Understanding catalysis

Localized surface plasmon resonance can be used to control the energy flow in plasmonic core-shell Ag–Pt nanocubes and excite energetic charge carriers in the thin Pt shell, which can then drive CO oxidation.

The pyrophosphate analog imidodiphosphate (PNP) alters the reaction equilibrium of human DNA polymerase β, and the resulting increase in the rate of pyrophosphorolysis enables kinetic and structural dissection of this reverse reaction of the enzyme.

Ligand development underlies many advances in Pd-catalysed cross coupling but has seen limited application in the growing field of Ni catalysis. Now, a phosphine framework is shown to enable Ni-catalysed Suzuki coupling of acetals. Parameterization studies provide structural insight into ligand success and a quantitative model to facilitate further ligand design.

Identifying trends in electrocatalytic activity for carbon dioxide reduction can help with catalyst design, but are difficult to define. Here, the authors develop an electrochemical kinetic model of the process, identifying scaling relations relating transition state energies to CO adsorption energy on metal surfaces.

The oxidative prowess of cytochrome P450s has been suggested to stem from the electron-donating axial ligand. Now, a selenocysteine-ligated P450 compound I has been trapped and characterized providing an avenue to examine this hypothesis. Measurements reveal that the selenolate-ligated compound I cleaves C–H bonds more rapidly than the wild-type equivalent.

Atmospheric CO₂ can be transformed into valuable hydrocarbons by reaction with H₂, but CO is the favoured kinetic product. Here, Liu and co-workers show that plasmonic rhodium nanoparticles not only reduce the activation energy for CO₂hydrogenation, but also photo-selectively produce methane.

Experimental work and computational modeling together reveal a suite of catalytic roles of the GlcN6P cofactor in the glmS ribozyme, including activation of the nucleophile, electrostatic stabilization, and alignment of the active site.

The conversion of lignin by catalytic fast pyrolysis into useful fine chemicals is a promising route to fuel production, however selectivity and conversion are still not optimal. Here, the authors investigate the reaction mechanism by detection of reactive intermediates responsible for the formation of key products.

Our increasing understanding of non-covalent interactions involving aromatic systems is reviewed, and the use of these insights in the design of small-molecule catalysts and enzymes is surveyed.

Transition metal catalysis is well established as an enabling tool in synthetic organic chemistry. Photoredox catalysis has recently emerged as a method to effect reactions that occur through single-electron-transfer pathways. Here we review the combination of the two to show how this provides access to highly reactive oxidation states of transition metals and distinct activation modes that further enable the synthetic chemist.