Mesoionic carbenes (iMICs) and anionic dicarbenes (ADCs) are readily accessible by the deprotonation of C2-arylated 1,3-imidazolium salts, which are prepared by the direct C2-arylation of classical N-heterocyclic carbenes (NHCs). The implications of iMICs as potent σ-donor ligands in organometallic catalysis and ADCs as unique building-blocks in accessing conceptually new main-group heterocycles with an annulated C₄E₂ ring are showcased.

Stabilizing liquids based on supramolecular assembly (non-covalent intermolecular interactions) has attracted significant interest, due to the increasing demand for soft, liquid-based devices. Recent advances in structuring liquids based on non-covalent intermolecular interactions are highlighted and a perspective is provided on future directions to inspire further studies on structured liquids based on supramolecular assembly.

This review discusses recent developments in the chemistry of photocatalytic biomass conversion into chemicals and fuels, emphasizing the role of experimental factors and materials design. A critical technological analysis to facilitate the scaling up of this technology is provided based on the reported research studies and industrial need.

The field of carbon isotope labeling has recently explored new alternative avenues for better dealing with the hurdles of radiochemistry. This review focuses on the emerging opportunities provided by carbon isotope exchange (CIE) technologies. By dramatically reducing the number of steps and radioactive waste generated in preparation of tracers, CIE has great potential for accelerating clinical development of pharmaceuticals.

A silver copper nanocluster with a golden ratio pentangle structure is prepared. It shows promising photothermal conversion. It is a novel alloy nanocluster with a sandwich-like kernel (diameter≈0.9 nm and length≈0.25 nm), and gives insight into the relationship between structure and photothermal properties.

A glycoproteomics platform, Click-iG, is reported that integrates metabolic labeling of glycans with clickable unnatural sugars, an optimized MS method, and a tailored version of pGlyco3 software to enable simultaneous enrichment and profiling of three types of intact glycopeptides: N-linked, mucin-type O-linked, and O-GlcNAcylated glycopeptides.

A thiophene-based covalent triazine polymer facilitates effective conversion of O₂→H₂O₂→⋅OH→Cl⋅→Cl₂^.− in the aqueous phase. Cl₂^.−, with a longer lifetime, transfers into organic phase and activates C(sp³)−H bonds to generate unstable dichlorinated intermediates by successive hydrogen abstraction and chlorination. These unstable intermediates hydrolyze into either aldehydes or ketones with higher selectivity than that of benzyl dichloride.

The photoluminescence mechanism of crystalline diphosphonium iodide salts strongly depends on anion-π interactions. In the case of iodide–π charge transfer combined with electrostatically controlled packing effects, high quantum yields (Φ_em up to 0.75) and fast radiative rate constants (k_r of up to 2.77×10⁵ s⁻¹) of phosphorescence have been realized at room temperature, which are exceptionally rare for metal-free systems.

A new catalytic foldamer constructed of α- and bespoke δ-residues forms a helix which is not only stabilized by intramolecular H-bonds, but also by apolar interactions not observed in foldamer secondary structures until now. The resulting scaffold gives a useful juxtaposition of functionality and leads to bifunctional catalysis as demonstrated through an aldolase-like process.

Lignin and synthetic phenolic polymers are difficult to degrade and reprocess. Through thiol-aldehyde polycondensation, degradable and reprocessable phenolic polymers with tensile strength up to 64 MPa were prepared from bioderived phenolic compounds. The developed method is promising for facile preparation of macromolecular antioxidants and dynamic networks.

Top-down mass spectrometry using infrared multiphoton dissociation (IRMPD) of native membrane proteins such as G protein-coupled receptors (GPCRs) provides good sequence coverage from native protein ions. We observe successive cleavage of adjacent amino acids, specifically within transmembrane helices, enabling unambiguous identification of membrane proteins and their complexes.

Highly cooperative CO₂ adsorption on a flexible cesium-exchanged phillipsite, a channel-based small-pore zeolite, is operated by an unprecedented adsorption phenomenon: structural breathing (the narrow-to-wide pore) is associated with the crowding and dispersal of large Cs⁺ ions, depending on the CO₂ pressure, termed the ‘cation crowding’ mechanism.

An enantioselective hydrophosphination of cyclopropenes that occurs at ambient temperature is reported. It proceeds through a copper-phosphido intermediate while various cyclopropylphosphines can now be accessed in high yields and enantioselectivities. Enrichment of phosphorus stereocenters is also demonstrated via a dynamic kinetic asymmetric transformation (DyKAT) process. Experimental studies and DFT calculations provide mechanistic insight.

Thermochemical degradation utilizing AlCl₃ recovers benzene from polystyrene in quantitative yields. The subsequent addition of acyl/alkyl and sulfinyl chlorides to the same reactor produces aryl ketones and sulfides in moderate to high yields. The one-pot cascade degradation–upcycling reactions present an effective strategy for converting polystyrene to valuable chemicals, including benzophenone, acetophenone, and diphenyl sulfide.

Densely functionalized phenols can be easily obtained through formal [2+2+1+1] cycloaddition of two different alkynes and two molecules of CO. The new benzannulation strategy allows efficient regioselective installation of up to five different substituents on a phenol ring. The resulting phenols have a substitution pattern different from and complementary to those obtained from Dötz and Danheiser benzannulations.

An efficient synthesis of multisubstituted cyclohexenes has been achieved from tetrahydropyrans (easily accessible via many synthetic approaches). The process operates via a tandem 1,5-hydride shift–aldol condensation mediated by simple aluminium reagents (e.g. Al₂O₃), enabling the synthesis of cyclohexenes (>40 examples) bearing substituents at each position around the cyclohexene ring with high levels of chemo-, stereo- and regioselectivity.

Reducing the complexity of crystallizable fragment glycans dramatically increased the efficiency of the conjugation of large payloads to antibodies via fucosyltransferase-mediated unnatural fucosylation. An anti-human epidermal growth factor receptor 2 and anti-cluster of differentiation 3 bispecific antibody was synthesized which enabled the recruitment and activation of endogenous cytolytic T lymphocyte cells for tumor killing within organoids.

A novel covalent organic polymer with ordered periodic cationic sites is proposed to tackle the concentration polarization and drive the equilibrium of the nitrogen reduction reaction in the forward direction. With the given potential unchanged, the suppressed overpotential can be much liberated, ultimately leading to a 24-fold improvement generated in the Faradaic efficiency (73.74 %).

Analytical treatment allows determining all thermodynamic and kinetic parameters of reversible electrocatalytic oxidation and production of dihydrogen mediated by DuBois/Shaw nickel bisdiphosphine complexes bearing pendant bases. This analysis shed light on the key activity descriptors responsible for reversible vs. bidirectional catalysis and paves the way towards rational optimization of such molecular catalysts

Photocatalytic CO₂ reduction for efficient ethanol production is challenging. A 2D/2D S-Scheme heterojunction comprised of black phosphorus and bismuth tungstate (BP/BWO) was constructed for CO₂ reduction, coupled with benzylamine (BA) oxidation to N-benzylidenebenzylamine (BDA). The catalyst generates ethanol with high yield and selectivity. This work provides insight into heterogeneous photocatalysts based on cooperative photoredox systems.

Asymmetrical cyclic peptides constructed by dynamic covalent chemistry provide a platform for the investigation of naturally occurring chirality inversion, ring-chain tautomerism, and hierarchical assembly. The insertion of a 4-imidazolidinone ring promotes the formation of intertwined nanostructures. The reversibility can be tuned by changing the pH value without producing other chemical waste except water.

An unusual “NOS” bond with a bridging oxygen atom can form under oxidising conditions between a cysteine and a lysine residue. Now the reaction mechanisms for the formation of single and double NOS bonds in proteins have been computationally investigated. More than 30 reactions were considered for oxidation pathways involving different reactive oxygen species, providing a comprehensive overview of cysteine oxidation pathways.

Highly efficient electron/hole separation and collection has been achieved by in situ interface bonding of an ultrathin high-crystallinity Ta₃N₅ mono-grain shell and conductive NbN_x nanorod core. The photoanode attains a photocurrent density of 7 mA cm⁻² at 1.23 V RHE with a Ta₃N₅ shell thickness of less than 30 nm.

A novel class of G4-targeting organic-platinum hybrids, L¹-cispt and L¹-transpt, designed to covalently bind to the G4 binding site, could activate the retinoic acid-induced gene I (RIG-I) pathway, induce immunogenic cell death (ICD) and stimulate potent immunotherapy in vivo. This study highlights the importance of the rational combination of specific spatial recognition and covalent binding in G4-targeting drug design.

Donor-acceptor functionality has been incorporated into the π-conjugated monomeric structure to program self-assembly pathways, directing the formation of parallel-stacked supramolecular polymers as metastable species and slip-stacked ones as the thermodynamically stable species.

The closed-loop recycling of vinylogous urethane vitrimers made from acetoacetate-terminated polyethyleneglycol and tris(2-aminoethyl)amine is presented. Treatment with water allows the selective and quantitative recovery of the monomers, even from mixed waste streams. The modular synthetic approach allows the synthesis of materials that cover a broad range of mechanical properties and that are easy to reprocess.

Polyoxometalate-cyclodextrin cluster-organic supramolecular framework (POM-CD-COSF)-based battery separator as an ideal lightweight barrier (ca. 0.3 mg cm⁻²) was first directly involved in the lithium-sulfur battery (Li−S) system to suppress the polysulfide shuttle effect through supramolecularly recognizing polysulfide guests and then catalyzing their conversion while simultaneously accelerating Li⁺ ions diffusion.

A targeting CARG-¹O₂ was designed as a “singlet oxygen battery” for the efficient treatment of MRSA deep-tissue infections. CARG-Py was able to store singlet oxygen by pre-irradiation and produce singlet oxygen over a time course of approximately 30min. CARG-¹O₂ potently combats biofilm-associated infections and disrupts MRSA biofilms, and it exerted a beneficial therapeutic impact in a MRSA-induced model of pneumonia.

Breaking the coordination symmetry of Cu site in atomically precise Cu₆ cluster forms Cu-S₂N₁ site, which rank the d_x²_-y² orbital as the highest occupied d orbital to favor the specific coordination between C atom of CO₂ and Cu−S₂N₁ site. This binding mode is conductive to the generation of *COOH instead of *OCHO, thereby switching the product of electrocatalytic CO₂ reduction reaction to higher-valued hydrocarbons.

We describe N1-tert-butylated 1,2,4-triazinium salts as new bioorthogonal reagents. These heterodienes are stable under biological conditions and react selectively and at high rates with strained alkynes such as BCN, allowing efficient modification of biomolecules. The unique ionic character makes the compounds more water soluble and cell permeable. These features enable efficient labeling of intracellular targets in living cells.

Microfluidic experiments yield compositionally pure Ni(OH)₂ membranes that show internal microscale structures such as parallel bands, dendritic trees, and disorganized spots. These light-scattering patterns result from nonclassical crystallization and nanoparticle aggregation. The particles form in the flowing NiCl₂ solution and self-organize aggregation zones—that for band patterns—move over the membrane surface in the upstream direction.

The potential reactivities of fluoroaryl sulfoxides have been unlocked by precisely constructing and elaborating their temporarily dearomatized intermediates via a robust [5,5]-sulfonium-rearrangement-triggered dearomatization/rearomatization process. Impressively, fluorine has shown its irreplaceable role for the success of the reaction.

The crystal structure of type-II red phosphorus is investigated by various structural characterizations, including 3D electron diffraction, atomic-resolution STEM imaging, and powder X-ray diffraction. A triclinic unit cell with a large volume containing around 250 phosphorus atoms is identified via 3D electron diffraction. The twisted wavy tubular motif, a new variation of building blocks in phosphorus, is also revealed via STEM.

Monomeric small protein ligands, referred to as U-body constructs, were developed from ubiquitin and macrocyclic peptide pharmacophores via genetic implantation (lasso-grafting) and spacer optimization, showing antagonist or “enhancer” activity for a receptor tyrosine kinase MET. Subsequently, multimeric U-body-based proteins, U-bodies, were constructed, exhibiting potent agonist activity for MET.

Indium nanoparticles on chitosan-derived N-doped defective graphene (In/N-dG) create bifunctional active centers that integrate chemical adsorption and electrocatalytic capabilities for CO₂ electrolysis. The electrocatalyst demonstrated outstanding performance for the CO₂ reduction reaction with a nearly 100 % Faradaic efficiency toward HCOOH across a wide potential window and with high current density.

Autonomous stress-relaxation by dynamic jammed assemblies of nanoparticles and lipids at the interface was demonstrated. Such a lipid-based self-relaxing system may find applications in soft robots, medical and materials applications.

A simple method was developed for Pt₁−Fe₁/nanodiamond dual-single-atom catalyst construction. Synergistic chemoselective hydrogenation of nitroarenes was achieved, whereby hydrogen is activated on the Pt₁−Fe₁ dual site and nitro group is preferentially adsorbed at the Fe₁ site. The activation energy is decreased, resulting in an appreciable catalytic performance (3.1 s⁻¹ turnover frequency, ca. 100 % selectivity, and a scope of 24 substrates).

The chiral hybrid antimony halides R-/S-(C₅H₁₂NO)₂SbCl₅ have excitation-dependent emission originating from the synergistic effects of ligand and self-trapped excitons, and exhibit reversible structural transformation between non-emissive R-/S-(C₅H₁₂NO)₂SbCl₅ ⋅ DMF upon exposure to DMF and heat. CPL switch, chiral optical logic gate and anti-counterfeiting applications have been investigated based on the multiple stimuli-responsive properties.

Cobalt-porphyrin-based covalent organic frameworks (Co-Por-COFs) were prepared with different donor building units. Their photophysical studies indicated that the Co-Por-COFs with higher charge-carrier density and longer conjugation length led to a more efficient charge separation with a reduced exciton binding energy, resulting in an enhanced photocatalytic activity of CO₂ reduction into CO.

A series of covalent organic cages with aggregation-induced emission characteristics were elegantly prepared through the reduction of preorganized metallacages. These covalent cages performed well as energy donors for the construction of artificial light-harvesting systems for the photocatalytic dehalogenation reaction.

A dual-asymmetric Y-series acceptor is developed using unidirectional sidechain engineering. Thanks to the low energy loss and efficient charge transfer properties, the corresponding organic solar cells achieved an efficiency of 19.23 %, which is one of the highest values among annealing-free devices.

Fe single atom catalysts with sulfur and epoxy groups near the atomically dispersed metal centers (Fe1/NSOC) are designed for highly efficient oxygen reduction reactions. The presence of sulfur and epoxy groups modulates the electronic structure of Fe centers, while the epoxy groups also participate in the reduction reaction through reversible cleavage, lowering the energy barrier by functioning as an anchor site for OH* intermediates.

A combination of DFT calculations and experiments were used to discover a large class of exfoliable h-MAB phases and their derivative h-MBenes. A representative 2D h-MBene, HfBO, was successfully synthesized by selectively etching the In layers from Hf₂InB₂. The synthesized 2D HfBO was demonstrated to show lithium-ion storage performance for the first time.

Ga-1 anchors to mitochondria by binding to the membrane phospholipids and results in the dysfunction of the electron transfer chain as well as iron release, eventually triggering ferroptosis. In addition, Ga-1 inhibits protein disulfide isomerase in the endoplasmic reticulum, breaking the antioxidant glutathione system. Both actions synergistically induce ferroptosis. In addition, exogenous polyunsaturated fatty acid enhances ferroptosis.

This work unveils a T-shaped organoboron system with three stable oxidation states, which allowed for the isolation of geometrically constrained superacidic boron dication, ambiphilic boron radical cation and superbasic borylene.

Two stable Co^II-based metal-organic cages are efficient catalysts for photocatalytic synthesis of H₂O₂ in pure water and O₂ or air atmospheres. The metal-nonmetal active site operates synergistically during photocatalytic H₂O₂ synthesis and the reaction substrate can more fully contact the catalytically active site through host–guest chemistry of cages, ultimately achieving a high H₂O₂ production rate.

A crystalline network is constructed by incorporating rhenium complexes and triazine ring structures as catalytic sites via robust −C=C− bonding. Appreciable charge-separation and transfer efficiency drive both the photocatalytic oxidative and reductive reactions in the conversion of CO₂ to CO with H₂O, and without any additional sacrificial agents or photosensitizers.

A straightforward method of controlled partial linker thermolysis allows the microporous metal–organic framework (MOF) photocatalyst UiO-66-NH₂ to expand its porosity with a tailored pore environment. The resulting material accommodates single-site Cu species, shows significant mesoporosity and enhanced charge photogeneration. It has excellent performance in photocatalytic reactions for the functionalization of terminal alkynes.

Tandem catalysis effects in electrochemical CO₂ reduction were investigated through an isotopic labelling strategy involving the co-reduction of ¹³CO₂/¹²CO mixtures. The results provide evidence that tandem catalysis does indeed occur in neutral electrolyte but is curtailed under acidic conditions. This is due to Cu becoming less effective at utilizing tandem-supplied CO in the presence of hydronium ions.

Multiple functionalities were enabled by a single cathode modifier: i) for the cathode, it can work as an effective catalyst to promote cathode reaction kinetics; ii) for the anode, trace amounts of dissolved In and Se ions are incorporated as LiInS₂ and LiInSe₂ in the anode solid electrolyte interface to facilitate reversible Li deposition/stripping.

Local reconstruction of imine-linked covalent organic frameworks (COFs) unlocks visible-light-promoted photocatalytic H₂ evolution. The keto units in skeletal building blocks are active injectors, where hot π-electrons are emitted to Pt nanoparticles across a polyvinylpyrrolidone (PVP) insulting layer for reduction of protons to H₂. A new benchmark H₂ production rate of 53 mmol g⁻¹ h⁻¹ was achieved over β-ketoenamine-linked COFs.

A tunable covalent organic framework (COF) platform with three azole-related linkages was prepared through linker exchange reactions. The linkage microenvironment changes the photoelectric properties and photocatalytic performance. The thiazole linkage was more favorable than the oxazole and imidazole linkages for the formation of *O₂ intermediate in H₂O₂ production.

Modifying the surface of oleate-coated hydrophobic particles to render them stable in aqueous biological environments is often challenging. We present a one-step reaction, to form a bilayer consisting of oleate and dodecylamine moieties, which provides excellent stability and versatility as it allows further functionalization via carbodiimide chemistry.

Fast, low-cost parahydrogen-hyperpolarization via Signal Amplification By Reversible Exchange (SABRE) enables in vivo metabolic magnetic resonance imaging. We demonstrate the first in vivo application of SABRE-hyperpolarized [1-¹³C]pyruvate-d₃ in a purified, aqueous solution with ≈30 mM [1-¹³C]pyruvate-d₃ polarized to ≈11 %, obtained by rapid solvent evaporation and metal filtering. This achievement paves the way for affordable and widespread metabolic imaging applications.

Novel step-by-step approach for the synthesis of polyampholyte nanogel-in-microgel colloids (NiM−C) was developed by incorporating nanogels into microgels via droplet-based microfluidics yielding different internal morphologies including phase-separated coacervates, statistically distributed coacervates and core–shell like arrangements by variation of synthesis parameters such as nanogel concentration, ionic strength and pH value.

Pyrazolones represent an important structural motif in active pharmaceutical ingredients. A polyfunctional Cu^II-1,2,3-triazolium-aryloxide catalyst which enables their addition to nitroolefins with high enantio- and diastereocontrol is presented. DFT studies show that the catalyst adopts a rigid chiral cage structure by intramolecular hydrogen bonding. The products were used to form bioactive compounds, pyrazolidinones and β,γ’-diaminoamides.

A heterotelechelic dilinker enables the generation of a polymer network exclusively via dual-colour irradiation. In contrast, single-colour irradiation results in polymer functionalization.

A selective way for the nucleophilic substitution of the cyclo-As₅ ligand in [Cp*Fe(η⁵-As₅)] (I) was found, resulting in first As₅R entities. By the reduction of I, an access to the dianionic compound [(Cp*Fe)₂{μ-η⁴:η⁴-As₁₀}]²⁻ (4), and by using As-based nucleophiles, the straightforward formation of tetramers representing the largest polyarsenide-containing (As₂₀) molecular complexes could be achieved.

The bimetallic cluster [Ni₃(GaTMP)₇] reversibly forms di-, tetra- and hexahydride species under hydrogen pressure in solution, that were characterized by low temperature COSY and ROESY NMR experiments and DFT calculations. The work conceptually relates properties of molecular, atom-precise transition metal main-group bimetallic clusters to the respective solid-state phase in catalysis.

Nonbenzenoid acepleiadylene (APD) has been explored as a new building block to construct organic electronic material (APD-IID), which exhibits higher hole mobility than its pyrene-based isomers because of the stronger intermolecular interaction induced by the unique charge-separated character. These results demonstrate the superiority of nonbenzenoid arenes in the future development of organic semiconducting materials.

A nitrone-linked covalent organic framework, COF-115, has been synthesized for the first time via polycondensation reaction. The sorption analyses of COF-115 revealed a porosity of 1387 m²/g, and a superior potential for atmospheric water harvesting and CO₂ capture applications compared to their imine-based analogs. Finally, COF-115 was found to undergo a photochemical rearrangement to the corresponding amide-linked material.

An electron-rich and oxidation-resistant ligand is effective at stabilizing high-valent iron-oxo intermediates involved in the water oxidation reaction. UV/Vis, XAS, EPR, electrochemical and kinetic measurements, allow a high-valent Fe^V(O) species that participates in O−O bond formation with higher reactivity and shorter lifetime to be tracked in a real catalytic water oxidation reaction.

The structure of tetra-tert-butyl-s-indacene is a computational challenge. Highly correlated methods and popular DFT functionals predict a bond-delocalized D_2h symmetry, but excellent agreement between experimental and computed proton chemical shifts suggests a true C_2h geometry.

Unprotected cis-2,3-diarylpiperidines are synthesized from readily available piperidines in only three operations. The key step is a palladium-catalyzed cross-coupling reaction between aryl halides and endocyclic 1-azallyl anions, elusive intermediates derived from the in situ deprotonation of 2-aryl-1-piperideines. This cross-coupling reaction can be achieved enantioselectively with a chiral mono-phosphine ligand.

A new type of chiral pincer silyl ligand is developed, which enables an Iridium-catalyzed atroposelective intermolecular C−H silylation reaction. Key to the success of this transformation is the use of a novel chiral PSiSi-ligand, which facilitates the C−H silylation process with high chemical, regio- and stereo-control via a multi-coordinated silyl iridium complex.

Carboxy-terminal diglycine-modified succinate compounds undergo autohydrolysis at physiological pH. This process converts supramolecular assemblies from nanofibers to nanoparticles for fast cellular uptake. This approach also restores drug efficacy, promoting effective intracellular therapeutics.

A NiH-catalyzed dynamic kinetic asymmetric transformation (DYKAT) of easily accessible racemic and isomeric mixture of cycloalkenes and a NiH-catalyzed desymmetrization transformation of prochiral cyclic alkenes are reported. This migratory hydroalkylation process produces enantioenriched thermodynamically disfavored 1,2-cis disubstituted cycloalkanes with excellent levels of regio-, diastereo- and enantioselectivities.

A new late-stage functionalization of complex molecules enables the installation of cyclopropene rings with excellent efficiency, thus reaching an uncharted cyclopropenylated chemical space. The cyclopropene ring generally improves the metabolic stability of the cyclopropenylated drug molecules and serves as a unique scaffold to access broad range of medically-relevant motifs.

We report an efficient C−H functionalization process, enabling the regioselective installation of carbonyls in light and heavy hydrocarbons by using inexpensive carbon monoxide. Safe processing of hazardous CO and flammable alkanes is ensured in flow, with high gas-liquid mass transfer rates and fast reaction kinetics. Our method demonstrates the valorization of gaseous reagents, coupling light alkanes, CO, and an olefin as a terminal radical trap.

We demonstrate the synergistic approach of in situ generated iridium nanoparticles in photoredox-catalyzed and CH-functionalization hydrogen isotope exchange with deuterium and tritium gas.

The rapid generation of carbonate radical anions (CO₃^.−) in the oxidation of Fe^II by O₂ in the presence of bicarbonate (HCO₃⁻) is shown. The results highlight the importance of considering the formation of CO₃^.− in the geochemical cycling of iron and carbon and show that the presence of bicarbonate dramatically changes the mechanism and kinetics of the reaction of Fe(H₂O)₆²⁺+O₂ under physiological and environmental conditions.