Themed collection 2021 ChemSci Pick of the Week Collection

Cost-effective and atom-efficient isotopic enrichment enables ¹⁷O NMR spectroscopy of microporous materials to be used to probe local structure and disorder and to explore chemical reactivity.

A pair of enantiomeric organic ferroelectrics (R and S)-10-camphorsulfonylimine show the highest T_c among the known single-component organic ferroelectrics.

The N-glycans structures affect the mechanistic properties of the SARS-CoV-2 S, fine-tuning the glycoprotein. The evolution of the glycan shield led to the loss of N370 glycosylation in SARS-CoV-2 S, where the RBD cleft can bind host-cell glycans.

d–d excitations can accelerate C–S reductive eliminations of nickelacycles via intersystem crossing to a repulsive ³(C-to-Ni charge transfer) state inducing Ni–C bond homolysis. This homolytic photoreactivity is common for organonickel(II) complexes.

This report describes a breakthrough in a project to design minor groove binders to recognize any sequence of DNA.

Simple and available reagents are combined in this new three-component isocyanide-based multicomponent reaction providing an interesting and straightforward way to prepare complex and highly functionalized cyclopentenyl rings.

In ion pairing catalysis, the structures of advanced intermediates are often not accessible. Here, we present a combined experimental and computational study of ternary complexes in Brønsted acid catalysis, which show unexpected H-bond switching.

The synthesis and photophysical properties of phenolic barbiturics are reported. These molecules convert absorbed ultraviolet light to heat with high fidelity and may be suitable for inclusion in foliar sprays to boost crop protection and production.

Rh(III)-catalyzed ortho-alkynylation of nitro-(hetero)arenes leads to a wide variety of alkynylated nitroarenes via a turnover-limiting electrophilic C–H ortho-metalation.

The different roles of the anion, cyclic and linear carbonates, and additive in mixed-carbonate electrolytes are revealed. The anion–solvent exchange mechanism and factors influencing the solid electrolyte interphase (SEI) formation are deciphered.

The actinide allenylidenes [{(NR₂)₃}An(CCCPh₂)]⁻ (An = U, Th, R = SiMe₃) feature significant ligand-to-metal donation bonding and partial AnC double bond character.

The dispersity of polymers is efficiently controlled in aqueous atom transfer radical polymerization by modulating the reversible dissociation of the bromide ion from the copper deactivator.

Dipyrrolonaphthyridinedione appended with para- or meta-nitrophenyl substituents exhibits strong fluorescence from a ¹ππ* S₁ state.

A persulfide/hydrogen sulfide generation strategy through artificial substrates for 3-mercaptopyruvate sulfurtransferase (3-MST) is reported, which enhances cellular persulfides, attenuates reactive oxygen species (ROS), and alleviates inflammation.

Catalyst data created through high-throughput experimentation is transformed into catalyst knowledge networks, leading to a new method of catalyst design where successfully designed catalysts result in high C₂ yields during the OCM reaction.

The methylene-bridged trianglamine (TA) can selectively capture 1-chlorobutane from a mixture of 1-chlorobutane and 2-chlorobutane due to the greater thermodynamic stability of the TA-based host–guest complex formed with 1-chlorobutane.

We report the synthesis and robust crystallization of a trimacrocyclic hexasubstituted benzene and guanidium mediated by unprecedented labile halide hexasolvate clusters, viz. [Cl(CHCl₃)₆]⁻, [Br(CHCl₃)₆]⁻, [I(CHCl₃)₆]⁻, and [Br(CHBr₃)₆]⁻.

A real-space characterization of dynamic non-covalent interactions in molecular assemblies and chemical reactions at the atomic bond level.

The reactions of organic peroxy radicals with alkenes, overlooked until now, could be more significant than expected for some RO₂ in the atmosphere.

We demonstrated that the ten-eleven translocation (TET) dioxygenase-mediated oxidation of 5-methylcytosine followed by direct decarboxylation of 5-carboxylcytosine constitutes a novel pathway for active DNA demethylation in mammalian genomes.

Temperature artifacts in protein structures impact the utility of structural information in computation by misleading validation and application of computational methods in discovering bioactive molecules.

An efficient synthesis of non-hydrolyzable inositol pyrophosphate analogs was developed to subsequently investigate the regulation of insulin-degrading enzyme by these hyperphosphorylated signaling molecules.

Stabilising protein–protein interactions is challenging, yet therapeutically important. Native mass spectrometry can be used to monitor binding equilibria, allowing identification and measurement of novel protein–protein interaction stabilisers.

Free three-dimensional carborane carbanions, which are inorganic siblings of deprotonated aryls with the “naked” anionic carbon atom are reported.

The library of isostructural porous frameworks enables a systematic survey to optimize the structure and functionality of porous materials.

New Os(II) half-sandwich complexes bearing a pendant alcohol prompt reversible tether-ring formation upon aquation, protecting Os against deactivation. Excitingly, these complexes mediate hydrogenation of pyruvate to lactate inside cancer cells.

N-Alkylpyridinium salt of chiral amines undergoes phosphite mediated stereoretentive migrations to generate chiral alkylpyridines. The role of phosphite on reactivity and stereoselectivity were examined to achieve a catalytic asymmetric version.

Enzymatic bioconjugation to introduce positron-emitting radionuclides (⁸⁹Zr, ⁶⁴Cu) into an anti-EGFR antibody fragment allows same day imaging with positron emission tomography.

An efficient route to the HCV antiviral agent uprifosbuvir was developed in 5 steps from readily available uridine in 50% overall yield.

A catalytic dearomatization of indoles with D–A aminocyclopropane monoesters for the synthesis of highly substituted indolines.

Ion clustering of dilute chromium species was unexpectedly revealed in a high-temperature molten chloride salt, challenging several long-held assumptions regarding specific ionic interactions and transport in molten ionic media.

Triggered by heating, a poly(2-alkyl-2-oxazoline) block copolymer undergoes seeded growth in water forming length tuneable nanorods. Morphology and composition combine to impart low immune cell association and promising blood circulation lifetimes.

Installation of oversized functions within a metal–organic cage may “burst” or even transform the molecular cage itself.

Active site FeV-cofactor of the V-nitrogenase and the EPR spectrum of the reduced cofactor showing ⁵¹V-hyperfine coupling.

A novel scheme for the automated calculation of the conformational entropy together with a modified thermostatistical treatment provides entropies with unprecedented accuracy even for large, complicated molecules.

Bioorthogonal probes have been developed to enable quantitative and site-specific profiling of itaconate modifications in Salmonella.

Acenes in the Greek cross (+) stack orientation exhibit selective hole and electron transfer coupling based on gerade symmetry in frontier molecular orbitals.

Carotenoids are essential constituents of plant light-harvesting complexes. This in silico study shows that carotenoid binding is mainly driven by van der Waals interactions with the surrounding chlorophylls rather than hydrogen bonds to the protein.

Probe-based electrochemical techniques can be used to map carrier transport and recombination within two-dimensional semiconductors.

‘Alchemical’ quantum algorithm for the simultaneous optimisation of chemical composition and electronic structure for material design. By exploiting quantum mechanical principles this approach will boost drug discovery in the near future.

Adding an external electric field to reactions driven by quantum mechanical tunneling brings a whole new dimension to the idea of switch chemistry.

A series of dihetero[8]helicenes have been synthesized in a stereoselective manner through an organosulfur-based synthetic strategy, which has enabled clarifying the effect of the endocyclic atoms on physical properties.

A first-in-class reductively cleavable linker system that enables parallel and traceless purification of peptides through a safety-release is introduced with three linker types and showcased by rapid production of 20 personalized neoantigen peptides.

Compression is used to derive a long sought-after connection between two central chemical concepts – van-der-Waals (vdW) radii and electronegativity – and how these relate to the driving forces behind chemical and physical transformations.

A single molecule footprinting-Seq assay at single nucleotide resolution was developed for measuring the distribution and kinetic binding of proteins on DNA.

A “protecting group strategy” for unstable lacunary polyoxomolybdates enabled successful synthesis of two types of tetranuclear manganese clusters.