An organic matrix can assist the crystallization of all-organic perovskites at temperatures lower than the phase transition point of black phase CsPbX₃ perovskite. This low-temperature crystallization takes place through the formation and decomposition of an intermediate state which is reminiscent of an organic–inorganic perovskite matrix.

This Review describes the basic principles of water electrolysis, key aspects of the oxygen evolution reaction (OER), and significant criteria for the development of new catalysts. Recent advances in catalysts based on Co, Ni, and Fe oxides are described, and a brief perspective is given on green hydrogen production and the challenges of water electrolysis.

Ring-opening copolymerisation (ROCOP) is a powerful living polymerisation that yields numerous alternating copolymers with precisely placed heteroatoms in the polymer backbones. This Review summarizes the state-of-the-art of this important method, describes the principles of the catalysis, and illustrates the potential of the different monomer combinations and resulting polymers. Trends and future challenges of this approach and the resulting materials are highlighted.

The conformational behaviour of an intrinsically disordered protein responsible for protecting tardigrades against extreme stress has been characterized. The protein assembles into fibres and fibrillar gels as a function of temperature and concentration. The disordered tails remain flexible within the gel cavities, which can encapsulate client proteins in their native state.

Through-space electronic conjugation between a redox mediator and molecular Cr complex enables emergent co-electrocatalytic activity for the electrochemical reduction of carbon dioxide to carbon monoxide. In the reduced forms, the aromatic portions interact through a combination of dispersion forces, π conjugation, and weak coordination of the sulfone to Cr.

Direct urea synthesis from NH₃ and CO₂ was achieved over Pd/LTA-3A powered solely by solar energy. Pd nanoparticles serve the dual function of catalyzing the dissociation of NH₃ and providing the photothermal driving force for reaction with CO₂, while the absorption capacity of LTA-3A removes by-product H₂O, shifting the equilibrium towards urea production.

Carbene insertion into Si−H bonds of silsesquioxane silanes was accomplished using Rh^II catalysis and diazo compounds as carbene precursors. Silsesquioxanes with up to eight Si−H bonds were functionalized up to gram-scale. Diazo compounds with a fluorinated octyl group and BODIPY fluorophore were accessed to highlight the utility of diazo chemistry. Further transformations including a cross-coupling and ester deprotection are demonstrated.

Thioester linked oligo(T) nucleic acids are utilized for an efficient enrichment of mRNA from total RNA under ambient temperature. The selective binding of uncharged oT TENA to the poly(A) tail of the mRNA and release via a self-immolative degradation of thioester backbone under ambient temperature were the key features that enabled this approach.

Tetrahedral carbon and analogous four-coordinate main-group compounds are configurationally stable, but we report intramolecular P-epimerization of chiral phosphiranium cations under mild conditions. How? In the proposed mechanism, P-C cleavage yields an intermediate pendant β-carbocation which promotes low-barrier pyramidal inversion at phosphorus, while hyperconjugative stabilization from a P-C σ-bond preserves the cation's C-chirality.

A photocatalytic sulfonylcarbocyclization of terminal alkynes using SEt as a traceless directing group is developed, providing a facile access to highly substituted cyclopentenes and indenes from readily available starting materials. It represents a new advance on anti-Baldwin 5-endo-trig radical cyclization of all-carbon systems, which may be valuable for the fast construction of five-membered carbocycles.

A mild visible light-induced palladium-catalyzed alkyl Heck reaction of diazo compounds and N-tosylhydrazones is reported. This method features Brønsted acid assisted generation of hybrid palladium C(sp³)-centered radical intermediate and broad reaction scope, highlighting the diverse applicability and the potential utility of this protocol in late-stage functionalization.

Synthetic access to modified RNA is of high importance. Both the gold standard—chemical solid-phase synthesis—and enzymatic methods have limitations. The present study offers a best-of-both-worlds approach and enabled the synthesis of a tRNA derivative with four modifications. This approach is compatible with a whole toolbox of light-reactive and other modifications.

A simple nickel catalyst converts terminal alkynes and formic acid to α-chiral carboxylic acids in high enantioselectivity. The reaction proceeds via the hydrocarboxylation of alkynes and enantioselective transfer hydrogenation of acrylic acids.

Electrochemical measurement of the early aggregation of α-Syn and exocytosis event of PC12 revealed a new neuroprotective role of VD that can inhibit the α-Syn monomers aggregation into α-Syn oligomers and modulate exocytosis. This research provides an efficient strategy for early treatment and prevention of the neurodegenerative diseases associated with α-Syn oligomers.

Crack the code of egg-tempera paints: The macroscopic and microscopic properties of egg-tempera paint prepared with green earth are highlighted via rheology and NMR relaxometry.

Making drugs in the brain! Fully-biocompatible Au catalysis enables for the first time the localized uncaging of a neuroactive agent, the anxiolytic drug fluoxetine, directly in the head of zebrafish by using catalytically-enhanced Au-polymer composites as safe catalytic reactors.

Solving alkynes of problems with palladium. A palladium-catalyzed domino cyclization of alkyne-tethered carbamoyl chlorides and aryl iodides with alkyne-tethered aryl nucleophiles is reported. This methodology unsymmetrically links heterocycles along a tetrasubstituted olefin with >20:1 E/Z selectivity and up to 96 % yield.

A slender single crystal based on azine exhibits controllable plastic bending and fluorescence enhancement upon UV light irradiation or acid vapor fuming, as well as elastic bending under external force and mechanoresponsive fluorescence. This is the first smart single crystal exhibiting fluorescence lit up upon bending triggered by UV light irradiation and exposure to acid.

Open, dynamic, and elusive membrane motifs are labeled without chemical or physical interference to image their order and tension in living cells: Fast release with light from specific targets liberates the original small-molecule flipper probe in the innermost leaflet of the nuclear envelope, the inner leaflet of the plasma membrane, or along the secretory pathway to address current questions of biological significance.

Single vesicular catecholamine concentrations in the intracellular environment were calculated based on the narrowed distributions of vesicular content and size obtained with 100 nm open CNPs. We have shown that vesicular dense core size and content increase while catecholamine concentrations are essentially unchanged after exposure to L-DOPA.

For the first time, we prepared continuous polycrystalline Prussian blue (PB) membrane showing precise dye rejection and monovalent ion discrimination ability. The introduction of a calcined NiFe-CO₃ layered double hydroxide buffer layer on the substrate was found to play a paramount role in the formation of PB membrane with desirable microstructure and performance.

We report a remote arylation in less than 10 min reaction time at room temperature over a distance of up to 11 carbons. The unprecedented speed is enabled by the air-stable Pd^I dimer [Pd(μ-I)(PCy₂^tBu)]₂.

Strong intramolecular Pt⋅⋅⋅Pt/π–π interactions confined by rigid bridges lead to fast radiative decay and high-efficiency red and near-infrared (NIR) phosphorescence from triplet metal-metal-to-ligand charge transfer (³MMLCT) excited states. Together with short emission lifetimes, high-performance red and NIR organic light-emitting diodes (OLEDs) have been demonstrated.

A gigantic molecule composed of 1072 atoms was designed and synthesized to install two types of nitrogen dopants in a defective nanotube molecule. Charge-transfer interactions originating from the pyridinic and pyrrolic nitrogen dopants were disclosed by solution-phase analyses, and 3-nm molecular structures and a unique helical assembly were revealed by crystallographic analyses.

A π→π* interaction is discovered to be by far the main stabilizing contribution in the benzofuran–formaldehyde adduct, resulting in an interaction energy of −16.1 kJ mol⁻¹. The characterization of eleven singly-substituted isotopologues allowed for an accurate semi-experimental equilibrium structure determination, which points out a carbon–carbon distance (3.2257±0.0006 Å) between formaldehyde and benzofuran shorter than the sum of the carbon van der Waals radii.

Ag⁺-coordination-mediated assembly of β-peptide foldamers led to the formation of distinctive metal–peptide frameworks with unique interwoven topologies. Formation of the network structures was accompanied by unusual conformational distortions of the foldamer ligands. These new metal–peptide frameworks built from modular foldamers may provide useful molecular platforms for further structural evolution and mechanistic investigation.

Selective ¹H^α-detected NMR methods were developed to study cis/trans isomerization in intrinsically disordered proteins (IDPs) under physiological conditions. Using p53TAD^1–60 proline (Pro) isomers with low population were identified and the variation of the cis/trans-Pro equilibrium was monitored upon phosphorylation. Statistical analysis was performed to investigate how the amino acid type influences Pro isomer formation.

Benzyl vinyl ethers have selectively been arylated at either α or β position by fine-tuned Heck-type palladium catalyses. In contrast to previous protocols, no excess of arylating reagent or substrate chelation is necessary. For achieving good yields and high α/β-selectivities various factors determining the catalytic system had to be optimized. The results of DFT computational studies correlate selectivity with electron richness on the Pd center.

A scalable N-trifluoromethylative cyclization strategy is reported to construct N-CF₃ tetrazoles/imidazoles/1,2,3-triazoles. N-CF₃ nitrilium derivatives are obtained via the N-trifluoromethylation of nitriles and well used as NCF₃-containing synthons in 1,3-dipolar cyclizations for the first time. A generic platform for accessing diverse N-CF₃ azoles is thus provided.

An intramolecular hydrosilylation strategy was developed for the asymmetric synthesis of chiral monohydrosilanes. This protocol is suitable for the synthesis of dihydrobenzosilole-, tetrahydrobenzosiline- and oxatetrahydrobenzosiline-based monohydrosilanes with excellent diastereo-, regio-, and enantioselectivities. Notably, the catalyst loading could be reduced to 0.1 mol %.

Phosphines turned to be powerful directing groups for the electrophilic C−H borylation of arenes. The reaction involves P-stabilized boreniums as key intermediates. It provides a direct, efficient, and general way of preparing phosphine–boranes.

A branched [8]catenane was synthesized from a one-pot procedure with good efficiency. Rigidifying/loosening the mechanical bond in the core, middle or periphery of the [8]catenane resulted in, respectively a large, middle and small degree of change in the catenane dynamics and flexibility.

The facile synthesis of C-aryl nucleoside analogues from readily available furanose acetates and aryl iodides is disclosed. This nickel-catalyzed cross-electrophile coupling showed good functional-group compatibility and excellent β-selectivity. The high chemoselectivity with respect to aryl iodides enabled the efficient preparation of a variety of C-aryl halide furanosides suitable for various post-functionalization reactions.

A one-pot sequence involving an exo-Diels–Alder reaction followed by a Lewis acid gold(I) catalyzed cyclization has allowed access to three complex polycyclic scaffolds. Structural diversity is obtained by varying solvent and the ligand of the gold(I) catalyst. An additional Diels–Alder step generates tetracyclic cores possessing up to 5 stereocenters.

We report the use of interfaced proline residues as the “key” to unlock enzyme evolvability and thus access biocatalysts with highly improved catalytic performance.

An inexpensive cobalt catalyst enables the combination of benzylic CH-borylation and dehydrocoupling to an overall acceptorless dehydrogenative functionalization of hydrocarbons at mild conditions. Mechanistic studies indicate a tandem catalysis via molecular Co^I catalysts.

Thylakoid membranes were introduced into an in vitro biosystem for the synthesis of polyhydroxybutyrate to enable the conversion of light energy into biological energy through the regeneration of NADPH and ATP (see picture). The use of thylakoid membranes as a green engine in this way is a promising strategy for light-powered cell-free biomanufacturing.

The structures of a geranyl pyrophosphate (GPP) C6-methyltransferase, BezA, and its complex with S-adenosyl homocysteine were solved by X-ray crystallography. Further analysis based on site-directed mutagenesis and computational calculations provided the molecular basis of the methylation reaction. Furthermore, an unprecedented farnesyl pyrophosphate C6-methyltransferase was created by introducing a W210A substitution.

A series of hydro-stable metalloporphyrin-bridged metal-phenate frameworks are constructed, which exhibit artificial photosynthetic activity under visible-light irradiation without photosensitizer or sacrificial agent. Activity is boosted by substitution of the Fe-oxo chain for an In-oxo chain, and further enhanced by addition of the uncoordinated hydroxyl groups of catechol into the scaffold.

Inspired by the natural extracellular vesicle-cell fusion process, we introduced the fusogenic spherical nucleic acid (fuso-SNA) to achieve spatially controlled cell membrane engineering with DNA by using a liposome fusion-based transport (LiFT) approach. We demonstrated asymmetric DNA modifications on the cell membrane with orthogonal functionalities on each side, realizing applications such as heterotypic cell assembly and intracellular metabolites detection.

Two classes of tetrasubstituted axially chiral olefins have been accessed in excellent enantioselectivity via Rh^III-catalyzed asymmetric C−H activation assisted by a migratable directing group.

A new class of upconversion (UC) nanocrystals of CsLu₂F₇:Yb/Er are developed to achieve efficient UC through triplet sensitization of NIR dye IR808, resulting in a 1309-fold enhancement in UC luminescence intensity and a more than 180-fold improvement of the absolute UC quantum yield over bare counterparts. Sensitive detection of intracellular ClO⁻ is demonstrated by virtue of the 808-nm/980-nm dual excited ratiometric UC luminescence.

Full-color emission is achieved from a single fluorescent component by incorporating it into polyurethane matrices. Facilitated by the chemical structure of polyurethanes, the emission color could be modulated from blue to red by simply tuning the density of the chromophores, via either synthetic or physical approaches.

Intercalation of Mo₃S₁₃²⁻ into MgAl-layered double hydroxide (LDH) gives a new material, Mo₃S₁₃-LDH, which exhibits enormous adsorption capacities of noble metal silver (q_m^Ag=1073 mg g⁻¹) and toxic Hg²⁺ (q_m^Hg=594 mg g⁻¹) as well as high uptake selectivity for Ag⁺ and Cu²⁺. Both S₂²⁻ and Mo⁴⁺ in Mo₃S₁₃-LDH contribute to the reduction of Ag⁺ to metallic Ag⁰.

The direct synthesis of new (Z)-(1-alken-1-yl)pentafluoro-λ⁶-sulfanes was performed via the photoinitiated anti-hydropentafluorosulfanylation of terminal alkynes. The reaction of SF₅Cl with 24 substrates in the presence of (TMS)₃SiH as a H-atom donor gave access to the undocumented Z-isomer. The origins of this unusual selectivity were investigated by DFT calculations, which provide a better understanding of the geometry and reactivity of SF₅-substituted vinylic radicals.

Peripherally π-extended corannulenes with five azahelicene units were prepared and their structural dynamics were studied experimentally and theoretically. This motif contains many conformational isomers owing to the helical and bowl chiralities. The interconversion networks were explored by using GRRM17 program, which revealed that the co-existing corannulene and azahelicene moieties lower the activation energy barriers for some isomerization processes.

Acenes and peri-acenoacenes should be seen as π-conjugated systems containing one and two localized aromatic sextets, respectively, flanked with ortho-fused diene fragments. The vertical extension of TIPS-PEN, TIPS-PPP, has been prepared from a dione precursor and absorbs at longer wavelengths, is 16 times more stable, exhibits a 2D brickwall motif in crystals with stronger π–π interactions and a smaller reorganization energy.

Here we created active metal–oxide interfaces in porous single-crystalline CeO₂ monoliths with in situ exsolved single-crystalline Ni nanoparticles and show efficient and durable CH₄/CO₂ reforming at a relatively low temperature of 450 °C.

The ability of phosphates to act as efficient arynophiles is demonstrated. The resulting aryne phosphate reaction is a versatile tool for arene phosphorylation or phosphate arylation. A broad scope of variously arylated phosphate products is culminating in novel nucleotide analogues and a benchmarking octaphosphorylation.

Newly synthesized tetramesityldiborane(4) shows exceptional chemical stability and blue/orange dual fluorescence capability associated with the B−B bond rotation in the excited state. The relative intensity of the dual fluorescence is sensitive to the viscosity of the medium, highlighting the potential of this diborane(4) as a ratiometric viscosity sensor.

The synthesis and properties of a perylene bisimide dye bridged by one or two quinquethiophene units are described. The compounds show panchromatic light absorption in the UV/Vis spectrum, multiple reversible redox processes, and a highly efficient charge separation by photoinduced electron transfer.

The DAP mediated prebiotic phosphorylation of nucleosides/nucleotides/oligonucleotides produces a spectrum of the corresponding mono-, di-, and tri(amido)phosphorylated derivatives which are substrates for both prebiotic-oligomerization and biotic-polymerization/ligation. The compatibility of the phosphorylation and activation chemistry across a broad spectrum of (oligo)nucleos(t)ide structures suggests a smoother transition from chemistry to biology.

Visible-light-induced β-carbonyl alkylation of pyridines was developed by employing various cyclopropanols and N-amidopyridinium salts under mild conditions. This method provides an effective tool for the synthesis of valuable β-pyridyl-functionalized carbonyl frameworks with excellent C4 selectivity and the late-stage functionalization of complex and medicinally relevant molecules.

Porous aromatic frameworks (PAFs) with stable carbon–carbon linkages and chemically modifiable pores were shaped into continuous membranes, which are capable of separating industrially valuable gas mixtures, including H₂/N₂ and CO₂/N₂. With modulation of the pore structure or chemical environment, the separation performance of continuous PAF membranes exceeded their corresponding Robeson's upper bounds.

A series of calix[4]pyrrole-based crosslinked polymer networks was synthesized via Sonogashira–Hagihara polycondensation. One system, C[4]P-BTP, was found to be highly effective for iodine capture from water with an uptake capacity of 3.24 g g⁻¹ and quick kinetics (k_obs=7.814 g g⁻¹ min⁻¹). Flow-through adsorption experiments revealed that C[4]P-BTP was able to remove 93.2 % of iodine from an aqueous phase with a flow rate of 1 mL min⁻¹.

3D imide-bonded covalent organic framework (COF) composed of cobalt-phthalocyanine subunits has been prepared and used in CO₂ reduction reaction electrocatalysis, showing the high CO₂-to-CO conversion Faradaic efficiency. In particular, the active electrocatalytic centers and current density (j_CO) of this 3D COF have been significantly improved in comparison to that of the 2D COF electrocatalyst with the same phthalocyanine subunits.

Drug-like inhibitors for bacterial carbohydrate-binding proteins called lectins are challenging. Computational and experimental analyses (NMR and SPR) of related β-propeller lectins from Burkholderia ambifaria (BambL), Ralstonia solanacearum (RSL), and Aspergillus fumigatus (AFL) identified druggable secondary pockets, which will support the design of allosteric inhibitors as new therapeutics against antibiotic-resistant pathogens.

The synthesis, in vitro and in vivo evaluation of a vesicular ibrutinib-Cy3.5 hosting nanocarrier is reported. In vivo, it shows a significant enrichment of the drug in xenograft lymphoma tumors in immune-compromised mice and gave a significantly better response at much lower dosage than the original untargeted drug.