Articles in 2021

Artificial metalloenzymes (ArMs) combine the reaction scope of chemocatalysts with the selectivity of enzymes. This Review discusses the prospects and recent progress in utilizing ArMs in whole cells for applications in diverse areas such as drug therapy and integration with biosynthetic pathways.

Ribozymes that use the cellular cofactor S-adenosyl-l-methionine to methylate RNA remained elusive. Now, such a ribozyme is reported by identifying natural sequences that are active in vitro; and crystal structures of the ribozyme with and without the cofactor are determined.

Enantioselective C(sp³)–C(sp³) coupling plays an important role in organic synthesis, but limitations remain. Now, cobalt-catalysed enantioselective C(sp³)–C(sp³) coupling between achiral fluoroalkenes and alkyl halides enables the streamlined and auxiliary-free synthesis of chiral fluoroalkanes.

The challenge in non-oxidative coupling of methane lies in the activation of the first C–H bond while avoiding further dehydrogenations, which lead to the formation of coke. Here, atomically thin platinum nanolayers on two-dimensional molybdenum titanium carbides are reported as a superior catalyst for this reaction owing to reduced coke formation.

The valorization of CO₂ via its hydrogenation to methanol is a highly sought-after reaction although only a handful of catalysts can efficiently promote this transformation. Here, the authors engineer the interface of a copper catalyst supported on a silica–molybdenum MXene composite, achieving a remarkable performance in the reduction of CO₂ to methanol.

Periselective catalytic asymmetric cross-Diels–Alder reactions between two different conjugated dienes remain underdeveloped. Now, the selectivity challenges are overcome in such a reaction of electron-poor 2-pyrones and unactivated conjugated dienes, and an ambimodal transition state is identified.

Despite its importance in the context of natural gas engines emissions treatment, methane oxidation remains challenging. Now, the authors introduce an approach to stabilize PdO_x rafts on ceria by trapping Pt single atoms in the support resulting in a superior catalyst for this transformation.

Chemoselective reactions are often characterized by an activity–selectivity trade-off that renders their optimization difficult. Here gold nanoparticles equipped with a platinum monolayer are introduced that, thanks to lattice expansion and ligand effect, achieve a remarkable performance for the chemoselective hydrogenation of halonitrobenzenes

Establishing structure–activity relationships is crucial for the design of improved catalysts. Now, by developing a method based on electrochemical scanning tunnelling microscopy, the active sites of graphene/iron/platinum interfaces are visualized with atomic-scale precision in real time during the hydrogen evolution reaction.

Harnessing a clean, affordable and inexhaustible source of energy is an immense scientific challenge. Scientists moved a step closer in 1972 when the first practical device for direct solar power-to-fuel conversion was reported.

The Haber–Bosch process was introduced at the beginning of the twentieth century; however, its mechanism remained controversial for many years. Thus, a comprehensive mechanistic picture was provided in the eighties.

To produce chemicals and fuels from CO₂ and water while storing excess energy from renewable resources will play a big role in sustainability. Three decades ago, we learned that copper possesses the unique ability to break the stable CO₂ bonds and to form C–C bonds, a key step towards higher-value products.

The old catalysis literature still has much to offer to the research community. This issue presents a selection of retro News & Views articles that highlight some key historical developments in the subareas of catalysis.

More than 35 years ago, telomerase activity was discovered by Elizabeth H. Blackburn and Carol W. Greider. Today, this enzyme is a promising approach to curing some age-related diseases as well as cancer, but it took time for telomerase to be in the spotlight.

Methods for the direct one-step replacement of a hydrogen atom in a C–H bond by an organic functional group can create enormous possibilities for synthetic applications. On the way to solve this challenge, the discovery of the reaction of organopalladium complexes with olefins opened a new era in catalysis and organic chemistry.

Reductive aminases show strong potential for the sustainable synthesis of chiral amines, but their application in industrial scale processes is lacking. Now, such an enzyme is screened and engineered allowing its use in commercial manufacturing of abrocitinib JAK1 inhibitor in multi-metric tons.

Solvent structuring affects the energy landscape of catalytic reactions, but the quantitative understanding of such effects remains difficult. Now, the structure of water within the micropores of different zeolites is disclosed together with the effects that its reorganization has over alkene epoxidation catalysis.

Information on how metabolic networks respond to the utilization of a non-natural carbon source remains scarce. Now, yeast’s response and adaption to xylose as an alternative carbon source is investigated; cell engineering enhanced growth provides an improved platform to produce chemicals from xylose.

The design of artificial organelles for applications in living cells faces several challenges such as cellular uptake, stability and biocompatibility. Now, fusion of exosomes creates beneficial nanoreactors and their use for compartmentalized biocatalytic cascade reactions in cells is demonstrated.

The mechanism of heterogeneous aqueous-phase aerobic oxidations remains under debate. Now, it has been shown that the reaction can be described as two coupled electrochemical half-reactions for oxygen reduction and substrate oxidation, and the thermochemical rates can be derived from the electrochemical half-reactions via the application of mixed potential theory.