Themed collection 2021 Chemical Science HOT Article Collection

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.

We evaluate the improvements over the past two decades in intrinsic activity of electrocatalysts for sustainable energy conversion, and highlight opportunities from tuning the electrolyte.

Solid-state NMR (ssNMR) is a versatile technique that can be used for the characterization of various materials, ranging from small molecules to biological samples, including membrane proteins, as reviewed here.

A review of the physicochemical properties of single-ion conducting polymer electrolytes is presented. The standard characterization method, remarkable electrochemical properties and perspectives are further highlighted.

Short aliphatic groups are prevalent in bioactive small molecules and play an essential role in regulating physicochemistry and molecular recognition phenomena.

HNO (nitroxyl, azanone), joined the ‘biologically relevant reactive nitrogen species’ family in the 2000s.

The impending implementation of billions of Internet of Things and wireless sensor network devices has the potential to be the next digital revolution, if energy consumption and sustainability constraints can be overcome.

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.

Electrochemical CO₂ reduction reaction (CO₂RR) is a promising way to remove CO₂ and convert it into useful industrial products. Single-atom site catalysts provide opportunities to regulate the active sites of CO₂RR catalysts at the atomic level.

Diverse templating materials and assembly strategies can be used to induce collective optical activity on achiral plasmonic building blocks. We present the advances, applications, challenges, and prospects of plasmonic–excitonic hybrids.

For more than a century, the dehydrogenative formation of N–N bonds has remained mostly confidential. Several cross-dehydrogenative N–N coupling methods have appeared recently, promising a soon to come broad applicability of the concept.

State-of-the-art tendency, present critical issues and future opportunities of anode active materials in potassium ion batteries are systematically summarized.

The electrochemical carbon dioxide reduction reaction (CO₂RR) offers a promising solution to mitigate carbon emission and at the same time generate valuable carbonaceous chemicals/fuels.

“Solvent effects” at interfaces in heterogeneous catalysts are described by transition state theory treatments that identify kinetic regimes associated with molecular clustering and the solvation of such clusters by extended molecular networks.

SACs can be efficiently used to load biologics such as proteins, CRISPR–Cas9, DNA and RNA and release them on-demand.

An exceptionally strong ferrocene-containing, cationic boratriptycene-type Lewis acid is stabilized by a weak Fe⋯B through-space interaction.

We introduce highly affine epitope-imprinted polymer-based microarrays for selective protein detection by surface plasmon resonance imaging as shown through the selective recognition of the receptor binding domain of SARS-CoV-2 spike protein.

The first observed luminescence emission spectra of Pr(IV) complexes are assigned to a ligand-based emission. Binding of the triphenylsiloxide ligand to the Pr(IV) ion leads to an unprecedented large red shift of its triplet state.

Following the seminal theoretical work on the pleated β-sheet published by Pauling and Corey in 1951, the rippled β-sheet was hypothesized by the same authors in 1953.

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

In the self-assembly of crystalline-coil block copolymers in solution, heating followed by different cooling rates can lead to different structures.

An efficient and versatile approach for the late-stage generation of oligonucleotide conjugates by diselenide-selenoester ligation (DSL)–deselenization/alkylation was developed.

A new strategy to design atomically precise multivariate metal–organic frameworks is presented. This is achieved by linking two preformed metal–organic cages via a precisely tuned Rh–aniline interaction.

An extended, multivalent DNA nanotweezer that undergoes large-scale molecular motion upon protein recognition is presented. Our method based on “printing-elongation-folding” combines the DNA-minimal aspect of DNA tile-based assembly, with complexity of DNA origami.

Hybrid poly(N-isopropylacrylamide)-based microgels are templated from inverse Pickering emulsions, and the tunable wettability renders as-prepared emulsions with reversible feature.

We report a general method for the preparation of enantiomerically enriched secondary alkylmagnesium reagents, which undergo highly stereoselective transition-metal free electrophilic aminations, leading to α-chiral amines in up to 97% ee.

Active-material solubility is critical in determining NRFB energy density, yet a predictive model accounting for solid-state cohesion energy has remained elusive. Herein we present such, based on an empirically calibrated computational framework.

Ir-catalyzed asymmetric double AAA reaction of cyanoacetate was developed, affording cyanoacetate derivatives in high yield with excellent stereocontrol. Notably, quasi-DKR is involved in the sequential protocol with two distinct allylic carbonates.

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.

Single-molecule circuits using silicon contacts are robust, conductive, controllable, and highly reproducible in blinking experiments, with enhanced conductance in break-junctions owing to residual dangling bonds.

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.

The heterobimetallic actinide nitride [(NR₂)₃U^V(μ-N)Th^IV(NR₂)₃] (R = SiMe₃) has an m_J = 5/2 ground state and its highest energy 5f excited state is primarily 5f-N_nitride σ-antibonding in character.

A robust Pd/NHC ligand synergistic strategy that enables the exquisite regioselective and chemodivergent C–F bond functionalization of gem-difluorocyclopropanes with simple ketones, is reported.

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.

Coordination geometry and Lewis acidity of Ga and Al (bulk and surface) sites in mixed oxide gallia–alumina nanoparticles is correlated with the performance in propane dehydrogenation.

This study demonstrates the viability of the thiolate/disulfide redox couple in AZIB applications, and provides an in-depth study on the electrochemical mechanism of Zn-thiolates electrode materials.

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.

We have achieved the selective monitoring of H₂O₂ fluctuation in vivo free from O₂ interference by a single-atom Cu–N₂ electrocatalyst.

A chemical-vapor deposition-like strategy was developed for the synthesis of versatile core–shell transition metal sulfide (TMS)@carbon heterostructured nanowires for electrochemical sodium ion storage.

Enhancement by displacement. A single methyl group displaces a water molecule from the binding site of FKBPs, resulting in the most potent binders known, outperforming the natural products FK506 and rapamycin in biochemical and cellular assays.

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 coupled electron transfer (ET) and ion transport (IT) processes in conductive nanopipettes, at both steady and transient states, are elucidated and quantified by experiments and simulation.

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.

Reaction dynamics simulations on a high-level ab initio analytical potential energy surface reveal a novel oxide ion substitution channel for the OH⁻ + CH₃F reaction.

With changing pH four different structural regions in Ga³⁺ aqueous solutions are observed. In contrast the effects of different anions and concentrations are minimal.

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.

Bixbyite-like In₁₂-oxo clusters with labile coordination sites show tunable solubility, varying film quality and distinct lithography patterning performance.

This article provides a lifeline for those lost in the sea of the molecular machine learning potentials by providing a balanced overview and evaluation of popular potentials.

A molecular dynamometer is designed to analyze the variation of sub-piconewton interaction between a specific protein and the membrane on living cells.

Reversible formation of covalent adducts between a thiol and a membrane-anchored Michael acceptor has been used to control the activation of a caged enzyme encapsulated inside vesicles.

A 9H-indeno[1,2-b]pyrazine-2,3-dicarbonitrile (IPC) moiety in asymmetric non-fullerene acceptors promotes the formation of a densely packed crystalline structure, enabling efficient and long-term stable organic solar cells.

Nickel complexes with a dppf ligand can form inactive dinickel(II) complexes during Suzuki–Miyaura cross-coupling reactions. However, these complexes can react with Grignard reagents in Kumada–Tamao–Corriu cross-coupling reactions.

A constant-potential first-principles and microkinetic model is developed to uncover the nature of heterogeneous Ni–N–C catalysts. It highlights the crucial role of a pyrrolic-type NiN₄ moiety in electrochemical CO₂ reduction.

A practical and stable heterogeneous copper catalyst has been developed for dehalogenative deuteration via water–gas shift reaction at low temperature, allowing deuteration of diverse (hetero)aryl halides with good functional group tolerance.

Metal- and photocatalyst-free reductive Heck cyclization of indoles under light irradiation was developed and used to prepare polycyclic compounds and functionalize natural product analogues in moderate to good yields.

RAFT aqueous dispersion polymerization of 4-hydroxybutyl acrylate (HBA) affords shape-shifting thermoresponsive diblock copolymer nano-objects. ¹H NMR studies suggest that such behavior involves uniform plasticization of the PHBA block.

Rh(II)-catalyzed asymmetric cycloisomerization of azaenyne through a cap-tether synergistic modulation strategy was described. Diverse centrally and axially chiral isoindazoles were prepared and directed C–H late-stage modifications were developed.

An unexpected reactivity between a titanium imido complex and internal alkynes was unveiled yielding titanaazacyclobutenes instead of the expected [2 + 2] cycloaddition products.

A change in the sign of the ground state electron spin polarization (ESP) is reported in complexes where an organic radical (nitronylnitroxide, NN) is covalently attached to a donor–acceptor chromophore via two different meta-phenylene bridges.

DeepLigBuilder, a novel deep generative model for structure-based de novo drug design, directly generates 3D structures of drug-like compounds in the target binding site.

The main protease (M^pro) of SARS-CoV-2 is central to viral maturation and is a promising drug target. In silico methods reveal structural aspects of how it binds to its 11 natural cleavage sites, the design of novel peptide inhibitors, and insights into drug design.

A novel pillar[5]arene-derived (P5) COF was rationally designed and synthesized, which exhibited superior performance in selective gas adsorption and paraquat binding.

A peptoid-based modular approach using oligo(N-substituted alanine) as a reprogrammable template enables independent optimization of N-substituents and facile development of cell-permeable inhibitors of protein–protein interactions.

Protein–ligand binding interactions are characterized by the para-H₂ based hyperpolarization technique SABRE and flow-NMR. Binding to the protein is identified by R₂ change of a ligand first interacting with the Ir polarization transfer catalyst.

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.

Albumin-targeting of a maleimide-containing oxaliplatin-releasing platinum(IV) prodrug results in tumor-specific drug delivery and activity as shown by LA-ICP-MS, isotope-labeling and NanoSIMS in cell culture and in vivo.

A pair of room-temperature-stable Mn^III–alkylperoxo complexes were characterized and shown to oxidize PPh₃. Thermal decomposition studies provide evidence of both homolysis and heterolysis of the Mn^III–alkylperoxo O–O bond.

Carbon dioxide-based multiblock polymers are synthesised, in one-pot, from a mixture of monomers using a highly selective and active heterodinuclear Co(II)Mg(II) catalyst.