Themed collection 2022 ChemSci Pick of the Week Collection

Chemistry, the science of transformation of matter, is fundamental to achieving sustainability through ensuring biogeochemical flows do not transgress planetary boundaries. This requires urgent changes in chemistry education, research and industry.

This perspective highlights the growing body of literature that leverages polarity reversal (umpolung reactivity) for the selective modification of proteinogenic functionalities and identifies opportunities for further innovation.

SRM, an advanced nanoscopy technique demands a transition from being a niche sophisticated technique to standard routine method for material characterization. The roadmap of necessary developments through multidisciplinary collaboration is discussed.

The thermodynamics of amyloid formation has largely been neglected compared to kinetic studies. In this review, the current state of the experimental exploration of amyloid thermodynamics is presented and important open questions are highlighted.

The structure of porcine AAP (pAAP) in a covalently bound complex with meropenem was determined by cryo-EM to 2.1 Å resolution, showing the mammalian serine-protease inhibited by a carbapenem antibiotic.

Vanadium nitride quantum dots are immobilized on graphene to controllably create coordination-unsaturated edge/corner V sites for the efficient aerobic oxidation of thiophenic sulfides.

The metastable trilacunary heteropolyoxomolybdate [PMo₉O₃₁(py)₃]³⁻; py = pyridine) and the ditopic pyridyl bearing diarylethene (DAE) (C₂₅H₁₆N₂F₆S₂) self-assemble via a facile ligand replacement methodology to yield the photo-active molecular capsule [(PMo₉O₃₁)₂(DAE)₃]⁶⁻.

The complex {(TMEDA)₂Li}{[Ti(N(TMS)₂)₂]₂(μ-η²:η²-N₂)₂} (5-Li) was the only transition metal N₂ complex ever reported with two side-on N₂ adducts. Reanalysis of 5-Li has revealed that it is an inverse-sandwich toluene adduct, not an N₂ adduct.

The rates of mechanochemical reactions are generally found to increase exponentially with applied stress.

To effectively identify helical peptide binders from a phage library, we developed “pattern enrichment analysis,” which finds the enriched three-residue patterns by comparison with a control sample.

A facile but robust method to precisely synthesize well-defined LiF-tipped CoF₂-nanorod heterostructures is established.

We present a reliable methodology for the calculation of excited state exchange interactions in molecular three-spin systems. Such calculations will help to establish how to optimise inter-spin communication in photogenerated multi-spin systems.

Graph neural network-based continuous embedding is used to replace a human expert-derived discrete atom typing scheme to parametrize accurate and extensible molecular mechanics force fields.

Nanostructured high-entropy materials such as alloys, oxides, etc., are attracting extensive attention because of their widely tunable surface electronic structure/catalytic activity through mixing different elements in one system.

NHC-Lewis acid cooperative catalyzed dynamic kinetic resolution (DKR) of transiently generated γ,γ-disubstituted indole 2-carboxaldehydes leading to the enantioselective synthesis of tetracyclic ε-lactones is reported.

Transferable selectivity profiles allow data from intermolecular reactions using iminium substrates to be applied to predict intramolecular reactions involving thioniums.

We identified two drug-like antitubercular hits with submicromolar inhibition constants against the target 1-deoxy-D-xylulose-5-phosphate synthase (DXPS) with a new mode of action and promising activity against drug-resistant tuberculosis.

A semi-continuous flow platform allows the safer end-to-end production of cyclic phosphate monomers providing an easier access to polyphosphoesters and their applications.

This twisted superhelicene employed its twists and loops to shine chiral emission into the NIR region. The proof of its promising applicability in optoelectronic devices is the analogous chiroptical properties obtained in solution and thin films.

Critical chain length dividing small-molecule crystallization from macromolecular crystallization was determined for discrete polyketones to be as short as pentamer.

The interplay of fluorination, flexibility, and mass affects the transport properties of imide ionic liquids. Here we show how the combination of experimental and theoretical techniques can disentangle such confounding variables.

Trimeric M₃(CO)₁₂ (M = Ru, Os) reacts with typical inorganic oxidants to unwanted side products. Yet, the 9,10-dichlorooctafluoroanthracene radical cation deelectronates these under CO pressure to give the first homotrimetallic [M₃(CO)₁₄]²⁺ salts.

The design of (1) Möbius aromatic interlocked boron wheel Mn₂B₁₀H₁₀, (2) Hückel aromatic boron analogs of naphthalene (M₂@B₁₀H₈; M = Mn and Fe), and (3) metal boride monolayers (FeB₅ and Fe₂B₅), creating a molecules to materials continuum.

The reactivity, stereo-, and chemoselectivity of a tripeptide are so high that it catalyzes conjugate addition reactions with high stereoselectivity in complex compound mixtures—even in cell lysates.

Extended polymeric structures based on redox-active species are of great interest in emerging technologies related to energy conversion and storage.

Na-^IVAl-DMSN acts as both antigen carriers and modulators to “hyperactivate” dendritic cells (DCs) via potassium (K⁺) efflux dependent pyroptosis, eventually leading to enhanced adaptive and innate immunity.

A heterodinuclear Al(III)/K(I) organometallic ring-opening copolymerization catalyst shows exceptional rates, end-group selectivity and good loading tolerance to deliver monodisperse polyesters with molar masses up to 91 kg mol⁻¹.

The synthesis, structures and electronic properties of the first four heteroanionic compounds containing both hydride and transition oxometalate ions are reported.

We reported a new method capable of adjusting the lattice structure of solid surfaces with sub-angstrom precision and achieved in situ and continuous control over electrochemical activity.

The divalent thulium complex [Tm(Cp^ttt)₂] activates CO to form reductive CO dimerization or trimerization products. These complexes further react with electrophiles, including CO₂, yielding multicarbon oxygenates and original C–H activation products.

Dynamic dimerization of GOx-loaded microcapsules with β-gal//hemin/G-quadruplex-bridged T₁/T₂-loaded microcapsules guides the bi-directional intercommunication of the three catalysts cascade.

Using a collection of natural and unnatural amino acids, we synthesized a set of fluorescent activity-based probes for the fast, direct, and simultaneous detection of coagulation factors in human plasma.

We report a programmable strategy to construct multi-alignment media via peptide self-assembly for the measurement of independent sets of residual dipolar couplings (RDCs).

The electronic states of Ag nanoclusters were reversibly controlled driven by protonation/deprotonation of polyoxometalate ligands.

A dual-level kinetic control was exploited to fabricate a family of atomically precise silver nanoclusters.

Stannoles are introduced as a new, spontaneously aromatizing diene for [4 + 2] cycloadditions that can be easily introduced into diverse conjugated systems, facilitating the efficient synthesis of complex PAHs and their π-extension.

In ruthenium catalysts for olefin metathesis, carbene ligands of high trans influence/effect suppress decomposition via β-H elimination, but increase susceptibility to bimolecular decomposition.

Benchmarked van der Waals density functional theory calculations are used to create a force-field to describe biomolecule interactions at the aqueous MoS₂ interface, which can recover interfacial biomolecule adsorption with high structural fidelity.

We demonstrate the facile synthesis and characterization of stereoregular polysaccharides from the biomass-derived platform molecule levoglucosan via metal-triflate mediated cationic-ring opening polymerization.

We present a data-driven approach combining deep learning-enabled active learning with coarse-grained simulations and alchemical free energy calculations to discover small molecules to selectively permeate cardiolipin membranes.

Low valent cations of tin and lead were used to form hydridotetrylene coordination compounds. The mobility of the hydrogen substituent was investigated in deprotonation equilibria as well as in 1,2-H-shift reactions.

We report the alternating copolymerization of caprolactone and epoxide through the in situ formation of pre-sequenced spiroorthoester monomer.

PIGNet, a deep neural network-based drug–target interaction model guided by physics and extensive data augmentation, shows significantly improved generalization ability and model performance.

Starting with potassium acyltrifluoroborates (KATs), N-unprotected chiral α-aminoboronic acids are prepared in three simple steps without chromatography. This facile methodology will tap the broad potential of these valuable compounds.

An unprecedented strategy was proposed for recycled interfacial biocatalysis in a CO₂-responsive emulsion stabilized by soft protein particles. The recycled enzyme maintained its catalytic activity, with a conversion yield over 90% after 30 cycles.

A chemical system comprising a series of chiral acids of differing pK_a, a metal, and a conformationally labile chromophore responds to pH with a CD spectrum that reports the absolute stereochemistry of the most basic anion in the mixture.

In the presence of the bulky monophosphine P^tBu₃, palladium usually prefers to react with Ar–Cl over Ar–OTf bonds. However, strongly coordinating solvents can bind to palladium, inducing a reversal of selectivity.

Crystal structure prediction suggests that the low-energy polymorphs of ROY have already been found, but a new high-pressure form is predicted.

Two barbiturate dyes with regioisomeric thiophene-cored twisted π-systems show strongly enhanced emission through supramolecular polymerization. The supramolecular polymers thus formed exhibit distinct emission colors and degree of agglomeration.