The C−F functionalization of acid fluorides has recently emerged as a new disconnection in transition-metal catalysis. Selective decarbonylative and non-decarbonylative transformations are presented together with first evidence on ligand-controlled selectivity.

Highly efficient organocatalysis: Enantioselective carbonyl catalysis has become one useful subbranch of organocatalysis and has proved to be very efficient for the activation of simple amines. In this Minireview, recent advances in enantioselective carbonyl catalysis will be discussed.

Mass-independent isotope effect is a new type of isotopic chemistry that does not follow the traditional isotope fractionation rule. It has been widely used in understanding the origin and evolutions of our solar system, Earth, Mars, life, and modern Earth's atmospheric and environmental physics and chemistry. This Minireview presents the history and most recent advances on this isotope effect, from quantum level understanding to its application in nature.

Fantastic four: Generally, enzymes are highly selective catalysts for single reactions. However, some enzymes instead control a series of reactions in a cascade-like fashion. This Review highlights four types of enzymatic cascade strategies, mediated by nucleophilic, electrophilic, pericyclic, and radical-based reactions, observed in the biosynthesis of complex natural products

Gd₂O₃ nanoscrolls have been synthesized by colloidal synthesis. This material shows tumor-microenvironment-induced biodegradation, allowing the targeted release of anticancer agents, significantly inhibiting tumor growth, with negligible cellular and tissue toxicity, both in vitro and in vivo.

The precise alignment of multiple layers of metal–organic framework (MOF) thin films, or MOF-on-MOF films, over macroscopic length scales is presented. The MOF-on-MOF films are fabricated by epitaxially matching the interface. This strategy allows the synthesis of aligned MOF films that cannot be grown on a Cu(OH)₂ surface.

A luminescent back reflector (LBR) capable of photon upconversion (UC) is used to improve the light harvesting of Mo:BiVO₄ photoelectrodes. The LBR converts the wavelengths of 600–650 nm and 350–450 nm into a wavelength that can be absorbed by a Mo:BiVO₄ photoelectrode. Mo:BiVO₄/LBR exhibits a photocurrent density of 5.25 mA cm⁻² at 1.23 V versus the reversible hydrogen electrode.

COF it up! Three regioregular porphyrin-based porous covalent organic frameworks (COFs) with excellent nonlinear optical (NLO) properties are presented. Por-COF-HH and its metalated congeners, Por-COF-ZnCu and Por-COF-ZnNi, were prepared by Schiff base condensation of tetrasubstituted porphyrin aldehydes and amines. The NLO switching and high-parameter values obtained for these Por-COFs are promising for optical switching and optical limiting devices.

On the same wavelength: A promising strategy to screen environmentally friendly, biocompatible, and efficient electrochemiluminophores is proposed via rigidification of the shell of Au nanoclusters by host–guest recognition.

What has it got in its pocketses? A single asparagine-to-glycine mutation in the aryl acid adenylation domain EntE gives a novel promiscuous enzyme that accepts a range of non-native substrates, in particular, aryl acids functionalized with cyano, nitro, bromo, and iodo groups. Co-crystal structures with non-hydrolysable aryl-AMP analogues revealed the origins of the substrate promiscuity to be an enlarged active-site pocket.

Small fluorophores: A family of small multi-color benzodiazole fluorophores for non-invasive imaging of essential metabolites in live cells and in vivo is described.

Mind the step! DFT-based ab initio molecular dynamics studies reveal the origin of the experimentally observed bimodal CO₂ velocity distribution on Pt surfaces. While CO₂ formed at terrace sites desorbs directly with high velocities, it is trapped in a chemisorption well when formed at step sites. This is due to an electron transfer to an antibonding CO₂ orbital and leads to a desorption with low velocities and a broader angular distribution.

Chloride carriers as cotransporters for organic ion pairs: Calix[6]arene tris(thio)ureas, bearing a cavity that can accommodate primary ammonium ions, can perform the cotransport of PrNH₃Cl across a lipid bilayer, as well as Cl⁻/NO₃⁻ antiport. The advantage of the cavity is highlighted by comparing calixarenes to receptors without a cavity, and by attempting to transport bulkier alkylammonium ions, which cannot be complexed in the cavity.

The right alignment: The structural and electronic properties of cadmium phosphochlorides were investigated experimentally and using density-functional-theory calculations. The positions of the valence band maxima and conduction band minima allow these systems to be used in the hydrogen evolution reaction.

Dumbbell charge transfer: The synthesis of an all-fullerene electron donor–acceptor conjugate, C₆₀-Lu₃N@I_h-C₈₀, is reported. In the dumbbell-like system, one fullerene moiety acts as the donor (Lu₃N@I_h-C₈₀) while the other acts as the acceptor (C₆₀). Spin conversion of the charge-separated singlet state into the corresponding triplet state slows down the charge recombination by one order of magnitude.

Fits to a T: A three-coordinate low-spin cobalt(I) complex with an acridane-based pincer ligand was synthesized. It reacts with H₂ and PhSiH₃ by σ-complexation at the cobalt center, which has an empty orbital. In this example, the homolysis of a σ-bond by bimolecular hydrogen atom transfer (HAT) occurs rather than oxidative addition.

A unique and versatile strategy is proposed to fine-tune the persistent luminescence over the entire visible spectral region with narrow bandwidth and highly synchronized afterglow decay. It uses a CaAl₂O₄:Eu²⁺,Nd³⁺ (CAO) afterglow phosphor as the single energy storage source and all-inorganic CsPbX₃ (X=Cl, Br, and I) perovskite quantum dots (PeQDs) as efficient light conversion materials.

Walking on sunshine: A non-autonomous DNA walker can processively move two steps back and forth on a defined path and is powered exclusively by light irradiation in an orthogonal fashion. Irradiation at different wavelengths, in a defined sequence, leads to precise control over the motion and position of the walker at every step. The non-invasive regulation of multistep processive motion is the first critical achievement towards nanoscale robotics.

A polarizing pair: Circularly polarized electrochemiluminescence from a chiral organic molecule is observed. The macrocyclic scaffold leads to an efficient excimer formation between two pyrene moieties that are covalently attached. As a result, highly polarized emission is obtained upon electrochemical excitation.

No limits: The commercially available phenanthroline serves as an efficient catalyst to promote the stereoselective formation of α-1,2-cis glycosides. The selectivity of this newly developed catalyst system is not limited by the nature of the protecting groups on the coupling partners.

Face time: Isotopically labelled microsized Li₂O₂ particles with an Li₂¹⁶O₂/electrode interface and Li₂¹⁸O₂/electrolyte interface were fabricated. On-line electrochemical mass spectroscopy showed that upon Li₂O₂ oxidation ¹⁸O₂ was evolved for the first quarter of the charge capacity followed by ¹⁶O₂. These observations unambiguously demonstrate that oxygen loss starts at the Li₂O₂/electrolyte interface instead of the electrode/Li₂O₂ interface.

Electric youth: A stable, non-corrosive perfluorinated pinacolatoborate Mg electrolyte was developed for rechargeable Mg battery applications. This electrolyte has a Coulombic efficiency of 95 % and an overpotential of 197 mV, enabling reversible Mg deposition, and an anodic stability of up to 4.0 V vs. Mg. This was used to produce a high voltage, rechargeable Mg/MnO₂ battery with a discharge capacity of 150 mAh g⁻¹.

The collaborative coordination of CO at diatomic Ni-Fe sites anchored on nitrogenated carbon is the key to a new nickel–iron catalyst developed for the electroreduction of CO₂. The catalyst achieves a high Faradaic efficiency of 98 % at −0.7 V, outstanding turnover frequency, and robust electrode durability.

Through thick and thin: Since the thickness of two-dimensional (2D) PtSe₂ flakes can be controlled by adjusting synthesis conditions, their layer-dependent catalytic activity for the hydrogen evolution reaction could be investigated from both theoretical and experimental perspectives. Structure–activity correlations were drawn, providing new insights for the design and synthesis of ultrathin catalysts.

Twist and shine: Homotruxene, a non-planar arene, was obtained by trimerization of 1-tetralone. Due to its geometry, the molecule possesses unique luminescence properties for a pure hydrocarbon: pronounced spin–orbit coupling and a high triplet energy lead to room-temperature phosphorescence, while triplet–triplet annihilation causes a substantial delayed fluorescence.

Hit the spot: A copper-functionalized triphenylphosphonium-modified metal–organic framework catalyzed localized drug synthesis in mitochondria through a site-specific copper-catalyzed azide–alkyne cycloaddition (CuAAC) reaction (see picture). This system has wide applicability for the in situ synthesis of drugs with good biocompatibility and has unique advantages for improving the efficacy of active drugs and avoiding side effects.

Double agent: P K-edge XANES and TDDFT calculations were used to quantify how nontrigonal structural deformations affect the electronic structure and reactivity of a series of P(NNN) compounds. The results suggest that biphilic P^III reactivity reported previously with and without a transition-metal host stems from a common low-lying phosphorus-based acceptor orbital that becomes energetically accessible in response to nontrigonal P^III distortions.

Electrifying: An efficient asymmetric electrosynthesis was developed with high yields and excellent enantioselectivities by using a chiral Ni catalyst. Mechanistic studies suggest that the Lewis-acid-bound radical intermediate, from a single-electron anodic oxidation, selectively reacts with a benzylic radical species to generate the desired adducts.

Shuffle the rings: An unusual furan rearrangement biogenetically connecting the eremophilane natural product microsphaeropsisin B and its regioisomer periconianone C is postulated. Strong experimental support for this intriguing mechanistic pattern is provided by total synthesis, with an α-ketol rearrangement.

Bright lights, small dots: Achieving long-wavelength-excitable near-infrared semiconducting polymer dots with simultaneously high fluorescence quantum yield, strong absorption cross-section, narrow absorption-emission bandwiths, and large Stokes shift by employing a BODIPY-based donor/donor-acceptor system.

Circularly polarized luminescence of charge-transfer complexes was demonstrated for the first time. The complexes feature a large g_lum value owing to charge-transfer interactions. Benefiting from the large magnetic dipole transition moment in the charge-transfer state, the CPL activity of mixed-stack CT complexes exhibited large circular polarization.

Six pack: Cyclohexanehexone (C₆O₆) is synthesized and applied as a cathode material in lithium-ion batteries that exhibit an ultrahigh capacity of 902 mA h g⁻¹ (1533 Wh kg⁻¹). As a result of its limited dissolution, C₆O₆ shows relatively good cycling stability (a capacity retention of 82 % after 100 cycles at 50 mA g⁻¹) in ionic liquid electrolyte.

MgBu₂ proved to be an efficient catalyst for the hydroboration of terminal and internal alkynes, achieving good yields and selectivities. The compatibility with many functional groups makes the Mg-catalyzed hydroboration of alkynes very attractive as a late stage functionalization procedure. Moreover, experimental investigations together with DFT calculations provide insight into the reaction mechanism.

Masking reagent-free: Organozirconium-catalyzed copolymerization of ethylene with polar amino-olefins proceeds with high activity and high polar monomer incorporation in the absence of a masking reagent. Experimental and DFT mechanistic analysis show that the high activity is attributable to favorable olefin over amino group coordination.

Slow and steady wins the race: An atomically dispersed Zn–N–C catalyst with an ultrahigh loading of single Zn atoms of 9.33 wt % (see HAADF-STEM image) was successfully prepared by decreasing the annealing rate to 1° min⁻¹. The Zn–N–C catalyst exhibited comparable ORR activity to that of the corresponding Fe–N–C catalyst, and greater ORR stability in both acidic and alkaline media.

An H₂O₂-assisted top-down approach was proposed to synthesize brightly luminescent sulfur quantum dots (SQDs), which allows simultaneous control over the final size, tuning of their emission color, and improving their emission quantum yield (up to 23 %) by eliminating surface traps. White light emitting diodes using blue emissive SQDs and orange emissive copper nanoclusters are also demonstrated.

Busy BEE: A biredox eutectic electrolyte (BEE) is derived from the intermolecular interactions between the redox-active molecules N-butylphthalimide and 1,1-dimethylferrocene. Given the high concentration of active materials, the flow cell based on the BEE delivers stable cycling performance, and high volumetric capacity and power density. The facile and effective strategy has potential for high-performance nonaqueous redox flow batteries for high-energy storage systems.

Ultrathin, binary MOF nanosheets (NSs) have been successfully prepared for the first time and directly used as efficient oxygen evolution reaction (OER) catalysts. The binary MOF NSs exhibit a highly composition-dependent OER activity. The optimized Ni–Fe–MOF NSs are highly active and stable towards the OER.

In silico(n): Machine learning makes it possible to quantify the local structure in amorphous solids and the local atomically resolved energy at the same time, as demonstrated here for an ensemble of amorphous and liquid Si structures.

Rezinking zinc batteries: Aqueous zinc-ion batteries based on VOPO₄ cathodes and a water-in-salt electrolyte displayed highly reversible oxygen redox chemistry at high voltages (see graph). The oxygen redox process not only led to increased capacity and a higher average operating voltage of the Zn/VOPO₄ batteries, but also improved rate capability and cycling performance.

Under pressure Mo/ZSM-5 catalysts display much better methane dehydroaromatization performance in a wide range of conditions. An eightfold increase in aromatic productivity is obtained by increasing the reaction pressure from 1 to 15 bar. These findings are rationalized by the reversible growth of coke species and better utilization of the zeolite micropores.

Twisted intramolecular charge shuttle (TICS): In TICS systems, the donor and acceptor moieties dynamically switch roles in the excited state due to an approximately 90° intramolecular rotation that is induced upon photoexcitation. This results in charge shuttling. TICSs exist in several families of fluorophores and could be utilized in the construction of fluorescent probes.

Triggered release: A thermoresponsive carrier comprising gold nanostars coated with ZIF-8 stabilized with an amphiphilic polymer was developed for the light-triggered release of encapsulated cargo inside cells. This nanocomposite, which is stable in aqueous solution (even when stored in cells), combines thermoplasmonic and high drug-loading capabilities.

Wall to wall: The upgrade of CH₄ by direct non-oxidative methane conversion is facilitated by a Fe/SiO₂ millisecond catalytic wall reactor. The reactor design results in stable methane conversion, C₂₊ selectivity, coke yield, and long-term durability.

Connect the dots: A cationic carbon quantum dot (cQD) probe emits spectrally distinguishable fluorescence signals upon binding to DNA (green) and RNA (red) in live cells, thereby enabling real-time imaging of DNA and RNA localization and motion. The probe can penetrate through various types of biological barriers in cells and in vivo for super-resolution microscopy and time-lapse imaging of chromatin and nucleoli during cell division and C. elegans growth.

Model DyKAH: The first Brønsted acid catalyzed dynamic kinetic asymmetric hydroamination (DyKAH) of racemic allenes and asymmetric hydroamination of dienes with both high E/Z selectivity and enantioselectivity is presented. The transformation proceeds through a new catalytic asymmetric model involving a reactive π-allylic carbocationic intermediate. This method affords expedient access to diverse enantioenriched, bioactive aza-heterocycles.

H(igh)–F(ive): The combination of a multidentate ligand, (EtO)₃SiH, and N-fluorobenzenesulfonimide (NFSI) proved critical in facilitating an iron-catalyzed hydrofluorination of unactivated alkenes to provide a variety of substituted fluorinated compounds. The reaction was shown to proceed by a radical mechanism and to be suitable for the fluorination of various biologically active substrates.

Improving charge transfer: A ternary heterojunction was designed, in which polymeric carbon nitride (PCN) and Fe₂O₃ served as the hydrogen evolution photocatalyst and the oxygen evolution photocatalyst, respectively, while reduced graphene oxide (RGO) acted as an electron transfer “freeway”. This all-solid-state Z-scheme system showed promising activity for photocatalytic stoichiometric water splitting under simulated sunlight irradiation.

Computationary, my dear Watson! The amalgamation of olefin strain energy (OSE) and DU8+ analysis brings to the fore a powerful combination of in silico methods that can be deployed in concert by those undertaking natural product structure determination.

Starting blocks: Structurally controlled poly(vinylamide)s and poly(vinylamine)s were synthesized by organotellurium-mediated polymerization (TERP) of acyclic vinylamides and subsequent hydrolysis of the amides. A block copolymer with a poly(vinylamine) segment was also synthesized.

A new branch! A novel strategy for the mild, highly branch-selective and redox-neutral allylic C−H amidation is described. Naturally occurring and abundant carboxylic acids were converted into the corresponding dioxazolones and reliably coupled with terminal and internal olefins. The synthetic value of this transformation was demonstrated in the coupling of complex and bioactive scaffolds.

Filled to the brim: Two types of Janus nanocups were prepared from ABC triblock terpolymers through cross-linking and disassembly of shape-anisotropic “tulip-bulb” microparticles. Both nanocups feature mirrored Janus properties that allow selective filling of the cup interior or the exterior with compatible materials.

Tight and loose: Covalent (R)-amino acid modifiers are novel tools for probing the activity and oligomerization of the bacterial ClpXP protease. Substoichiometric binding strengthens the ClpX–ClpP interaction. Depending on the substitution of the compound, proteolysis is either stimulated or efficiently inhibited by formation of an unprecedented complex assembly.

No protection needed: A strategy employing a highly efficient λ-orthogonal photochemical procedure by selective excitation of photosensitive groups paves the way to precision monodisperse sequence-defined linear macromolecules without any need for protection-group chemistry. The chain growth is based on a two-monomer system that enables protection group free convergent chain extension on-demand.

Fragmentation of the chemokine-receptor CCL19/CCR7 binding domain led to a hexapeptide as a template for de novo peptide design. Computer-generated peptides were characterized in terms of their binding to CCl19. Potent ligands were identified as starting points for developing innovative protein–protein interaction modulators.