Research articles

Arabinogalactan RN1 displays potent anti-pancreatic-cancer activity; however, the structure–activity relationship of RN1 is unclear. Now the synthesis of RN1 and a library of glycans are reported, using an iterative preactivation-based one-pot glycosylation strategy. Biological analysis reveals that a decasaccharide is the active structural domain of RN1.

Synthesizing phase-pure, higher-quantum-well thickness (n) 2D halide perovskites is challenging. Now, a general method, termed kinetically controlled space confinement, to synthesize 2D perovskites is reported. Transformation from low n-values to high n-values is achieved by tuning the temperature or time of crystallization.

β-Lactone-containing natural products are rare. Now, a polyketide with a unique cyclopentane–β-lactone skeleton is reported. The key enzymes identified for the formation of the bicyclic core are a non-ribosomal peptide synthetase-like module with a β-lactone ring forming esterase and peptidyl carrier protein, thioester reductase and condensation domains.

Unravelling the formation of binary nanocrystal phases is challenging. Here, by combining in situ small-angle X-ray scattering and molecular dynamics simulations, we show that AlB₂ and NaZn₁₃ superlattices undergo classical homogeneous nucleation consistent with the presence of short-range attractive interactions guiding the crystallization process.

In this approach, metal–organic framework (MOF) glasses are synthesized by the desolvation of mononuclear metal complexes. The MOF glasses are composed of transition metals and either carboxylate, pyridyl or azolate ligands. Their porous structures and formation of monoliths are regulated in this process.

High-entropy alloys (HEAs) have interesting properties, but the synthesis of uniform HEAs is challenging. Here design principles are established for the synthesis of core–shell nanoparticles, which can be thermally annealed to produce uniform HEA nanoparticles in a predictable manner.

The selective synthesis of non-symmetrical diamides and amido-esters is a challenge. Now a Pd-catalysed dicarbonylation method is reported that generates non-symmetrical diamides and amido-esters through diamino- and amino-alkoxy carbonylations of propargylic acetates using two different nucleophiles. Mechanistic studies reveal that the process occurs through a sequential carbonylation process.

Arynes are often generated using strong bases or fluoride sources, limiting functional group tolerance. Now, stable triaryloxonium salts are transformed into arynes and subsequently trapped using cycloaddition reactions by treatment with potassium phosphate at room temperature. This functional group-tolerant method proceeds by an elimination, unimolecular, conjugate base-like elimination mechanism to form the aryne.

While enzyme-mediated oligosaccharide synthesis is versatile, it is often limited by the availability of glycosyl transferases. Now a chemoenzymatic strategy is reported, comprising enzymatic assembly of a core oligosaccharide followed by chemical manipulations, to produce a library of glycans that reveal binding specificities of serum antibodies.

Centring structure-directing agents govern structure assembly to consistently obtain sodalite topology backbone, yielding more than 20 isoreticular zeolite-like metal–organic frameworks with tailored pore apertures and porosity.

Direct synthesis of nitric acid from nitrogen and oxygen is attractive but is challenging under mild conditions. Now, direct conversion of air to nitric acid is achieved under mild conditions via a hydroxyl-radical-mediated hetero-homogeneous electrochemical route at the cathode.

A chemical dedoping technique is introduced to mitigate excessive electron doping in molecular cation intercalated MoS₂, producing a stable bulk monolayer material with monolayer-like optical properties but a much larger optical cross-section.

The synthesis of polycyclic conjugated hydrocarbons with antiaromatic moieties is realized by the thermal rearrangement of dibromomethylene-functionalized molecular precursors on a hot Au(111) metal surface.

The reversible deactivation process in polymerization using chain-end hydrogen atoms remains underexplored and difficult to control. Now, deprotonation–protonation equilibrium-driven C(sp³)–H alkylation polymerization of cyclopropanes is reported using the cooperative catalysis of an organic base and a metal salt to control the polymerization.

Shape-controlled multimetallic nanoparticles remain elusive due to large existing miscibility gaps. Now, a low-temperature (≤80 °C) non-equilibrium synthesis of nanosurface alloys with tunable size, shape and composition is reported. The nanosurface alloys can be used as selective and phase-stable CO₂ reduction electrocatalysts.

Polymetallic rings are formed via the collision-induced dissociation of larger complexes. Ion mobility mass spectrometry can be used to determine whether the formed polymetallic complexes are cyclic or acyclic.

The electroreduction of CO to methanol catalysed by supported cobalt phthalocyanine molecules is hindered by low selectivity and poor mechanistic understanding. Here a mechanism-guided reaction based on systematic kinetic studies is used to achieve an improved methanol Faradaic efficiency of roughly 85%.

meta-Selective acylation of arenes typically requires directing groups or steric hindrance. Now, a combined N-heterocyclic carbene and organic photoredox catalysed of electron-rich arenes, using acyl imidazoles as acylating agents, is reported. Mechanistic studies reveal the process proceeds through single-electron oxidation and radical–radical coupling steps.

Suzuki-type cross-coupling for C(sp²)–C(sp³) bond formation with aliphatic halides remains challenging with tertiary aliphatic halides and under transition-metal-free conditions. Now, a transition-metal-free C(sp²)–C(sp³) cross-coupling of α-(pseudo)halo aliphatic ketones with boronic acids via a 1,4-metallate shift is reported which is compatible with tertiary aliphatic halides, allowing for 1,3-disubstituted products.

Developing reaction conditions for radical–radical cross-dehydrogenative amination reactions is challenging. Now a nickel-catalysed asymmetric electrochemical cross-dehydrogenative amination reaction between acylimidazoles and nitrogen nucleophiles is developed to access structurally diverse α-amino carbonyls that can be used to synthesize (+)-γ-secretase inhibitor, (+)-flamprop-methyl and (+)-flamprop-isopropyl.