Reviews & Analysis

Site-specific attachment of a programmable motif, such as a synthetic nucleic acid tag, on a target protein can facilitate functional studies of proteins in cells or modulation of protein activity. Now, a small genetically encoded peptide enables the templated incorporation of a peptide nucleic acid tag onto membrane proteins in live cells.

Mimicking biosynthetic pathways can provide access to medicinally important natural products, but generating the reactive species used by nature can often be difficult. Now, a photoredox-based strategy has been developed to access a reactive radical intermediate postulated to be involved in complex lignan biosynthesis.

As a consequence of their high instability, main-group carbonyl complexes are rare — only a few have been detected, typically in low-temperature matrices. Now, two silicon–carbonyl complexes have been isolated using innovative substituent patterns at the Si centre; their reactivity resembles that of their transition-metal counterparts.

Artificial photosynthesis represents a promising method of generating hydrogen for our clean and sustainable energy needs. Now, photocatalytic nanofibres have been developed that incorporate photosensitizers and catalysts into well-defined self-assembled structures for efficient hydrogen production.

Metabolic labelling with unnatural sugars can be used to selectively label tumours with chemical tags. These tags then enable the targeted delivery of molecular cargo including diagnostic and therapeutic agents. This Review Article discusses progress in the design and delivery of unnatural sugars for metabolic labelling of tumour cells and the subsequent development of tumour-targeted chemistry.

Interactions between two bodies that are both attractive and repulsive — such as predators chasing prey — are common in nature. Similar chasing behaviour has now been engineered in self-propelling microdroplets and controlled through fundamental physical and chemical mechanisms.

It’s generally assumed that primitive forms of cellular life arose from nucleic acids and peptides compartmentalized within vesicles — all underpinned by a non-enzymatic protometabolism. Three studies now provide new insights into the ancient chemistry that may have supported early biology.

The #ScienceTwitter community was recently treated to a virtual campaign under the hashtags #BlackInChem and #BlackChemistsWeek. This event highlighted past and present contributions from Black people in the field and offered unique opportunities for networking, mentorship, and recognition, say Abraham Beyene and Priera Panescu.

The manner in which adjacent sheets stack in layered covalent organic frameworks largely influences their material properties, including chemical stability, crystallinity and porosity. The layer stacking of a COF has now been probed locally, showing disorder that is not detected through long-range characterization.

Labelling proteins at internal sites holds promise for generating novel protein conjugates in a programmable fashion. Now, a chemoenzymatic approach, dubbed LACE, enables the site-specific modification of recombinant proteins that contain a short genetically encoded tag.

The past decade has seen unprecedented growth in the development of chemical methods that proceed by mechanisms involving radical intermediates, but controlling absolute stereochemistry has been a longstanding challenge in this area. This Review Article examines how attractive non-covalent interactions between a chiral catalyst and the substrate can exert enantiocontrol in radical reactions.

How atoms organize during the earliest stages of nucleation has been a subject of speculation for over a century. Using atomically resolved electron microscopy, the formation and ordering of metal clusters from individual atoms has now been observed in carbon nanotubes that serve as ‘test tubes’.

The [2+2] photocycloaddition of two double-bond moieties is arguably the most efficient way to form a four-membered ring, but this route is rarely used to construct azetidine rings. Now, the development of an isoxazoline carboxylate cycloaddition partner offers a general approach to synthesize diverse azetidine products.

Electrophilic groups that undergo sulfur-exchange chemistry with protein nucleophiles can serve as the functional basis of chemical proteomic probes. A new addition to this class, sulfuramidimidoyl fluoride (SAF), which can be included in an array of covalent small molecule probes, exhibits a unique reactivity profile with proteins.

After years of speculation on the origins of symmetry-making and -breaking during crystallization, time-resolved in situ scanning probe microscopy and all-atom molecular dynamics simulations have shown that the formation of olanzapine crystals largely occurs by the incorporation of centrosymmetric dimers into growth sites.

Controlling the formation of ordered and predictable patterns in dissipative reaction–diffusion processes is challenging. Now, liquid vibrations induced by audible sound have been shown to direct the formation of spatiotemporal patterns in switchable chemical systems and assemblies.

Chemical systems can show complex behaviour that is not seen in individual molecules or reactions. Helena S. Azevedo, Sarah L. Perry, Peter A. Korevaar, and Dibyendu Das report on the emergence of this complex behaviour, which was discussed at the Virtual Symposium on Systems Chemistry

Enzymes that methylate using S-adenosyl-l-methionine — nature’s methyliodide — are abundant and often promiscuous; however, a preference for alkylation over methylation has been neither observed in nature nor engineered. Now, carboxymethylation has been demonstrated using engineered methyltransferases.

Recent research has shown that vibronic coherences are one of the primary drivers for ultrafast light-induced processes. Now, ultrafast spectroscopy has been used to uncover vibronic coherences in the excited-state dynamics of an iron complex, leading to its redesign and the drastic prolonging of its excited-state lifetime.