemicals via multistep processes. Now, directly treating acid-grade fluorspar with dipotassium hydrogen phosphate (K₂HPO₄) under mechanochemical conditions affords a fluorinating reagent for direct S–F and C(sp³/sp²)–F bond construction, bypassing the need for HF production.

Chiral halogen-bonding catalysts have emerged as a new approach towards asymmetric catalysis, but enantioselectivities have thus far remained low. Now, fine-tuning the substrate–catalyst halogen–halogen interactions is shown to significantly enhance enantioselectivity for a model anion-binding-catalyzed dearomatization reaction.

To solve the environmental disaster that is generated by legacy plastics accumulation, researchers are looking to design plastics with enhanced end-of-life options, but many circular plastics do not meet industrial requirements. Here, we highlight a metal-free approach to produce chemically recyclable poly(1,3-dioxolane) with ultra-high molecular weight and comparable properties to one of the most produced plastics, polyethylene.

Economical and high-efficiency synthesis of single-atom catalysts is a tremendous challenge hampering their large-scale industrialization, which is mainly attributed to the complex equipment and processes necessary for both top-down and bottom-up synthesis methods. Now, a facile three-dimensional printing approach tackles this dilemma. From a solution of printing ink and metal precursors, target materials with specific geometric shapes are prepared with high output, directly and automatically.

Combining the superior photovoltaic performance of three-dimensional perovskites and the intrinsic durability of two-dimensional perovskites, the construction of 3D/2D perovskite bilayer heterojunctions is a promising strategy to realize efficient and stable perovskite solar cells, but it is still a challenge to control the phase purity, film thickness, orientation, and crystal structure of 2D perovskites. Now, a solution-processing strategy has overcome this challenge by directly coating a tailored single-crystal 2D perovskite ink on as-prepared 3D perovskite films, resulting in effective, ultra-stable and phase-pure 3D/2D perovskite bilayer heterojunctions.

Organic–inorganic lead halide perovskites are highly promising materials for solar cell devices, but their widespread commercialization is hindered by their poor environmental stability. Now, porous organic cages are shown to stabilize methylammonium lead iodide films under hot and humid conditions.

The role of selenium in proteins and nucleic acids is well-established, but the pathway for incorporating selenium into small molecules remains unknown. Now, using bioinformatics tools, a selenium-incorporating gene cluster is discovered from immense genomic data, leading to the identification of selenoneine from microorganisms and the elucidation of a selenium incorporation pathway.

[n]cycloparaphenylenes feature extensive para-conjugation that leads to useful electronic and optoelectronic properties, but their strained topology prevents their conversion into planar macrocycles. Now, on-surface coupling of cleverly designed precursors affords planar π-extended [12]cycloparaphenylene.

Tooth enamel possesses outstanding viscoelasticity as well as stiffness — a combination of properties often considered a trade-off. Now, a bi-directional freezing method affords a biomimetic composite with mechanical properties superior to those of enamel.

Electrically conductive two-dimensional metal–organic frameworks have emerged as promising materials for electronic and energy storage devices, but their stacked nature offers limited accessibility to the framework pores. Now, pillaring a conductive 2D MOF is shown to enhance gravimetric capacitance by more than double.

Small changes in protein structure can have pronounced effects on protein–protein interactions, but quantifying this has only recently become possible. Now, the binding landscapes of three homologous enzyme–inhibitor complexes are quantified and shown to depend on whether the inhibitor binds its natural target or a structurally similar protein.

Understanding heat conduction in solids is fundamental to the design of high-performing thermoelectric materials. Now, a combined computational and experimental study shows how local order paired with long-range disorder leads to a desirable reduction in thermal conductivity while retaining high electron mobility in the Zintl phase Eu₂ZnSb₂.

DNA-templated synthesis of chiral inorganic assemblies often requires chemical modification of the template. Now, a route exploiting the native chemistry of unmodified DNA origami templates provides access to 3D chiral assemblies.

Mechanical forces can induce a biochemical response in cells. Now, it is shown that a molecular motor can exert enough force on the surface of a cell to induce a biochemical response too.

Lewis acid additives such as aluminium can enable fascinating new reactivity in transition metal catalysts, but few catalytic intermediates have been characterised. Now, a nickel-aluminium pincer complex offers new mechanistic insight into transmetalation, and new potential for reactivity.