Research articles

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.

Modelling the structural transitions of flexible metal-organic frameworks provides key insight into their breathing behaviours, but molecular dynamics simulations performed to date do not typically account for finite size and surface effects affecting the phase transition mechanism. Here, the authors present an approach that allows for the analysis and control of the volume of finite-size structures during molecular dynamics simulations, using a tetrahedral tessellation of nanocrystallite volume.

PAPP-A and PAPP-A2 are two isoforms of pregnancy-associated plasma protein A that cleave insulin-like growth factor binding proteins (IGFBPs) to modulate insulin-like growth factor signaling, however the structure and function of PAPP-A2 remain underexplored. Here, the authors report the cryo-EM structure of PAPP-A2, computational modeling of the PAPP-A2/IGFBP5 complex, and biochemical studies that reveal unique structural features and a lower IGFBP5 cleaving efficiency compared with PAPP-A.

To meet the rising demand for sustainable and simple polymer syntheses, organocatalytic polymerizations are a powerful tool. Here, the authors report the quasi-alternating polymerization of oxirane monomers at room temperature and in solvent-free conditions catalyzed by potassium acetate complexed by 18-crown-6 ether, leading to well-defined polyethers with varied comonomer content and low dispersity values.

Traditional peptide synthesis iteratively elongates the chain from the C-terminus to the N-terminus (C-to-N), however, this process requires excess N-carbamate-protected amino acids and condensation reagents to minimize epimerization. Here, the authors report an alternative N-to-C elongation strategy by catalytic peptide thioacid formation and oxidative peptide bond formation without requiring condensation reagents and excessive protecting group manipulations.

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.

Designing peptides that bind to specific protein targets is crucial for peptidic drug development, however, traditional computer-aided binder design is outperformed by AlphaFold2. Here, the authors develop a peptide binder designing tool by combining Foldseek, ESM-IF1 and AlphaFold2 to increase the success rate.

On-surface synthesis is a key tool to access low dimensional carbon-based nanomaterials with atomic precision. Here, the authors synthesize a nitrogen-doped nanographene structure with an [18]annulene pore on Ag(111) through sequential debromination, aryl–aryl coupling, cyclodehydrogenation and C–N coupling reactions from a 3,12-dibromo-7,8-diaza[5]helicene precursor.

Heterotopic ossification (HO) is the pathological formation of bone in soft tissues involving hydroxyapatite (HA) formation in vivo, however, the exact mechanism of HA formation remains debated. Here, the authors demonstrate the chemical mapping of human HO and the transformation of amorphous calcium carbonate in physiological conditions and reveal the role of ATP in bone mineralisation.

Dry reforming of methane (DRM) is a promising method for sustainable valorisation of methane and carbon dioxide, but its application is hampered by sintering of the active catalytic phase and coke formation. Here, the authors study DRM with non-noble metal atoms in supported gallium-rich liquid alloys which suppress both catalyst sintering and coke formation.

Volatile organic compounds are found on a majority of surfaces where they change surface properties and act as reactants, however, their diffusion flow rates remain undetermined. Here, the authors show that isoprene travels approximately 1 μm/s on zirconia under ultrahigh vacuum and is polymerized by an electron beam.

Networks of interacting DNA oligomers have various applications in molecular biology, chemistry and materials science, however, kinetic dispersions during DNA hybridization can be problematic for some applications. Here, the authors reveal that limiting unnecessary duplexes using in-silico optimization can reduce in-vitro kinetic dispersions by as much as 96%.

Polycyclic aromatic hydrocarbons (PAHs) are the main precursors to soot particles in combustion systems, but the transition from gas-phase species to organic soot clusters is still not fully understood. Here, the authors study infant soot particles with mass spectrometry and kinetic Monte Carlo simulations and identify peri-condensed PAHs to be the most thermodynamically stable species.

Free energy perturbation (FEP) is a well-recognized computational technique to predict the relative affinities of protein-ligand interactions, however, the exact accuracy of FEP prediction remains uncertain. Here, the authors assess the current accuracy of the leading FEP workflow by assembling a benchmark dataset, and highlight reliable protocols to maximize the accuracy of FEP in prospective studies.

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.

Various fatty acids and aldehydes can be synthesized from acetylene and carbon monoxide by nickel sulfide catalysts under volcanic hydrothermal conditions compatible with aqueous early earth conditions, however, their chemical complexity remains underexplored. Here, the authors use ¹³C-labelling together with untargeted ultrahigh-resolution mass spectrometry to categorize carboxylic acid functional groups, revealing C2-addition driven compound diversity as well as new sulfur containing classes.

Alcohol dehydrogenases (ADH) are known to be efficient and stereoselective biocatalysts for reducing prochiral carbonyl compounds to chiral alcohols; however, their catalytic performances remain limited for application. Here, the authors demonstrate the wide substrate scope of a L. kefir ADH variant with anti-Prelog specificity to generate (R)-alcohols.

C-substituted morpholines and morpholinones are important building blocks in organic synthesis and pharmacophores in medicinal chemistry, however, diverse C3-disubstituted morpholines/morpholinones remain difficult to access. Here, the authors develop a facile construction of C3-disubstituted morpholinone bearing an aza-quaternary center achieved by ZnCl₂-catalyzed cyclizative 1,2-rearrangement.

Spirocyclic tetrahydronaphthyridines (THNs) are valuable structural motifs in medicinal chemistry, but the modular and scalable synthesis of this specific motif remains challenging. Here, the authors develop an automated and continuous flow synthesis of 1,8-THN and 1,6-THN analogues based on photoredox-catalysed hydroaminoalkylation, demonstrating the concise synthesis of the spirocyclic THN core of Pfizer’s MC4R antagonist PF-07258669.

One-dimensional carbon chains are highly reactive allotropes that have been synthesized to date only in the protective environment of carbon nanotubes. Here, the author uses DFT simulations to show that carbon chains can be encapsulated in α-MnO₂ containing open structural channels which stabilize cumulene chains due to their structural commensurability, whereas the triple bonds in polyyne chains exhibit excessive steric repulsion to the oxide ions bordering the channel.