Browse Articles

The effective control of chirality on surfaces is crucial for applications such as enantioselective heterogeneous catalysis and nonlinear optics. Here, the authors study the on-surface synthesis of organometallic polymers and their chiral expression on Ag(110), demonstrating that kinetic effects play an important role in determining polymer chirality.

CO₂ electrolyzers with gas diffusion electrodes take advantage of improved mass transport of gaseous CO₂ to the catalyst surface to afford increased current densities, but the complex and coupled multi-phase processes occurring inside the electrolysis device are not fully understood. Here, the authors use a two-dimensional volume-averaged model of the cathode side of a microfluidic CO₂ to CO electrolysis device with a gas diffusion electrode and find that under high cathodic potential, the catalyst layer is prone to forming H₂ and CO bubbles, mirroring observed experimental electrode instability.

Boroxines, resulting from the reversible dehydration of boronic acids, have been incorporated as structural units into functional materials and molecular assemblies, but their applicability is restricted to non-aqueous environments owing to their inherent water instability. Now, a boroxine structure spontaneously formed from the 2-hydroxyphenylboronic acid dimer enables water-compatible dynamic B–O covalent bonds, expanding their future applicability.

Fluorescence-based oligonucleotide probes, also known as molecular beacons (MBs), are popular for detecting nucleic acids with high specificity. Here, the authors demonstrate self-sequestration of MB-based biosensors and target strands within peptide-based coacervates, increasing local concentrations and significantly increasing the sensitivity and kinetics of the DNA biosensors.

Ipatasertib is a potent Akt (protein kinase B) inhibitor synthesized via a chemoenzymatic process. Here, the authors use mutational scanning and algorithm-aided enzyme engineering to optimize a ketoreductase from Sporidiobolus salmonicolor and generate a 10-amino acid substituted variant exhibiting a 64-fold higher k_cat and improved yield for the relevant alcohol intermediate, with ≥ 98% conversion and a diastereomeric excess of 99.7% (R,R-trans) from 100 g L⁻¹ ketone after 30 h.

African swine fever virus type II DNA topoisomerase (AsfvTop2) is known to change DNA topology by employing a complex catalytic cycle and is involved in the early stages of viral gene replication, however, the structural and regulatory functions of AsfvTop2 remain underexplored. Here, the authors use cryo-EM to demonstrate six conformers of apo-AsfvTop2 as well as the structures of AsfvTop2-DNA-inhibitor complexes, revealing experimental evidence of their substrate binding mechanism that also shed light to other enzymes.

The effects of co-solutes on protein solubility, stability and function have been well studied, however, some of the theories appear inconsistent and no clear theoretical framework has been established. Here, the authors investigate the NMR titrations of protein barnase with Hofmeister ions and osmolytes to distinguish binding effects from solvent perturbation and provide a coherent explanation for solute effects.

Covalent cysteine labeling is an important tool in protein modification, however, current methodologies suffer from limited reactivities and require the prior synthesis of individual derivative reagents. Now, a covalent cysteine labeling method that converts the cysteinyl thiol into episulfonium electrophiles in situ has been developed, enabling reactions with various nucleophiles in one step.

Dual-controlled molecular release is of importance in the construction of controlled delivery systems with high anti-interference capabilities, but has been underexplored in the context of guest release from supramolecular entities. Here, the authors report a coordination cage whereby changes in both the coordinative metal cation and the solvent system are needed to induce guest release.

Pomalidomide is an E3 ligase recruiter exploited by PROTACs to degrade target proteins, but its application is hampered by the off-target degradation of other vital endogenous zinc finger (ZF) proteins. Now, the off-target ZF binding of pomalidomide-based PROTACs is evaluated by a high-throughput imaging screening platform, and minimization of off-target degradation as well as enhanced potency are achieved through selective functionalization at the C5 position of the phthalimide ring.

The atomically precise on-surface synthesis of carbon-based nanostructures is of relevance for electronic and optoelectronic devices, but achieving control over such architectures remains challenging. Here, the authors demonstrate the selective stepwise on-surface synthesis of nitrogen-doped porous carbon nanoribbons with well-defined topologies and structures, and predict variable band gaps dependent on ribbon width.

Sorbicillactone A is a nitrogen-containing sorbicillinoid that displays various bioactivities, identified from a sponge-derived Penicillium chrysogenum strain. The first and so far obly total synthesis of sorbicillactone A led to the racemate in 12 linear steps and a 0.13% overall yield. Here, the authors develop a chemoenzymatic stereoselective total synthesis of sorbicillactone A in 4 steps and 11% yield by using the enzyme SorbC for the enantioselective oxidative dearomatization of sorbillin to sorbicillinol followed by addition of an azlactone unit.

Although depolymerization methods for various commodity plastics and several engineering plastics have been developed, such methods for robust super engineering plastics that have very high heat and chemical resistance are nearly unexplored. Here, the authors report the catalytic depolymerization-like chemical decomposition of oxyphenylene-based super engineering plastics such as polyetheretherketone, polysulfone, and polyetherimide using thiols via selective carbon–oxygen main chain cleavage to form monomer-type molecules, namely electron-deficient arenes with sulfur functional groups and bisphenols.

Recently, a medium-density amorphous ice (MDA) was synthesized via ball-milling of hexagonal ice, adding complexity to our understanding of the phase diagram of supercooled water and amorphous ice. Here, the authors use molecular dynamics simulations to show that, depending on the employed pressure, isobaric cooling can generate a continuum of amorphous ices with densities that expand in between those of low- and high-density amorphous ices, with some of these amorphous ices being remarkably similar to MDA.

Bivalent molecules comprising dual functional motifs often exhibit strong target binding, however arriving at the optimal structure is challenging. Here, the authors employ EGFR as a model system for understanding a subtle difference in the linker structure of bivalent inhibitors to enhance binding against drug-resistant EGFR mutants.

The signal transducing interface between biosamples and detection devices plays a key role in translating electrochemical reactions into output signals and often governs detection limits and biocompatibility of the sensor. Here, the author reviews syntheses and properties of electrochemical interfaces of field-effect transistor-based biosensors.

Ultraprecise spectral line lists of molecules such as water, omnipresent in various environments, can be used to calibrate high-resolution spectra, which is particularly relevant for exoplanet transit observations. Here, the authors use measured spectra and network theory to achieve ultraprecise characterization of H₂¹⁶O and H₂¹⁸O hubs, the most relevant quantum states within a spectroscopic network.

Electronic energy transfer (EET) between chromophores is a critical process for solar energy funneling, and recent studies using scanning tunneling microscopy have shown that chromophores deposited on solid substrates in such conditions display peculiar EET features. Here, hybrid ab initio and electromagnetic modeling provide a comprehensive theoretical analysis of tip-enhanced EET.

Nickel organic compounds play a crucial role in organic and bioinorganic chemistry, however, their potential role in prebiotic chemistry is not well understood. Here, the authors identify the formation of a nickel bis(dithiolene) from nickel sulfide under an acetylene-containing volcanic hydrothermal experimental environment and reveal its role in the transformation of acetylene to acetaldehyde.