Articles in 2021

Camptothecin derivatives are precursors of potent anticancer agents, but their biosynthesis remains largely unknown. Here two cytochrome P450 monooxygenases are shown to regiospecifically oxidize camptothecin, yielding 10- and 11- hydroxylated derivatives, which are subsequently used to produce a suite of known anticancer drugs and derivatives.

Antiwear additives are crucial to ensuring the reliable operation of lubricated machine components, but virtual screening to obtain new additives has hardly been explored. Here, the authors use nonequilibrium molecular dynamics simulations with a reactive force field to investigate the mechanochemical dissociation of phosphate esters with different alkyl substituents to inform future molecular design.

The semi-hydrogenation of alkynol to cis-enol is a critical process in the industrial production of fine and intermediate chemicals, but viable alternatives to lead-free palladium-based catalysts for this reaction are scarce. Here, an intermetallic PdZn/ZnO nanoparticle catalyst is designed and its reactivity described.

Protein-ligand binding can induce the formation of cryptic allosteric pockets not found in the unbound protein, but predicting this computationally can be challenging. Here a combined computational and experimental workflow identifies ligands for H. pyloriglutamate racemase, finding that coupled dynamics of the enzyme dimer are dampened by ligand binding.

Photo-induced darkening of red cinnabar (α-HgS) often dramatically changes the appearance of artworks, but the reduction mechanism of Hg²⁺ remains unclear. Here, the authors propose an alternative pathway for the blackening reaction of cinnabar, considering its semiconductor properties and pigment-binder interactions

In situ and real-time characterization of dynamic airborne particles is important for fundamental as well as applied atmospheric chemistry, but imaging usually requires trapping the particles. Here the authors use an integrated digital in-line holographic microscope coupled with a flow tube to study moving <200 nm-sized particles without optical traps.

Environmentally friendly binders for energy materials may improve sustainability, but can suffer from poor performance. Here a gel derived from graphene oxide and starch is used as a hybrid binder for supercapacitors, providing good rate performance and stability over 17,000 cycles.

Bismuth organic frameworks can display interesting phosphorescent properties, but the relationship between structure and optical activity remains underexplored. Here two bismuth organic frameworks with differing bismuth coordination number and intermetallic distance are contrasted.

Anions in fluorophore solutions commonly act as fluorescence quenchers. Here, the formation of hydrogen bonds between acetate anions and urea-derived fluorophores leads to aggregation-induced emission enhancement in the solid state.

Phosphatidylinositol-4,5-bisphosphates are involved in membrane regulation and signalling in eukaryotes, with the distribution of acyl chains changing in response to stimuli. Here, molecular dynamics simulations and fluorescence spectroscopy experiments show that increasing acyl chain saturation increases the ordering of lipid nanodomains in artificial membranes.

Solution activity is commonly modelled empirically or using electrostatic models. Here a mass-action solution model with defined equilibria is used to describe solution activity of neutral, symmetric, and asymmetric salt solutions over a wide range of concentrations.

Landomycins are promising anti-cancer agents with the potential to bypass common resistance pathways, but their mechanism of action remains incompletely understood. Here a mechanism is proposed involving intracellular sequential thiol-Michael and oxidation reactions, which depletes endogenous thiols and induces reactive oxygen species formation.

Polyamines play an important role in biogenic silica formation, however, their effects on silica particle size and condensation have not been well described. Here the authors show that bioinspired polyamine length affects silica particle size and extent of condensation.

Self-propelled nanoparticles may find medical applications. Here Mg–Fe₃O₄ based Janus nanoparticles powered by water are shown to efficiently capture cancer cells in serum and whole blood samples.

Copper-catalysed annulation of allenylidenes provides an opportunity to target the alpha, beta, or gamma positions of the allenylidene, but achieving this control is challenging. Here substrate control allows selectivity between these three positions in the enantioselective cyclisation of ethynyl benzoxazinanones and sulfamate-derived cyclic imines.

n-type organic semiconductors exhibiting two-dimensional isotropic charge transport are rarely reported. Here the authors show that using bulky substituents, BQQDI demonstrates near-isotropic charge transport, resilience to dynamic disorder, as well as high electron mobility both in single- and polycrystalline thin-film transistors.

Chemical reactions often require multiple random encounters between reactants, but a general, analytical treatment such imperfect transport-limited/influenced reactions in confined spaces has not yet been proposed. Here, the authors predict the full kinetics of these reactions for Markovian processes in large confining volumes.

Force-dependent transitions can provide insights into the free-energy landscape of proteins. Here, the authors observe the folding and unfolding dynamics of the model protein Csp using magnetic tweezers, from which a free-energy landscape with two energy barriers and a transient intermediate state is constructed.

Diffraction imaging offers high spatiotemporal resolution, but fitting complex molecular structure data is expensive. Here, the authors use a machine learning algorithm with a convolutional neural network to retrieve a complex and large molecule, fenchone (C₁₀H₁₆O), from laser-induced electron diffraction data without the need for fitting or ab initio calculations.

Crude oil upgrading under a methane environment can lead to improved oil quality as well as catalyst stability, but the role of methane in the reaction remains poorly understood. Here, the authors show that methane prevents coke formation inside the pores of the charged catalyst due to preferable adsorption.