Sulfur-based electrode materials are currently regarded as promising candidates for sodium-storage technologies, especially for sodium-ion (Na-ion) and room-temperature sodium–sulfur (RT-NaS) batteries. In this Minireview on the progress of electrodes based on metal sulfides and elemental sulfur, material design and performance enhancement are highlighted and sodium-storage mechanisms for both battery systems are discussed.

The deadly nature of the puffer fish has been known to mankind since the dawn of civilization. However, the compound responsible for this fatal activity was isolated only in the early 20^th century and has been widely known to the scientific community as tetrodotoxin since then. This review traces its history, isolation, structural elucidation, biology, and synthesis. The syntheses of unnatural derivatives are covered as well.

A surface digging effect of supported Ni NPs on an amorphous N-doped carbon is described, during which the surface-loaded Ni NPs etch and sink into the carbon support underneath to prevent sintering. The sinking Ni NPs could be transformed into thermodynamically stable and active metal-defect sites for activation of C−H bonds for methane oxidation by simply elevating temperature.

I pod: The synergic effect of the strong binding of RuO₂ to I₂ and the strong solvation effect of DMSO to I₂ is found to invert the direction of the well-known reaction I⁻+I₂⇌I₃⁻ to the left-hand side. A Li–O₂ battery with the Li/DMSO+LiI/RuO₂ structure had enhanced stability compared to one with TEGDME.

It′s not rocket science: Co-crystallization of a hypergolic decaborane building block designed for hydrogen bonding with energetic but not hypergolic or explosive fuel molecules enables the simple and rapid synthesis of new hypergolic materials with tunable energetic properties and ultrashort ignition delays down to 1 ms.

The conjugate borylation of α,β-disubstituted cyclobutenones allows access to tertiary cyclobutylboronates in up to 98:2 er with high diastereoselectivity. The synthetic versatility of the products is displayed by the orthogonal functionalization of both the ketone and boronic ester.

Quick access: An N-heterocyclic carbene (NHC)-catalyzed chemoselective reaction of bromoenals and aminobenzaldehydes was developed for quick access to dihydroquinolines with excellent enantioselectivity. The dihydroquinoline products can be readily transformed into a diverse set of functional molecules such as pyridines and chiral piperidines.

Long time no C: Aculenes are a class of norsesquiterpenes (C₁₄) that are derived from daucane sesquiterpenes (C₁₅), but the biosynthetic basis of the demethylation remained unknown. Three novel P450 monooxygenases were discovered to catalyze a stepwise demethylation process, and a new ent-daucane cyclase was also discovered. This work sheds light on how nature performs enzymatic demethylation and reveals new tools to expand chemical diversity.

All in a twirl: The gram-scale synthesis of a series of azaoxa[7]-, [10]-, and [13]helicenes is described. The synthesis is based on iterative oxidative furan formation between 3,6-dihydroxycarbazoles and/or 2-naphthols. The optically pure [13]helicenes can be synthetically functionalized both at the termini (see picture: blue) and the periphery (red).

Switchability: Nonsymmetrical ditopic ligands (L) drive the formation of a dynamic Pd₂L₄ open cage that is capable of turn-on/off anion binding through stoichiometry-driven structural transitions of the host cage.

Autoxidation of benzaldehyde in the presence of uranium results in the in situ generation of organic peroxide and the isolation of novel nanotubular uranyl peroxide phases. Owing to the constant low-level production of peroxide, the uranium phase is formed in remarkably high yield and uniform structure.

Soft matter, hard shell: pH-responsive hydrogels that can chelate Fe³⁺ were prepared from guanosine-5′-hydroxamic acid (HA). At high pH, the hydrogel binds thiazole orange, signaled by enhanced fluorescence. The HA units can also act as a supramolecular siderophore to form red complexes with Fe³⁺, which allowed the patterning of the hydrogel surface with FeCl₃.

A highly efficient asymmetric cascade reaction of β,γ-unsaturated α-ketoesters and diazoimides was realized by using a bimetallic rhodium(II)/chiral N,N′-dioxide-zinc(II) catalytic system. The corresponding oxa-bridged oxazocine products bearing different substituents were obtained in moderate to excellent yields with excellent enantioselectivity under mild reaction conditions.

Connecting the dots: Energy transfer (ET) from carbon dots embedded in crystalline Mn-containing open-framework matrices results in high-efficiency red room-temperature phosphorescence (RTP) emissions. Varying the carbon dot precursors and the heteroatom coordination geometries enables the emissions to be tuned from red to green/yellow.

Strike while the iron is hot: Iron doping greatly improves electrochemical N₂ reduction over TiO₂ nanoparticle for ambient N₂-to-NH₃ fixation with excellent selectivity. The Fe-TiO₂ catalyst attains a high Faradaic efficiency of 25.6 % and a large NH₃ yield of 25.47 μg h⁻¹ mg_cat⁻¹ at −0.40 V in 0.5 m LiClO₄ versus a reversible hydrogen electrode. The synergistic effect of bi-Ti³⁺ sites and oxygen vacancies are responsible for the superior activity.

Going for a spin: A rotary-evaporation-induced enantioselective aggregation of achiral phthalocyanines is reported. The chiral induction mechanisms are proposed, pioneering a novel scientific field in terms of linking macroscopic mechanical rotations to nanoscale molecular chirality.

Low-temperature-processed, UV-inert ZnTiO₃ as a mesoporous layer was introduced in SnO₂-based planar perovskite solar cells. The application of ZnTiO₃ modified the interface of SnO₂/perovskite, and significantly improve the UV stability and lifetime of devices. The low-temperature mesoporous structure expands the choice for transmission layer and electrode materials.

Protective coating: Li amalgam was studied for Li protection. The rational design of a Li anode with such a protective layer affords much improved cycling performance at practically high currents and capacities. Coupled with high-loading cathodes, the protected hybrid anodes demonstrate significantly improved cell stability, indicating its reliability for practical development of Li metal batteries.

Vaporous materials: Although generally stable, zeolitic imidazolate frameworks (ZIFs) can undergo post-synthetic linker exchange (PSLE) in solution under mild conditions. A novel, solvent-free approach to PSLE through exposure to linker vapor is presented.

One way or the other: Enynes bearing a tethered carbonyl group are transformed into furans upon catalytic hydrogenation using a ruthenium catalyst. Strikingly though, the reaction can follow two distinct pathways, each of which involves discrete metal carbene intermediates. They differ in that the hydrogenation and carbene formation are either synchronized (gem-hydrogenation) or fully uncoupled.

The dynamics of the nucleation of precious metal nanocrystals were studied at three different temperatures (20, 50, and 100 °C) by aberration-corrected transmission electron microscopy. A fast, and apparently linear, acceleration of the rate of nucleation was observed against increasing temperature (78.8, 117.7, and 176.5 pm min⁻¹, respectively).

Single electron transfer to diphenyldiazomethane–borane adducts generates transient radical anions that effect C−H bond activations. Such reductions provide a strategy to stabilize weak and even undetectable donor–acceptor adducts.

From crops to CROP: Cationic ring-opening polymerization (CROP) of biomass-derived levoglucosenyl methyl ether yields a semicrystalline thermoplastic unsaturated polyacetal. The double bonds can undergo hydrogenation and thiol–ene reactions as well as crosslinking, thus making this polyacetal potentially interesting as a reactive functional material.

A highly diastereo- and enantio-selective method for the asymmetric synthesis of molecules containing helicene and stereogenic axes was developed based on organocatalysis. Various compounds bearing both helical and axial stereogenic elements were obtained in excellent enantioselectivities.

Coordination mode matters: The first example of carboxy group assisted, remote-selective meta-C(sp²)−H activation through a possible κ² coordination has been developed, thus suppressing the ortho-C−H activation thorugh κ¹ coordination. Besides meta-C−H olefination, direct meta-arylation of hydrocinnamic acid derivatives with low-cost aryl iodides has been achieved for the first time. These findings may motivate the exploration of novel selectivities and reactivities for carboxyl assisted C−H activation reactions.

A practical anti-Markovnikov hydrotrifluoromethylthiolation of unactivated alkenes using (CF₃SO₂)₂O and H₂O as the SCF₃ and H sources was achieved through deoxygenative reduction with PMePh₂ and photoredox radical processes. This reaction is the first example of using (CF₃SO₂)₂O as a trifluoromethylthiolating reagent and provides a new strategy for radical trifluoromethylthiolation.

3 in 1: A convenient and efficient domino aryne process was developed under transition-metal-free conditions to afford tetra- and pentacyclic ring systems. Chemoselective control at both the 1,2-aryne and 2,3-aryne stages enabled three new chemical bonds, namely one C−N and two C−C bonds, and two benzofused rings to be constructed concomitantly.

A weak moment: By employing ligand control and a weak directing group as key design elements, an efficient and diversity-oriented method for the synthesis of C-alkylated pyrrolidines has been developed. This nickel hydride catalyzed hydroalkylation achieves two different regioselectivites of the same substrates to yield both 2- and 3-alkylated pyrrolidines.

MXene Ti₃C₂T_x nanosheets were functionalized by hydrophilic or hydrophobic groups to tune the size and wettability of 2D nanochannels for elucidating the molecular transport mechanism of lamellar membranes. Hydrophilic nanochannels induce ordered alignment of polar molecules, which contributes to their fast transport, and thus their permeance is much higher than that in hydrophobic nanochannels with disordered molecular configuration.

F trick: A metal free and highly regioselective oxidative arylation reaction of fluorophenols is described.

Beyond natural: A protein catalyst was engineered to perform selective halogenation of a fragment of martinelline, a pharmaceutically relevant non-native substrate. Directed evolution of non-heme iron halogenase WelO5* afforded a variant with an up to 400-fold higher apparent k_cat and a 290-fold higher TTN for this target substrate than the wildtype enzyme while achieving high stereo- and regioselectivity (>99 %).

From bulk properties to a molecular level understanding: Solid-state NMR spectroscopy complemented by X-ray diffraction data and calculations gives insights into the loading-dependent structure of micelles formed by amphiphilic triblock copolymers. As coordination sites in the core become saturated, stabilization of higher loadings requires coordination by the hydrophilic corona, which compromises dissolution.

Chain reaction: A fluoride salt cleaves the N–N bond of an iron trimethylsilyl nitrilimine complex and generates the terminal nitride, fluorotrimethylsilane, and cyanide. The complementary reactivity of nitrilimine and azido ligands provides a new approach for the synthesis of metal terminal nitrido complexes.

An azobenzene setup was used to examine London dispersion in conjunction with solvent interactions between linear alkyl chains. ¹H NOESY NMR analysis indicated additional long-range interactions with the opposite phenyl core in the Z-isomer. This work provides rare insight into the stabilizing contributions of highly flexible groups in an intra- as well as an intermolecular setting.

Six centuries after the discovery of the simplest nitric acid ester, methyl nitrate (H₃CONO₂), experimental solid-state and gas-phase structures as well as energetic properties are compared with those of the new monofluorine-substituted analogue, fluoromethyl nitrate (FH₂CONO₂).

A hydrodynamics-based approach for the organization and assembly of fibrillar building blocks into hierarchical macrostructures with multiscale control over the nanostructure leads to exceptional mechanical properties. For the first time, structure–property relationships are understood depending on specific ion effects for wet and dry nanofibrillar systems.

Together alone: Single Rh atoms were encapsulated within MFI zeolites under in situ hydrothermal conditions and a ligand-protected direct H₂ reduction. The catalyst gave a high turnover frequency of 699 mol  (mol_Rh)⁻¹ min⁻¹ at 298 K for ammonia borane (AB) hydrolysis and exhibited superior catalytic efficiency in shape-selective tandem hydrogenation of nitroarenes by coupling with the hydrolysis of AB.

The four core disaccharides required for heparan sulfate (HS)/heparin oligosaccharide synthesis were efficiently generated from natural polysaccharides. Rapid access to these key building blocks will greatly facilitate the generation of comprehensive libraries of HS oligosaccharides for unlocking the sulfation code and understanding the roles of glycosaminoglycans in physiology and disease.

Functionalization of P ligands: The first metal complexes of diorganopentaphosphorus cations [P₅R₂]⁺ (R=Cy, iPr) have been prepared from tetrachlorogallate salts [P₅R₂]GaCl₄ and cyclopentadienyl cobalt and nickel complexes (Cp^Ar=C₅(C₆H₄-4-Et)₅). The installation of additional chloro, cyano, and cyclohexyl groups on the pentaphosphorus scaffold illustrates a useful strategy to access highly functionalized polyphosphorus ligands.

Skeletal rearrangement of 1D metal–organic chains (MOCs) occurs via a concurrent atom shift and bond cleavage on Cu(111) at room temperature. Cu-catalyzed debromination of organic monomers generates 1,5-dimethylnaphthalene diradicals that coordinate to Cu adatoms to form MOCs. Bond-resolved atomic force microscopy and DFT reveal that a relief of internal strain drives skeletal rearrangement.

The biological conversion of NO into N₂O is important to the global N-cycle. A cobalt heme model couples NO in the presence of a Lewis acid. DFT calculations provide insight into the role of the Lewis acid in activating the bound NO towards this N−N bond forming reaction.

The fix is N: Tuning the local electronic structure of Au nanoparticles with positive valence sites can boost conversion of N₂ to NH₃ by controlling N₂ adsorption and the concomitant energy barrier of NRR. The introduction of a metal with local electronic structure can offer a new direction for the fabrication of highly efficient catalysts for the N₂ reduction reaction (NRR).

Strong N−X⋅⋅⋅⁻O−N⁺ (X=I, Br) halogen bonds, by using oxygen as halogen bond acceptor, are obtained from N-halosaccharins and aromatic N-oxides. The donor–acceptor-dependent tunable X⋅⋅⋅O distances are investigated by using computational methods, solution NMR spectroscopy, and X-ray diffraction analysis.

A geometrical E→Z isomerisation of alkenyl silanes proceeding through selective energy transfer is enabled by an organic sensitiser and displays high selectivity for trisubstituted systems. Mixed bis-nucleophiles (Si, Sn, B) also undergo facile isomerisation, thereby enabling a formal anti-metallometallation.

Under the microscope: Galvanic replacement reactions between Ag nanowires and Au ions in aqueous solution is observed by liquid cell transmission electron microscopy under an electron beam.

Strong enough to bend: A coordination driven self-assembly strategy secures the appropriate head-to-tail alignment of anthracene moieties gave large Pt-based linear polymer crystals through a [4+4] cycloaddition of anthracene in a single-crystal to single-crystal fashion. The reversible contraction of unit-cell volume upon irradiation or heating gave a photoactuator.

A molybdenum polyoxometalate (POM) derived from bulk Mo₂C exhibits unique redox conversion and NIR-II photothermal conversion behavior in tumor microenvironment. Via intratumoral redox reactions, POM can generate ¹O₂ and deplete GSH for enhanced and sustained chemodynamic therapy.

Solid as a rock: The unsatisfactory electrochemical performance in solid-state batteries originates from internal strain-induced contact loss, heterogeneous phase transformation, and the augmentation of metallic surface passivation layers. With in situ growth of solid sulfide electrolyte into 3D FeS₂ microstructure, these issues can be significantly inhibited and superior electrochemical performance can be achieved.

Planting a seed: The hetero-epitaxial growth of a SSZ-13 (CHA-type) zeolite seed layer with the ZSM-58 (DDR-type) precursor is reported. The resulting membranes show excellent CO₂ perm-selectivities, having maximum CO₂/N₂ and CO₂/CH₄ separation factors (SFs) as high as about 17 and 279, respectively, at 30 °C. In the presence of water vapor, a CO₂/N₂ SF of about 14 and CO₂/CH₄ SF of about 78 at 50 °C were recorded.

Reach new heights: A single-molecule construct was designed and used to determine the effects of phosphorylation on the mechanical stability of the α-catenin/β-catenin complex, which is a component of cell–cell adherens junctions. Phosphorylation reduces the mechanical stability of the α-catenin/β-catenin complex.

Luminescent metal halide: A novel 0D metal halide material (C₉NH₂₀)₉[Pb₃Br₁₁](MnBr₄)₂ has two distinct emitting centers, self-trapped excitons (STE) residing on [Pb₃Br₁₁]⁵⁻ clusters and ⁴T₁-to-⁶A₁ transitions of Mn²⁺ ions in [MnBr₄]²⁻ tetrahedral units. This is the first example of Mn²⁺ emission and STE emissioncoexisting in a single crystalline material and allows white light-emitting diodes (WLEDs) to be fabricated.

Co doped: Cobalt-doped NiS₂ nanosheets (NSs) with optimal e_g¹ electron configurations and enhanced Ni³⁺ content exhibit excellent activity and stability for the hydrogen evolution reaction (HER) in alkaline media. DFT results reveal that a Co-NiS₂ NSs surface abnormally sensitizes Ni-3d bands towards higher electron-transfer.

A new phase: By leveraging membrane domains and DNA tethers, synthetic vesicles may be designed to selectively fuse and initiate biological reactions upon content mixing.

The prebiotic starting molecules bis-urea (biuret) and tris-urea (triuret) directly react with ribose. The urea-ribosides are remarkably stable because of a network of intramolecular, bifurcated hydrogen bonds, which even allowed the synthesis of phosphoramidite building blocks and incorporation of the units into RNA. Urea-containing RNA bases are therefore good candidates for a proto-RNA world.

A long-standing secret unveiled: The mammalian lectin responsible for the recognition of the core fucose on N-glycans is Dectin-1, a known anti-β-glucan lectin. Dectin-1 recognizes aromatic amino acids adjacent to the N-terminal asparagine at the glycosylation site as well as a core fucose. This heterovalent interaction is the origin of the efficacy and unique recognition pattern of Dectin-1.

Treatment with elastin polypeptides, a component of the brain extracellular matrix (ECM), increases levels of β-amyloid, associated with Alzheimer's disease, both in vitro and in vivo. This is associated with the occurrence of early-stage cognitive impairment in animals. This provides a new insight into Alzheimer's disease pathogenesis.

Where does the H₂ go? Using an F₄₂₀-reducing [NiFe]-hydrogenase from Methanosarcina barkeri as a model enzyme, it is shown that the protein backbone provides a strained chelating scaffold that tunes the [NiFe] active site for efficient H₂ binding and conversion. The protein matrix also directs H₂ diffusion to the [NiFe] site via two gas channels and allows the distribution of electrons between functional protomers through a subunit-bridging FeS cluster.