Articles in 2023

The catalytic cycle of formate dehydrogenase is generally assumed to involve an apoenzyme state according to the Theorell–Chance mechanism. Now, based on single-molecule experiments and multiscale simulations of formate dehydrogenase from Candida boidinii, an alternative mechanism that bypasses the apoenzyme state is proposed.

The practical optimizations of heterogeneous catalytic processes and reactor engineering are intertwined, but often what occurs inside the reactor remains elusive. Now, the molecular diffusion and carbon number of hydrocarbon products during Fischer–Tropsch synthesis on a Ru/TiO₂ catalyst are spatially resolved via magnetic resonance imaging in a pilot-scale fixed-bed reactor.

Large-scale deployment of electrocatalytic hydrogenations using water as a hydrogen source is hampered by poor solubility and difficult product separation. Here the authors propose a dual hydrogenation approach, with palladium membranes used as both anode and cathode, to produce hydrogen—enabled at the anode by the low-potential oxidation of formaldehyde—that permeates to adjacent chemical compartments, where the hydrogenation of organic substrates occur.

The cleavage of C–C bonds in hydrocarbons is traditionally entrusted to precious metal catalysts, whereas common non-reducible oxides are considered unreactive. Now, the authors report nanostructured silica-embedded zirconia nanoparticles that are competent for the hydrogenolysis of polyethylene with remarkable performance.

Hydrofunctionalization of α-olefins with mineral acids usually proceeds with Markovnikov selectivity. Now, a strategy based on synergistic phase transfer and photoredox catalysis is developed to facilitate anti-Markovnikov addition of aqueous hydrochloric and nitric acid to unactivated alkenes.

Lithium–sulfur batteries are promising energy storage devices where catalysis can play an important role, but developing design principles for optimal performance remains a challenge. Now, a series of p-block metal sulfide cathodes are evaluated, revealing a direct correlation between the p electron gain of sulfur in the sulfide material and the apparent activation energy for the sulfur reduction reaction.

Placing extra-framework aluminium species in the proximity of Brønsted acid sites is one of the most effective ways of tuning the energetics of zeolite-catalysed reactions. Here, using pentane cracking as an example, the authors show that grafting extra-framework silica species instead represents a valuable alternative way to modulate zeolite acitivty.

Albicidin is a peptide antibiotic that has shown great promise for inhibiting DNA topoisomerase of fluoroquinolone-resistant Gram-negative pathogens, but its mode of action is not fully clear. Now, cryoelectron microscopy structures of albicidin–gyrase complexes provide detailed insights into the mechanism of this natural product.

The design of complementary catalysts to target different C–H bonds in a specific molecule is challenging. Now, a pair of P450-based carbene transferase enzymes is engineered, which can selectively cyanomethylate either a C(sp³)–H or arene C(sp²)–H bond present in the same substrate.

The overall water splitting performance of semiconductor photocatalysts is often limited by recombination reactions occurring at the surface of metallic co-catalysts. Here, the authors demonstrate how the controlled deposition of aluminium oxide species on a Rh co-catalyst can strongly inhibit this phenomenon and enhance the performance of GaN–ZnO photocatalyst.

Insights on the mechanistic differences between artificial metalloenzymes (ArMs) with non-native metal centres and the free cofactor or natural enzymes are scarce. Now, a detailed mechanistic analysis of a cyclopropanation reaction catalysed by such an ArM is provided, revealing intriguing differences to the natural system.

Renilla luciferase is a popular bioluminescent enzyme, but the molecular details of its mechanism of action on luciferins such as coelenterazine remained elusive. Now, protein crystal structures and biochemical analyses provide an atomistic description of its catalytic mechanism.