2022 Editors' Highlights

The Editors and Editorial Board of Communications Chemistry are pleased to launch an Editors’ Highlights Collection featuring some of our favorite Articles published in the journal in 2022. Here we highlight each Article and outline why it was selected.

Platinum(IV) complexes have the potential to overcome several limitations and reduce adverse effects of platinum-based cancer therapy. Resistance to clinically approved platinum(II) drugs is, at least in part, associated with elevated levels of glutathione. Here, the authors report on an oxaliplatin-based platinum(IV) prodrug, which releases L-buthionine-S,R-sulfoximine, an inhibitor of the rate-limiting enzyme in glutathione biosynthesis, to circumvent glutathione-based resistance mechanisms.

Determining the spatial ordering and hydrogen bonding dynamics of confined water molecules within nanopores remains challenging. Here, Raman spectroscopy and crystallographic studies show ice-like spatial ordering of unbound water molecules within the pores of the metal-organic framework HKUST-1 at room temperature.

The electronic structure evolution within a battery during cycling can provide crucial cues for its optimization, but insights on operando band structures are extremely challenging to obtain. Here, the authors determine the overall band structure of a model thin-film solid-state lithium battery via operando hard X-ray photoelectron spectroscopy, considering the cathode and anode sides.

Electrochemical synthesis has become a powerful tool, but the need for an electric power supply has disadvantages when considering sustainable development goals. Here, a streaming potential generated by a laminar flow of electrolyte in a microchannel acts as a driving force for electrode reactions, enabling electrochemical oxidative polymerization of aromatic monomers without an electric power supply.

Dry reforming of methane into syngas typically requires high temperatures, which can cause aggregation and deterioration of the catalyst. Here, the authors report a lanthanum nickel oxide catalyst prepared by in situ hydrogen reduction of LaNi_0.05Co_0.05Cr_0.9O₃ on a LaCrO₃ perovskite support that remains stable for over 100 h at 750 °C.

Mutations to oncogenic protein KRAS are responsible for some of the deadliest cancers, and KRAS is thus a key target for new antitumour agents. Here, a short bis-histidine peptide derived from the αH helix of the cofactor SOS1 is designed and shown to reversibly bind to KRAS with high affinity upon coordination to Pd(II), inhibiting KRAS-activated pathways in live cells.

Bringing enzymes and substrates together in confined compartments within porous systems can offer enhanced catalytic efficiency and increased lifetimes for the encapsulated enzymes. Here, the authors construct enzymatic compartments by spatiotemporal control of the self-assembly of catalytic peptide TPE-Q18H in hollow glucan particles, and demonstrate enhanced substrate-binding affinity and reaction kinetics as well as increased thermostability and resistance to hydrolysis.

Current crystal structure prediction methods for anticipating polymorphism are lacking in their ability to provide information on the depth of each energy minimum and the possible transition paths and energy barriers between polymorph structures. Here, a Monte Carlo threshold algorithm is applied to four polymorphic organic systems to estimate the energy barriers that separate the different polymorph structures and characterise the global structure of the energy landscapes of their molecular crystal structures.

The RquA protein is required for rhodoquinone biosynthesis; however, its exact function is not yet known. Here, the authors demonstrate that RquA is homologous to SAM-dependent methyltransferases but functions as an aminotransferase using Mn²⁺ as cofactor to convert ubiquinone to rhodoquinone.

In situ illumination of liquid-state NMR samples allows to characterise light-dependent chemical and biological phenomena, but, in practice, the position of an NMR sample deep within the bore of a spectrometer magnet renders such illumination challenging. Here, the authors demonstrate the working principles of a sample illumination device, with an LED array positioned directly at the top of special sample tube, which is inserted into the NMR spectrometer.

Bottom-up nanomaterial fabrication enables control over nano building-block structure and structure-property relationships, affording opportunities to engineer devices and materials with desirable electronic and optoelectronic behaviors. Here, the authors produce stable oligophenylene dithiol cross-linked gold nanoparticle nanosheets via interfacial self-assembly and show the emergent effects of the cross-linkers on the material’s electronic, optical and photoconducting properties.

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.

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.

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.

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.

Proton transfer between DNA bases can lead to mutagenic tautomers, but as their lifetimes are thought to be much shorter than DNA separation times their role during the DNA replication cycle is often overlooked. Here, the authors model the separation of the DNA base pair guanine-cytosine using density functional theory and find increased stability of the tautomer when the DNA strands unzip as they enter a helicase enzyme, effectively trapping the tautomer population.

Carbocyclic nucleosides show a broad spectrum of antiviral activity with enhanced flexibility, lipophilicity and metabolic stability, however, synthetic access to carbocyclic C-nucleosides (CC-Ns) remains very challenging. Here, the authors use an asymmetric Suzuki-Miyaura coupling reaction as the key C-C bond forming step to produce a variety of enantiomerically enriched CC-Ns, including antiviral showdomycin.

Two-dimensional colloidal nanoplatelets can assemble into materials with promising optical properties, and the influence of local curvature on these properties is an area of active interest. Here, the relationship between nanoplatelet geometry, self-assembly, and collective properties is reviewed.

Molecular dynamics simulations, used to study chemical and biophysical processes, rely on the accuracy of the employed force fields. Here, the authors review successes and key areas of difficulty in the development of additive and polarizable force fields, and discuss experimental data availability, how empirical refinement impacts parametrization, and highlight possible routes to further improve the accuracy of force fields.

Continuously evolving computational methods are crucial to improve our understanding of the thermophysical properties of molten salts, which are experimentally hard to probe but used widely from steel manufacturing to solar power generation. Here, the authors review computational method developments from early simulations to current machine learning tools, and conclude with an outlook on the challenges molten salt simulations still pose.

Aluminum–sulfur batteries have a theoretical energy density comparable to lithium–sulfur batteries, whereas aluminum is the most abundant metal in the Earth’s crust and the least expensive metallic anode material to date. Here, the authors review experimental and computational approaches to tailor the chemical interactions between sulfur host materials and polysulfides in Al-S batteries and point towards promising future research directions.

Control over chemical transformations in aqueous environments employing catalytic systems whose activity can be switched on/off is challenging. Here, the authors review the switchable catalytic systems that operate in aqueous environments in response to external stimuli, such as pH, temperature, light, small molecules, electric field, magnetic field and mechanical energy.

‘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.

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.

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.

Thermally activated delayed fluorescent (TADF) emitters are inexpensive and versatile materials for organic light emitting diodes (OLEDs) covering all colour regions. Here, the authors review double boron embedded multi resonant TADF emitters with particular attention to molecular design concepts, synthetic routes, optoelectronic properties, and OLED performance, providing future prospects for display applications.

Most of our knowledge about the chemical composition of the Earth’s interior is primarily retrieved by indirect observations, experiments and calculations that are limited to simple compositions. Here, the authors present the investigation of inclusions trapped in super deep diamonds as an alternative source of a wealth of information on the chemical state of the Earth’s interior through time.

The cluster approach is a very valuable technique for elucidating reaction mechanisms of enzymes. Here, the authors discuss the current status of this methodology, highlighting its strengths and weaknesses, and argue that it should be the method of choice for investigating enzymatic reaction mechanisms.

Adiabatic state preparation (ASP) represents an efficient way of generating correlated wave functions on quantum computers for subsequent quantum simulation. Here, the author discusses recent work that numerically studied the performance of ASP on strongly correlated molecules and presented several approaches of improving the quality of prepared ground state wave functions.

Pinpointing double bond (C=C) positions in native lipid extracts is beyond the capabilities of standard mass spectrometry-based approaches. This article highlights a novel untargeted workflow supported by the open-source software MS-RIDD, that allows for semi-automated annotation of C=C locations with high confidence.