Themed collection 2022 Chemical Science HOT Article 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.

The reflection (or ‘mirror’) symmetry of space is among the fundamental symmetries of physics. It is connected to the conservation law for the quantum number purity and its violation and has a fundamental relation to stereochemistry and molecular chirality.

This Perspective summarizes progress in the development of O₂-selective metal–organic frameworks for adsorptive air separations and identifies key metrics and design considerations toward optimizing material performance for practical applications.

Recent important advances in the synthesis of allenes via radical strategies are highlighted.

The proof is in the π: when more than one π-donor ligand is bound to a group 5 metal center, imido-based reactivity increases.

The molecular mechanisms of amyloid formation have been studied extensively in test tube reactions. This perspective article addresses the question to what extent these mechanisms apply to the complex situation in living cells and organisms.

Internal electrostatic field effects are poised to play a major role in the design of molecular coordination complexes and catalysts.

IRED-catalyzed reductive aminations have progressed from mg to ton scale, through advances in enzyme discovery, protein engineering and process biocatalysis.

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.

Mesoporous ordered films, from self-assembly to advanced applications.

A flurry of reports for preparing, functionalizing, and using bicyclo[1.1.0]butanes (BCBs) have positioned them to be powerful synthons with numerous applications. This review discusses the recent developments regarding this strained carbocycle.

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.

Femtosecond X-ray liquidography using X-ray free-electron lasers (XFELs) visualizes various aspects of reaction dynamics.

Sigma–hole mediated detection of anions is rapidly emerging as a new paradigm in supramolecular sensor chemistry. Herein, we provide an overview of this field including halogen bonding and chalcogen bonding optical, electrochemical and other sensors.

The recent progress of superhydrophilic/phobic electrodes, superaerophilic/phobic electrodes, superwettable patterned electrodes, Janus wettability electrodes and wettability switchable electrodes in electrochemical biosensing is reviewed.

The combination of electrochemiluminescence and semiconductor gives rise to a rich field at the interface of photoelectrochemistry, materials and analytical chemistry. It offers interesting possibilities for ultrasensitive (bio)detection, imaging and light conversion.

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 development of RNA imaging strategies in live cells is essential to improve our understanding of their role in various cellular functions.

Uranium(IV) alkyl cations have been prepared, and arene solvent coordination was shown to have a major impact on ethylene polymerization activity. Actinide-arene binding was studied experimentally in the solid state and solution, and computationally.

Activity-stability relations of multinary oxide photoanodes for solar water splitting were measured using an automated flow cell coupled to an ICP-MS and successively visualized with the help of data science tools like principal component analysis.

Chemoselective hydrogenation of CC, CO and CN bonds in α,β-unsaturated ketones, aldehydes and imines is accomplished at room temperature (27 °C) using a well-defined Mn(I) catalyst and 5.0 bar H₂.

A database of thousands of experimentally-derived or combinatorially enriched organocatalysts and fragments to navigate chemical space and optimize reaction properties.

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⁻.

A hydrogen atom coupled with electron transfer (H_adCET) mechanism is proposed for electrocatalytic NAD⁺ reduction on metal electrodes (Cu, Fe and Co), in contrast to the NAD˙ radical pathway on carbon electrodes.

A chemically robust single crystalline hollow MOF-801 containing Pt and Au nanoparticles was constructed by using UiO-66 as a sacrificial template for size selective catalysis with fast reaction kinetics under harsh chemical conditions.

A full palette of FQY (form ca. 0 to 98%) was covered by exchanging two groups in a series of nine compounds. The darkest (OMe/CF₃) and brightest (CF₃/OMe) are isomers. All experimental data are supported by TD-DFT calculations.

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.

An enantioselective dearomative cyclopropanation of naphthalenes has been developed, which constructed a range of tetracyclic compounds bearing multichiral centers in high enantioselectivity.

Polyacrylamide (PAM) was utilized to switch the crystallization pathway of TS-1 zeolite from classical to non-classical by virtue of the specific interaction between PAM and Si/Ti species, thus accelerating nucleation and enriching active sites.

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

Coupling the tunability of molecular catalysts and copper nanocatalysts opens up new possibilities towards the development of Cu-based catalysts with enhanced selectivity for multi-carbon product generation at low overpotential.

We designed a vinyl-boronic-acid protected by anthranilamide as a “transformable” monomer in radical polymerization to synthesize conventionally inaccessible copolymers, such as poly(vinyl alcohol-co-styrene) and poly(ethylene-co-acrylate).

A model for S_NAr reactivity is reported, built from relative rate data obtained by competition studies. Based only on molecular descriptors of the electrophile, the model predicts relative reactivity and site selectivity for many complex substrates.

The iconic cyclopentadienyliron dicarbonyl dimer ([CpFe(CO)₂]₂ or Fp₂) catalyzes phosphinidene group transfer from anthracene to activated alkenes, forming new phosphiranes diastereoselectively and with good isolated yields.

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.

We developed a workflow to identify and apply GFPxm163 as a new green fluorescent protein-based sensor for chloride.

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

A new chemiluminescence neuraminidase probe enables rapid screening of small molecules that inhibit viral replication, directly in influenza A-infected mammalian cells.

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.

Light is magic! The combination of Grubbs second generation catalyst, a well-known catalyst for E-selective olefin metathesis, with a photosensitizer enables efficient access to the contra-thermodynamic Z-isomers.

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.

A new route to provide alkoxysulfonyl radical species via electrochemical anodic oxidation of inorganic sulfites with alcohols is developed, affording sulfonate esters by subsequent alkene difunctionalization with these alkoxysulfonyl radicals.

We report here a triply interlocked cage with the ability to encapsulate planar guests in aqueous medium. This property was then employed to efficiently separate planar and non-planar aromatic hydrocarbons by aqueous extraction.

Diamine-appended metal–organic frameworks can be optimized as adsorbents for pressure-swing purification of crude natural gas. A cooperative CO₂ binding mechanism enables high CO₂ swing capacities and enhanced performance under humid conditions.

Here we describe the first examples of a new class of disulfide bridging reagents, designed to insert a ‘stable-labile’ linkage; which can then be exploited to generate dual functional antibody fragment conjugates.

BatteryDataExtractor is the first property-specific text-mining tool for auto-generating databases of materials and their property, device, and associated characteristics. The software has been constructed by embedding the BatteryBERT model.

We report for the first-time intramolecular singlet fission (SF) in the naphthalenediimide (NDI) scaffold constrained in a cyclophane architecture, while individually the NDI units does not satisfy the requisite energy criterion for SF.

The synthesis of red-shifted azobenzenes functionalised with heavy chalcogen and halogen substituents is reported, enabling photo-switching with red and near IR light and Z → E thermal isomerization rates spanning seven orders of magnitude.

Fully oxygen-tolerant photoinduced atom transfer radical polymerization (photo-ATRP) allowed the synthesis of well-defined polymers using a Cu catalyst and eosin Y at ppm levels in both aqueous and organic media.

Taking advantage of high penetration and reduced light scattering of NIR wavelengths, we demonstrate the syntheses of polymeric nanoparticles with consistent morphologies through thick barriers.

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.

Rules for designing 4-helix bundles are defined, tested, and used to generate de novo peptide assemblies and a single-chain protein.

A non-flammable, dilute, and hydrous organic electrolyte can homogenize Zn plating/stripping, suppress water decomposition, and form organic–inorganic hybrid interphase on Zn, thus contributing to highly reversible Zn metal batteries.

Mechanoresponsive diselenide-crosslinked microgels undergo controlled ultrasound-triggered degradation and can be used for protein delivery due to their dual protection properties acting as radical scavengers and conformation stabilizers.

A combined SOMC and DFT studies on the Union Carbide catalyst enable to propose that Cr(III)-H, formed at high-loading, are active in ethylene polymerization. We therefore design a well-defined supported CpCr(III)-R ethylene polymerization catalyst.

Both atomic geometry and the influence of surroundings (e.g., exogenously coordinated water) are key issues for determining the chemical environment of oxide surfaces, whereas the latter is usually ignored and should be considered in future studies.

A cyclization strategy of 2-nitroarylethanols under blue-light irradiation was developed, which is triggered by a photoexcited nitro-induced double hydrogen atom abstraction (d-HAA) process, delivering indoles, N–OH oxindoles and N–H oxindoles.

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

A new promising IR-NLO material SrCdSiS₄ with a 2D layered structure has been designed via a dual-site isovalent substitution strategy. Remarkably, it is the first report on an alkaline-earth metal-based IR-NLO material that breaks through the wall of E_g > 3.5 eV and d_eff > 1 × AgGaS₂.

The Ag⁺ cations oxidize and promote the activity of Rh-intermediates in the coupling of 2-aminopyridine and alkyne to form 7-azaindole.

A replication network of minimal nucleobase sequences is built from simple biological components. The network shows collective adaptability to changes in the environment, while disulfide exchange wires different auto- and cross-catalytic pathways.

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.

Combinatorial detergent synthesis permits access to an unexplored part of the detergentome and provides new directions for the preparation of custom-made detergents for future applications.

The iron-catalysed C(sp²)–H bond H/D exchange reaction using CD₃OD is reported for both heterocycles and alkenes. Characterisation of the key C–H metallation intermediates provided evidence for reversible protonation of the iron hydride catalyst.

Chiral gold nano-bipyramids (GBPs) with sea cucumber-like morphology and an optical anisotropy factor of 0.102 at 573 nm are reported, and used in the fight against bacterial infection both in vitro and in vivo.

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.

Flavanthrene derivatives can be designed into highly efficient and photostable singlet fission materials, owning to the N-doped two-dimensional angular fused acene framework, which is promising for photo energy conversion applications.