E-merging methods: The merging of a homogeneous photocatalytic system with an electrochemical cell has been recently applied to organic synthesis, allowing to realize net-oxidative photocatalytic processes in the absence of a chemical oxidant.

Modification of nanosheet membranes by crosslinking and functionalization has improved their stability, their separation functionality, and the scalability of membrane production while retaining the membranes’ excellent molecular transport properties. These improvements have enhanced the potential of nanosheet membranes in practical applications such as separation processes.

Soaking up the sun: This Review highlights recent achievements in solar-driven C₁ chemistry, especially in processes such as solar-driven Fischer–Tropsch synthesis, the water-gas-shift reaction, CO₂ hydrogenation, as well as CH₄ and CH₃OH conversion. Particular emphasis is placed on the rational design of catalysts, structure–reactivity relationships, as well as reaction mechanisms during the solar-driven processes.

In nine steps: The first copper-catalyzed intermolecular [5+2] homodimerization of hydroxy p-quinone is presented, furnishing bicyclo[3.2.1]octadienone core structures in typically good yields and excellent diastereoselectivities. Applying this synthetic approach enables a concise nine-step total synthesis of (−)-perezoperezone from commercially available 3,5-dimethoxytoluene.

Solid proof: The formation of a novel pentavalent plutonium solid phase was observed on the pathway from aqueous Pu^VI to PuO₂ nanoparticles by applying a high energy resolution fluorescence detection method at the Pu M₄ and L₃ edges and electronic structure calculations.

Induced volatolomics: A volatile organic compound (VOC) based probe is selectively converted by tumours into a VOC that diffuses into the blood stream and is then released in exhaled breath. The VOC in the exhaled breath can be detected and used as a diagnostic tool for cancer. This approach was used in the detection of several different tumours in mice, and for monitoring tumour growth and tumour response to chemotherapy.

Mg-ligand cooperative activation of HBpin: The enantioselective magnesium-catalyzed hydroboration of ketones using a (R)-(+)-BINOL derivative as a chiral ligand affords excellent yields and enantioselectivities. Experimental investigations together with DFT calculations provide insight into the reaction mechanism and the origin of enantioselectivity.

Little helper hydrogen bond: The dioxygen reactivity of a series of TMPA-based copper(I) complexes (TMPA=tris(2-pyridylmethyl)amine) was studied. Kinetic stabilization of the H-bonded [( TMPA)Cu^II(O₂^.−)]⁺ cupric superoxide species was achieved with X₁/X₂=−NH₂ and/or pivalamido (−HNC(O)C(CH₃)₃). The complexes show high reactivity towards phenolic substrates and substrates possessing moderate C−H bond-dissociation energies.

Deep Blue! Soluble contorted PAHs with two embedded azulene moieties with different degrees of curvature are synthesized and spectroscopically compared.

A tandem enzymatic strategy to enhance the scope of C-alkylation of small molecules via coupling the production of S-adenosyl methionine (SAM) cofactor analogues with C-(m)ethyl transfer to coumarin substrates, catalyzed by the methyltransferase (MTase) NovO, is described. This forms C-(m)ethylated coumarins in superior yield and greater substrate scope relative to that obtained using cofactors lacking nucleobase modifications.

In situ EPR and Mössbauer investigations reveal unprecedented oxygenation of a transient paramagnetic iron(V) nitrido intermediate yielding an iron nitrosyl species. Computational studies suggest that the N−O bond formation involves transfer of a formally closed-shell singlet O atom to the (FeN)²⁺ core concurrent with synergetic orbital interactions.

A multiplexed system that integrates inductive nanoelectrospray and field amplification micro-electrophoretic cleaning was developed for high-throughput bioassays. This system has ultra-high sensitivity and screening rates of 1.3–3.5 s per sample.

One-by-one electron oxidation of diarsenes [As₂] featuring very efficient π-donor N-heterocyclic vinyl substituents with GaCl₃ leads to the formation of radical cations [As₂]^+. and dications [As]²⁺ as crystalline solids. Experimental and computational studies revealed the delocalization of unpaired electron over the π-conjugated CAs₂C framework.

Pretty vacant: Copper vacancies induced in the CuO photocathode facilitates charge separation and transfer, leading to remarkably improved photoelectrochemcial performance. A simple O₂ treatment on the CuO photocathode leads to the formation of copper vacancies.

Oxidants will happen: The effective oxidation of spiro-OMeTAD is carried out by a hybrid polyoxometalate@metal–organic framework (POM@MOF) POM@Cu-BTC which can be used as the hole transport material (HTL). This composite oxidant contributes to enhanced efficiency, as well as improved long-time stability of perovskite solar cells (PSCs).

A clear case: The determination of glycan fucosyl positions with MS/MS is complicated due to rearrangements in the gas-phase, leading to erroneous structural assignments. Unique IMS arrival-time distributions of MS/MS fragments can be used to discriminate between fucosides originating from parent compounds and rearranged fucosyl residues, preventing misinterpretation of MS/MS spectra.

1T-MoS₂ coupled with NiS₂ was successfully synthesized in high phase purity by a spatially confined template method on a large scale. A different ratio of 1T-MoS₂ could be obtained by simply regulating the structure of the template. The hydrogen evolution reaction (HER) performance of the 1T-MoS₂/NiS₂ in alkaline media was studied.

Atroposelective [4+2]: A new organocatalyzed atroposelective arene formation reaction involves a carbene-catalyzed formal [4+2] cycloaddition of conjugated enals and α-aryl ketones. This study expands the synthetic potential of N-heterocyclic carbene (NHC) organocatalysis and provides a competitive pathway for the synthesis of axially chiral ligands, catalysts, and other functional molecules.

Growth on the water: A comprehensive kinetic study of the growth mechanism of MAPbBr₃ nanocrystals (NCs; MA=CH₃NH₃⁺) is made possible through the water–oil interfacial synthesis method. The overall reaction time of MAPbBr₃ NCs is thereby prolonged to tens of minutes by reducing the formation rate of PbBr₆⁴⁻ octahedra and the diffusion rate of MA.

Affairs of state: Aliphatic polyesters prepared from ethylene oxide and maleic anhydride undergo reversible transformation between amorphous and crystalline states through cis–trans isomerization of the C=C bonds in the polymer backbone without any change in either the molecular weight or dispersity of the polymer. A similar transformation was also observed with chiral unsaturated polyesters.

Inflamed: A new pathway to a long-known lipid mediator, PGE₂, was discovered in the red alga Gracilaria vermiculophylla (see Figure, top). Upon re-investigation of the biosynthesis in macrophages, 15-hydroperoxy-PGE₂ was also established as an intermediate in an alternative pathway in mammals.

Docking and migration: Both activated and unactivated alkenes can be modified by a radical-mediated monofluoroalkylative alkynylation, generating valuable products in a docking–migration process. Many complex natural products and drug derivatives can be readily functionalized with this approach.

Multifunctional organic emitter: One simple organic molecule exhibits aggregation-induced emission (AIE), thermally activated delayed fluorescence (TADF), room-temperature phosphorescence (RTP), and mechanoluminescence (ML) simultaneously.

Dancing in the dark: The synthesis of chalcogenide hybrid inorganic/organic polymers with enhanced long-wave infrared (LWIR) transparency is reported. Through the design of organic molecules based on DFT computations and IR-fingerprint engineering, a new class of polymers for LWIR thermal imaging is developed.

Chiral sulfoximines were synthesized by an unusual sulfur-selective alkylation of readily available sulfinamides with alkyl halides under basic conditions. Various chiral sulfinamides can also be obtained by acidic treatment of the obtained chiral sulfoximines (R¹=tert-butyl) by de-tert-butylation.

In a rare case of asymmetric twofold C−H activation, rhodium(III)-catalyzed oxidative [3+2] transannulation of two distinct classes of arenes with azabicyclic olefins occurred with high enantioselectivity to give variously substituted heterocyclic products containing two stereocenters (see scheme). The isolation of a chiral Rh^III intermediate aided the elucidation of the reaction mechanism.

Seeing is believing: A method capable of directly visualizing the loading of payload into the cavity of a gold nanocage was demonstrated. Pyrrole was used as a model, which could be polymerized to give solid polypyrrole deposited on the inner and outer surfaces of the nanocage.

The tin star: The first tin borate chloride Sn₂B₅O₉Cl is synthesized, and its birefringence is about 16 times that of isostructural Ba₂B₅O₉Cl activated via stereochemical activity lone pair.

Good COP good COF strategy: The facile construction of highly crystalline and porous covalent-organic frameworks (COFs) from amorphous covalent organic polymers (COPs) via linkage replacement is possible using a conversion strategy. Four COFs with high crystallinity and porosity are constructed.

Isolation of a classical diborane(5) complex of tantalum was achieved by the room-temperature reaction of [Cp*TaCl₄] with LiBH₄⋅THF followed by addition of S₂CPPh₃. Reactivity with metal carbonyls was also explored.

Open-cage fullerenes with a 19-membered orifice were prepared in three steps from C₆₀. Encapsulation of oxygen was achieved at room temperature under moderate pressure (50 atm), and the oxygen could be released slowly under ambient conditions. The activation energy of the oxygen-releasing process is 18.8 kcal mol⁻¹ and the half-life at 37 °C was 73 min, which makes this a potential oxygen-delivery material.

A rare diamond: The hs-{FeNO}⁷ complex 1, was characterized by spectroscopic methods and X-ray crystallography. Upon reduction, the diamond-core dimer 2 is formed by dimerization of an hs-{FeNO}⁸ intermediate, followed by a spin state change of the iron centers to low-spin (ls).

A titanium(III) complex catalyzes the reductive C−CN cleavage of geminal dinitriles. The reaction proceeds under unusually mild reaction conditions and tolerates numerous common functional groups. Mechanistic studies support a catalyst-controlled C−CN scission instead of a free-radical pathway.

Connected: The nucleophilicity parameters N and s_N of glutathione (GSH) were determined in aqueous solution at 20 °C to link published GSH reactivities (lg k_GSH) with Mayr's electrophilicity scale (E). The electrophilic reactivities of Michael acceptors determined in kinetic chemoassays can now be compared with reactivities of neutral and cationic electrophiles characterized on the E scale.

Small modifications have N effect: The controllable modification of graphene/V₈C₇ heterostructures by nitrogen is reported. Due to changes in the electronic structure of the different parts of the modified heterostructure, it displays an exceptional alkaline hydrogen-evolution capability, the most efficient alkaline hydrogen-evolution catalysis among transition-metal carbides reported thus far.

The pH dependent shift in the H_upd peak on Pt surfaces is demonstrated to be driven by the structure of interfacial water rather than the specific adsorption of cations on the electrode surface. The direct water-electrode interaction, which is dependent on the absolute electrode potential, likely holds the key to understanding the pH induced H_upd peak shift on the Pt surface.

Squaring the hole: Using N,N-diarylanilinosquaraines as the comonomers gives polysquaraine hole-transporting materials (HTMs) that have very high hole mobility. As a dopant-free HTM for α-CsPbI₂Br-based all-inorganic perovskite solar cells, the power conversion efficiency (PCE) can reach 15.5 %, among the best for all-inorganic PVSCs.

An atomically precise N-heterocyclic carbene-stabilized Au₂₅ nanocluster is successfully synthesized in a one-pot reaction. It exhibits much higher thermal stability in the solution form compared to Au₂₅ protected by thiol or phosphine ligands. The cluster displays excellent catalytic activity in the cycloisomerization of alkynyl amine as a homogeneous catalyst.

From the interplay between scanning tunneling microscopy and DFT calculations, the metal-mediated dehalogenative cycloaddition pathway on Ag(111) was established through real-space visualization of the stepwise evolution of competing surface-stabilized radicals and organometallic intermediates.

A radical shielding approach based on supramolecular complexation exploits the protection offered by a [10]cycloparaphenylene ([10]CPP) nanobelt encircling C₅₉N^. to stabilize this radical. The EPR signal of C₅₉N^.⊂[10]CPP showing characteristic ¹⁴N hyperfine splitting was observed even several weeks after its generation.

Hydration of ZnO surfaces: Comprehensive results from IRRAS and theory lead to a fundamental understanding of the surface chemistry of water on ZnO(10 0). The hydration is initiated by the formation of intact water monomers and proceeds by an autocatalytic dissociation of dimers and 2D adlayers, finally leading to the formation of various H-bonded 3D structures.

An eye for an eye: Two artificial predation strategies are spatially and temporally coupled to generate rudimentary tit-for-tat behavior in a ternary community of chemically interacting synthetic protocells.

Grow, little platelet: The on-surface reactions of nanoplatelets between the surface Cd sites and activated Se precursors in the solution is found to be strongly facet-dependent. The process occurs in two stages—rapid adsorption onto the non-polar side facets and slow surface reaction on the polar {100} basal facets—as well as one destructive (ripening) stage.

A simple change in the substituents on cyclopropene rings elicited strikingly different modes of metathesis reactivity, switching from living homopolymerization to either selective single-addition or alternating copolymerization. In both cases well-controlled polymers were obtained.

Amino-functionalized aluminum reagents enable effective coordinative chain transfer polymerization of butadiene with selective chain initiation by the aminoalkyl substituent. This is illustrated visually by the fluorescence of carbazole end groups.

In a fix: Graphene was introduced into Li-N₂ batteries to investigate the stability of the reaction cycle. The instability and hygroscopicity of the discharge product Li₃N leads to the low efficiency and irreversibility of Li-N₂ batteries. Moreover, modification by in situ generated Li₃N and LiOH reduces the loss and volume change of Li anodes during stripping and plating, thereby promoting the rechargeability of Li-N₂ batteries.

Palladium nanoparticles display orthogonal reactivity to molecular catalysts in the cross-coupling of aryl halides with aryl germanes. While aryl germanes are unreactive under L_nPd⁰/L_nPd^II catalysis, they display superior reactivity under Pd nanoparticle conditions. Owing to their electron richness, aryl germanes preferentially react by electrophilic aromatic substitution, and in turn are preferentially activated by the more electrophilic nanoparticles.

A study in contrast: An optical probe with turn-on chemiluminescence and NIR fluorescence in the presence of superoxide anion (O₂^.−) and N-acetyl-β-d-glucosaminidase (NAG), respectively, was synthesized. The probe enables real-time in vivo imaging and early detection of contrast-induced acute kidney injury.

Making the invisible visible: Shiga toxin B subunits (STxB) bind to liquid-ordered (l_o) domains in model membranes, implying that its receptor Gb₃ is localized in these l_o domains. The synthetic access to Gb₃ glycosphingolipids with labeled head groups allows quantification of their partitioning in coexisting l_o/l_d (liquid-disordered) phase giant unilamellar vesicles prior to STxB binding. The data clearly indicate an impact of the fatty acid (un)saturation and α-hydroxylation on the partitioning between phases.

Forgery-proof: A novel AIE molecule 1 is designed with high-contrasted and multi-state mechanochromic and photochromic properties. Based on these properties, 1 shows great potential for application in advanced multidimensional anti-counterfeiting, which was demonstrated by fabrication of a model banknote.

Poly(hexaazatrinaphthalene) (PHATN), an environmentally benign, abundant and sustainable polymer, is employed as a universal cathode material for metal batteries. Exceptional performance is observed in Na and in more challenging Mg and Al batteries. The electron-deficient pyrazine sites in PHATN are the redox centers to reversibly react with metal ions.

Near-infrared (NIR) light-triggered optogenetics with triplet–triplet annihilation-based photon upconversion (TTA-UC) is demonstrated. Triplet-lifetime extension by the covalent conjugation of donor and acceptor and a heat-induced conformational change of the hydrogel that prevents oxygen diffusion enables the formation of dendritic-spine-like structures by hippocampal neurons, induced by NIR-to-blue TTA-UC.

Detective work: DFT simulations and experimental results suggest that an alloyed large cation at the “A-site” can improve the performance of MAPbI₃ (MA=CH₃NH₃) single-crystal (SCs) based X-ray detectors. Thus, alloyed GAMAPbI₃ SCs (GA=guanidinium) are prepared and found to be one of the best-performing perovskite X-ray detectors.

Upon prolonged UV/Vis irradiation (weeks) terephthalate metal–organic frameworks decompose evolving CO₂. The percentage of evolved CO₂ depends on the structure and composition of the MOF.

Good made better: Controllable anodic oxidation of 2D Ti₃C₂T_x improves the rate performance of supercapacitor electrodes. The capacitance retention at 2000 mV s⁻¹ increases gradually from 38 % to 66 % by tuning the degree of anodic oxidation.

Discovered by oxidant: A novel umpolung strategy for α-functionalization of aldehydes with nucleophiles is presented. The strategy uses organocatalytic enamine activation and quinone-promoted oxidation to access O-bound quinol-intermediates that undergo nucleophilic substitution reactions.

Probes for like-charge attraction: Solid-state NMR spectroscopy discriminates hydrogen bonding in conventional ion pairs from that between ions of like charge in ionic liquids. The measured deuteron quadrupole coupling constants for both types of ‘doubly ionic hydrogen bonds’ differ significantly. The observed cationic clusters prevent ionic liquids from crystallizing and result in supercooling and glass formation.