Volume 3 Issue 1, January 2024

A macroscale scaffolding strategy for building arches and curved surfaces is translated to the molecular level for the face-selective design of zeolitic metal–organic frameworks (ZMOFs).

A kinetically controlled solution-phase synthesis produces nanoparticles of defined shape and multimetallic surface composition for catalytic applications.

Triaryloxonium salts are used as aryne precursors under mild and operationally simple conditions, allowing high functional-group tolerance, and cycloaddition reactions are used to trap the arynes generated.

An intercalation strategy has been developed to produce bulk-monolayer MoS₂ which retains single-layer semiconductor properties.

Direct conversion of air to nitric acid occurs under ambient conditions using a cathodic hetero-homogeneous electrocatalysis strategy.

A chemoenzymatic strategy is introduced whereby a glycan backbone is assembled enzymatically to give a core oligosaccharide that is subjected to chemical manipulations to install terminal epitopes. A library of oligosaccharides containing the human natural killer-1 epitope was synthesized, enabling evaluation of the binding specificities of serum antibodies of patients with anti-myelin-associated glycoprotein neuropathy.

A β-lactone compound — globilactone A — has been discovered through genome mining and heterologous expression of a biosynthetic gene cluster. Biosynthetic investigations unveiled the mechanism of the formation of the cyclopentane-β-lactone core.

Traditionally, enzymes were not commonly used as catalysts by organic and pharmaceutical chemists owing to insufficient stereoselectivity. However, this changed with the onset of directed evolution. This Review introduces mutagenesis methods, describes the enzyme-catalysed production of specific pharmaceuticals and presents further examples.

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.

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.

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.

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.

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.

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.

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.

Enantioselective γ-lactonization of unactivated C(sp³)–H bonds is a challenge using chemical methods. Now the biocatalytic enantioselective synthesis of γ-lactones from aliphatic carboxylic acids is reported, using a reengineered fatty acid hydroxylase, P450_BSβ. Crystallographic and computational analyses show the observed γ-regioselectivity arises from the mutants introduced into P450_BSβ.