Like candles on a Christmas tree describes the arrangement of the spins in the Co-Kagome nets of Sn₂Co₃S₂. Giant anomalous Hall effects are now related to its electronic finger print of a Weyl semimetal.

Aero smiths: Carbon aerogels exhibit many fascinating physical properties and great application potentials in widespread fields. This Review covers recent advances in synthetic strategies, physical properties, and multifunctional applications of two emerging carbon-nanofiber aerogels derived from chemosynthesis and biosynthesis approaches in a comparative perspective.

A HAT trick: The generation of highly reactive chlorine atoms through photoredox mediated reductive quenching of *[Ir(dF(CF₃)ppy)₂(dtbbpy)]⁺ with chloride is reported. The C−H functionalization of a variety of alkanes, alcohols, ethers, ester, amides, aldehydes, and silanes through hydrogen atom transfer (HAT) processes with chlorine atoms underwent efficient redox-neutral coupling reactions with activated alkenes.

Under pressure: Distinct luminescent responses to anisotropic grinding and isotropic compression are found for a donor–acceptor cocrystal, called CT-R. It shows a unique enhanced hypochromatic shift emission under grinding, but a remarkable bathochromic-shift emission under hydrostatic pressure.

Single extracellular vesicle (EV) flow cytometry analysis enabled by target-initiated engineering (TIE) of DNA nanostructures reveals unique molecular signatures of individual vesicles and differentiates EV sub-populations.

Memorable switching: A mixed monolayer comprising cross- and linearly conjugated molecules exhibited high conductance. When the linearly conjugated species were reversibly oxidized back to cross-conjugated species, destructive quantum interference was restored, and the conductance dropped, causing a memory effect (see picture).

Detecting bacteria: Headspace SERS allows selective detection of dimethyl disulfide above bacterial cultures. This volatile metabolic product can act as a marker for live bacterial cultures.

Metal-free activation of homoatomic E−E σ bonds (E=P, B) in white phosphorus (P₄) and bis(catecholato)diboron (B₂cat₂) with a 1,2-diboraallene is reported. The former affords B_nP₄ cages (n=2, 4), whereas the latter leads to the formation of a tetraborane featuring a B₄ chain through homonuclear catenation.

Monomer-like aggregates: Null exciton coupling in an ideal Greek cross-dipole (+) assembly affords monomer-like optical properties and an exceptional charge-filtering (selective hole transport) effect in orthogonal chromophore stacks.

SPiDER and the fly: A new fluorogenic β-galactosidase substrate, SPiDER-Red-βGal, based on a silicon rhodol scaffold and a carboxylic group as the intramolecular nucleophile, exhibited simultaneous activation of red fluorescence and labeling ability for intracellular proteins via a quinone methide intermediate. The probe can label lacZ-positive cells at single-cell resolution in vivo with perfect orthogonality to green fluorescent protein (GFP) markers.

Airy architecture: A new concept for the fabrication of nanostructures featuring 3D ordered, non-close-packed hollow sphere arrays is demonstrated through controlling dynamic changes in interfacial properties between template and precursor. The polymeric colloidal crystal provides defined confinement through its tetrahedral and octahedral voids where the arrays are formed as a result of a crystallization-induced rearrangement.

Phosphoaspartate modifications: A desthiobiotin-containing hydroxylamine (DBHA) chemical probe covalently labels modified aspartic acid residues in native proteomes. Coupled with isotopic labelling, DBHA-dependent proteomic profiling enables global quantification of changes in phosphoaspartate modification levels and protein levels.

Carbones contain C atoms possessing two lone pairs of electrons. Thus, along with σ-coordination to a metal ion, they have a further pair of electrons, rendering them capable of π-donation or geminal coordination to a second metal. Via formation of a [Fe(1)₂]ⁿ⁺ (n=2–5) redox series, where 1 is a tridentate carbodicarbene ligand, it is shown that this second pair of electrons also allows them to be redox-active.

Mirror, mirror: Chiral recognition of DNA plays crucial roles in many DNA-relevant events. The binding of ten pairs of iron helical metallohelices to enantiomeric G-quadruplex DNA was screened. The results clearly show mirror-image dependence for the Δ- and Λ-enantiomers binding to d- and l-DNA, respectively.

Mussel glue protein mimics: Adhesive mussel-inspired protein analogues were prepared by an enzyme-induced polymerization of oligopeptides. The polymers are generated by the formation of cysteinyldopa linkages that contribute to cohesion and adhesion of the protein analogues. Aspects of adhesion properties of mussel foot proteins were mimicked without the need to extract and purify or express native proteins.

PISA studies: A method to predict monomers suitable for use in polymerization-induced self-assembly (PISA) calculates the dependence of LogP_oct/surface area on the length of the growing polymer chain. Five new monomers for use in aqueous PISA via RAFT polymerization were identified.

Tip of the iceberg: Tip-enhanced Raman spectroscopy reveals the inclusion of phosphatidylinositol (PIP₂) phospholipid in tubulin-associated unit (Tau) filaments and provides an insight into protein secondary structure with nanoscale spatial resolution. Tau/phospholipid aggregates are implicated in deleterious mechanisms on neural membranes in Alzheimer's disease.

Bulk silicon can be nanostructured in a comparatively low-energy and environmentally benign approach of electrochemical Mg alloying/dealloying in molten salts at moderate temperatures. For lithium storage, the nanostructured Si exhibits a combination of high initial Coulombic efficiency, high specific capacity, and long cycling stability.

Trigger happy: The direct electrochemical oxidation of triarylamines at anodes triggers their nucleation and growth into supramolecular polymers. This mechanism can be defined as a supramolecular electropolymerization process. It is used to grow and precisely address single nanowires over a distance of 50 μm between two electrodes in a direct current electric field.

Molecular model kit: A large variety of silica-based colloidal molecules, including chiral ones, has been created through the covalent assembly of site-specifically functionalized patchy nanoparticles with complementary nanospheres.

A facile bottom-up method was developed to synthesize patterned gradient polymer brushes with precisely controlled grafting density and gradient architecture. Both terraced and smooth gradient brushes were synthesized with tunable gradient slopes.

L-Shaped: A new concept for the meta borylation of aromatic amides is described. It has been shown that while esters give para borylations, amides result in meta borylations. For achieving high meta selectivity, an L-shaped ligand is used and engages in an O⋅⋅⋅K noncovalent interaction with the moderately distorted amide carbonyl group, providing exceptional control for meta C−H activation/borylation.

Unprecedented social self-sorting occurs during the reaction of Ag₂O with two trisimidazolium salts featuring either an electron-poor H₃-A1(BF₄)₃ or an electron-rich H₃-D1(BF₄)₃ backbone to give the heteroligand assembly [Ag₃(A1)(D1)](BF₄)₃ most likely driven by π⋅⋅⋅π stacking interactions between the electron-rich and electron-poor ligand backbone groups.

Soft robot: An unprecedented photoresponsive hydrogel actuator enables earthworm-like peristaltic crawling and reverses its direction by scanning with a laser spotlight. This anomalous optical control was made possible by a rapid, large, repeatable, spatiotemporal, and anisotropic photothermal deformation of a hydrogel that contains gold nanoparticles in titanate nanosheets.

Giant ionic cluster: The utilization of highly negative polyoxometalates for the clustering of alkali metal cations has allowed the synthesis of a rare all-inorganic ionic porous material built from novel giant ionic clusters {K₄₂Ge₈W₇₂O₂₇₂(H₂O)₆₀} (K₄₂W₇₂), which exhibits high proton conductivity. The K₄₂W₇₂ not only is among the largest ionic clusters but also contains unprecedented core–shell K₆@K₃₆-H₂O cage.

A turn-on theranostics agent was developed by utilizing the in situ reaction of Cu₂O (see picture: brown) and endogenous H₂S (yellow) at colon tumor sites. Based on in vitro and in vivo experiments, excellent photoacoustic imaging and photothermal therapy were both confirmed after being triggered by this in situ reaction. Cu₉S₈ shown in green.

An efficient and practical phosphine-catalyzed vicinal difunctionalization of β-fluoroalkyl α,β-enones with TMSN₃ has been developed. Meanwhile, the asymmetry variant induced by the nucleophilic bifunctional phosphine P4 led to various chiral fluoroalkylated β-amino α-diazocarbonyl compounds in high yields and enantioselectivity.

Peroxide allowed: The development of hydrogen fuel cells is greatly hindered by the unwanted generation of H₂O₂ at the cathode. A non-Pt cathode catalyst is now shown to be capable of simultaneously reducing both O₂ and H₂O₂, thus rendering H₂O₂ a useful part of the feed stream. The applicability of this unique catalyst is demonstrated by employing it in a fuel cell running on H₂/CO and O₂/H₂O₂.

Side-by-side assembly: Supramolecular scaffold-templated side-by-side assembly of gold nanorods (GNRs) has been demonstrated by utilizing the sulfonate-containing alkynylplatinum(II) terpyridine complexes. Driven by non-covalent and directional Pt⋅⋅⋅Pt and π–π stacking interactions, the complexes show a high propensity to assemble in water with the plausible head-to-tail stacking arrangement to construct supramolecular scaffolds.

Inorganic versus organic: the molecular structures and Lewis basicities of triphenylphosphine and tris(2-borazinyl)phosphine appear similar but their hydrolysis and oxygenation chemistry could hardly be more contrasting.

A simple and straightforward method is shown to grow a closely packed and porous CN layer directly on a conductive substrate as a photoanode, and it has excellent photoelectrochemical activity. The CN photoanode exhibits an exceptionally low onset potential, a high photocurrent density, an external quantum efficiency of 8.5 % at 400 nm, and good stability over a wide pH range.

It'll be fixed in a Mo: N₂-into-NH₃ conversion is one of the most important processes in the chemical industry. A set of molybdenum on solid support materials catalyse N₂ fixation under just atmospheric pressure and only 400 °C. They allow for an in-depth elucidation of the mechanistic events taking place which is supported by DFT analysis.

Thin films containing segregated layers of digitally encoded polymers were prepared and characterized. An ASCII-encoded sentence of 160 bytes was stored in these films using a library of 16 different digital polyanions. The results show that abiotic coded matter can be organized in precise nanoscale morphologies.

The noncovalent sulfur⋅⋅⋅sulfur interaction in the dimethyl sulfide–SO₂ adduct has been investigated by combining rotational spectroscopy in supersonic expansion and quantum-chemical calculations and the first accurate semi-experimental equilibrium structure of this intermolecular adduct has been determined. A marked charge transfer takes place in the complex, whose stabilization energy thus is mainly determined by electrostatics and not by dispersion.

A one-pot strategy for the diversity-oriented construction of multicavity-containing supermacrocycles and their interconversion has been developed. With large cavities and multiple electron-deficient triazines, these supermacrocycles can accommodate large organic anions through unprecedented multiple anion–π interactions.

Rattling the cage: A UV-initiated thiol-ene reaction enables photoactivation-mediated decaging of isobutylene-caged thiols. With this strategy, the activity of the histone deacetylase inhibitor largazole can be switched off when stapled, but selectively switched on within cancer cells when irradiated with non-phototoxic light.

Terminal functionalization: Tetrapeptide grafting polyisoprenes were prepared with different sequences of polar groups. The terminal polar block promoted the toughness and stain-induced crystallization behavior of thermoplastic polyisoprene; these properties were comparable to vulcanized natural rubber.

Out of the clear blue: The title reaction was developed for preparing α-alkylated non-natural α-amino acids by transformation of glycine moieties. Mild conditions and good functional-group tolerance allow the modification of peptides using this method. Mechanistic studies revealed that a radical–radical coupling pathway is involved in the reaction.

Coming to light: Report herein is a highly regioselective, intermolecular, nickel-catalyzed photoredox allylic substitution that expands both the radical and electrophile scope of dual photoredox/Ni-catalyzed reactions. Quantum mechanical calculations shed light on the mechanistic pathway, supporting a Ni⁰ to Ni^II oxidative addition followed by an inner-sphere radical addition. PC=photocatalyst, RP=radical precursor.

One for many: A chemobiocatalytic strategy involving myoglobin-catalyzed olefin cyclopropanation in the presence of ex situ generated diazoacetonitrile enables the efficient synthesis of a broad range of nitrile-substituted cyclopropanes with high diastereo- and enantioselectivity. The enzymatic product could be further elaborated to afford a variety of functionalized chiral cyclopropanes.

Keep it basic: 2-Azaallyls anions and [1.1.1]propellane react at ambient temperature to forge a C−C bond. This operationally simple, atom-economical process gives access to new bicyclo[1.1.1]pentyl-substituted benzylamines.

Going axial: A catalytic and enantioselective dehydro-Diels–Alder (DDA) reaction is described. Consecutive thermal and chiral-rhodium-catalyzed intramolecular reactions of sulfur-tethered tetraynes, with a 1,3-diyne moiety, proceeded to give doubly cyclized products, where axial chirality was achieved for the resulting dibenzothiophenyl moieties. This is a new strategy for the generation of axial chirality along with the formation of benzene rings.

Family traits: The divergolides are a structurally disparate family of antibiotics that are synthesized by endophytes and isolated from mangroves off the Chinese coast. Reported here are the first syntheses of two members of the family that contain a bridged bicyclic acetal core. This unit was accessed by a telescoped sequence employing an asymmetric hetero-Diels–Alder reaction for fragment coupling and an oxidative carbon–hydrogen bond cleavage to enable acetal formation.

Bulking up: The bulky aryl group (Ar_L) of unsymmetrical diaryliodonium salts was exclusively incorporated at the α-position of unactivated terminal alkenes in a palladium-catalyzed intermolecular arylcarbonylation reaction (see scheme). The reaction occurs under very mild conditions and features excellent chemo- and regioselectivity and high functional-group tolerance.

Various unprotected carboxylic acids undergo enantioselective aldol reactions in the presence of a chiral phosphine oxide as a Lewis base catalyst. The carboxylic acids were activated with silicon tetrachloride to form the bis(trichlorosilyl)enediolates in situ, which subsequently underwent an aldol reaction with an aldehyde or a ketone to produce β-hydroxycarboxylic acids in high enantioselectivities of up to 92 % ee.

All in a twist: π-Conjugated macrocycles possessing a quadruply twisted topology were realized by conformational fixation using the insertion of a 1,4-phenylene bridge and Pd^II metalation. The syn-isomer of bis-Pd^II complexes displays aromatic character, and is thus identified as the first example of quadruply twisted Hückel aromatic molecule.

The missing link: Fungal chimeric diterpene synthases with prenyltransferase and terpene synthase domains fall into two clades (I+II) with six subclades (A–F). The present study reports the characterization of the first clade II-D enzyme, the structures of its products, and the cyclization mechanism. The observed 12R configuration reveals a uniform stereochemistry at this carbon for all clade II enzyme products.

New cat. on the block: C−H amination can be conveniently accomplished within a unique Br(−I/I) catalyst system, which opens versatile access to the synthesis of alkaloid building blocks.

Connect bor: Sterically unencumbered diborenes based on a benzylphosphine chelate undergo diboration reactions with bis(catecholato)diboron in the absence of a catalyst to yield tetraboranes.

The one and only: Nitrogen-atom transfer from the cluster ion to methane was observed as the only reaction channel for thermal gas-phase reactions of [CeON]⁺ with methane. Based on computational work, the neutral molecule formed corresponds to either CH₂NH₂ or CH₃NH. This reaction benefits from a rather weak OCe⁺−N bond and a highly efficient intersystem crossing.