2023 Editors' Highlights

At Communications Chemistry we are pleased to launch an Editors’ Highlights Collection featuring some of our favourite articles published in the journal in 2023. Here, we highlight each article and outline why it was selected.

Polyetheretherketone (PEEK) is an important super engineering plastic utilized in industries owing to its thermal stability and mechanical strength, however, its robustness hinders chemical recycling. Here, the authors report the depolymerization of insoluble PEEK using sulfur nucleophiles via carbon–oxygen bond cleavage and then treatment with organic halides to form various dithiofunctionalized benzophenones and hydroquinone monomers.

Understanding the complex mechanical behaviour of metal–organic frameworks is of importance for their real-world application. Here, an in situ micropillar compression method is demonstrated to provide valuable insights into the anisotropic mechanical properties of the HKUST-1 single crystal.

The collagen present in rare prehistoric bones allows for their age to be estimated by radiocarbon dating, but this method is destructive towards these precious archaeological remains. Here, the authors report a non-destructive method based on near-infrared hyperspectral imaging to precisely localize the collagen preserved in parts of ancient specimens suitable for radiocarbon dating.

Di-tert-butylphosphine is an important substituent in many phosphine ligands, however, its heterocyclic analogues have not yet been isolated. Here, the authors report the synthesis and isolation of 2,2,6,6-tetramethylphosphinane on a gram scale starting from ammonium hypophosphite, and its facile use as a building block in ligand construction.

Metallic nanoparticles are widely explored for boosting light-matter coupling of 2D materials, however, the target area for nanoparticle deposition is typically restricted to either the top or the bottom of 2D flakes. Here, the authors show tunable, edge-specific nanoparticle decoration using a laser, achieving arrays of silver nanoparticles that are self-limited in size along tungsten diselenide nanoribbon edges.

Polyphosphoesters (PPEs) are versatile polymers utilized in tissue engineering, as electrolytes, or flame retardants, but copolymers of different PPE subclasses are hardly explored. Here, the authors report general protocols for the organocatalyzed copolymerization of four different PPE subclasses, resulting in copolymers with varying amphiphilicity and gradient strength.

Fluorinated ketones can function as covalent warheads applied in the design of reversible covalent inhibitors, however, the reactivity of certain fluorinated moieties remains underexplored. Here, the authors investigate the species-specific lipophilicities of fluorinated geminal diketones in multicomponent equilibrium systems and reveal their potential as multifaceted warheads for reversible covalent drugs.

Structural biology has undergone a revolution thanks to cryo-EM and artificial intelligence-based model predictions; nonetheless, experimental phasing continues to be essential. Here, the authors utilize the long-wavelength I23 beamline at Diamond Light Source to solve macromolecular structures using single-wavelength anomalous diffraction techniques, showcasing their proficiency in phasing with lighter atoms.

Iron(III) molybdate is a commercial catalyst for selective oxidations such as oxidative dehydrogenation of methanol, but our understanding of the involved (sub)surface and bulk conversion processes remains limited. Here, the authors use modulation excitation IR, operando impedance, and multiwavelength Raman spectroscopy to show the mode of operation of this important catalyst.

Single-atom catalysts (SACs) are highly promising materials for applications such as electrocatalytic water splitting, but coordination geometries around catalyst centers remain the subject of debate. Here, the authors use spin-polarized ab initio molecular dynamics simulations to compare the aqueous reactivities of iron porphyrin and iron pyridine SACs embedded in graphene, and predict the interfacial water dissociative adsorption mechanism under a moderate electric field for an iron porphyrin SAC.

The reduction of dinitrogen to ammonia catalyzed by nitrogenase involves long-range conformational changes within the enzyme complex, however, direct biophysical evidence of communication between the Fe protein and the MoFe protein is lacking. Here, the authors combine millisecond time-resolved hydrogen-deuterium exchange mass spectrometry and normal mode analysis, revealing molecular-level insights into how the Fe protein alters the stability and dynamics of the MoFe protein near the active site in a nucleotide-dependent manner.

Atom-centered neural networks represent the state-of-the-art for approximating quantum chemical properties of molecules, such as internal energies, but the final atom pooling operation that is necessary to convert from atomic to molecular representations in most models remains relatively undeveloped. Here, the authors report a learnable pooling operation, usable as a drop-in replacement, that leverages an attention mechanism to model interactions between atom representations.

Non-cell-permeable cryoprotectants exhibit cryopreserving effects by preventing intracellular ice crystal formation, but these can damage cells due to high osmotic pressure and dehydration. Here, the authors developed a poly(zwitterion) isotonic cryoprotectant that forms a firm matrix around cells that prevents the influx of ice crystal nuclei without the need for high osmotic pressure and dehydration.

The electrolytic reduction of CO₂ in aqueous media promises a pathway for the utilization of the greenhouse gas by converting it to base chemicals, however, reactions at the electrodes and their proximity remain challenging to elucidate. Here, the authors use multinuclear in operando NMR to study CO₂ electrolysis in aqueous media and find that stable ion pairs in solution catalyze the bicarbonate dehydration reaction.

Bicyclobutanes are among the most highly strained organic compounds and are intriguing building blocks in organic synthesis. This review provides an overview of the recent developments in bicyclobutane synthesis, their synthetic utility and their modes of reactivity.

Constructing crystalline materials with specific stimuli-responsive dynamics and controlled molecular motion affords opportunities for innovative functionality and applications. Here, the authors discuss recent developments in dynamic solid-state framework materials across a range of material classes, exploring key phenomena associated with such complex dynamics.

Atomically precise metal nanoclusters display exciting optical and catalytic properties, but their long-term instability under ambient conditions hinders their practical application. Here, the authors review recent progress in creating nanohybrids from atomically precise nanoclusters and other more stable nanomaterials, forming hybrids with useful properties and improved stabilities.

Endothelial dysfunction is the early stage in the development of cardiovascular disease, however, molecular probes for diagnostics of endothelial dysfunction are still underexplored. Here, the authors review the specific nitric oxide and calcium sensors available in the context of detecting endothelial dysfunction.

Stereoregular polymers exhibit improved thermal and mechanical properties, making the development of enantioselective polymerization catalysts of significant importance. Here, the authors summarize catalyst design strategies and synthetic routes for enantioselective polymerizations of degradable or recyclable polymers from racemic monomers.

Artificial photosynthesis aims to produce fuels and chemicals from simple, abundant building blocks, such as water and carbon dioxide, with sunlight as a source of energy. Here, the authors review recent developments in biomimetic, compartmentalized vesicular systems towards artificial photosynthesis, and highlight challenges and opportunities in mimicking this complex natural reaction system.

Incorporating main group elements into amorphous porous organic polymers has enabled the fine tuning of the structures and properties of these materials. Here, the authors review studies in which the geometric structures and electronic properties of main group elements have influenced material structures and properties, and whereby their incorporation has enabled new strategies to synthesize such materials.

The formation of Li dendrites at the Li/electrolyte interface at practically relevant current densities (> 1 mA cm⁻²) is a critical issue hindering the deployment of non-flammable and non-toxic Li₇La₃Zr₂O₁₂ (LLZO) electrolyte in solid-state batteries. In this comment, the authors argue for an agreement to standardize measurements of the critical current density at which Li dendrites begin to penetrate the LLZO solid-state electrolyte.

The oxygen evolution reaction (OER) is a key enabler of sustainable chemical energy storage. Here, the author assesses the current status of protocols for benchmarking the OER in materials- and device-centered investigations and makes suggestions for more comparable data.