Articles in 2022

Photoinduced isomerization reactions can be used to efficiently dissipate absorbed energy in photosystems such as molecular motors, but the ultrafast processes are challenging to characterize. Here, the authors track the formation of the E and Z isomers of ethyl sinapate in real time via transient vibrational absorption spectroscopy and find that photoinduced internal conversion occurs at multiple points along the potential energy surface.

Hexahydromethanocarbazole is a bridged polycyclic scaffold present in drugs and photoactive organic materials, however the efficient synthesis of this scaffold remains challenging. Here, the authors develop a multicomponent reaction cascade via phenylnorbornyl palladium species to generate hexahydromethanocarbazole-based libraries with CYP11B1 inhibition activity.

The role of selenium in proteins and nucleic acids is well-established, but the pathway for incorporating selenium into small molecules remains unknown. Now, using bioinformatics tools, a selenium-incorporating gene cluster is discovered from immense genomic data, leading to the identification of selenoneine from microorganisms and the elucidation of a selenium incorporation pathway.

The SET-domain containing protein 2 (SETD2) is a protein lysine methyltransferase that has been shown to methylate the super-substrate peptide ssK36 100 times faster than the corresponding natural H3K36 peptide. Here, a combination of molecular dynamics simulations and biochemical experiments are applied to identify the mechanisms responsible for the increased activity of SETD2 towards ssK36.

NMR spectroscopy could be a robust and reliable method for binding detection in drug discovery, but DNA/RNA targets remain challenging to analyze. Here, the authors explore the perturbation of the ligand reactivity caused by complex formation as a binding indicator to identify best binders within mixtures of significant complexity, providing a conceptually different reactivity-based alternative within NMR screening methods.

Automated free energy calculations for the prediction of binding free energies of ligands to a protein target are gaining importance for drug discovery, but building reliable initial binding poses for the ligands is challenging. Here, the authors introduce an open-source workflow for building user-defined congeneric series of ligands in protein binding pockets for input to free energy calculations.

Studying the excitation energy transfer from carotenoids to bacteriochlorophyll a in purple photosynthetic bacteria could provide insights on how to optimize photosynthetic light-harvesting. Here, the authors study a carotenoid reconstituted core light-harvesting 1 complex from Rhodospirillum rubrum and find that the involvement of the intramolecular charge-transfer excited state of β-apo-8′-carotenal plays a key role in achieving an excitation energy transfer efficiency of ~77%.

Metal oxide nanoparticles functionalized by organic molecules are important building blocks for nanocomposites. Here, the authors study the adsorption of oleic acid on magnetite (001) and (111) surfaces experimentally by SXRD, LEED, FT-IRRAS and XRR, and employ a molecular dynamics force field specifically developed for magnetite/organic interfaces to determine molecular adsorption geometries, coverages, layer thicknesses and adsorption-induced structural changes in the substrate.

Silver-catalyzed hydroamidation of siloxy-alkynes is a successful approach for the hydroamidation of internal alkynes, however the mechanism of this reaction is poorly understood. Here, the authors use density functional theory calculations to reveal that the reaction takes place through a silver activated silylium ion migration mediated hydroamidation pathway.

¹⁰¹Tc is a lesser studied technetium isotope, but its unique nuclear properties and varying routes of production make it interesting for an array of applications where its shorter half-life can be exploited. Here, the authors review the discovery, nuclear properties, synthesis and separation, as well as applications of ¹⁰¹Tc, and point towards future research directions.

Ion separation membranes are of importance for a range of applications, including water treatment, raw material recovery, gas separation, and fuel cells, but traditional research and development methods can be expensive and time-consuming. Here, the authors review the capabilities and limitations of artificial intelligence in the design of high performing ion-selective membranes.

Understanding the relative strengths of metal–ligand and metal–metal interactions in ligated nanoclusters is key to tailoring their properties. Here, collision-induced dissociation of two series of atomically precise metal sulfide nanoclusters provides insight into the modulation of the core–ligand interactions of the atomically precise metal chalcogenide clusters.

Deep generative neural networks are increasingly exploited for drug discovery, but often the majority of generated molecules are predicted to be inactive. Here, an optimized protocol for generative models with reinforcement learning is derived and applied to design potent epidermal growth factor inhibitors.

Alanine substitution in peptides is crucial for studying peptide-based inhibitors of protein–protein interactions, but limited information is obtained from single alanine substitution. Here, the authors develop a label-free combinatorial alanine affinity selection platform to establish multi-alanine mutational tolerance and provide structure-activity relationships.

The electronic structures and open-shell diradical character of organic diradicaloids endow them with potentially useful optical, electronic and magnetic properties. Here, an open-shell nitrogen-centered diradicaloid is reported and shown to readily react with Lewis and Brønsted acids to form acid-base adducts, allowing for tuning of ground-state electronic structure, diradical character and spin density distribution.

Electrocatalytic oxygen evolution is a key reaction for water splitting, but the detailed atomic structures of single-crystal electrodes under cycling conditions are still not fully understood. Here, the authors study the oxygen evolution activity on Pt(111) during potential cycling and find that the current density reaches a maximum in the third cycle and is nine times higher than that in the initial cycle, owing to a roughened Pt(111) surface and formation of islands and atomic vacancies in the second subsurface Pt layer.

Coupling the photo-oxidation of biomass-derived substrates with water splitting in a photoelectrochemical cell enables efficient hydrogen generation at the cathode. Here, a photoelectrochemical device employing a nanostructured WO₃ photoanode displays photocurrents of 6.5 mA cm⁻² through oxidation of glucose, in turn producing valuable products in the form of gluconic and glucaric acids, erythrose and arabinose.

Direct conversion of methane to methanol has great industrial relevance, but required high reaction temperatures can lead to overoxidation of methane to carbon dioxide. Here, methanol is synthesized by one-step reaction of methane and water over a TiO₂ catalyst in a non-thermal plasma at room temperature and atmospheric pressure, which allows to isolate carbon dioxide-free methanol.

The chemical stability of alkali halides has caused them to be exploited as inert media in high-pressure, high-temperature experiments. Here, NaCl and KCl are unexpectedly found to react with yttrium, dysprosium and iron oxide in a laser-heated diamond anvil cell, producing Y₂Cl, DyCl, Y₂ClC and Dy₂ClC at ~40 GPa and 2000 K and FeCl₂ at ~160 GPa and 2100 K.

‘Molecular surgery’ is a useful method through which to create endohedral fullerenes that aren’t accessible by conventional physical methods of trapping small atoms and molecules. Here, the authors review the organic chemistry behind molecular surgery, describing the methods to access open-cage intermediates alongside the cage-closing chemistry.